Polypropylene resin composition and fibers using polypropylene resin composition

Abstract

Provided are: a polyolefin resin composition having excellent dye affinity; a polypropylene resin composition having excellent spinnability; dyed polypropylene fibers; and a method for producing dyed polypropylene fibers.

Description

Polypropylene resin composition and fiber using the polypropylene resin composition

[0001] The present invention relates to a polyolefin resin composition, a polypropylene resin composition, a dyed polypropylene fiber, and a method for producing the dyed polypropylene fiber.

[0002] Polypropylene is a non-polar material. Patent Document 1, for example, discloses a nonwoven fabric made of a resin composition containing polypropylene, thermoplastic polyethylene oxide (hydrophilic resin), a compatibilizer, and the like, with the aim of providing a durable nonwoven fabric made of a polypropylene resin composition and having excellent hydrophilicity.

[0003] Japanese Patent Application Publication No. 08-157650

[0004] Patent Document 1 does not disclose the use of dyes, and it is believed that the dyeability of a nonwoven fabric made from a resin composition such as that described in Patent Document 1 is insufficient, and that the spinnability is also insufficient. Patent Document 1 also does not use a hydroxyl-modified polyolefin (hydroxyl-modified polypropylene) as the polyolefin. Patent Document 1 also uses a very small amount of a compatibilizer, 0.1 to 2 parts by weight, and does not disclose good spinnability. Patent Document 1 also does not disclose fibers containing dyes, nor does it disclose fibers in a fibrous form that can be dyed. Under these circumstances, the problem to be solved by the present invention is to provide a polyolefin-based resin composition with excellent dyeability, or a polypropylene-based resin composition with excellent spinnability, dyed polypropylene-based fibers, and a method for producing dyed polypropylene-based fibers.

[0005] The present inventors have conducted extensive research in light of the above background and have completed the present invention, which is described in the following items [1] to

[35] .

[0006] Invention 1 [1] A polyolefin-based resin composition comprising 70 to less than 100 parts by weight of a hydroxyl-modified polyolefin (A1) and more than 0 to 30 parts by weight of a hydrophilic resin (B), wherein the hydrophilic resin (B) is a water-soluble resin or a water-absorbent resin having a water absorption capacity of 0.01 to 100 g / g, and the total of (A1) and (B) is 100 parts by weight. [2] The polyolefin-based resin composition according to [1], comprising 70 to 99 parts by weight of a hydroxyl-modified polyolefin (A1) and 1 to 30 parts by weight of a hydrophilic resin (B). [3] The polyolefin-based resin composition according to [1] or [2], wherein the hydroxyl-modified polyolefin is a hydroxyl-modified polypropylene. [4] The polyolefin-based resin composition according to any one of [1] to [3], wherein the hydroxyl-modified polyolefin is a terminal-hydroxyl-modified polypropylene. [5] The polyolefin resin composition according to any one of [1] to [4], wherein the hydroxyl-modified polyolefin is one-terminal hydroxyl-modified polypropylene. [6] The polyolefin resin composition according to any one of [1] to [5], wherein the hydrophilic resin (B) is thermoplastic polyethylene oxide. [7] The polyolefin resin composition according to any one of [1] to [6], wherein the hydrophilic resin (B) is polyvinyl alcohol. [8] The polyolefin resin composition according to any one of [1] to [7], wherein the hydrophilic resin (B) is a resin having a hydrophilic moiety and a hydrophobic moiety. [9] The polyolefin resin composition according to any one of [1] to [8], wherein the hydrophilic resin (B) is a resin having a hydrophilic portion and a hydrophobic portion, and the resin having a hydrophilic portion and a hydrophobic portion is a reaction bonded product of polypropylene oxide and polyethylene oxide, or a triblock copolymer of polypropylene oxide and polyethylene oxide, or a partially saponified polyvinyl alcohol, or a polymer in which polyethylene oxide is bonded to the end or in the chain of a polyolefin, or a polymer in which polyvinyl alcohol is bonded to the end or in the chain of a polyolefin, or a polymer in which partially saponified polyvinyl alcohol is bonded to the end or in the chain of a polyolefin.Invention 2

[10] A polypropylene-based resin composition comprising 50 parts by weight or more and less than 97 parts by weight of a polypropylene-based resin (A2), more than 0 parts by weight and 30 parts by weight or less of a hydrophilic resin (B), and 3 to 25 parts by weight of a compatibilizer (C), wherein the hydrophilic resin (B) is a water-soluble resin or a water-absorbent resin having a water absorption capacity of 0.01 to 100 g / g, and the total of (A2), (B), and (C) is 100 parts by weight.

[11] The polypropylene-based resin composition according to

[10] , comprising 3 to 20 parts by weight of a compatibilizer (C).

[12] The polypropylene-based resin composition according to

[10] , comprising 50 to 96 parts by weight of a polypropylene-based resin (A2), 1 to 30 parts by weight of a hydrophilic resin (B), and 3 to 25 parts by weight of the compatibilizer (C).

[13] The polypropylene-based resin composition according to

[12] , containing 3 to 20 parts by weight of a compatibilizer (C).

[14] A polypropylene-based resin composition comprising 50 parts by weight or more and less than 97 parts by weight of a polypropylene-based resin (A2), more than 0 parts by weight and 30 parts by weight or less of a hydrophilic resin (B), 3 to 25 parts by weight of the compatibilizer (C), and more than 0 parts by weight and 10 parts by weight or less of a compound (G) that crosslinks hydroxyl groups, wherein the hydrophilic resin (B) is a water-soluble resin or a water-absorbent resin having a water absorption capacity of 0.01 to 100 g / g, and the total of (A2), (B), (C), and (G) is 100 parts by weight.

[15] The polypropylene-based resin composition according to any one of

[10] to

[14] , wherein the polypropylene-based resin is a homopolypropylene.

[16] The polypropylene-based resin composition according to any one of

[10] to

[15] , wherein the hydrophilic resin (B) is a thermoplastic polyethylene oxide.

[17] The polypropylene-based resin composition according to any one of

[10] to

[16] , wherein the hydrophilic resin (B) is polyvinyl alcohol.

[18] The polypropylene-based resin composition according to any one of

[10] to

[17] , wherein the hydrophilic resin (B) is a resin having a hydrophilic portion and a hydrophobic portion.

[19] The polyolefin resin composition according to any one of

[10] to

[18] , wherein the hydrophilic resin (B) is a resin having a hydrophilic portion and a hydrophobic portion, and the resin having a hydrophilic portion and a hydrophobic portion is a reaction bonded product of polypropylene oxide and polyethylene oxide, or a triblock copolymer of polypropylene oxide and polyethylene oxide, or a partially saponified polyvinyl alcohol, or a polymer in which polyethylene oxide is bonded to the end or in the chain of a polyolefin, or a polymer in which polyvinyl alcohol is bonded to the end or in the chain of a polyolefin, or a polymer in which partially saponified polyvinyl alcohol is bonded to the end or in the chain of a polyolefin.

[20] The polypropylene resin composition according to any one of

[10] to

[19] , wherein the compatibilizer (C) is a modified polyolefin.

[21] The polypropylene resin composition according to any one of

[10] to

[20] , wherein the compatibilizer (C) is a modified polyolefin, and the modifying group of the modified polyolefin is one modifying group selected from maleic anhydride and a hydroxyl group.

[22] The polypropylene-based resin composition according to any one of

[10] to

[21] , wherein the hydrophilic resin (B) is at least one resin having a hydroxyl group.

[23] The polypropylene-based resin composition according to any one of

[10] to

[22] , wherein the hydrophilic resin (B) is at least one partially saponified polyvinyl alcohol.

[24] The polypropylene-based resin composition according to any one of

[14] to

[23] , wherein the compound (G) that crosslinks hydroxyl groups is a carbodiimide-based resin. Invention 3-1

[25] A dyed polypropylene-based fiber comprising 70 parts by weight or more but less than 100 parts by weight of a polypropylene-based resin (A2) and more than 0 parts by weight but not more than 30 parts by weight of a hydrophilic resin (B), wherein the hydrophilic resin (B) is a water-soluble resin or a water-absorbent resin having a water absorption capacity of 0.01 to 100 g / g, and wherein the total of (A2) and (B) is 100 parts by weight, and dyed with a dye (D) of the polypropylene-based resin composition.

[26] The polypropylene-based fiber according to

[25] , comprising 70 to 99 parts by weight of the polypropylene-based resin (A2) and 1 to 30 parts by weight of the hydrophilic resin (B).

[27] The polypropylene-based fiber according to

[25] or

[26] , wherein the polypropylene-based resin (A2) is homopolypropylene.

[28] The polypropylene-based fiber according to any one of

[25] to

[27] , wherein the hydrophilic resin (B) is thermoplastic polyethylene oxide.

[29] The polypropylene-based fiber according to any one of

[25] to

[28] , wherein the hydrophilic resin (B) is polyvinyl alcohol.

[30] The polypropylene-based fiber according to any one of

[25] to

[29] , wherein the hydrophilic resin (B) is a resin having a hydrophilic portion and a hydrophobic portion.

[31] The polypropylene-based fiber according to any one of

[25] to

[30] , wherein the hydrophilic resin (B) is a resin having a hydrophilic portion and a hydrophobic portion, and the resin having a hydrophilic portion and a hydrophobic portion is a reaction bonded product of polypropylene oxide and polyethylene oxide, or a triblock copolymer of polypropylene oxide and polyethylene oxide, or a partially saponified polyvinyl alcohol, or a polymer in which polyethylene oxide is bonded to the end or in the chain of a polyolefin, or a polymer in which polyvinyl alcohol is bonded to the end or in the chain of a polyolefin, or a polymer in which partially saponified polyvinyl alcohol is bonded to the end or in the chain of a polyolefin. Invention 3-2

[32] A dyed polypropylene fiber comprising 50 to less than 97 parts by weight of a polypropylene resin (A2), more than 0 to 30 parts by weight of a hydrophilic resin (B), and 3 to 25 parts by weight of a compatibilizer (C), wherein the hydrophilic resin (B) is a water-soluble resin or a water-absorbent resin having a water absorption capacity of 0.01 to 100 g / g, and the total of (A2), (B), and (C) is 100 parts by weight.

[33] A polypropylene fiber according to

[32] , comprising 3 to 20 parts by weight of a compatibilizer (C).

[34] A polypropylene fiber according to

[32] , comprising 50 to 96 parts by weight of a polypropylene resin (A2), 1 to 30 parts by weight of a hydrophilic resin (B), and 3 to 25 parts by weight of a compatibilizer (C).

[35] The polypropylene-based fiber according to

[34] , containing 3 to 20 parts by weight of a compatibilizer (C).

[36] A dyed polypropylene fiber comprising 50 to less than 97 parts by weight of a polypropylene resin (A2), more than 0 to 30 parts by weight of a hydrophilic resin (B), 3 to 25 parts by weight of a compatibilizer (C), and more than 0 to 10 parts by weight of a compound (G) that crosslinks hydroxyl groups, wherein the hydrophilic resin (B) is a water-soluble resin or a water-absorbent resin having a water absorption capacity of 0.01 to 100 g / g, and the total of (A2), (B), (C), and (G) is 100 parts by weight.

[37] A polypropylene fiber according to any one of

[32] to

[36] , wherein the compatibilizer (C) is a modified polyolefin, and the modifying group of the modified polyolefin is one type of modifying group selected from maleic anhydride and a hydroxyl group.

[38] The polypropylene-based fiber according to any one of

[32] to

[37] , wherein the compatibilizer (C) is a modified polypropylene, and the modifying group of the modified polypropylene is one type of modifying group selected from maleic anhydride and a hydroxyl group.

[39] The polypropylene-based fiber according to any one of

[32] to

[38] , wherein the hydrophilic resin (B) is at least one resin having a hydroxyl group.

[40] The polypropylene-based fiber according to any one of

[32] to

[39] , wherein the hydrophilic resin (B) is at least one type of partially saponified polyvinyl alcohol.

[41] The polypropylene-based fiber according to any one of

[36] to

[40] , wherein the compound (G) crosslinking hydroxyl groups is a carbodiimide-based resin.

[42] The polypropylene-based fiber according to any one of

[32] to

[41] , wherein the dye (D) is an aqueous dye.

[43] The polypropylene-based fiber according to any one of

[32] to

[42] , wherein the dye (D) is a reactive dye.

[44] The polypropylene-based fiber according to any one of

[32] to

[43] , wherein the dye (D) is an acid dye.

[45] The polypropylene-based fiber according to any one of

[32] to

[44] , wherein the dye (D) is a disperse dye.

[46] The polypropylene-based fiber according to any one of

[32] to

[45] , wherein the dye (D) is a direct dye.

[47] A method for producing a polypropylene-based fiber dyed with a dye (D), comprising melt-spinning a composition containing a polypropylene-based resin (A2) and a hydrophilic resin (B) into a fiber shape, and then dyeing the fiber with a dye (D) using water as a medium.

[0007] According to the present invention, it is possible to obtain a polyolefin-based resin composition with excellent dyeability, or a polypropylene-based resin composition with excellent spinnability, and a dyed polypropylene-based fiber. That is, according to Invention 1, it is possible to obtain a polyolefin-based resin composition with excellent dyeability, according to Invention 2, it is possible to obtain a polyolefin (polypropylene)-based resin composition with excellent spinnability, according to Invention 3-1, it is possible to obtain a dyed polypropylene-based fiber, and according to Invention 3-2, it is possible to obtain a dyed polypropylene-based fiber and a method for producing a dyed polypropylene-based fiber.

[0008] Invention 1: Polyolefin Resin Composition The polyolefin resin composition of the present invention is the following: A polyolefin resin composition comprising 70 to less than 100 parts by weight of a hydroxyl-modified polyolefin (A1) and more than 0 to 30 parts by weight of a hydrophilic resin (B), wherein the hydrophilic resin (B) is a water-soluble resin or a water-absorbent resin having a water absorption capacity of 0.01 to 100 g / g, and the total of (A1) and (B) is 100 parts by weight. The polyolefin resin composition of the present invention preferably comprises 70 to 99 parts by weight of the hydroxyl-modified polyolefin (A1) and 1 to 30 parts by weight of the hydrophilic resin (B), and more preferably comprises 72 to 98 parts by weight of the hydroxyl-modified polyolefin (A1) and 2 to 28 parts by weight of the hydrophilic resin (B). Hydroxyl-modified polyolefin (A1) The hydroxyl-modified polyolefin (A1) is preferably hydroxyl-modified polypropylene, terminal hydroxyl-modified polypropylene, or one-terminal hydroxyl-modified polypropylene.

[0009] [Method for Producing Hydroxyl-Modified Polyolefin (A1)] The hydroxyl-modified polyolefin (A1) of the present invention can be produced, for example, by the following production method: A method for producing a modified polyolefin, comprising step (1) of treating an olefin polymer having organometallic end groups 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%. <Step (1)> <Olefin Polymer Having Organometallic End Groups> Various examples of organometallic compounds can be given, such as residues of organozinc compounds, organoaluminum compounds, and organomagnesium compounds described in the section "<Organozinc Compounds>" below. Preferably, the metal in the olefin polymer having organometallic end groups is a zinc atom. Furthermore, various examples of organometallic end groups can be given, such as -ZnEt, -ZnMe, -ZnPr, -ZnnBu, and -ZnBu groups, as shown in the following chemical formulas. Furthermore, examples of the olefin polymer having an organometallic end group used in the production method of the present invention and the modified polyolefin produced therefrom include polypropylene having an organometallic end group and modified polypropylene, respectively, which are represented by the following chemical formulas.

[0010] 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 the olefin polymer having an organometallic end group is not particularly limited, but for example, the olefin polymer having an organometallic end group can be produced by the following method for producing a propylene polymer material: A method for producing a propylene polymer material comprising: a continuous supply step of continuously supplying propylene, the solid catalyst component for olefin polymerization, the organoaluminum compound, and the 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.

[0011] <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 used 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 with an internal electron donor and a titanium compound; (3) a method of dissolving a magnesium halide compound and a titanium compound in an electron donating solvent to obtain a solution, and then impregnating a support material with the solution; (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 hydrocarbonoxy groups with a halide compound, an internal electron donor and / or an organic acid halide.

[0012] Among these, a 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 compounds described in Patent Document (Japanese Patent Application No. 2018-531923) and combinations of two or more thereof. 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.

[0013] <Organoaluminum Compound> Examples of the organoaluminum compound to 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.

[0014] <External Electron Donor Compound> In the method for producing an olefin polymer having an organometallic end group, an external electron donor compound (external electron donor) can also be continuously supplied 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], 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 When there are multiple, they may be the same or different; R ８ represents a hydrocarbyl group having 1 to 20 carbon atoms, R ８ When there are a plurality of groups, they may be the same or different; and r represents an integer of 0 to 3.

[0015] R ７ and R ８ Examples of hydrocarbyl groups 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.

[0016] R ７ Examples of heteroatom-containing groups include oxygen atom-containing groups such as furyl, pyranyl, and perhydrofuryl groups; nitrogen atom-containing groups such as dimethylamino, methylethylamino, diethylamino, ethyl-n-propylamino, di-n-propylamino, pyrrolyl, pyridyl, pyrrolidinyl, piperidyl, perhydroindolyl, perhydroisoindolyl, perhydroquinolyl, perhydroisoquinolyl, perhydrocarbazolyl, and perhydroacridinyl groups; sulfur atom-containing groups such as thienyl; and phosphorus atom-containing groups. Among these, preferred are groups in which the heteroatom can be directly chemically bonded to the silicon atom of the silicon compound, and more preferred are dimethylamino, methylethylamino, diethylamino, ethyl-n-propylamino, and di-n-propylamino groups.

[0017] Examples of external electron donor compounds include 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, and 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 of the silane 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.

[0018] <Organic Zinc Compound> Examples of the organic zinc compound used in the method for producing an olefin polymer having an organometal-containing terminal group include dialkyl zincs such as dimethyl zinc, diethyl zinc, di-n-propyl zinc, di-n-butyl zinc, diisobutyl zinc, and di-n-hexyl zinc; diaryl zincs such as diphenyl zinc and dinaphthyl zinc; bis(cyclopentadienyl) zinc; and dialkenyl zincs such as diallyl zinc. Among these, dialkyl zincs are preferred, more preferably dimethyl zinc, diethyl zinc, di-n-propyl zinc, di-n-butyl zinc, diisobutyl zinc, or di-n-hexyl zinc, even more preferably dimethyl zinc or diethyl zinc, and particularly preferably diethyl zinc.

[0019] <Monomers Other Than Propylene> In the method for producing an olefin polymer having an organometal-containing terminal 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.

[0020] The olefin polymer having an organometallic end group is preferably a propylene homopolymer or a copolymer of propylene and another olefin, such as a propylene-ethylene copolymer, a propylene-1-butene copolymer, or a propylene-1-hexene copolymer. The intrinsic viscosity of the polymer is usually 0.5 to 15 dL / g, preferably 0.8 to 10 dL / g. The content of units of the other olefin in the copolymer is usually 0.01 to 50 wt%, preferably 0.1 to 40 wt%, based on 100 wt% of the copolymer.

[0021] <Continuous Supply Step> and <Continuous Withdrawal Step> The reactor used in the continuous supply step and continuous withdrawal step in the method for producing an olefin polymer having an organometallic terminal 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 unit, but it is also possible to construct a reactor 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,３ Impurities (e.g., AlHEt ２ When aluminum reacts with an organozinc compound, the organozinc compound is reduced to zinc. Since zinc is gray, the produced propylene polymer material becomes colored. This coloring can be avoided by feeding the organoaluminum compound and the organozinc compound to the reactor through separate lines. A propylene polymer material is obtained through a step of polymerizing propylene continuously fed in a continuous feeding step in the reactor (polymerization step), and then the propylene polymer material obtained in the reactor is continuously removed from the reactor.

[0022] The ratio of the supply rate of the organozinc compound in the continuous supply step to the production rate of the propylene polymer material in the continuous withdrawal step is preferably 20 to 1,000 (mmol-Zn / kg-PP), more preferably 20 to 500 (mmol-Zn / kg-PP). The ratio of the supply rate of the organozinc compound in the continuous supply step to the production 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 ratio of the supply rate of the organoaluminum compound in the continuous supply step to the production rate of the propylene polymer material in the continuous withdrawal step is preferably 1 to 30 (mmol-Al / kg-PP), more preferably 2 to 30 (mmol-Al / kg-PP).

[0023] In the continuous supply step, it is preferable to further continuously supply hydrogen gas to the reactor.

[0024] The number of polymerization steps in the method for producing an olefin polymer having an organometallic terminal group 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 for each step may be different from each other. The olefin polymer discharged from the final step is essentially a mixture of polymers produced in each step.

[0025] 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)).

[0026] 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.

[0027] 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.

[0028] In the polymerization step (hereinafter referred to as "main polymerization") in the method for producing an olefin polymer having an organometal-containing 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 usually 0.001 to 5 mol, preferably 0.005 to 3 mol, more preferably 0.01 to 1 mol, per mol of the organoaluminum compound.

[0029] 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.

[0030] 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 as a medium, 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 having 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.

[0031] In this polymerization, a prepolymerized solid catalyst component described below may be used instead of the solid catalyst component in order to improve the particle properties of the resulting olefin polymer powder. When a prepolymerized solid catalyst component is used in this polymerization, the use of an organoaluminum compound in this polymerization is not essential.

[0032] 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.

[0033] The amount of the organoaluminum compound used in the prepolymerization is usually 0.5 to 700 mol, preferably 0.8 to 500 mol, more preferably 1 to 200 mol per mol of titanium atom in the solid catalyst component.

[0034] The amount of the olefin to be prepolymerized is usually 0.01 to 1000 g, preferably 0.05 to 500 g, more preferably 0.1 to 200 g, per gram of the solid catalyst component.

[0035] The slurry concentration in the prepolymerization is preferably 1 to 500 g of solid catalyst component / liter of solvent, and more preferably 3 to 300 g of solid catalyst component / liter of solvent. The temperature in the prepolymerization is preferably −20 to 100° C., and more preferably 0 to 80° C. The polymerization time in the prepolymerization is usually 30 seconds to 15 hours. The partial pressure of the olefin in the gas phase in the prepolymerization is preferably 1 kPa to 2 MPa, and more preferably 10 kPa to 1 MPa, although this does not apply to olefins that are liquid at the pressure and temperature of the prepolymerization.

[0036] 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 olefin is fed initially. A chain transfer agent such as hydrogen may be added to adjust the molecular weight of the prepolymerized olefin polymer. In addition to the solid catalyst component and the organoaluminum compound, the prepolymerization may also use an organozinc compound or an external electron donor 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, relative to 1 mol of titanium atoms 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, relative to 1 mol of the organoaluminum compound.

[0037] In prepolymerization, examples of methods for supplying an external electron donor compound to a prepolymerization reactor include (1) a method of supplying it separately from the organoaluminum compound, and (2) a method of 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 a known method. Preactivation can be performed 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 be performed using 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 deposit, and the degree of preactivation allows for a stable storage time and 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 preactivation method is not particularly limited and can be carried out in a batch, semi-batch, or continuous manner.

[0038] <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, and carbon disulfide gas. The reactive gas compound is preferably at least one gas selected from the group consisting of oxygen gas and carbon dioxide gas. Examples of inert gases 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, a mixed gas containing a lower concentration of oxygen gas than air is preferred, and when the reactive gas compound is carbon dioxide gas, a mixed gas containing a higher concentration of carbon dioxide gas than air is preferred.

[0039] Step (1) is preferably carried out under conditions of a total pressure of 3 MPa or less. Carrying out a reaction under high-pressure conditions requires an expensive reaction vessel capable of withstanding high pressures, which is undesirable from an economic standpoint. It is more preferable to carry out the reaction under conditions of a total pressure of 0.1 MPa or more. Even more preferable is a total pressure of 0.1 to 1 MPa, and most preferable is a total pressure of 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 period for step (1) is preferably 1 to 120 minutes, more preferably 1 to 90 minutes, and even more preferably 1 to 60 minutes.

[0040] <Step (2)> In the present invention, the method for producing a hydroxyl group-modified polyolefin (A1) preferably further includes step (2) of treating the modified polyolefin obtained in step (1) with an active proton compound. <Active Proton Compound> Examples of active proton compounds 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.), and inorganic acids (concentrated hydrochloric acid, carbonic acid, etc.). Preferred active proton compounds are water, ethanol, methanol, etc. The time period for step (2) is preferably 1 to 120 minutes, more preferably 1 to 90 minutes, and even more preferably 1 to 60 minutes.

[0041] <Step (3)> In the present invention, the method for producing a hydroxyl-modified polyolefin (A1) preferably further includes step (3) of removing volatile compounds from the modified polyolefin obtained in step (1) or (2). Specific examples of step (3) include a method of reducing the pressure while heating the modified polyolefin, a method of passing nitrogen gas through the modified polyolefin while heating the modified polyolefin, and a method of continuously extracting and removing volatile compounds from the modified polyolefin with heated water or heated alcohol, followed by a reduction in pressure or a nitrogen gas pass. 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 (oligomeric) PPOH (e.g., 2-methyl-1-butanol and 2-methyl-1-pentanol). If (b) remains in the modified polyolefin, it may interfere with the functional expression of the modified polyolefin or may cause the modified polyolefin to have an odor. The time for step (3) is preferably 1 to 120 minutes. It is more preferably 1 to 90 minutes, and even more preferably 1 to 60 minutes.

[0042] <Step (4)> In the present invention, the method for producing a hydroxyl-modified polyolefin (A1) can include the following step (4): a method for producing a modified polyolefin, comprising step (4) of treating an olefin polymer having organometallic end groups with a mixture of a reactive gas compound and an active proton compound. That is, step (4) is a process for treating an olefin polymer having organometallic end groups using a combination of a reactive gas compound and an active proton compound. This process is highly efficient and economical, as it combines the reaction between the reactive gas compound and the active proton compound into a single step by selecting the reaction conditions. All raw materials and steps in step (4), including the organometallic, organometallic end groups, olefin polymer having organometallic end groups, 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 <Steps (1)> to <Steps (3)>. Typical reaction conditions for the treatment step (4) include dispensing an olefin polymer having organometallic end groups into a flask whose internal gas has been replaced with nitrogen gas, passing an oxygen / nitrogen gas mixture (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.

[0043] In the present invention, the olefin polymer having an organometallic end group used in the above-mentioned production method can be exemplified by the following propylene polymer material: A propylene polymer material satisfying 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). The (b) Mw / Mn is preferably 2.6 to 4.4. The propylene polymer material preferably contains (c) zinc atoms in the propylene polymer at a concentration of 20 to 1000 (mmol-Zn / kg-PP), more preferably 20 to 500 (mmol-Zn / kg-PP).The propylene polymer material preferably contains (d) aluminum atoms in the propylene polymer material at a concentration of 1 to 30 (mmol-Al / kg-PP), more preferably 2 to 30 (mmol-Al / kg-PP).

[0044] The propylene polymer material may be a propylene polymer composition of a propylene polymer and a catalyst residue.

[0045] The propylene polymer material comprises: (f) L ＊ a ＊ b ＊ Color difference ΔE between the propylene polymer material and the standard white board in color space ＊ Preferably, ab is 0 to 10, and more preferably, the color difference ΔE*ab is 0 to 6. ＊ a ＊ b ＊ Saturation C in color space ＊ The propylene polymer material preferably has a value of 0 to 4.0, and more preferably has a value of 0 to 3.0. ＊ 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. ＊ ab and saturation C ＊ In other words, the color difference ΔE*ab and the 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.

[0046] The method for producing the propylene polymer material is not particularly limited, but it can be produced by the production method mentioned above in the section <Olefin polymer having an organometallic terminal group>.

[0047] Polyolefin In the present invention, the polyolefin used in producing the hydroxyl group-modified polyolefin (A1) may be, for example, the following heterophasic propylene polymer material.

[0048] Heterophagic Propylene Polymerization Material In the present invention, a heterophasic propylene polymerization material having a propylene polymer portion (A1) and a propylene and 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 and 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.

[0049] Preferably, the heterophasic propylene polymer material comprises: 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; and a polymer (II) containing 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 having an intrinsic viscosity of 1.5 to 8.0 dL / g. More preferably, the content of polymer (I) is 40 to 99% by mass, and the content of polymer (II) is 1 to 60% by mass.

[0050] 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 content of such 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).

[0051] Examples of the monomer other than propylene include ethylene and α-olefins having 4 or more carbon atoms. Among these, 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.

[0052] 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.

[0053] 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.

[0054] The content 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 polymer material.

[0055] 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.

[0056] In polymer (II), the content 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%.

[0057] In polymer (II), the at least one α-olefin selected from the group consisting of ethylene and α-olefins having from 4 to 12 carbon atoms is preferably at least one selected from the group consisting of ethylene and α-olefins having from 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.

[0058] Examples of 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 these, propylene-ethylene copolymer, propylene-1-butene copolymer, and propylene-ethylene-1-butene copolymer are preferred, and propylene-ethylene copolymer is more preferred.

[0059] The content of 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 polymer material.

[0060] The content of xylene-insoluble (CXIS) components 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 content of xylene-soluble (CXS components) components in the heterophasic propylene polymerization material is preferably 1 to 60 mass %, more preferably 5 to 55 mass %, based on the total mass of the heterophasic propylene polymerization material.

[0061] In this embodiment, it is considered that the CXIS component in the heterophasic propylene polymer material is mainly composed of polymer (I), and the CXS component in the heterophasic propylene polymer material is mainly composed of polymer (II).

[0062] 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- (propylene-ethylene)-(propylene-ethylene) polymerization material, (propylene-ethylene)-(propylene-ethylene-1-butene) polymerization material, (propylene-ethylene)-(propylene-ethylene-1-hexene) polymerization material, (propylene-ethylene)-(propylene-ethylene-1-octene) polymerization material, (propylene-ethylene)-(propylene-ethylene-1-decene) polymerization material, (propylene-ethylene)-(propylene-1-butene) polymerization material, (propylene-ethylene)-(propylene-1-hexene) (propylene-ethylene)-(propylene-1-octene) polymerization material, (propylene-ethylene)-(propylene-1-decene) polymerization material, (propylene-1-butene)-(propylene-ethylene) polymerization material, (propylene-1-butene)-(propylene-ethylene-1-butene) polymerization material, (propylene-1-butene)-(propylene-ethylene-1-hexene) polymerization material, (propylene-1-butene)-(propylene-ethylene-1-octene) polymerization material, (propylene-1-butene)-(propylene-ethylene- (propylene-1-decene) polymerization material, (propylene-1-butene)-(propylene-1-butene) polymerization material, (propylene-1-butene)-(propylene-1-hexene) polymerization material, (propylene-1-butene)-(propylene-1-octene) polymerization material, (propylene-1-butene)-(propylene-1-decene) polymerization material, (propylene-1-hexene)-(propylene-1-hexene) polymerization material, (propylene-1-hexene)-(propylene-1-octene) polymerization material, (propylene-1-hexene)-(propylene-1-decene) polymerization material,(propylene-1-octene)-(propylene-1-octene) polymeric materials, and (propylene-1-octene)-(propylene-1-decene) polymeric materials.

[0063] 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.

[0064] As the heterophasic propylene polymer material, a (propylene)-(propylene-ethylene) polymer material, a (propylene)-(propylene-ethylene-1-butene) polymer material, a (propylene-ethylene)-(propylene-ethylene) polymer material, a (propylene-ethylene)-(propylene-ethylene-1-butene) polymer material, or a (propylene-1-butene)-(propylene-1-butene) polymer material is preferred, and a (propylene)-(propylene-ethylene) polymer material is more preferred.

[0065] The intrinsic viscosity number ([η]I) of the polymer (I) is preferably 0.10 to 3.00 dL / g, more preferably 0.50 to 2.0 dL / g, and even more preferably 0.70 to 1.50 dL / g.

[0066] 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.

[0067] 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.

[0068] The intrinsic viscosity number ([η]I) of the polymer (I) can be measured, for example, by forming the polymer (I) and then measuring the intrinsic viscosity number of the polymer.

[0069] 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 contents of polymer (II) and polymer (I).

[0070] [η]II=([η]whole-[η]I×XI) / XII (6) [η]whole: intrinsic viscosity number (dL / g) of the heterophasic propylene polymerization material [η]I: intrinsic viscosity number (dL / g) of polymer (I) XI: ratio of the mass of polymer (I) to the total mass of the heterophasic propylene polymerization material (mass of polymer (I) / mass of heterophasic propylene polymerization material) XII: ratio of the mass of polymer (II) to the total mass of the heterophasic propylene polymerization material (mass of polymer (II) / mass of heterophasic propylene polymerization material)

[0071] 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 differential scanning calorimeter DSC8500 (manufactured by PerkinElmer). The sample 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 then XII was determined using the following formula: XII = (1 - (heat of fusion of heterophasic propylene polymer material) / 105) x 100

[0072] XI and XII may be calculated from the material balance during polymerization.

[0073] 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.

[0074] 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.

[0075] 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.

[0076] 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.

[0077] The isotactic pentad fraction means the isotactic fraction in pentad units. That is, the isotactic pentad fraction indicates the content of a structure 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.

[0078] In this specification, the isotactic pentad fraction is １３ It refers to the value measured by C-NMR spectrum. 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 spectrum is defined as the isotactic pentad fraction. １３ The method for measuring the isotactic pentad fraction by C-NMR spectroscopy is described, for example, in A. Zambelli et al., Macromolecules, 6, 925 (1973). １３ The assignment of absorption peaks obtained by C-spectrometry is based on the description in Macromolecules, 8, 687 (1975).

[0079] 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 the 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.

[0080] 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 moldability 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.

[0081] In producing the polymer (I) and the 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.

[0082] Fossil resource-derived monomers are derived from carbon found in underground resources such as petroleum, coal, and natural gas, and generally contain almost no carbon-14 (C). Methods for producing fossil resource-derived monomers include known methods, such as cracking petroleum-derived naphtha, ethane, etc., and producing olefins by dehydrogenation of ethane, propane, etc.

[0083] Plant-derived monomers are derived from carbon circulating on the earth's surface as plants and animals, and generally contain a certain proportion of carbon-14 (14C). Examples of methods for producing plant-derived monomers include known methods, such as cracking bionaphtha, vegetable oil, animal oil, etc., dehydrogenation of biopropane, methods of separating alcohol from fermented products such as sugars extracted from plant materials such as sugarcane and corn, and subjecting the alcohol to a dehydration reaction (JP Patent Publication Nos. 2010-511634, 2011-506628, 2013-503647, etc.), and methods of subjecting ethylene obtained from plant-derived ethanol to a metathesis reaction with n-butene (WO 2007 / 055361, etc.).

[0084] Chemically recycled monomers are derived from carbon generated by the decomposition or combustion of waste, and their carbon-14 (14C) content varies depending on the waste. Methods for producing chemically recycled monomers include known methods, such as a method of thermally decomposing waste plastics (JP Patent Publication No. 2017-512246, etc.), a method of cracking waste vegetable oil, waste animal oil, etc. (JP Patent Publication No. 2018-522087, etc.), and a method of gasifying, converting to alcohol, and dehydrating waste such as food waste, biomass waste, food waste, waste oil, waste wood, waste paper, and waste plastic (JP Patent Publication No. 2019-167424, WO2021 / 006245, etc.).

[0085] When two or more of fossil resource-derived olefins, plant-derived olefins, and chemically recycled olefins are used, 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 compound / plant-derived compound, fossil resource-derived compound / chemically recycled compound, plant-derived compound / chemically recycled compound, or fossil resource-derived compound / plant-derived compound / chemically recycled compound as a raw material or production intermediate in the olefin production process.

[0086] 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 carbon-14 (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.

[0087] 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.

[0088] <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 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 with an internal electron donor and a titanium compound; (3) a method of dissolving a magnesium halide compound and a titanium compound in an electron-donating solvent to obtain a solution, and then impregnating a support material with the solution; (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 hydrocarbonoxy groups with a halide compound, an internal electron donor and / or an organic acid halide.

[0089] Among these, a 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 compounds described in Patent Document (Japanese Patent Application No. 2018-531923) and combinations of two or more thereof. 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.

[0090] <Organoaluminum Compound> Examples of the organoaluminum compound 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.

[0091] <External Electron Donor Compound> In the production method of the present invention, an external electron donor compound (external electron donor) can also be continuously supplied 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], 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 When there are multiple, they may be the same or different; R ８ represents a hydrocarbyl group having 1 to 20 carbon atoms, R ８When there are a plurality of , 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.

[0092] R ７ and R ８ Examples of hydrocarbyl groups 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. ７ R 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, and more preferably a methyl group, an ethyl group, an n-propyl group, a tert-butyl group, a cyclohexyl group, or a diethylamino group. ８ is preferably a methyl group or an ethyl group, and more preferably a methyl group.

[0093] R ７Examples of heteroatom-containing groups include oxygen atom-containing groups such as furyl, pyranyl, and perhydrofuryl groups; nitrogen atom-containing groups such as dimethylamino, methylethylamino, diethylamino, ethyl-n-propylamino, di-n-propylamino, pyrrolyl, pyridyl, pyrrolidinyl, piperidyl, perhydroindolyl, perhydroisoindolyl, perhydroquinolyl, perhydroisoquinolyl, perhydrocarbazolyl, and perhydroacridinyl groups; sulfur atom-containing groups such as thienyl; and phosphorus atom-containing groups. Among these, preferred are groups in which the heteroatom can be directly chemically bonded to the silicon atom of the silicon compound, and more preferred are dimethylamino, methylethylamino, diethylamino, ethyl-n-propylamino, and di-n-propylamino groups.

[0094] Examples of external electron donor compounds include 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, and 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 of the silane 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.

[0095] <Organic Zinc Compound> Examples of the organic zinc compound used in the production method of the present invention include dialkyl zincs such as dimethyl zinc, diethyl zinc, di-n-propyl zinc, di-n-butyl zinc, diisobutyl zinc, and di-n-hexyl zinc; diaryl zincs such as diphenyl zinc and dinaphthyl zinc; bis(cyclopentadienyl) zinc; and dialkenyl zincs such as diallyl zinc. Among these, dialkyl zincs are preferred, more preferably dimethyl zinc, diethyl zinc, di-n-propyl zinc, di-n-butyl zinc, diisobutyl zinc, or di-n-hexyl zinc, even more preferably dimethyl zinc or diethyl zinc, and particularly preferably diethyl zinc.

[0096] 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.

[0097] 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.

[0098] 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 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 usually 0.001 to 5 mol, preferably 0.005 to 3 mol, more preferably 0.01 to 1 mol, per mol of the organoaluminum compound.

[0099] 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.

[0100] 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 having different polymerization conditions. The polymerization conditions may also be continuously changed within a single reactor. A chain transfer agent such as hydrogen may be used to adjust the molecular weight of the propylene polymer material obtained by the polymerization.

[0101] In this polymerization, a prepolymerized solid catalyst component described below may be used instead 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 this polymerization, the use of an organoaluminum compound in this polymerization is not essential.

[0102] 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 the resulting mixture is polymerized in a slurry state using a solvent. Examples of the solvent used for the 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 may be used in place of a part or all of the solvent. Alternatively, prepolymerization may be performed in the presence of a viscous substance such as an olefin wax to obtain a prepolymerized catalyst that is stable during storage and handling. The prepolymerization method is not particularly limited, and may be performed in a batch, semi-batch, or continuous manner.

[0103] The amount of the organoaluminum compound used in the prepolymerization is usually 0.5 to 700 mol, preferably 0.8 to 500 mol, more preferably 1 to 200 mol per mol of titanium atom in the solid catalyst component.

[0104] The amount of the olefin to be prepolymerized is usually 0.01 to 1000 g, preferably 0.05 to 500 g, more preferably 0.1 to 200 g, per gram of the solid catalyst component.

[0105] The slurry concentration in the prepolymerization is preferably 1 to 500 g of solid catalyst component / liter of solvent, and more preferably 3 to 300 g of solid catalyst component / liter of solvent. The temperature in the prepolymerization is preferably −20 to 100° C., and more preferably 0 to 80° C. The polymerization time in the prepolymerization is usually 30 seconds to 15 hours. The partial pressure of the olefin in the gas phase in the prepolymerization is preferably 1 kPa to 2 MPa, and more preferably 10 kPa to 1 MPa, although this does not apply to olefins that are liquid at the pressure and temperature of the prepolymerization.

[0106] 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 olefin is fed initially. A chain transfer agent such as hydrogen may be added to adjust the molecular weight of the prepolymerized olefin polymer. In addition to the solid catalyst component and the organoaluminum compound, the prepolymerization may also use an organozinc compound or an external electron donor 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, relative to 1 mol of titanium atoms 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, relative to 1 mol of the organoaluminum compound.

[0107] In prepolymerization, examples of methods for supplying an external electron donor compound to a prepolymerization reactor include (1) a method of supplying it separately from the organoaluminum compound, and (2) a method of 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 a known method. Preactivation can be performed 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 be performed using 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 deposit, and the degree of preactivation allows for a stable storage time and 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 preactivation method is not particularly limited and can be carried out in a batch, semi-batch, or continuous manner.

[0108] The heterophasic propylene polymer material obtained in the polymerization process of the present invention has organometallic end groups containing organozinc at at least a portion 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 organometallic end groups or a heterophasic propylene polymer material modified with hydroxyl groups. It may also be a polymer material containing the polymer produced by combining the polymerization process of the present invention with another polymerization process.

[0109] 3. Method for Producing Heterophagic Propylene Polymerization Material The method for producing a heterophasic propylene polymerization material of the present invention is, for example, as follows: A method for producing a heterophasic propylene polymerization material, comprising: a first polymerization step of polymerizing propylene 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; and a second polymerization step of copolymerizing propylene with at least one selected from the group consisting of ethylene and α-olefins having 4 to 12 carbon atoms in the presence of the polymer (I) and the contact product described below to form a polymer (II).

[0110] 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.

[0111] An example of a method for producing the heterophasic propylene polymer material will now be described. This method includes: (Step 1) a propylene polymerization step; (Step 2) a propylene and α-olefin copolymerization step; and (Step 3) a reactive gas compound treatment step.

[0112] (Step 1) Propylene polymerization step: Step 1-a, in which a monomer containing propylene is polymerized in a liquid phase in the presence of a specified amount of diethyl zinc under conditions where the hydrogen / propylene ratio is appropriate to obtain at least a portion of a propylene-based polymer (a); and Step 1-b, in which a monomer containing propylene is polymerized in a gas phase in the presence of a specified amount of diethyl zinc under conditions where the hydrogen / propylene ratio is appropriate to obtain at least a portion of a propylene-based polymer (a). (Step 2) Propylene and α-olefin copolymerization step: Step 1-a, in which 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 specified amount of diethyl zinc under conditions where the hydrogen / propylene ratio is appropriate to obtain a propylene-based copolymer (b). (Step 3) Reactive gas compound treatment step: A step of treating the propylene polymer (b) obtained through (Step 1) and (Step 2) with a reactive gas compound to obtain a heterophasic propylene polymer modified with hydroxyl groups.

[0113] 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 a gaseous state to propylene in a liquid state at the reactor supply section. In the case of polymerization in a gaseous phase, the hydrogen / propylene ratio refers to the ratio of the amounts of hydrogen in a gaseous state to propylene in a gaseous state at the reactor outlet. In this specification, for example, the expression "the hydrogen / propylene ratio is 1 mol ppm" means "the hydrogen / propylene ratio is 1 x 10 －６ mol / mol" and hydrogen is 1 x 10 －６ 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.

[0114] [Step 1-a] In step 1-a, for example, a liquid-phase polymerization reactor is used to polymerize a monomer containing propylene in the presence of a polymerization catalyst, hydrogen, and diethylzinc. The composition of the monomers used in the polymerization can be appropriately adjusted based on the type and content of the structural units constituting the propylene polymer (a). The content 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.

[0115] Examples of the liquid phase polymerization reactor include a loop type liquid phase reactor and a vessel type liquid phase reactor.

[0116] Examples of the polymerization catalyst include Ziegler-Natta catalysts and metallocene catalysts, with Ziegler-Natta catalysts being preferred. Examples of Ziegler-Natta catalysts include catalysts containing the above-mentioned solid catalyst component for olefin polymerization, an aluminum compound, and an electron donor compound. A catalyst pre-activated by contacting with a small amount of olefin can also be used as the polymerization catalyst.

[0117] 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.

[0118] The polymerization temperature can be, for example, 0 to 120° C. The polymerization pressure can be, for example, normal pressure to 10 MPaG.

[0119] Step 1-a may be carried out continuously in multiple stages using a plurality of reactors in series.

[0120] [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 type and content of the structural units constituting the propylene polymer (a). The content 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.

[0121] Examples of gas phase polymerization reactors include vessel type reactors, fluidized bed type reactors, and spouted bed type reactors.

[0122] 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 fall within the above range.

[0123] 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.

[0124] 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.

[0125] 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.

[0126] Specific examples of the polymerization catalyst are the same as those mentioned above.

[0127] 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, atmospheric pressure to 10 MPaG, or 1 to 5 MPaG.

[0128] [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, for example, a liquid phase reactor such as a loop type or a vessel type can be used. When carried out in a gas phase, for example, a gas phase reactor such as a vessel type reactor, a fluidized bed type reactor, or a spouted bed type reactor can be used.

[0129] 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 content of the structural units constituting the propylene-based copolymer (b). The content of 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% by mass, or 35 to 50% by mass, based on the total mass of the monomers.

[0130] Specific examples of the polymerization catalyst are the same as those mentioned above.

[0131] In the case of polymerization 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. In the case of polymerization 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.

[0132] The propylene polymer (a) and the propylene copolymer (b) may be produced in separate steps, and the polymerization catalysts 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.

[0133] 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.

[0134] 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.

[0135] The order of steps 1 and 2 and step 3 can be selected as follows: (a) Step 3 is carried out 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 2. (a) can be achieved by carrying out step 3 before carrying out a deactivation treatment after the polymerization step or simultaneously with the deactivation treatment. (b), (c), and (d) can be achieved by causing 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.

[0136] Hydroxyl-modified heterophasic propylene polymer material In the present invention, the hydroxyl-modified heterophasic propylene polymer material is preferably the following: A heterophasic propylene polymer material having a propylene-based polymer portion (A1) and a propylene-α-olefin copolymer portion (A2), in which (A1) and / or (A2) are partially modified with hydroxyl groups. The amount of —OH (hydroxyl group) contained in the hydroxyl-modified (A1) and / or (A2) is preferably 0.01×10 －３ wt% to 100 x 10 －３ wt%, more preferably 0.03 × 10 －３ wt% to 50 x 10 －３ wt%, more preferably 0.05 × 10 －３ wt% to 10 x 10 －３ The amount of —OH (hydroxyl group) is 0.01×10 －３ When the amount of -OH (hydroxyl group) is less than 100×10 wt %, the coating property of the resulting heterophasic propylene polymer material modified with hydroxyl groups may be insufficient. －３ If the content exceeds 100% by weight, the impact strength of the resulting heterophasic propylene polymer material modified with hydroxyl groups may be insufficient. Preferably, the propylene polymer portion (A1) is a propylene homopolymer portion.

[0137] The site of modification with a hydroxyl group may be (A1) only, (A2) only, or both (A1) and (A2). However, (A2) only or both (A1) and (A2) are preferred, and (A2) only is most preferred.

[0138] The bonding site in the polymer chain of the —OH (hydroxyl group) contained in the hydroxyl-modified (A1) and / or (A2) is preferably a terminal of the polymer chain, and particularly preferably only one terminal (one end). Because polymer chain terminals have higher mobility than the polymer chain itself, the hydroxyl groups bonded to the polymer chain terminals can effectively contribute to reactions and interactions with polar resins, inorganic fillers, and other fillers. Furthermore, by limiting the site of modification by hydroxyl groups to one terminal of the polymer chain, the number of hydroxyl groups per polymer chain is one or less. Therefore, when reacting with or interacting with polar resins, inorganic fillers, and the like, gelation due to a crosslinking reaction does not occur in principle, and deterioration of the appearance or mechanical properties does not occur. Furthermore, because the hydroxyl group is bonded to only one terminal 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 impaired, allowing the effects of the hydroxyl group to be utilized.

[0139] 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.

[0140] 1. Method for producing a heterophasic propylene polymerization material modified with hydroxyl groups In the present invention, the method for producing a heterophasic propylene polymerization material modified with hydroxyl groups is as follows: A method for producing a heterophasic propylene polymerization material in the presence of a solid catalyst component for olefin polymerization and an organoaluminum compound, the method comprising the following steps (1) to (3) and satisfying condition (i): (1) a propylene polymerization step (A), (2) a propylene and α-olefin copolymerization step (B), (3) a reactive gas compound treatment step (C), (i) carrying out (A) and / or (B) in the presence of an organozinc compound.

[0141] 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 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 stabilized in any non-polymerization reaction step 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 groups include hydroxyl groups and carboxyl groups. The propylene polymer material of the present invention may be a polymer material having organometallic end groups, or a terminally stabilized polymer material that has undergone any non-polymerization reaction step. It may also be a polymer material containing the polymer produced by combining the polymerization step of the present invention with another polymerization step.

[0142] 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 preferably water, methyl alcohol, and ethyl alcohol, and even more preferably water.

[0143] 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 solid catalyst component for olefin polymerization and the aluminum compound described above. 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) (propylene and α-olefin copolymerization step) in the above production method can be the same as the second polymerization step described above.

[0144] In the present invention, the above-mentioned production method can also employ a continuous supply step and a continuous withdrawal step, and 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 may also be supplied to multiple reactors. In the above-mentioned production method of the present invention, for example, in the continuous supply step, it is preferable that the organoaluminum compound and the organozinc compound are continuously supplied to the reactor using separate lines. That is, when the organoaluminum compound (e.g., AlEt ３ Impurities (e.g., AlHEt ２When the organozinc compound reacts with the aluminum compound, the organozinc compound is reduced to zinc. Because zinc is gray, the resulting propylene polymer material is discolored. Such discoloration can be avoided by supplying the organoaluminum compound and the organozinc compound to the reactor through separate lines. In the production method of the present invention, for example, a propylene polymer material is obtained through a polymerization step (a polymerization step) in which propylene continuously supplied in a continuous supply step is polymerized in the reactor, and the propylene polymer material obtained in the reactor is then continuously withdrawn from the reactor. In this continuous withdrawal step, the propylene, the solid catalyst component for olefin polymerization, the organoaluminum compound, and a portion of the organozinc compound supplied in the continuous supply step are also withdrawn, and their concentrations in the reactor are maintained within a certain range. Maintaining the concentration of the organozinc compound consumed during the polymerization reaction within a certain range is particularly important in maintaining a constant structure of the hydroxyl-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 will differ between the initial stage and the final stage of polymerization. The supply rate of each component supplied in the continuous supply 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 portion of the continuous supply step and at least a portion of the continuous withdrawal step are carried out simultaneously.

[0145] The feed rate of the organozinc compound in the continuous feed step relative to the production rate of the propylene polymer material in the continuous removal step is preferably 20 to 1,000 (mmol-Zn / kg-PP), more preferably 20 to 500 (mmol-Zn / kg-PP).

[0146] In the continuous supply step, the ratio of the supply rate of the organozinc compound 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).

[0147] The feed rate of the organoaluminum compound in the continuous feed 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).

[0148] In the continuous supply step, it is preferable to further continuously supply hydrogen gas to the reactor.

[0149] 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 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.

[0150] 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.

[0151] Reactive Gas Compound 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 also 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%, even more 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.

[0152] Reactive Gas Compound Treatment Step The reactive gas compound treatment step can be carried out, for example, under conditions of a total pressure of 3 MPa or less. Carrying out a 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 conditions of a total pressure of 0.1 MPa or more. More preferably, the total pressure is 0.1 to 1 MPa, and most preferably, 0.1 to 0.2 MPa. 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.

[0153] When a polymeric material having organometallic end groups is treated with a reactive gas compound in an optional non-polymerization reaction step, it is preferable to further treat it with an active proton compound. The treatment time 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 an optional non-polymerization reaction step, the treatment with the reactive gas compound and the treatment with the active proton compound may be carried out simultaneously. That is, the polymeric material having organometallic end groups may be treated with a mixture of the reactive gas compound and the active proton compound. In this case, the number of treatments can be reduced, which is preferable in terms of efficiency and economy.

[0154] The terminal-stabilized polymer material that has undergone any non-polymerization reaction step is preferably further treated in a step of removing volatile compounds. Specific examples of the step of removing volatile compounds include a method of reducing pressure while heating, a method of passing nitrogen gas while heating, and a method of continuously extracting and removing volatile compounds with heated water or heated alcohol, followed by a method of reducing pressure or passing nitrogen gas. Examples of volatile compounds include (a) dilution solvents such as propylene, hydrogen gas, hexane, and heptane; (b) ethanol and low-molecular-weight (oligomeric) alcohols (e.g., 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 that were added in the non-polymerization reaction step. If (b) remains in the propylene polymer material, it may interfere with the functional expression of the propylene polymer material or may cause the propylene polymer material to have an odor. The time required for the step of removing volatile compounds is preferably 1 to 120 minutes. It is more preferably 1 to 90 minutes. It is more preferable that the time is 1 to 60 minutes.

[0155] 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, even more preferably 160 to 168°C, and most preferably 161 to 168°C.

[0156] In the present invention, the heat of fusion (ΔH) of the propylene polymer material is preferably 80 to 150, more preferably 100 to 135.

[0157] Polypropylene Composition In the present invention, the polypropylene composition can be one of the following: A polypropylene composition comprising the heterophasic propylene polymer material and a polymer having a polar group.

[0158] Polymers Having Polar Groups The polar groups of polymers having polar groups are functional groups that can react with or interact with hydroxyl groups. Specific functional groups may be carboxyl groups, carbonyl groups, isocyanate groups, epoxy groups, carbodiimide groups, oxazoline groups, or amino groups. Polymers containing carboxyl groups may also be polymers having unsaturated carboxylic acids or derivatives of unsaturated carboxylic acids. Examples of unsaturated carboxylic acids include maleic acid, fumaric acid, itaconic acid, acrylic acid, and methacrylic acid. In addition, examples of 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 include maleic anhydride, itaconic anhydride, methyl acrylate, ethyl acrylate, butyl acrylate, glycidyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, glycidyl methacrylate, monoethyl maleate, diethyl maleate, monomethyl fumarate, dimethyl fumarate, acrylamide, methacrylamide, monoamide maleate, diamide maleate, monoamide fumarate, maleimide, N-butylmaleimide, and sodium methacrylate. Compounds that dehydrate to produce unsaturated carboxylic acids during graft polymerization onto polypropylene, such as citric acid and malic acid, may also be used. The polymer used in the polymer having a polar group is not particularly limited. Examples include homopolymers, copolymers, and terpolymers of olefins, etc.

[0159] 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.

[0160] 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.

[0161] 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.

[0162] <<Coupling Compound>> In the present invention, the heterophasic propylene polymer material may be formed by a covalent bond between the heterophasic propylene polymer material and a polymer having a polar group. Preferably, a hydroxyl group of the heterophasic propylene polymer material is covalently bonded to a carboxylic acid anhydride residue or a residue of a carboxylic acid anhydride derivative of the polymer having a polar group. The covalent bond is preferably an ester bond.

[0163] <<Method for Producing a Coupling Product>> A coupling product can be produced by melt-kneading a heterophasic propylene polymerization material and a polymer having a polar group in an extruder, or by heating a heterophasic propylene polymerization material and a 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 product is a graft-modified product and / or a block-modified product comprising the following segment (I) and segment (II): Segment (I): A propylene polymerization segment containing 90% by weight or more of structural units derived from propylene, relative to 100% by weight of the total weight of the propylene polymerization 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, wherein 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 the structural units derived from ethylene are more than 10 wt% and not more than 99 wt% relative to 100 wt% of the total weight of the ethylene-α-olefin copolymer segment. A coupling catalyst can also be added during production of the coupled product.

[0164] <<Coupling Catalyst>> Addition of a coupling catalyst covalently bonds hydroxyl groups and polar groups in the heterophasic propylene polymer material, forming a coupling product in which the heterophasic propylene polymer material and a polymer having a polar group are covalently bonded. The coupling product can be either a graft or block type. Adding a coupling catalyst to form a coupling product can impart toughness, such as impact resistance and tensile elongation. Examples of coupling catalysts include metal compounds, nitrogen-containing compounds, and Bronsted acids. Preferred are inorganic metal compounds such as metal oxides, metal hydroxides, metal alkoxides, metal carboxylates, metal enolates, and metal carbonates. 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 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 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 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 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, tin carboxylate, etc. Specific examples of metal enolates 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, tin enolate, etc. Specific examples of metal carbonates 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 titanium oxide, zirconium oxide, iron oxide, cobalt oxide, nickel oxide, copper oxide, and zinc oxide. Specific examples of transition metal hydroxides include titanium hydroxide, zirconium hydroxide, iron hydroxide, cobalt hydroxide, nickel hydroxide, copper hydroxide, and zinc hydroxide. Specific examples of transition metal alkoxides include titanium alkoxides, zirconium alkoxides, iron alkoxides, cobalt alkoxides, nickel alkoxides, copper alkoxides, and zinc alkoxides.Preferred examples of the transition metal alkoxide include tetraalkyl titanates such as tetrastearyl titanate, tetraisopropyl titanate, and tetranormalbutyl titanate, and tetraalkyl zirconates such as tetrastearyl zirconate, tetraisopropyl zirconate, and tetranormalbutyl zirconate. Specific examples of the transition metal carboxylate include titanium carboxylate, zirconium carboxylate, iron carboxylate, cobalt carboxylate, nickel carboxylate, copper carboxylate, and zinc carboxylate. Preferred examples of the transition metal carboxylate include titanium carboxylates such as titanium stearate and titanium octanoate, and zirconium carboxylates such as zirconium stearate and zirconium octanoate. Specific examples of transition metal enolates include titanium enolate, zirconium enolate, iron enolate, cobalt enolate, nickel enolate, copper enolate, and zinc enolate. Preferable transition metal enolates 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 titanium carbonate, zirconium carbonate, iron carbonate, cobalt carbonate, nickel carbonate, copper carbonate, and zinc carbonate. Preferred inorganic transition metal compounds are transition metal oxides, transition metal hydroxides, transition metal alkoxides, and transition metal enolates.

[0165] Thermoplastic Elastomers In the present invention, the heterophasic propylene polymer material and the polypropylene composition described above can be mixed with known thermoplastic elastomers in a powder state or a hot-molten state. Specific examples of the thermoplastic elastomer 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.

[0166] Fillers In the present invention, the heterophasic propylene polymer material and polypropylene composition described above can be mixed with known fillers in a powder state or a hot-melt 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.

[0167] Other Components 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 such 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.

[0168] Hydrophilic Resin (B) The hydrophilic resin (B) is a water-soluble resin or a water-absorbent resin having a water absorption capacity of 0.01 to 100 g / g. Preferably, the water absorption capacity is 0.03 to 95 g / g. The hydrophilic resin (B) is preferably a thermoplastic polyethylene oxide, polyvinyl alcohol, or a resin having a hydrophilic portion and a hydrophobic portion. The hydrophilic resin (B) is preferably a resin having a hydrophilic portion and a hydrophobic portion, and the resin having a hydrophilic portion and a hydrophobic portion is a reaction bonded product of polypropylene oxide and polyethylene oxide, a triblock copolymer of polypropylene oxide and polyethylene oxide, a partially saponified polyvinyl alcohol, a polymer in which polyethylene oxide is bonded to the end or in the chain of a polyolefin, a polymer in which polyvinyl alcohol is bonded to the end or in the chain of a polyolefin, or a polymer in which partially saponified polyvinyl alcohol is bonded to the end or in the chain of a polyolefin.

[0169] Examples of the hydrophilic resin (B) in the present invention include polyethylene oxide, polyalkylene oxide, polyvinyl alcohol, polyvinylpyrrolidone, cellulose, and starch. Polymers or copolymers of acrylates or methacrylates having a hydroxyl group, such as polyhydroxyethyl acrylate, polyhydroxyethyl methacrylate, and polyhydroxybutyl acrylate, may also be used. These are preferably thermoplastic from the viewpoint of dispersibility. Multiple types may also be used.

[0170] The polyvinyl alcohol that can be used as the hydrophilic resin (B) in the present invention is preferably a heat-meltable polyvinyl alcohol, such as JMR "H type," "M type," or "L type" having a saponification degree of 90 mol% or less, manufactured by Japan Vinyl Acetate & Poval Co., Ltd.

[0171] In addition, the hydrophilic resin (B) in the present invention preferably has a hydrophobic moiety therein. By having a hydrophobic moiety, compatibility with polypropylene is improved, resulting in a dispersion state that is favorable for dyeing. As the hydrophobic moiety, one having high compatibility with polypropylene is more preferable.

[0172] Examples of hydrophobic moieties in the hydrophilic resin (B) include polyolefins such as polypropylene, polypropylene oxide, and unsaponified acetyl groups in partially saponified polyvinyl alcohol. These may be bonded to either the end or the chain of the hydrophilic resin, and multiple types or multiple bonds may be bonded. The bonding method is not important. For example, resins having hydrophilic and hydrophobic moieties include a reaction bonded product of polypropylene oxide and polyethylene oxide (Aquacork TWB (manufactured by Sumitomo Seika Chemicals Co., Ltd.)), a triblock copolymer of polypropylene oxide and polyethylene oxide (ADEKA Pluronic (registered trademark) (manufactured by ADEKA Corporation), Newpol (Sanyo Chemical Industries, Ltd.)), partially saponified polyvinyl alcohol, a polymer in which polyethylene oxide is bonded to the end or chain of a polyolefin, a polymer in which polyvinyl alcohol is bonded to the end or chain of a polyolefin, and a polymer in which partially saponified polyvinyl alcohol is bonded to the end or chain of a polyolefin. Multiple types of these may be used.

[0173] The polyethylene oxide that can be used as the hydrophilic resin (B) in the present invention has a weight-average molecular weight of 3,000 to 5,000,000, preferably 5,000 to 500,000. Thermoplastic polyethylene oxide is particularly preferred, and its weight-average molecular weight is preferably 3,000 or more, more preferably 10,000 or more, and particularly preferably 50,000 or more, and is preferably 1,000,000 or less, and more preferably 600,000 or less.

[0174] The flow initiation temperature of the thermoplastic polyethylene oxide is preferably 40°C or higher, more preferably 50°C or higher, in order to maintain the properties of the molded product, and is preferably 200°C or lower, more preferably 160°C or lower in terms of moldability.

[0175] Specific examples of the thermoplastic polyethylene oxide include "ALKOX E-30" and "ALKOX R-1000" (both trade names) manufactured by Meisei Chemical Industry Co., Ltd. (both are linear polyethylene oxides obtained by ring-opening polymerization of ethylene oxide, and have molecular weights of 300,000 to 500,000 and 250,000 to 300,000, respectively).

[0176] The thermoplastic polyethylene oxide may be partially crosslinked with, for example, a diisocyanate compound or a triisocyanate compound. Crosslinking can further improve durability without impairing hydrophilicity. However, if the degree of crosslinking is too high, the fluidity during molding decreases, so it is preferable to adjust the degree of crosslinking in addition to the molecular weight.

[0177] The above-mentioned partial crosslinking refers to a crosslinking having properties that do not adversely affect molding processability, such as maintaining fluidity during spinning and spinnability while maintaining properties such as hydrophilicity and durability such as washing resistance in a resin composition obtained by heat-melting and mixing the crosslinked thermoplastic polyethylene oxide with a polyolefin and a surfactant, or by heat-melting and mixing the polyolefin, a surfactant and a compatibilizer, and the degree of crosslinking is preferably about one bond participating in crosslinking (two bonds are crosslinked) per weight average molecular weight of 100,000 to 200,000.

[0178] In the present invention, the hydrophilic resin (B) may be a mixture of 100 parts by weight of highly hydrophilic polyethylene oxide and 1 to 30 parts by weight of more hydrophobic polypropylene oxide or ethylene oxide-propylene oxide copolymer as the polyalkylene oxide.

[0179] As the hydrophilic resin (B), a thermoplastic water-absorbing resin can also be used, which is obtained by reacting a polyalkylene oxide obtained by mixing 100 parts by weight of polyethylene oxide having a weight-average molecular weight of 10,000 to 500,000 with 1 to 30 parts by weight of polypropylene oxide having a weight-average molecular weight of 500 to 50,000 or an ethylene oxide-propylene oxide copolymer having a weight-average molecular weight of 500 to 50,000, with a low-molecular-weight diol having a molecular weight of 500 or less, and a diisocyanate compound.

[0180] That is, in order to obtain the thermoplastic water-absorbing resin as the hydrophilic resin (B), a mixture of 100 parts by weight of highly hydrophilic polyethylene oxide and 1 to 30 parts by weight of more hydrophobic polypropylene oxide or ethylene oxide-propylene oxide copolymer can be used as the polyalkylene oxide.

[0181] The polyethylene oxide used has, for example, a weight average molecular weight of 10,000 to 500,000, preferably 20,000 to 200,000.

[0182] The weight average molecular weight of the polypropylene oxide or ethylene oxide-propylene oxide copolymer is, for example, in the range of 500 to 50,000, preferably 1,000 to 30,000.

[0183] The mixing ratio of the mixture of polyethylene oxide and polypropylene oxide or ethylene oxide-propylene oxide copolymer used as the polyalkylene oxide is, for example, 100 parts by weight of polyethylene oxide to 1 to 30 parts by weight, preferably 3 to 20 parts by weight of polypropylene oxide or ethylene oxide-propylene oxide copolymer. If the amount of polypropylene oxide or ethylene oxide-propylene oxide copolymer added is less than 1 part by weight, excellent compatibility will not be achieved, while if it is more than 30 parts by weight, it will be difficult to impart hydrophilic properties to the hydrophobic resin, which is not preferred.

[0184] Examples of low molecular weight diols having a molecular weight of 500 or less include aliphatic or aromatic diols such as ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol, dipropylene glycol, trimethylene glycol, 1,3-butanediol, 2,3-butanediol, 1,4-butanediol, 1,5-pentanediol, hexylene glycol, octylene glycol, glyceryl monoacetate, glyceryl monobutyrate, 1,6-hexanediol, 1,9-nonanediol, and 1,4-bishydroxyethylbenzene, with 1,4-butanediol being preferred. These low molecular weight diols can be used alone or as a mixture of two or more.

[0185] Examples of the diisocyanate compound include aliphatic or aromatic diisocyanates such as 1,6-hexamethylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 1,8-dimethylbenzene-2,4-diisocyanate, 2,4-tolylene diisocyanate, 2,2'-dimethyl-4,4'-diphenylmethane diisocyanate, 1,3- or 1,4-bis(isocyanatomethyl)benzene, 1,3- or 1,4-bis(isocyanatomethyl)cyclohexane, 4,4'-dicyclohexylmethane diisocyanate, and isophorone diisocyanate. 4,4'-diphenylmethane diisocyanate, 2,4-tolylene diisocyanate, and the like are preferably used. These diisocyanate compounds can be used alone or as a mixture of two or more.

[0186] In the present invention, for example, the proportions of polyalkylene oxide, low molecular weight diol, and diisocyanate compound used are selected so that the ratio (R value) of the sum of the number of terminal hydroxyl groups of the polyalkylene oxide and the number of active hydrogens in the low molecular weight diol to the number of isocyanate groups in the diisocyanate compound is 0.5 to 2.0, preferably 0.8 to 1.8. If the R value is less than 0.5, the resulting resin will be water-soluble. On the other hand, if the R value exceeds 2.0, a chemical crosslinking reaction will occur, making the resin insoluble in organic solvents and impairing its thermoplasticity, which is undesirable. The number of moles of polyalkylene oxide is determined by dividing the weight by the average molecular weight.

[0187] The method of reacting a polyalkylene oxide and a low molecular weight diol with a diisocyanate compound is generally a method of reacting them in a solution state using an appropriate solvent. It is also possible to react them in a dispersed state, or to mix them uniformly in a powder or solid state and then heat them to a predetermined temperature to react them, but from the viewpoint of industrial implementation, it is preferable to continuously feed each raw material in a molten state and mix and react them in a multi-screw extruder.

[0188] The reaction temperature for the above reaction is usually 50 to 210°C. The reaction can also be accelerated by adding a small amount of triethylamine, triethanolamine, dibutyltin diacetate, dibutyltin dilaurate, stannous octoate, triethylenediamine, etc. to the reaction system. The polypropylene resin composition of the present invention can also contain additives such as plasticizers, stabilizers, fillers, lubricants, and pigments.

[0189] Thus, by reacting a polyalkylene oxide and a low-molecular-weight diol with a diisocyanate compound, a thermoplastic water-absorbing resin having excellent compatibility with hydrophobic general-purpose resins can be obtained. The resin has excellent compatibility with polyolefin resins and exhibits excellent processability when molded into films, sheets, fibers, etc.

[0190] A specific example of the resin obtained by reacting the polyalkylene oxide and low molecular weight diol with a diisocyanate compound is "AQUACORK" (trade name) (a reaction bond of polypropylene oxide and polyethylene oxide) manufactured by Sumitomo Seika Chemicals Co., Ltd. Such resins may be used alone or in combination of two or more.

[0191] The weight average molecular weight of polypropylene oxide or ethylene oxide-propylene oxide triblock copolymer that can be used as the hydrophilic resin (B) in the present invention is preferably in the range of 500 to 50,000, and more preferably 1,000 to 20,000.

[0192] In the present invention, the following can also be used as the hydrophilic resin (B): ADEKA PLURONIC (registered trademark) L, P, F series (nonionic surfactants in which polypropylene glycol serves as a hydrophobic group and is rendered hydrophilic by the addition of ethylene oxide: for example, ADEKA PLURONIC (registered trademark) F-38, L-44, L-62, L-64, F-68, F-108, F-127, 25R-1, 25R-2, 17R-2, 17R-3, 17R-4, etc.) ADEKA PLURONIC (registered trademark) TR series (ethylenediamine-based surfactants exhibiting slight cationic properties: for example, ADEKA PLURONIC (registered trademark) TR-913R, etc.) ADEKA PLURONIC (registered trademark) Reverse Type SANYO CHEMICAL INDUSTRIES, LTD. NEWPOL PE series (for example, NEWPOL PE-68, PE-78, PE-108, PE-128, etc.)

[0193] Invention 2 According to Invention 2, a polypropylene-based resin composition with excellent spinnability can be obtained. Polyolefin-based resin composition The polypropylene-based resin composition of the present invention is as follows. A polypropylene-based resin composition comprising 50 parts by weight or more and less than 97 parts by weight of a polypropylene-based resin (A2), more than 0 parts by weight and 30 parts by weight or less of a hydrophilic resin (B), and 3 to 25 parts by weight of a compatibilizer (C), wherein the hydrophilic resin (B) is a water-soluble resin or a water-absorbent resin having a water absorption capacity of 0.01 to 100 g / g, and the total of (A2), (B), and (C) is 100 parts by weight. The polypropylene-based resin composition of the present invention preferably comprises 50 to 96 parts by weight of the polypropylene-based resin (A2), 1 to 30 parts by weight of the hydrophilic resin (B), and 3 to 25 parts by weight of the compatibilizer (C). A polypropylene-based resin composition comprising 50 to less than 97 parts by weight of a polypropylene-based resin (A2), more than 0 to 30 parts by weight of a hydrophilic resin (B), 3 to 25 parts by weight of a compatibilizer (C), and more than 0 to 10 parts by weight of a compound (G) that crosslinks hydroxyl groups, wherein the hydrophilic resin (B) is a water-soluble resin or a water-absorbent resin having a water absorption capacity of 0.01 to 100 g / g, and the total of (A2), (B), (C), and (G) is 100 parts by weight. The polypropylene-based resin composition of the present invention preferably contains 3 to 20 parts by weight of the compatibilizer (C). Use of this polypropylene-based resin composition improves spinnability when the polypropylene-based resin composition is spun.

[0194] Polypropylene Resin (A2) In Invention 2, the polypropylene resin (A2) used in the polypropylene resin composition of the present invention is preferably a homopolypropylene. The polypropylene resin (A2) can be the same as the polypropylene or heterophasic propylene polymer material exemplified as a raw material for producing the hydroxyl group-modified polyolefin (A1) used in Invention 1. The polypropylene or heterophasic propylene polymer material can be produced by the same production method as exemplified in Invention 1.

[0195] Hydrophilic Resin (B) In Invention 2, the hydrophilic resin (B) used in the polypropylene resin composition of the present invention can be the same as the hydrophilic resin (B) used in Invention 1 above. The hydrophilic resin (B) is preferably thermoplastic polyethylene oxide, polyvinyl alcohol, or a resin having a hydrophilic portion and a hydrophobic portion. The hydrophilic resin (B) is preferably a resin having a hydrophilic portion and a hydrophobic portion, and the resin having a hydrophilic portion and a hydrophobic portion is a reaction bonded product of polypropylene oxide and polyethylene oxide, a triblock copolymer of polypropylene oxide and polyethylene oxide, a partially saponified polyvinyl alcohol, a polymer in which polyethylene oxide is bonded to the end or in the chain of a polyolefin, a polymer in which polyvinyl alcohol is bonded to the end or in the chain of a polyolefin, or a polymer in which partially saponified polyvinyl alcohol is bonded to the end or in the chain of a polyolefin.

[0196] The hydrophilic resin (B) is preferably at least one resin having a hydroxyl group. Examples of the hydrophilic resin (B) include polyvinyl alcohol, polyethylene oxide, polyethylene glycol, polyglycerin, and ethylene-vinyl alcohol copolymer. Among these, the resin having a hydroxyl group is preferably polyvinyl alcohol, polyethylene oxide, or polyethylene glycol, more preferably polyvinyl alcohol, from the viewpoint of improving dyeability. The polypropylene-based resin composition may contain only one type of resin having a hydroxyl group, or may contain two or more types. In one aspect of the polypropylene-based resin composition according to this embodiment, the hydrophilic resin (B) is a partially saponified polyvinyl alcohol, a reaction bond of polypropylene oxide and polyethylene oxide and a partially saponified polyvinyl alcohol, or a triblock copolymer of polypropylene oxide and polyethylene oxide and a partially saponified polyvinyl alcohol.

[0197] Polyvinyl alcohol is a water-soluble polymer obtained as a hydrolysis (saponification) product of vinyl acetate. Examples of polyvinyl alcohol include various polyvinyl alcohols such as low-saponification products, partially saponified products, and fully saponified products. Examples of polyvinyl alcohol include various polyvinyl alcohols such as polyvinyl alcohols having functional groups such as carboxylic acid, sulfonic acid, quaternary ammonium salt, polyethylene oxide group, and acetoacetyl group; and copolymer polyvinyl alcohols of ethylene, butene, butenediol, etc.

[0198] From the viewpoint of obtaining fibers with good kneading processability and excellent dyeability, the saponification degree of the polyvinyl alcohol is preferably from 10 to 100, more preferably from 50 to 100, and even more preferably from 60 to 90. In one aspect of the polypropylene resin composition according to this embodiment, the hydrophilic resin (B) is a partially saponified polyvinyl alcohol having a saponification degree of from 10 to 100.

[0199] From the viewpoint of obtaining fibers with good kneading processability and excellent dyeability, the degree of polymerization of the polyvinyl alcohol is preferably from 100 to 2000, more preferably from 100 to 1500, and even more preferably from 100 to 1000. In one aspect of the polyolefin resin composition according to this embodiment, the hydrophilic resin (B) is a partially saponified polyvinyl alcohol having a degree of polymerization of from 100 to 2000.

[0200] As the polyvinyl alcohol, commercially available products may be used, such as Denka Poval manufactured by Denka Co., Ltd., Kuraray Poval manufactured by Kuraray Co., Ltd., JMR, JL, JR, and JP manufactured by Nippon Vinyl Acetate & Poval Co., Ltd., and Poval manufactured by Nippon Vinyl Acetate & Poval Co., Ltd.

[0201] From the viewpoint of obtaining fibers with good spinnability and excellent dyeability, the content of the hydrophilic resin (B) having a hydroxyl group is more than 0 part by weight and not more than 30 parts by weight, preferably 5 parts by weight or more and not more than 30 parts by weight, more preferably 5 parts by weight or more and not more than 25 parts by weight, based on 100 parts by weight of the total of (A2), (B), (C), and (G). When the polypropylene resin composition contains two or more types of hydrophilic resins (B), the content of the hydrophilic resins (B) is the total content thereof.

[0202] Compatibilizer (C) The compatibilizer (C) is preferably a modified polyolefin. The compatibilizer (C) is preferably a modified polyolefin, and the modifying group of the modified polyolefin is one type of modifying group selected from maleic anhydride and a hydroxyl group. The compatibilizer (C) is preferably a modified polypropylene, and the modifying group of the modified polypropylene is one type of modifying group selected from maleic anhydride and a hydroxyl group. The compatibilizer (C) may be the same as the hydroxyl group-modified polyolefin (A1) described in Invention 1 above.

[0203] The compatibilizer may be one that is compatible with both components to be mixed, such as maleic anhydride grafted polyolefin, ethylene-ethyl acrylate copolymer, ethylene-methacrylic acid copolymer, etc. Among these, maleic anhydride grafted polyolefin is preferred because of its high compatibilizing ability and ease of handling.

[0204] The maleic anhydride grafted polyolefin is a polyolefin obtained by graft copolymerizing 100 parts of maleic anhydride with 100 parts of polyolefin, and has an intrinsic viscosity of 0.4 dl / g or more and 3.0 dl / g or less, preferably 0.5 dl / g or more and 1.0 dl / g or less.

[0205] The compatibilizer (C) can be a modified polypropylene, and the modified polypropylene can be a polypropylene modified by modification with maleic anhydride. Compared to unmodified polypropylene, the modified polypropylene has excellent dispersibility of the hydrophilic resin (B), and can improve spinnability while maintaining the effect of improving dyeability due to the addition of the hydrophilic resin (B).

[0206] In the maleic anhydride-modified polypropylene, the graft modification rate of maleic anhydride may be 0.01 to 2.50% by mass. The graft modification rate of maleic anhydride is the content of maleic anhydride in the maleic anhydride-modified polypropylene. When the graft modification rate is within this range, excellent spinnability can be exhibited while satisfying the properties of polypropylene. If the modification rate of maleic anhydride is low, spinnability may not be satisfactory. Furthermore, if the modification rate is high, there is a risk of incompatibility with unmodified PP. If the graft modification rate is 0.01 to 1.00% by mass, compatibility with unmodified PP can be satisfied. The amount of succinic anhydride residues may be considered as the graft modification rate of maleic anhydride.

[0207] From the viewpoint of obtaining fibers having good spinning processability and excellent dyeability, the content of the compatibilizer (C) is 3 parts by weight or more and 25 parts by weight or less, preferably 5 parts by weight or more and 25 parts by weight or less, and more preferably 5 parts by weight or more and 20 parts by weight or less, based on 100 parts by weight of the total of (A2), (B), (C), and (G). When the polypropylene resin composition contains two or more types of compatibilizers (C), the content of the compatibilizers (C) is the total content thereof.

[0208] [Compound (G) that Crosslinks Hydroxyl Groups] The compound (G) that crosslinks hydroxyl groups may be a crosslinking agent that crosslinks hydroxyl groups contained in a resin having hydroxyl groups. The crosslinking agent is preferably a compound that bonds two or more hydroxyl groups together to crosslink them. As the crosslinking agent, known compounds that chemically react with hydroxyl groups to crosslink (chemical crosslinking) or physically interact with hydroxyl groups to crosslink (physical crosslinking) can be used.

[0209] Examples of crosslinks between hydroxyl groups include coordinate bonds with metal ions (preferably chelate bonds) and ionic bonds with metal ions.

[0210] Examples of functional groups contained in the crosslinking agent include a carboxyl group, an isocyanate group, an aldehyde group, a hydroxyl group, a phenolic hydroxyl group, an epoxy group, an amino group, an N-methylol group, and a vinyl group.

[0211] Examples of such crosslinking agents include metal compounds, polycarboxylic acid compounds, polyisocyanate compounds, aminoaldehyde compounds, glyoxal compounds, polyepoxy compounds, carbodiimides, carbodiimide resins, melamine compounds, amino compounds, and vinyl compounds. Among these, the crosslinking agent is preferably at least one selected from the group consisting of zirconium compounds, titanium compounds, carbodiimides, carbodiimide resins, boron compounds, polycarboxylic acid compounds, polyisocyanate compounds, aminoaldehyde compounds, glyoxal compounds, and polyepoxy compounds, and more preferably at least one selected from the group consisting of zirconium compounds, titanium compounds, carbodiimides, carbodiimide resins, boron compounds, polyisocyanate compounds, and polycarboxylic acid compounds. In one aspect, in the polypropylene resin composition according to this embodiment, the compound (G) that crosslinks hydroxyl groups is a carbodiimide resin.

[0212] Examples of the metal compound include a boron compound, a titanium compound, a zirconium compound, and an aluminum compound.

[0213] Examples of boron compounds include at least one of boric acid and boric acid salts (hereinafter also referred to as boric acid (salt)), such as boric acid, potassium borate, and sodium borate (borax), or salts thereof.

[0214] Examples of titanium compounds include titanium, titanium acetylacetate, triethanolamine titanate, titanium ammonium lactate, titanium lactate, salts of inorganic acids, organic titanium alkoxides [Ti(OR)4], organic titanium acylates [Ti(OCOR)n(OR)4-n], organic titanium chelate compounds, organic titanium polymers or organic titanium oligomers [partial hydrolysis condensates of organic titanium alkoxides or organic titanium acylates, etc.: -(Ti(OR)nO)m-], and the like. Specific examples of organic titanium acylates include polyhydroxytitanium stearate, and the like. Examples of organic titanium chelate compounds include titanium lactate (e.g., Orgatix TC-310 manufactured by Matsumoto Fine Chemical Co., Ltd.) and titanium triethanolamine (e.g., Orgatix TC-400 manufactured by Matsumoto Fine Chemical Co., Ltd.). Examples of inorganic acid salts include titanium tetrachloride, and the like.

[0215] Examples of zirconium compounds include zirconium, zirconium fluoride, zirconium chloride, zirconium bromide, zirconium sulfate, zirconium nitrate, zirconium carbonate, ammonium zirconium carbonate, potassium zirconium carbonate, zirconium acetate, zirconium stearate, zirconium octylate, zirconium citrate, zirconium lactate, zirconium phosphate, zirconium oxalate, zirconic acid, zirconate salts, ammonium zirconium carbonate, zirconium tetraacetylacetonate (e.g., Orgatix ZC-150 manufactured by Matsumoto Fine Chemical Co., Ltd.), zirconium monoacetylacetonate (e.g., Orgatix ZC-540 manufactured by Matsumoto Fine Chemical Co., Ltd.), zirconium bisacetylacetonate, zirconium monoethylacetoacetate, and zirconium acetate.

[0216] Examples of aluminum compounds include inorganic acid salts such as aluminum sulfate, aluminum lactate, aluminum chloride, basic polyaluminum chloride, and aluminum nitrate.

[0217] In addition to the compounds listed above, other metal compounds include zinc sulfate and satin white.

[0218] In addition to the compounds listed above, various metal alkoxides can also be used as the metal compound. When a metal alkoxide is used as the crosslinking agent, crosslinking of the hydroxyl groups contained in the hydrophilic resin (B) is generally carried out by a method called a sol-gel method.

[0219] Specifically, first, the metal alkoxide is hydrolyzed to produce a metal hydroxide and an alcohol, and then the metal hydroxide and the hydroxyl groups contained in the hydrophilic resin (B) undergo dehydration condensation, thereby crosslinking the hydroxyl groups contained in the hydrophilic resin (B).

[0220] For example, when tetraethoxysilane is used as the metal alkoxide, first, orthosilicic acid and ethanol are produced by hydrolysis of the tetraethoxysilane, and then, the orthosilicic acid and hydroxyl groups contained in polyvinyl alcohol as the hydrophilic resin (B) undergo dehydration condensation, whereby the hydroxyl groups contained in the polyvinyl alcohol are crosslinked via silicon.

[0221] The metal alkoxide contains two or more alkoxy groups such as, for example, a methoxy group, an ethoxy group, or a propoxy group.

[0222] Examples of metal elements contained in metal alkoxides include barium, calcium, magnesium, aluminum, boron, gallium, indium, lanthanum, silicon, zirconium, titanium, tin, etc. Among these, the metal elements are preferably silicon, zirconium, titanium, or aluminum.

[0223] Examples of metal alkoxides include metal alkoxides containing a divalent metal element such as dimethoxybarium, diethoxybarium, dipropoxybarium, dimethoxycalcium, diethoxycalcium, dipropoxycalcium, dimethoxymagnesium, diethoxymagnesium, and dipropoxymagnesium; trimethoxyaluminum, triethoxyaluminum, tripropoxyaluminum, triisopropoxyaluminum, trimethoxyboron, triethoxyboron, tripropoxyboron, triisopropoxyboron, trimethoxygallium, triethoxygallium, tripropoxygallium, triisopropoxygallium, trimethoxyindium, and triethoxyindium; Examples of metal alkoxides include metal alkoxides containing a trivalent metal element, such as tripropoxyindium, triisopropoxyindium, trimethoxylanthanum, triethoxylanthanum, tripropoxylanthanum, and triisopropoxylanthanum; and metal alkoxides containing a tetravalent metal element, such as tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetraisopropoxysilane, tetrabutoxysilane, tetramethoxyzirconium, tetraethoxyzirconium, tetrapropoxyzirconium, tetraisopropoxyzirconium, tetrabutoxyzirconium, tetramethoxytitanium, tetraethoxytitanium, tetrapropoxytitanium, tetraisopropoxytitanium, and tetrabutoxytitanium.

[0224] The metal alkoxide may be represented by the following formula (1): R1nM(OR2)m-n (1) (In formula (1), R1 and R2 represent an alkyl group, M represents a metal element, m represents the valence of the metal element M, and n represents an integer satisfying the relationship 0≦n≦m−1. R1 and R2 may be the same or different from each other.)

[0225] Examples of such metal alkoxides include methyltrimethoxysilane, methyltriethoxysilane, methyltrippropoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltrippropoxysilane, propoxytrimethoxysilane, propoxytriethoxysilane, and propoxytrippropoxysilane.

[0226] Examples of polycarboxylic acid compounds include malic acid, citric acid, glutaric acid, and adipic acid.

[0227] Examples of polyisocyanate compounds include aromatic diisocyanates such as phenylene diisocyanate (PDI), tolylene diisocyanate (TDI), naphthalene diisocyanate (NDI), and 4,4'-diisocyanatodiphenylmethane (MDI); aromatic aliphatic diisocyanates such as xylylene diisocyanate (XDI); aliphatic or alicyclic diisocyanates such as hydrogenated TDI, hydrogenated XDI, hydrogenated MDI, hexamethylene diisocyanate (HMDI), and isophorone diisocyanate (IPDI), and polyol adducts thereof, which are derivatives thereof; biuret compounds; tri- or higher functional polyisocyanates that are trimers; trifunctional isocyanates such as lysine triisocyanate (LTI); and various oligomers or polymers containing isocyanates.

[0228] The polyisocyanate compound may be a urethane compound or a polyurethane compound.

[0229] Examples of aminoaldehyde compounds include urea-formaldehyde resin, melamine-formaldehyde resin, polyamide-polyurea resin, and polyamide-epichlorohydrin.

[0230] Examples of glyoxal compounds include glyoxal, urea-glyoxal resin, and dialdehyde starch.

[0231] Examples of polyhydric epoxy compounds include ethylene glycol diglycidyl ether, epichlorohydrin, triglycidyl isocyanurate, and polyamide epoxy resins.

[0232] The carbodiimide is preferably a carbodiimide compound having a repeating unit represented by the following general formula (1): -N=C=N-R １ - (1) (wherein, R １ represents a divalent organic group.

[0233] The carbodiimide may be any compound having two or more carbodiimide groups, and includes carbodiimide oligomers and polymers (carbodiimide-based resins). Specific examples of oligomers include dimers in which two identical or different carbodiimide monomers are bonded together, and oligomers in which multiple carbodiimide monomers are bonded together and have a molecular weight of less than 10,000 (preferably less than 5,000). Examples of the carbodiimide monomer include aliphatic carbodiimide compounds such as diisopropylcarbodiimide and dioctadecylcarbodiimide; aromatic carbodiimide compounds such as diphenylcarbodiimide, bis(2,6-dimethylphenyl)carbodiimide, bis(2,6-diethylphenyl)carbodiimide, bis(2,6-diisopropylphenyl)carbodiimide, bis(2,6-di-tert-butylphenyl)carbodiimide, N,N'-di-o-tolylcarbodiimide, N,N'-di-p-tolylcarbodiimide, bis(2,4,6-trimethylphenyl)carbodiimide, bis(2,4,6-triisopropylphenyl)carbodiimide and bis(2,4,6-triisobutylphenyl)carbodiimide; and alicyclic carbodiimide compounds such as dicyclohexylcarbodiimide. Examples of carbodiimide resins include aliphatic polycarbodiimide compounds such as poly(diisopropylcarbodiimide), aromatic polycarbodiimide compounds such as poly(4,4'-diphenylmethanecarbodiimide), poly(p-phenylenecarbodiimide), poly(m-phenylenecarbodiimide), poly(diisopropylphenylenecarbodiimide), and poly(triisopropylphenylenecarbodiimide), and alicyclic polycarbodiimide compounds such as poly(4,4'-dicyclohexylmethanecarbodiimide).Examples of such products include cyclic carbodiimide compounds such as Hydrostab 3 (trade name) (oligomer of carbodiimide compound; manufactured by Schafer Additivesysteme GmbH), Carbodilite HMV-15CA (trade name) (poly(4,4-dicyclohexylmethane carbodiimide) terminally capped with isocyanate; manufactured by Nisshinbo Chemical Inc.), Carbodilite LA-1 (manufactured by Nisshinbo Chemical Inc.), Elastostab H01 (manufactured by Nisshinbo Chemical Inc.), Stabaxol P (manufactured by RheinChemie), and Carbodista TCC-NP (manufactured by Teijin Limited). These compounds may be used alone or in combination.

[0234] The carbodiimide resin may be produced by a known production method, such as that described in JP-A-59-187029, etc. Examples of such production methods include a method in which a monoisocyanate compound, a diisocyanate compound, and a triisocyanate compound are heated in a non-reactive organic solvent in the presence of a catalyst such as 3-methyl-1-phenyl-2-phosphorate oxide to cause decarboxylation, thereby converting the isocyanate group into a carbodiimide group, thereby obtaining a carbodiimide resin.

[0235] Examples of the amine compound include ethylenediamine, hexamethylenediamine, diethylenetriamine, dipropylenetriamine, triethylenetetramine, tetraethylenepentamine, N-aminoethylpiperazine, 1,4-bis(3-aminopropyl)piperazine, trimethylhexamethylenediamine, and polyoxypropylenediamine.

[0236] Examples of melamine compounds include trimethylol melamine and melamine resin.

[0237] Examples of vinyl compounds include bisvinylsulfonylmethyl ether.

[0238] From the viewpoint of obtaining fibers having good spinning processability and excellent dyeability, the content of the compound (G) that crosslinks hydroxyl groups is more than 0 part by weight and not more than 10 parts by weight, preferably 0.1 part by weight to 5 parts by weight, more preferably 0.2 part by weight to 3 parts by weight, and even more preferably 0.2 part by weight to 1 part by weight, where the total content of the compounds (A2), (B), (C), and (G) is 100 parts by weight. When the compound (G) that crosslinks hydroxyl groups is a combination of two or more types, the content of the compound (G) that crosslinks hydroxyl groups is the total content.

[0239] Invention 3-1 According to Invention 3-1, dyed polypropylene fibers with excellent dyeability can be obtained. Dyed Polypropylene Fiber The dyed polypropylene fiber of the present invention is as follows. A dyed polypropylene fiber containing 70 to less than 100 parts by weight of a polypropylene resin (A2) and more than 0 to 30 parts by weight of a hydrophilic resin (B), wherein the hydrophilic resin (B) is a water-soluble resin or a water-absorbent resin having a water absorption capacity of 0.01 to 100 g / g, and the total of (A2) and (B) is 100 parts by weight. The dyed polypropylene fiber of the present invention preferably contains 70 to 99 parts by weight of a polypropylene resin (A2) and 1 to 30 parts by weight of a hydrophilic resin (B). The use of this polypropylene resin composition improves spinnability when the polypropylene resin composition is spun. The dyed polypropylene fiber in Invention 3-1 can be produced by the same production method as exemplified in Invention 3-2 below.

[0240] Polypropylene Resin (A2) In Invention 3-1, the polypropylene resin (A2) is preferably a homopolypropylene. In Invention 3-1, the polypropylene resin (A2) may be the same as the polypropylene resin (A2) used in Invention 2 above, and may be produced by the same production method as exemplified in Invention 2. In addition, in Invention 3-1, the polypropylene resin (A2) may be the same as the hydroxyl group-modified polyolefin (A1) used in Invention 1 above, and may be produced by the same production method as exemplified in Invention 1.

[0241] Hydrophilic Resin (B) In Invention 3-1, the hydrophilic resin (B) can be the same as the hydrophilic resin (B) used in Inventions 1 or 2 above. The hydrophilic resin (B) is preferably thermoplastic polyethylene oxide, polyvinyl alcohol, or a resin having a hydrophilic portion and a hydrophobic portion. The hydrophilic resin (B) is preferably a resin having a hydrophilic portion and a hydrophobic portion, and the resin having a hydrophilic portion and a hydrophobic portion is a reaction bonded product of polypropylene oxide and polyethylene oxide, a triblock copolymer of polypropylene oxide and polyethylene oxide, a partially saponified polyvinyl alcohol, a polymer in which polyethylene oxide is bonded to the end or in the chain of a polyolefin, a polymer in which polyvinyl alcohol is bonded to the end or in the chain of a polyolefin, or a polymer in which partially saponified polyvinyl alcohol is bonded to the end or in the chain of a polyolefin.

[0242] Dye (D) In ​​Invention 3-1, the dye (D) is preferably an aqueous dye, and particularly preferably a reactive dye, an acid dye, a disperse dye, or a direct dye. An aqueous dye refers to a dye dissolved or dispersed in water.

[0243] As the dye (D), various dyes can be used alone or in combination depending on the purpose, and dyeing can be carried out using a conventional dyeing method, such as immersing a compatible material in a dye.

[0244] [Dyeing Process] The dyed polypropylene fiber of the present invention can be produced by a method including a dyeing process. The dye used in the dyeing process can be the same as the dye (D) described above. The dyeing process is not particularly limited, but can include a typical dyeing method, such as immersing the compatible solution in a dispersion of a disperse dye, heating to 130°C, dyeing for about 30 minutes, removing excess dye from the surface of the compatible solution, washing with water, dehydrating, and drying. The dyeing process can be carried out after the cooling and solidifying process, or between or together with the above-mentioned processes. For example, after obtaining a melt of the polypropylene resin composition, a dye can be added to the melt, dyeing the melt, and then molding the melt.

[0245] In the present invention, the following dyeing processes can be used. Disperse dyes: A polymer is immersed in a disperse dye heated to 130°C for 30 minutes. Cationic dyes: A polymer is immersed in a cationic dye heated to 120°C for 30 minutes. Acid dyes: A polymer is immersed in an acid dye heated to 100°C for 30 minutes. Direct dyes: A polymer is immersed in a direct dye heated to 90°C for 30 minutes. Reactive dyes: A polymer is immersed in a reactive dye heated to 60°C for 30 minutes.

[0246] The reactive dye that can be preferably used as the dye (D) is preferably a reactive dye for cellulose fibers, and is commercially available, for example, from Huntsman Chemical, Dystar, Sumitomo Chemical Co., Ltd., or Nippon Kayaku Co., Ltd. under the trade names "Sumifix Supra Yellow 3RF," "Remazol Yellow 3RS," "Novacron Red FN-2BL," "Kayacion Blue A-B," "Levafix Brilliant Blue E-BRA," or "Novacron Blue 4R."

[0247] The reactive dye usable as dye (D) may be a reactive dye for polyamide fibers. The reactive dye for polyamide fibers is a reactive dye developed primarily for dyeing polyamide fibers (e.g., a reactive dye for nylon fibers).

[0248] Such reactive dyes for polyamide fibers are commercially available from Huntsman or Dystar under the trade names "Eriofast Yellow 5G", "Eriofast Yellow R", "Eriofast Red 2B", "Eriofast Blue 3R", "Eriofast Orange 4R", "Eriofast Blue 3G", "Telon Yellow RN", "Telon Red RNC", "Telon Rubine RN" or "Telon Royal RN".

[0249] The dyeing composition may contain a reactive dye for cellulose fibers as a second dye in addition to the reactive dye for polyamide fibers. The combined use of a reactive dye for cellulose fibers can further improve the vividness, productivity, and fastness of dyeing cellulose fibers. The second dye component is any reactive dye for cellulose fibers that exhibits yellow, magenta, cyan, or other hues.

[0250] Examples of disperse dyes that can be preferably used as the dye (D) in the present invention include azo-based dyes such as benzene azo-based dyes (monoazo, disazo, etc.), heterocyclic azo-based dyes (thiazole azo, benzothiazole azo, quinoline azo, pyrizone azo, imidazole azo, thiophene azo, etc.), anthraquinone-based dyes, quinoline-based dyes, nitro-based dyes, coumarin-based dyes, methine-based dyes, and amino ketone-based dyes.

[0251] Dyeing using disperse dyes can be carried out under the same dyeing conditions as for conventional thermoplastic resins that are easily dyeable, such as polyester resins. More specifically, atmospheric dyeing can be carried out using a dyebath containing the disperse dye. For example, the dyeing can be carried out under atmospheric pressure at a temperature of typically 50 to 100°C, preferably 80 to 100°C, for typically 10 to 120 minutes, preferably 30 to 90 minutes. In this case, it is preferable to start raising the temperature from around 50°C.

[0252] Dyeing may also be carried out under pressure, for example, at a pressure of 101 to 400 kPa, preferably 150 to 350 kPa, and at a temperature of usually 90 to 140° C., preferably 110 to 130° C. In this case, the dyeing time is usually 10 to 120 minutes, preferably 30 to 90 minutes.

[0253] Invention 3-2 According to Invention 3-2, dyed polypropylene fibers with excellent dyeability can be obtained. Dyed Polypropylene Fiber The dyed polypropylene fiber of the present invention is as follows. A dyed polypropylene fiber containing 50 to less than 97 parts by weight of a polypropylene resin (A2), more than 0 to 30 parts by weight of a hydrophilic resin (B), and 3 to 20 parts by weight of a compatibilizer (C), wherein the hydrophilic resin (B) is a water-soluble resin or a water-absorbent resin having a water absorption capacity of 0.01 to 100 g / g, and the total of (A2), (B), and (C) is 100 parts by weight. The dyed polypropylene fiber of the present invention preferably contains 50 to 96 parts by weight of the polypropylene resin (A2), 1 to 30 parts by weight of the hydrophilic resin (B), and 3 to 20 parts by weight of the compatibilizer (C). A dyed polypropylene fiber comprising 50 to less than 97 parts by weight of a polypropylene resin (A2), more than 0 to 30 parts by weight of a hydrophilic resin (B), 3 to 25 parts by weight of a compatibilizer (C), and more than 0 to 10 parts by weight of a compound (G) that crosslinks hydroxyl groups, wherein the hydrophilic resin (B) is a water-soluble resin or a water-absorbent resin having a water absorption capacity of 0.01 to 100 g / g, and the total of (A2), (B), (C), and (G) is 100 parts by weight. The polypropylene resin composition of the present invention preferably contains 3 to 20 parts by weight of the compatibilizer (C). By using the above polypropylene resin composition, the dyed polypropylene fiber exhibits good dyeability.

[0254] Polypropylene Resin (A2) In Invention 3-2, the polypropylene resin (A2) may be the same as the polypropylene resin (A2) used in Invention 2 above, and may be produced by the same production method as exemplified in Invention 2. In addition, in Invention 3-1, the polypropylene resin (A2) may be the same as the hydroxyl group-modified polyolefin (A1) used in Invention 1 above, and may be produced by the same production method as exemplified in Invention 1.

[0255] Hydrophilic Resin (B) In Invention 3-2, the hydrophilic resin (B) can be the same as the hydrophilic resin (B) used in Invention 1 or 2 above.

[0256] Compatibilizer (C) In Invention 3-2, the compatibilizer (C) can be the same as the compatibilizer (C) used in Invention 2 above. In Invention 3-2, preferably, the compatibilizer (C) is a modified polyolefin, and the modifying group of the modified polyolefin is one modifying group selected from maleic anhydride and a hydroxyl group. Preferably, the compatibilizer (C) is a modified polypropylene, and the modifying group of the modified polypropylene is one modifying group selected from maleic anhydride and a hydroxyl group.

[0257] Dye (D) In ​​Invention 3-2, the dye (D) can be the same as the dye (D) used in Invention 3-1 above. In Invention 3-2, the dye (D) is preferably a water-based dye, more preferably a reactive dye, an acid dye, a disperse dye, or a direct dye. A water-based dye refers to a dye dissolved or dispersed in water.

[0258] Compound (G) for Cross-Linking Hydroxyl Groups In Invention 3-2, the compound (G) for cross-linking hydroxyl groups can be the same as the compound (G) for cross-linking hydroxyl groups used in Invention 2 above.

[0259] According to Invention 3-2, the method for producing dyed polypropylene-based fibers of the present invention is as follows. This method for producing polypropylene-based fibers dyed with dye (D) involves melt-spinning a composition containing a polypropylene-based resin (A2) and a hydrophilic resin (B) into a fiber shape, followed by dyeing using a dye (D) in water. The dyed polypropylene-based fibers obtained by this production method can be the dyed polypropylene-based fibers described in Inventions 3-1 and 3-2 above. The composition used in this production method can also contain a compatibilizer (C) and a hydroxyl-crosslinking compound (G) in addition to the polypropylene-based resin (A2) and the hydrophilic resin (B). The polypropylene-based resin (A2), hydrophilic resin (B), compatibilizer (C), dye (D), and hydroxyl-crosslinking compound (G) used in this production method can be the same as those described above.

[0260] <Polypropylene-based Fiber> The polypropylene-based fiber of this embodiment can be formed from the polypropylene-based resin composition described above. The polypropylene-based fiber can be formed from the polypropylene-based resin composition by a conventionally known method, for example, a melt spinning method.

[0261] The tensile strength of the polypropylene-based fiber of this embodiment is preferably 2.0 to 7.0 cN / dtex, more preferably 2.0 to 6.0 cN / dtex, and even more preferably 3.0 to 6.0 cN / dtex.

[0262] The polypropylene-based fiber of this embodiment can be applied to textile products such as clothing, bedding coverings, blankets, lap blankets, carpets, etc. Examples of clothing include underwear, undergarments, shirts, jumpers, sweaters, pants, training wear, sportswear, tights, belly warmers, scarves, hats, gloves, socks, earmuffs, and cold weather clothing. Furthermore, the surface of the fabric may be raised like fleece.

[0263] The polypropylene-based fibers of this embodiment can be produced by feeding pellets of the polypropylene-based resin composition described above into an extruder with a cylinder temperature set to 180 to 260°C, melting them, and discharging them from a multi-hole nozzle also set to 180 to 260°C to produce fibers such as POY (pre-sawn yarn). Further, by heating and stretching the resulting mixture with a roll or the like, fibers such as FDY (fully drawn yarn) and DTY (draw textured yarn) can be produced. Furthermore, by discharging a resin composition from a multi-hole nozzle and further heating and stretching the resulting mixture with a roll, fibers such as FDY (fully drawn yarn) can be produced.

[0264] The method for producing a molded article from the polypropylene resin composition described above may include other steps in addition to the steps of producing a melt of the resin composition, molding, cooling and solidifying, and dyeing. For example, it may include a processing step of processing the molded article into a predetermined shape after the cooling and solidifying step.

[0265] Specifically, when a yarn is produced from the polypropylene-based resin composition, the steps include a drawing step in which the yarn after the cooling and solidifying step is heated again and drawn, a heat treatment step in which distortion of the yarn is removed by heat treatment, a cutting step in which the yarn is cut to a predetermined length, and a winding step in which the yarn is wound around a bobbin or the like.

[0266] In addition, when producing a film, the film after the cooling and solidifying step may be subjected to a stretching step in which the film is stretched lengthwise or widthwise, a corona treatment step for improving the adhesion of ink or adhesive, a flame treatment step, a chemical treatment step, a winding step in which the film is wound up on a winder, etc., and the like.

[0267] As described above, according to the present invention, it is possible to provide a polypropylene-based resin composition, a polypropylene-based resin molded article, and a method for producing a polypropylene-based resin molded article, which are particularly suitable for general clothing applications because they can be dyed with dyes.

[0268] The dyed polypropylene fiber of the present invention can be obtained by subjecting the polypropylene resin composition to a known melt spinning process. The melt spinning process is not limited to a winder process, and air spinning processes such as spunbonding and meltblowing can also be used.

[0269] The dyed polypropylene-based fiber of the present invention can be processed into a nonwoven fabric, which can be produced using the dyed polypropylene-based fiber of the present invention. Here, nonwoven fabric literally means "non-woven fabric" and is a sheet made by bonding fibers together, which is neither a knitted fabric nor a paper or film. There are no particular restrictions on the method for bonding the fibers together, and any known appropriate method may be selected depending on the purpose and application.

[0270] The dyed polypropylene-based fibers of the present invention are not limited to polypropylene fibers of the types specifically described in the examples of this specification, but may also include fibers formed into threads by melting a resin and extruding it through pores using various combinations of components included in the present invention, or composite fibers in which the resin is exposed on all or part of the fiber surface, such as core-sheath structures and side-by-side structures.

[0271] The present invention will be specifically described below, but the present invention is not limited in any way by the following examples.

[0272] Materials Used In the Examples and Comparative Examples, the following materials were used to prepare polypropylene resin compositions.

[0273] 1. Polyolefin Resin (A) Hydroxyl Group-Modified Polyolefin (A1) <Synthesis of One-End Hydroxyl Group-Modified Polypropylene-1> (PPOH-1) MFR (230°C, Load 21.2 N): 25 g / 10 min; Terminated End OH Ratio: 8%. [Preparation of Solid Catalyst Component] A solid catalyst component for olefin polymerization was obtained according to the method described in Example 1 of JP 2009-173870 A. [Prepolymerization] 1.5 L of n-hexane, which had been thoroughly dehydrated and degassed, 30.7 mmol of triethylaluminum (hexane solution), and 4.0 mmol of cyclohexylethyldimethoxysilane (hexane solution) were placed in a 2 L stainless steel autoclave equipped with a stirrer. 13 g of the solid catalyst component for olefin polymerization prepared above was added thereto, and 46 g of propylene was continuously fed over approximately 30 minutes while maintaining the temperature inside the autoclave at approximately 3 to 10°C, to carry out prepolymerization. The prepolymerized slurry was then transferred to a 160 L stainless steel autoclave equipped with a stirrer, and 130 L of sufficiently purified liquid butane was added to form a slurry of prepolymerized catalyst components, which was then stored at a temperature of 10° C. or less. [First-stage propylene polymerization (liquid-phase polymerization reaction)] Propylene homopolymerization was carried out using a 42 L vessel-type slurry polymerization reactor equipped with a stirrer. The liquid level in the slurry polymerization reactor was adjusted to 18 L, and propylene, hydrogen, triethylaluminum, cyclohexylethyldimethoxysilane, and the slurry of prepolymerized catalyst components prepared above were continuously fed to the reactor to carry out polymerization. The reaction conditions were as follows: polymerization temperature: 70°C, pressure: 3.86 MPaG, propylene feed rate: 26 kg / hour, hydrogen feed rate: 130.1 NL / hour, triethylaluminum feed rate: 29.0 mmol / hour (hexane solution), cyclohexylethyldimethoxysilane feed rate: 4.4 mmol / hour (hexane solution), and prepolymerized catalyst component slurry feed rate (solid catalyst component equivalent): 0.51 g / hour. The amount of propylene polymer component (A) continuously discharged from the reactor was 2.3 kg / hour. The obtained slurry containing propylene polymer component (A) was continuously transferred to the reactor for the second step without deactivation. [Second-stage propylene polymerization (gas-phase polymerization reaction)] Internal volume: 1.4 m ３Propylene 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 held 29.6 kg of propylene polymer material, the polymerization temperature was 83°C, the polymerization pressure was 1.6 MPaG, the superficial gas velocity inside the reactor was 0.144 m / sec, the hydrogen concentration in the gas phase was 0.12 mol%, and the propylene concentration was maintained at 97.9 mol%. Diethylzinc was also supplied at 151.9 mmol / h (hexane solution). A separate supply line was used to feed diethylzinc to the reactor. The propylene polymer material continuously discharged from the reactor was 8.3 kg / h, and was continuously transferred to a post-treatment step. While continuously receiving the resulting propylene polymer material 7, 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 through for 1 hour at a flow rate of 20 Nm ３ The propylene polymer material was then contacted with dry air for 1 hour and then with water-containing air for 1 hour.

[0274] Synthesis of Single-End Hydroxyl-Modified Polypropylene-2 ​​(PPOH-2) MFR (230°C, load 21.2N): 11 g / 10 min; OH-Terminated End Rate: 9%. [Preparation of Solid Catalyst Component] A solid catalyst component for olefin polymerization was obtained according to the method described in Example 1 of JP 2009-173870 A. [Prepolymerization] 1.5 L of n-hexane, which had been thoroughly dehydrated and degassed, 30.7 mmol of triethylaluminum (hexane solution), and 4.0 mmol of cyclohexylethyldimethoxysilane (hexane solution) were placed in a 2 L stainless steel autoclave equipped with a stirrer. 13 g of the solid catalyst component for olefin polymerization prepared above was added thereto, and 46 g of propylene was continuously fed over about 30 minutes while maintaining the temperature inside the autoclave at about 3 to 10°C, to carry out prepolymerization. The prepolymerized slurry was then transferred to a 160 L stainless steel autoclave equipped with a stirrer, and 130 L of sufficiently purified liquid butane was added to form a slurry of prepolymerized catalyst components, which was then stored at a temperature of 10° C. or less. [First-stage propylene polymerization (liquid-phase polymerization reaction)] Propylene homopolymerization was carried out using a 42 L vessel-type slurry polymerization reactor equipped with a stirrer. The liquid level in the slurry polymerization reactor was adjusted to 18 L, and propylene, hydrogen, triethylaluminum, cyclohexylethyldimethoxysilane, and the slurry of prepolymerized catalyst components prepared above were continuously fed to the reactor to carry out polymerization. The reaction conditions were as follows: polymerization temperature: 70°C, pressure: 3.87 MPaG, propylene feed rate: 26 kg / hour, hydrogen feed rate: 130 NL / hour, triethylaluminum feed rate: 27.8 mmol / hour (hexane solution), cyclohexylethyldimethoxysilane feed rate: 4.2 mmol / hour (hexane solution), and prepolymerized catalyst component slurry feed rate (solid catalyst component equivalent): 0.45 g / hour. The amount of propylene polymer component (A) continuously discharged from the reactor was 1.9 kg / hour. The obtained slurry containing propylene polymer component (A) was continuously transferred to the reactor for the second step without deactivation. [Second-stage propylene polymerization (gas-phase polymerization reaction)] Internal volume: 1.4 m ３Propylene 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 held a propylene polymer material capacity of 30.4 kg, the polymerization temperature was 83°C, the polymerization pressure was 1.95 MPaG, the superficial gas velocity inside the reactor was 0.126 m / sec, the hydrogen concentration in the gas phase was 0.12 mol%, and the propylene concentration was maintained at 97.8 mol%. Furthermore, diethylzinc: 101.1 mmol / h (hexane solution) was supplied. A separate supply line was used to supply diethylzinc to the reactor. The amount of propylene polymer material continuously discharged from the reactor was 9.4 kg / h, and this was continuously transferred to a post-treatment step. While continuously receiving the resulting propylene polymer material 7, 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 through for 1 hour at a flow rate of 20 Nm ３ The propylene polymer material was then contacted with dry air for 1 hour and then with water-containing air for 1 hour.

[0275] Synthesis of Single-End Hydroxyl-Modified Polypropylene-3 (PPOH-3) MFR (230°C, load 21.2 N): 160 g / 10 min; OH-Terminated End Rate: 8%. [Preparation of Solid Catalyst Component] A solid catalyst component for olefin polymerization was obtained according to the method described in Example 1 of JP 2009-173870 A. [Prepolymerization] 1.5 L of n-hexane, which had been thoroughly dehydrated and degassed, 30.7 mmol of triethylaluminum (hexane solution), and 4.0 mmol of cyclohexylethyldimethoxysilane (hexane solution) were placed in a 2 L stainless steel autoclave equipped with a stirrer. 13 g of the solid catalyst component for olefin polymerization prepared above was added thereto, and 46 g of propylene was continuously fed over about 30 minutes while maintaining the temperature inside the autoclave at about 3 to 10°C, to carry out prepolymerization. The prepolymerized slurry was then transferred to a 160 L stainless steel autoclave equipped with a stirrer, and 130 L of sufficiently purified liquid butane was added to form a prepolymerized catalyst component slurry, which was then stored at a temperature of 10° C. or less. [First-stage propylene polymerization (liquid-phase polymerization reaction)] Propylene homopolymerization was carried out using a loop reactor with a total internal volume of 30 L. Propylene, hydrogen, triethylaluminum, cyclohexylethyldimethoxysilane, and the prepolymerized catalyst component slurry prepared above were continuously fed to the reactor, and polymerization was carried out in a liquid-filled state with no gas phase present. The reaction conditions were as follows: polymerization temperature: 70°C, pressure: 4.4 MPaG, propylene feed rate: 78 kg / hour, hydrogen feed rate: 50.8 NL / hour, triethylaluminum feed rate: 38.4 mmol / hour (hexane solution), cyclohexylethyldimethoxysilane feed rate: 5.7 mmol / hour (hexane solution), and prepolymerized catalyst component slurry feed rate (solid catalyst component equivalent): 0.60 g / hour. The amount of propylene polymer component (A) continuously discharged from the reactor was 3.5 kg / hour. The obtained slurry containing propylene polymer component (A) was continuously transferred to the reactor for the second step without deactivation. [Second-stage propylene polymerization (gas-phase polymerization reaction)] Internal volume: 1.4 m ３Propylene 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 held 22.7 kg of propylene polymer material, the polymerization temperature was 83°C, the polymerization pressure was 1.95 MPaG, the superficial gas velocity inside the reactor was 0.186 m / sec, the hydrogen concentration in the gas phase was 0.19 mol%, and the propylene concentration was maintained at 95.7 mol%. Furthermore, diethylzinc: 199.9 mmol / h (hexane solution) was supplied. A separate supply line was used to feed diethylzinc to the reactor. The amount of propylene polymer material continuously discharged from the reactor was 10.6 kg / h, and this was continuously transferred to a post-treatment step. While continuously receiving the resulting propylene polymer material 7, 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 through for 1 hour at a flow rate of 20 Nm ３ / h and dried. The propylene polymer material was then contacted with dry air for 1 hour, and then with air containing water for another 1 hour. <Method for calculating the hydroxyl end rate> The hydroxyl end rate in the modified propylene polymer was measured using the following method. Model: Bruker AVANCE600 Probe: 10mm Cryoprobe Measurement solvent: Mixture of 1,2-dichlorobenzene / 1,2-dichlorobenzene-d4 = 75 / 25 (volume ratio) Measurement temperature: 135°C Pulse repetition time: 4 seconds Pulse width: 45° Number of integrations: 5120 Magnetic field strength: 600MHz (1H) Measurement standard: Tetramethylsilane Measurement nuclide: 13C The integrals of the following peaks (a1 to a5) were calculated when the integral of all peaks present between 50 and 10 ppm was set to 1,000,000. These values ​​were substituted into the following formulas to determine the initiation end integral and OH end integral of the modified propylene polymer: a1 (68.39 ppm): CH2OH a2 (45.25 ppm): CH3CH2CH(CH3)CH2 a3 (41.74 ppm): CH2CH(CH3)CH2OH a4 (39.48 ppm): CH2CH2CH3 a5 (29.36 ppm): CH2CH3 Initiation end integral of propylene polymer material = a4 + (a2 + a5) / 2 OH end integral = (a1 + a3) / 2 End end OH conversion rate = [OH end integral] / [initiation end integral of propylene polymer material] × 100 (%)

[0276] Polypropylene resin (A2) Homopolypropylene 1 (hPP-1, Noblen R101 manufactured by Sumitomo Chemical Co., Ltd.) MFR (230°C, load 21.2N): 16g / 10min

[0277] 2. Hydrophilic Resins (B) Hydrophilic Resin 1 (Aquacork TWB manufactured by Sumitomo Seika Chemicals) Reaction bond of polypropylene oxide and polyethylene oxide Water absorption capacity: 25 g / g Hydrophilic Resin 2 (JMR-10M manufactured by Japan Vinyl Acetate & Poval Co., Ltd.) Water-soluble partially saponified polyvinyl alcohol Degree of polymerization: 220, degree of saponification: 65 mol% Hydrophilic Resin 3 (Pluronic F-108 manufactured by ADEKA Corporation) Water-soluble triblock copolymer of polypropylene oxide and polyethylene oxide Hydrophilic Resin 4 (JL-05E manufactured by Japan Vinyl Acetate & Poval Co., Ltd.) Water-soluble partially saponified polyvinyl alcohol Degree of polymerization: 620, degree of saponification: 82 mol%

[0278] 3. Compatibilizer (C) Maleic Anhydride-Modified Polypropylene 1 (MAHPP-1) Content of succinic anhydride residues in modified polyolefin: 0.11 mass% Intrinsic viscosity: 0.8 dl / g Synthesis Example 2 described in WO2020 / 009090 was used. The amount of succinic anhydride residues may be considered as the graft modification rate of maleic anhydride. <Content of succinic anhydride residues in maleic anhydride-modified polypropylene> １ In the H-NMR spectrum, the integral value of the signals of methine protons and / or methylene protons of the succinic anhydride moiety generated by maleic anhydride modification in the 2.40-3.40 ppm region was compared with the integral value of the proton signals in the alkane region to calculate the content of succinic anhydride residues in the maleic anhydride-modified polypropylene.

[0279] 4. Dyes Reactive dye 1: Sumifix Supra Red 3BF Reactive dye 2: Sumifix Supra Blue BRF 150% gran Acid dye 1: Aminyl Red E-3BL Disperse dye 1: Sumikaron Red E-RPD Direct dye 1: Sumilight Supra Red 4BL 170% Cationic dye 1: TaiAcryl Red AD-GRLT

[0280] 5. Additives Antioxidant 1 (Sumitomo Chemical Co., Ltd., Sumilizer GP) Antioxidant 2 (Sumitomo Chemical Co., Ltd., Sumilizer GA80)

[0281] 6. Compound (G) for crosslinking hydroxyl groups Crosslinking agent 1 (Carbodilite HMV-15CA, manufactured by Nisshinbo Chemical Co., Ltd.) Carbodiimide resin: Poly(4,4'-dicyclohexylmethanecarbodiimide) terminally capped with isocyanate, carbodiimide equivalent: 262 g / mol

[0282] The above materials were melt-kneaded and produced into fibers as follows to obtain resin compositions, which were then subjected to dyeing evaluation.

[0283] --- Invention 1 will be exemplified below. <Production of Polypropylene Resin Composition> (Synthesis Example 1) A homogeneous mixture of 95 parts by weight of PPOH-1, 5 parts by weight of Hydrophilic Resin 1, 0.2 phr of Antioxidant 1, and 0.2 phr of Antioxidant 2 was melt-kneaded in a twin-screw extruder (manufactured by Technovel Corporation, KZW-15, screw diameter 15 mm, L / D = 45, temperature 200°C, rotation speed 500 rpm, output 4 kg / hr) while purging with nitrogen to obtain polypropylene resin composition (E-1). The MFR (230°C, load 21.2 N) of polypropylene resin composition (E-1) was 24 g / 10 min.

[0284] Synthesis Example 2 A polypropylene resin composition (E-2) was obtained in the same manner as in Synthesis Example 1, except that PPOH-1 was used in an amount of 90 parts by weight and hydrophilic resin 1 in an amount of 10 parts by weight. The MFR (230°C, load 21.2 N) of the polypropylene resin composition (E-2) was 31 g / 10 min.

[0285] Synthesis Example 12 A polypropylene resin composition (E-10) was obtained in the same manner as in Synthesis Example 1, except that 90 parts by weight of PPOH-2 and 10 parts by weight of Hydrophilic Resin 3 were used. The MFR (230°C, load 21.2 N) of the polypropylene resin composition (E-10) was 23 g / 10 min.

[0286] <Production of Polypropylene Fiber> (Example 1) A polypropylene resin composition (E-1) was fed into an extruder set at a cylinder temperature of 210°C to melt it, and then extruded from a 48-hole nozzle also set at 210°C. The extruded composition was further heated and stretched 3.2 times between a first roll at 115°C and a second roll at 130°C to obtain a 150 denier / 48 filament polypropylene fiber (F-1).

[0287] (Example 2) A polypropylene-based fiber (F-2) was obtained in the same manner as in Example 1, except that the polypropylene-based resin composition (E-2) was used instead of the polypropylene-based resin composition (E-1) and the cylinder temperature and nozzle temperature were set to 200°C.

[0288] (Comparative Example 1) A polypropylene fiber (F-3) was obtained in the same manner as in Example 1, except that PPOH-2 was used instead of the polypropylene resin composition (E-1) and the cylinder temperature and nozzle temperature were set to 230° C. That is, in Comparative Example 1, the hydrophilic resin (B) was not used.

[0289] Example 13 The polypropylene resin composition (E-10) was fed into an extruder whose cylinder temperature was set to 200°C, melted, and extruded from a 24-hole nozzle also set to 200°C. The extruded material was further heated and stretched 2.8 times between a first roll at 100°C and a second roll at 120°C to obtain a 58 denier / 24 filament polypropylene fiber (F-12).

[0290] The dyeing evaluation of the polyolefin fibers obtained in each of the examples and comparative examples was carried out by the following method.

[0291] <Dyeing with reactive dye> Cylindrical mesh samples were prepared using the polypropylene fibers obtained in each Example and Comparative Example, and the cylindrical mesh samples were immersed for 120 minutes in an aqueous solution of reactive dye 1 heated to 60°C. At this time, Glauber's salt, soda ash, and a penetrant were used as appropriate. The obtained cylindrical mesh samples were washed with water, soaped in a surfactant aqueous solution at 98°C for 20 minutes, and then dried.

[0292] <Dyeing with Acid Dye> Cylindrical net-shaped samples were prepared using the polypropylene fibers obtained in each Example and Comparative Example, and the cylindrical nets were immersed for 30 minutes in an aqueous solution of Acid Dye 1 heated to 100°C. At this time, a leveling agent, a pH adjuster, and a penetrant were used as appropriate. After dyeing, the samples were dried.

[0293] <Dyeing with direct dye> Cylindrical net-shaped samples were prepared using the polypropylene fibers obtained in each Example and Comparative Example, and the cylindrical nets were immersed for 45 minutes in an aqueous solution of direct dye 1 heated to 98°C. At this time, Glauber's salt, a penetrating agent, and a fixing agent were used as appropriate. After dyeing, the samples were dried.

[0294] <Dyeing with cationic dye> Cylindrical net-shaped samples were prepared using the polypropylene fibers obtained in each Example and Comparative Example, and the cylindrical nets were immersed for 60 minutes in an aqueous solution of cationic dye 1 heated to 120°C. At this time, a penetrant and a pH adjuster were used as appropriate. After dyeing, the samples were dried.

[0295] The dyeing results of the polypropylene fibers obtained in each of the Examples and Comparative Examples are shown in Tables 1 and 5. The dyed fibers were visually evaluated as O, and the undyed fibers were evaluated as ×.

[0296]

[0297]

[0298] The above materials were melt-kneaded and pressed into a film as follows to obtain a resin composition, which was then subjected to dyeing evaluation.

[0299] <Production of Polypropylene-Based Resin Composition> (Synthesis Example 3) A mixture of 90 parts by weight of PPOH-3 and 10 parts by weight of Hydrophilic Resin 2 was uniformly mixed and melt-kneaded in a small kneader (HAAKE Minilab) at a temperature of 180°C and a screw rotation speed of 100 rpm for 10 minutes to obtain a polypropylene-based resin composition (E-3).

[0300] Synthesis Example 4 A polypropylene resin composition (E-4) was obtained in the same manner as in Synthesis Example 3, except that PPOH-3 was used in an amount of 80 parts by weight and Hydrophilic Resin 2 in an amount of 20 parts by weight.

[0301] Synthesis Example 5 A polypropylene resin composition (E-5) was obtained in the same manner as in Synthesis Example 3, except that 70 parts by weight of PPOH-3 and 30 parts by weight of Hydrophilic Resin 2 were used.

[0302] <Production and dyeing of polypropylene-based press film> (Example 3) Polypropylene-based resin composition (E-3) was sandwiched between iron plates equipped with 100 μm spacers, preheated in a compression molding machine at 180° C. for 5 minutes, and subjected to a pressure of 50 kgf / cm at 180° C. ２ After pressing at 50 kgf / cm at 30°C, ２ The film was cooled under pressure to obtain a polypropylene-based press film (G-3). The polypropylene-based press film (G-3) was immersed for 80 minutes in an aqueous solution of reactive dye 2 heated to 60°C. At this time, Glauber's salt and soda ash were used as appropriate. The obtained press film was dried.

[0303] (Example 4) A polypropylene-based press film (G-4) was obtained in the same manner as in Example 3, except that the polypropylene-based resin composition (E-4) was used instead of the polypropylene-based resin composition (E-3). Then, the press film sample was dyed.

[0304] (Example 5) A polypropylene-based press film (G-5) was obtained in the same manner as in Example 3, except that the polypropylene-based resin composition (E-5) was used instead of the polypropylene-based resin composition (E-3). Then, the press film sample was dyed.

[0305] Comparative Example 2 A polypropylene-based press film (G-5) was obtained in the same manner as in Example 3, except that PPOH-3 was used instead of the polypropylene-based resin composition (E-3), and then the press film sample was dyed. That is, in Comparative Example 2, the hydrophilic resin (B) was not used.

[0306] The dyeing results of the polypropylene-based press films obtained in each of the Examples and Comparative Examples are shown in Table 2. Those that were visually dyed were evaluated as ◯, and those that were not dyed were evaluated as ×.

[0307] ---The following provides an example of Invention 2.

[0308] The above materials were melt-kneaded as follows to obtain a resin composition, which was then evaluated for spinnability.

[0309] <Production of Polypropylene Resin Composition> (Example 6 (Synthesis Example 6)) A mixture of 85 parts by weight of hPP-1, 10 parts by weight of Hydrophilic Resin 1, and 5 parts by weight of MAHPP-1 was uniformly mixed and melt-kneaded in a small kneader (Labo Plastomill manufactured by Toyo Seiki Seisaku-sho, kneading temperature: 180°C, screw rotation speed: 80 rpm, kneading time: 5 minutes) to obtain a polypropylene resin composition (E-6).

[0310] Example 7 (Synthesis Example 7) A polypropylene resin composition (E-7) was obtained in the same manner as Synthesis Example 6, except that the amounts of hPP-1 and MAHPP-1 were changed to 80 parts by weight and 10 parts by weight, respectively.

[0311] Comparative Example 3 (Synthesis Example 8) A polypropylene resin composition (E-8) was obtained in the same manner as in Synthesis Example 6, except that the amounts of hPP-1 and MAHPP-1 were changed to 89 parts by weight and 1 part by weight, respectively. That is, in Comparative Example 3, the amount of the compatibilizer (MAHPP-1) used was as small as 1 part by weight (less than 3 parts by weight).

[0312] Example 14 (Synthesis Example 13) A polypropylene resin composition (E-11) was obtained in the same manner as in Synthesis Example 6, except that the amounts of hPP-1 and MAHPP-1 were changed to 70 parts by weight and 20 parts by weight, respectively. Comparative Example 8 (Synthesis Example 14) A polypropylene resin composition (E-12) was obtained in the same manner as in Synthesis Example 6, except that the amounts of hPP-1 and MAHPP-1 were changed to 60 parts by weight and 30 parts by weight, respectively.

[0313] The spinnability of the polypropylene resin compositions obtained in each of the Examples and Comparative Examples was evaluated by the following method.

[0314] <Evaluation of spinnability> Pellets of the polyolefin resin composition obtained in each example and comparative example were placed in a Capillograph manufactured by Toyo Seiki Seisaku-sho, and spun under the conditions of barrel temperature: 190°C, extrusion speed: 10 mm / min, orifice diameter: 0.5 mmφ (L / D: 20), acceleration: 200 m / min^2 (initial take-up speed: 10 m / min, take-up speed 200 m / min, arrival time: 1 minute), to evaluate the take-up speed at yarn breakage.

[0315] The results of evaluation of the spinnability of the polypropylene resin compositions obtained in each of the Examples and Comparative Examples are shown in Tables 3 and 6.

[0316]

[0317] ---The following provides examples of Invention 3 (Invention 3-1, Invention 3-2).

[0318] The above materials were melt-kneaded and produced into fibers as follows to obtain resin compositions, which were then subjected to dyeing evaluation.

[0319] <Production of Polypropylene Resin Composition> (Synthesis Example 9) A homogeneous mixture of 95 parts by weight of hPP-1, 5 parts by weight of Hydrophilic Resin 1, 0.2 phr of Antioxidant 1, and 0.2 phr of Antioxidant 2 was melt-kneaded in a twin-screw extruder (manufactured by Technovel Corporation, KZW-15, screw diameter 15 mm, L / D = 45, temperature 200°C, rotation speed 500 rpm, output 4 kg / hr) while purging with nitrogen to obtain a polypropylene resin composition (E-9). The MFR (230°C, load 21.2 N) of the polypropylene resin composition (E-9) was 15 g / 10 min. In Synthesis Example 9, no compatibilizer (C) was used.

[0320] Synthesis Example 15 A homogeneous mixture of 90 parts by weight of hPP-1, 10 parts by weight of hydrophilic resin 3, 0.2 phr of antioxidant 1, and 0.2 phr of antioxidant 2 was melt-kneaded in a twin-screw extruder (manufactured by Technovel Corporation, KZW-15, screw diameter 15 mm, L / D=45, temperature 200°C, rotation speed 500 rpm, output 4 kg / hr) while purging with nitrogen to obtain a polypropylene resin composition (E-13). The MFR (230°C, load 21.2 N) of the polypropylene resin composition (E-13) was 39 g / 10 min.

[0321] Synthesis Example 16 A polypropylene resin composition (E-14) was obtained in the same manner as in Synthesis Example 15, except that 80 parts by weight of hPP-1, 10 parts by weight of MAHPP-1, and 10 parts by weight of hydrophilic resin 3 were used. The MFR (230°C, load 21.2 N) of the polypropylene resin composition (E-14) was 31 g / 10 min.

[0322] Synthesis Example 17 A polypropylene resin composition (E-15) was obtained in the same manner as in Synthesis Example 15, except that the amounts of hPP-1 were 85 parts by weight, MAHPP-1 were 5 parts by weight, and hydrophilic resin 1 were 10 parts by weight. The MFR (230°C, load 21.2 N) of the polypropylene resin composition (E-15) was 19 g / 10 min.

[0323] Synthesis Example 18 A polypropylene resin composition (E-16) was obtained in the same manner as in Synthesis Example 15, except that 80 parts by weight of hPP-1, 10 parts by weight of MAHPP-1, and 10 parts by weight of hydrophilic resin 1 were used. The MFR (230°C, load 21.2 N) of the polypropylene resin composition (E-16) was 18 g / 10 min.

[0324] Synthesis Example 19 A mixture of 70 parts by weight of hPP-1, 10 parts by weight of Hydrophilic Resin 1, and 20 parts by weight of MAHPP-1 was uniformly mixed and melt-kneaded in a small kneader (Labo Plastomill manufactured by Toyo Seiki Seisaku-sho, kneading temperature: 180°C, screw rotation speed: 80 rpm, kneading time: 5 minutes) to obtain a polypropylene resin composition (E-17).

[0325] Synthesis Example 25 A homogeneous mixture of 72.75 parts by weight of hPP-1, 7 parts by weight of MAHPP-1, 10 parts by weight of Hydrophilic Resin 1, 10 parts by weight of Hydrophilic Resin 4, 0.25 parts by weight of Crosslinker 1, 0.2 phr of Antioxidant 1, and 0.2 phr of Antioxidant 2 was melt-kneaded in a twin-screw extruder (manufactured by Technovel Corporation, KZW-15, screw diameter 15 mm, L / D=45, temperature 200°C, rotation speed 500 rpm, output 4 kg / hr) while purging with nitrogen to obtain a polypropylene resin composition (E-18). The MFR (230°C, load 21.2 N) of the polypropylene resin composition (E-18) was 13 g / 10 min.

[0326] Synthesis Example 26 A polypropylene resin composition (E-19) was obtained in the same manner as in Synthesis Example 25, except that 72.5 parts by weight of hPP-1 and 0.5 parts by weight of Crosslinker 1 were used. The MFR (230°C, load 21.2 N) of the polypropylene resin composition (E-19) was 14 g / 10 min.

[0327] Synthesis Example 27 A polypropylene resin composition (E-20) was obtained in the same manner as in Synthesis Example 25, except that the amount of hPP-1 was 72.25 parts by weight and the amount of Crosslinker 1 was 0.75 parts by weight. The MFR (230°C, load 21.2 N) of the polypropylene resin composition (E-20) was 12 g / 10 min.

[0328] Synthesis Example 28 A polypropylene resin composition (E-21) was obtained in the same manner as in Synthesis Example 25, except that 72 parts by weight of hPP-1 and 1 part by weight of Crosslinker 1 were used. The MFR (230°C, load 21.2 N) of the polypropylene resin composition (E-21) was 13 g / 10 min.

[0329] <Production of Polypropylene Fiber> (Synthesis Example 10) The polypropylene resin composition (E-9) was fed into an extruder set at a cylinder temperature of 220°C to melt it, and then extruded from a 48-hole nozzle also set at 220°C. The extruded material was further heated and stretched 3.2 times between a first roll at 115°C and a second roll at 130°C to obtain a 150 denier / 48 filament polypropylene fiber (F-10).

[0330] Synthesis Example 11 A polypropylene fiber (F-11) was obtained in the same manner as in Synthesis Example 10, except that hPP-1 was used instead of the polypropylene resin composition (E-9) and the cylinder temperature and nozzle temperature were set to 230°C.

[0331] Synthesis Example 20 The polypropylene resin composition (E-13) was fed to an extruder whose cylinder temperature was set to 200°C to melt it, and then extruded from a 24-hole nozzle also set to 200°C. The extruded material was further heated and stretched 2.8 times between a first roll at 100°C and a second roll at 120°C to obtain a 57 denier / 24 filament polypropylene fiber (F-13).

[0332] Synthesis Example 21 A 58 denier / 24 filament polypropylene fiber (F-14) was obtained in the same manner as in Synthesis Example 20, except that the polypropylene resin composition (E-14) was used instead of the polypropylene resin composition (E-13).

[0333] Synthesis Example 22 A 60 denier / 24 filament polypropylene fiber (F-15) was obtained in the same manner as in Synthesis Example 20, except that the polypropylene resin composition (E-15) was used instead of the polypropylene resin composition (E-13).

[0334] Synthesis Example 23 A 58 denier / 24 filament polypropylene fiber (F-16) was obtained in the same manner as in Synthesis Example 20, except that the polypropylene resin composition (E-16) was used instead of the polypropylene resin composition (E-13).

[0335] Synthesis Example 24 The polypropylene resin composition (E-17) was charged into a Capillograph manufactured by Toyo Seiki Seisaku-sho, and spun under the conditions of a barrel temperature of 200°C, an extrusion speed of 5.7 mm / min, an orifice diameter of 0.5 mmφ (L / D: 20), and a take-up speed of 60 m / min, to obtain a polypropylene fiber (F-17).

[0336] Synthesis Example 29 The polypropylene resin composition (E-18) was charged into a Capillograph manufactured by Toyo Seiki Seisaku-sho, and spun under the conditions of a barrel temperature of 200°C, an extrusion speed of 5.7 mm / min, an orifice diameter of 0.5 mmφ (L / D: 20), and a take-up speed of 60 m / min, to obtain a polypropylene fiber (F-18).

[0337] Synthesis Example 30 Polypropylene fiber (F-19) was obtained in the same manner as in Synthesis Example 29, except that the polypropylene resin composition was changed to polypropylene resin composition (E-19).

[0338] Synthesis Example 31 Polypropylene fiber (F-20) was obtained in the same manner as in Synthesis Example 29, except that the polypropylene resin composition was changed to polypropylene resin composition (E-20).

[0339] Synthesis Example 32 Polypropylene fiber (F-21) was obtained in the same manner as in Synthesis Example 29, except that the polypropylene resin composition was changed to polypropylene resin composition (E-21).

[0340] <Dyeing with reactive dye> (Example 8) A cylindrical mesh sample was prepared using polypropylene fiber (F-10), and the cylindrical mesh was immersed for 120 minutes in an aqueous solution of reactive dye 1 heated to 60°C. At this time, Glauber's salt, soda ash, and a penetrant were used as appropriate. The obtained cylindrical mesh sample was washed with water, soaped in a surfactant aqueous solution at 98°C for 20 minutes, and then dried.

[0341] Comparative Example 4 The same procedure as in Example 8 was carried out except that polypropylene fiber (F-11) was used instead of polypropylene fiber (F-10). That is, in Comparative Example 4, the hydrophilic resin (B) was not used.

[0342] Example 15 The same procedure as in Example 8 was carried out except that polypropylene fiber (F-13) was used instead of polypropylene fiber (F-10).

[0343] Example 16 The same procedure as in Example 8 was carried out except that polypropylene fiber (F-14) was used instead of polypropylene fiber (F-10).

[0344] Example 17 The same procedure as in Example 8 was carried out except that polypropylene fiber (F-15) was used instead of polypropylene fiber (F-10).

[0345] Example 18 The same procedure as in Example 8 was carried out except that polypropylene fiber (F-16) was used instead of polypropylene fiber (F-10).

[0346] Example 19 The same procedure as in Example 8 was carried out except that polypropylene fiber (F-17) was used instead of polypropylene fiber (F-10).

[0347] Example 20 The same procedure as in Example 8 was carried out except that polypropylene fiber (F-18) was used instead of polypropylene fiber (F-10).

[0348] Example 21 The same procedure as in Example 8 was carried out except that polypropylene fiber (F-19) was used instead of polypropylene fiber (F-10).

[0349] Example 22 The same procedure as in Example 8 was carried out except that polypropylene fiber (F-20) was used instead of polypropylene fiber (F-10).

[0350] Example 23 The same procedure as in Example 8 was carried out except that polypropylene fiber (F-21) was used instead of polypropylene fiber (F-10).

[0351] <Dyeing with Acid Dye> (Example 9) A cylindrical mesh sample was prepared using polypropylene fiber (F-10), and the cylindrical mesh was immersed for 30 minutes in an aqueous solution of Acid Dye 1 heated to 100°C. At this time, a leveling agent, a pH adjuster, and a penetrant were used as appropriate. After dyeing, the sample was dried.

[0352] Comparative Example 5 The same procedure as in Example 9 was carried out except that polypropylene-based fiber (F-11) was used instead of polypropylene-based fiber (F-10). That is, in Comparative Example 5, the hydrophilic resin (B) was not used.

[0353] <Dyeing with Disperse Dye> (Example 10) A cylindrical mesh sample was prepared using polypropylene fiber (F-10), and the cylindrical mesh was immersed for 60 minutes in an aqueous solution of Disperse Dye 1 heated to 120°C. At this time, a dispersant, a pH adjuster, and a penetrant were used as appropriate. After dyeing, the sample was dried.

[0354] <Dyeing with Direct Dye> (Example 11) A cylindrical mesh sample was prepared using polypropylene fiber (F-10), and the cylindrical mesh was immersed for 45 minutes in an aqueous solution of Direct Dye 1 heated to 98°C. At this time, Glauber's salt, a penetrating agent, and a fixing agent were used as appropriate. After dyeing, the sample was dried.

[0355] Comparative Example 6 The same procedure as in Example 11 was carried out except that polypropylene-based fiber (F-11) was used instead of polypropylene-based fiber (F-10). That is, in Comparative Example 6, the hydrophilic resin (B) was not used.

[0356] <Dyeing with cationic dye> (Example 12) A cylindrical mesh sample was prepared using polypropylene fiber (F-10), and the cylindrical mesh was immersed for 60 minutes in an aqueous solution of cationic dye 1 heated to 120°C. At this time, a penetrant and a pH adjuster were used as appropriate. After dyeing, the sample was dried.

[0357] Comparative Example 7 The same procedure as in Example 12 was carried out except that polypropylene-based fiber (F-11) was used instead of polypropylene-based fiber (F-10). That is, in Comparative Example 7, the hydrophilic resin (B) was not used.

[0358] The dyeing results of the polypropylene-based fibers obtained in each of the Examples and Comparative Examples are shown in Tables 4, 7, and 8. Visual evaluation showed that dyed fibers were rated as ◯, darkly dyed fibers as ⊚, and undyed fibers as x.

[0359]

[0360]

[0361]

[0362] The polyolefin resin composition and polypropylene resin composition, as well as the dyed polypropylene fibers of the present invention, which have excellent dyeability, can be used in textile products such as clothing, bedding coverings, blankets, lap blankets, car seats, and carpets. Examples of clothing include underwear, undergarments, shirts, jumpers, sweaters, pants, training wear, sportswear, tights, belly warmers, scarves, hats, gloves, socks, earmuffs, and cold weather clothing. The fabric surface may also be raised, as in fleece. Other examples include fillers and compatibilizers for other resins (e.g., for improving strength, heat resistance, paintability, adhesion, printability, etc.), and raw materials for synthesizing graft polymers and block polymers with other resins (e.g., grafting and blocking followed by use as a compatibilizer for improving strength, heat resistance, paintability, adhesion, printability, etc.). Furthermore, the polyolefin resin composition and the dyed polypropylene fibers can 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. Among these, particularly preferred are automobile parts such as door trims, pillars, instrument panels, and bumpers.Furthermore, the material is suitably used for various 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 has high applicability in various industrial fields, such as the transportation machinery industry, the electrical and electronics industry, and the building and construction industry.

Claims

1. A polyolefin-based resin composition comprising 70 to less than 100 parts by weight of a hydroxyl-modified polyolefin (A1) and more than 0 to 30 parts by weight of a hydrophilic resin (B), wherein the hydrophilic resin (B) is a water-soluble resin or a water-absorbent resin having a water absorption capacity of 0.01 to 100 g / g, and the total of (A1) and (B) is 100 parts by weight.

2. The polyolefin resin composition according to claim 1, comprising 70 to 99 parts by weight of the hydroxyl-modified polyolefin (A1) and 1 to 30 parts by weight of the hydrophilic resin (B).

3. The polyolefin resin composition according to claim 1 or 2, wherein the hydroxyl-modified polyolefin is a hydroxyl-modified polypropylene.

4. The polyolefin resin composition according to claim 1 or 2, wherein the hydroxyl-modified polyolefin is a terminal hydroxyl-modified polypropylene.

5. The polyolefin resin composition according to claim 1 or 2, wherein the hydroxyl-modified polyolefin is a polypropylene modified with a hydroxyl group at one end.

6. The polyolefin resin composition according to claim 1 or 2, wherein the hydrophilic resin (B) is a thermoplastic polyethylene oxide.

7. The polyolefin resin composition according to claim 1 or 2, wherein the hydrophilic resin (B) is polyvinyl alcohol.

8. The polyolefin resin composition according to claim 1 or 2, wherein the hydrophilic resin (B) is a resin having a hydrophilic portion and a hydrophobic portion.

9. The polyolefin resin composition according to claim 1 or 2, wherein the hydrophilic resin (B) is a resin having a hydrophilic portion and a hydrophobic portion, and the resin having a hydrophilic portion and a hydrophobic portion is a reaction bond of polypropylene oxide and polyethylene oxide, or a triblock copolymer of polypropylene oxide and polyethylene oxide, or a partially saponified polyvinyl alcohol, or a polymer having polyethylene oxide bonded to the end or in the chain of a polyolefin, or a polymer having polyvinyl alcohol bonded to the end or in the chain of a polyolefin, or a polymer having partially saponified polyvinyl alcohol bonded to the end or in the chain of a polyolefin.

10. A polypropylene-based resin composition comprising 50 parts by weight or more and less than 97 parts by weight of a polypropylene-based resin (A2), more than 0 parts by weight and 30 parts by weight or less of a hydrophilic resin (B), and 3 to 25 parts by weight of a compatibilizer (C), wherein the hydrophilic resin (B) is a water-soluble resin or a water-absorbent resin having a water absorption capacity of 0.01 to 100 g / g, and the total of (A2), (B), and (C) is 100 parts by weight.

11. The polypropylene resin composition according to claim 10, further comprising 3 to 20 parts by weight of a compatibilizer (C).

12. The polypropylene resin composition according to claim 10, comprising 50 to 96 parts by weight of the polypropylene resin (A2), 1 to 30 parts by weight of the hydrophilic resin (B), and 3 to 25 parts by weight of the compatibilizer (C).

13. The polypropylene resin composition according to claim 12, further comprising 3 to 20 parts by weight of a compatibilizer (C).

14. A polypropylene-based resin composition comprising 50 or more and less than 97 parts by weight of a polypropylene-based resin (A2), more than 0 parts by weight and not more than 30 parts by weight of a hydrophilic resin (B), 3 to 25 parts by weight of a compatibilizer (C), and more than 0 parts by weight and not more than 10 parts by weight of a compound (G) that crosslinks hydroxyl groups, wherein the hydrophilic resin (B) is a water-soluble resin or a water-absorbent resin having a water absorption capacity of 0.01 to 100 g / g, and the total of (A2), (B), (C), and (G) is 100 parts by weight.

15. The polypropylene resin composition according to any one of claims 10 to 14, wherein the polypropylene resin is a homopolypropylene.

16. A polypropylene resin composition according to any one of claims 10 to 14, wherein the hydrophilic resin (B) is a thermoplastic polyethylene oxide.

17. A polypropylene resin composition according to any one of claims 10 to 14, wherein the hydrophilic resin (B) is polyvinyl alcohol.

18. A polypropylene resin composition according to any one of claims 10 to 14, wherein the hydrophilic resin (B) is a resin having a hydrophilic portion and a hydrophobic portion.

19. The polyolefin resin composition according to any one of claims 10 to 14, wherein the hydrophilic resin (B) is a resin having a hydrophilic portion and a hydrophobic portion, and the resin having a hydrophilic portion and a hydrophobic portion is a reaction bond of polypropylene oxide and polyethylene oxide, or a triblock copolymer of polypropylene oxide and polyethylene oxide, or a partially saponified polyvinyl alcohol, or a polymer having polyethylene oxide bonded to the end or in the chain of a polyolefin, or a polymer having polyvinyl alcohol bonded to the end or in the chain of a polyolefin, or a polymer having partially saponified polyvinyl alcohol bonded to the end or in the chain of a polyolefin.

20. A polypropylene resin composition according to any one of claims 10 to 14, wherein the compatibilizer (C) is a modified polyolefin.

21. A polypropylene resin composition according to any one of claims 10 to 14, wherein the compatibilizer (C) is a modified polyolefin, and the modifying group of the modified polyolefin is one type of modifying group selected from maleic anhydride and a hydroxyl group.

22. A polypropylene resin composition according to any one of claims 10 to 14, wherein the hydrophilic resin (B) is at least one resin having a hydroxyl group.

23. A polypropylene resin composition according to any one of claims 10 to 14, wherein the hydrophilic resin (B) is at least one partially saponified polyvinyl alcohol.

24. The polypropylene resin composition according to claim 14, wherein the compound (G) that crosslinks hydroxyl groups is a carbodiimide resin.

25. Dyed polypropylene fiber containing 70 parts by weight or more and less than 100 parts by weight of polypropylene resin (A2) and more than 0 parts by weight and 30 parts by weight or less of hydrophilic resin (B), wherein the hydrophilic resin (B) is a water-soluble resin or a water-absorbent resin having a water absorption capacity of 0.01 to 100 g / g, and the total of (A2) and (B) is 100 parts by weight, and dyed with dye (D) of the polypropylene resin composition.

26. The polypropylene-based fiber according to claim 25, comprising 70 to 99 parts by weight of the polypropylene-based resin (A2) and 1 to 30 parts by weight of the hydrophilic resin (B).

27. A polypropylene fiber according to claim 25 or 26, wherein the polypropylene resin (A2) is a homopolypropylene.

28. Polypropylene fiber according to claim 25 or 26, wherein the hydrophilic resin (B) is a thermoplastic polyethylene oxide.

29. Polypropylene fiber according to claim 25 or 26, wherein the hydrophilic resin (B) is polyvinyl alcohol.

30. Polypropylene-based fibers according to claim 25 or 26, wherein the hydrophilic resin (B) is a resin having a hydrophilic portion and a hydrophobic portion.

31. Polypropylene-based fibers according to claim 25 or 26, wherein the hydrophilic resin (B) is a resin having a hydrophilic portion and a hydrophobic portion, and the resin having a hydrophilic portion and a hydrophobic portion is a reaction bond of polypropylene oxide and polyethylene oxide, or a triblock copolymer of polypropylene oxide and polyethylene oxide, or a partially saponified polyvinyl alcohol, or a polymer having polyethylene oxide bonded to the end or in the chain of a polyolefin, or a polymer having polyvinyl alcohol bonded to the end or in the chain of a polyolefin, or a polymer having partially saponified polyvinyl alcohol bonded to the end or in the chain of a polyolefin.

32. Dyed polypropylene fiber comprising 50 to less than 97 parts by weight of polypropylene resin (A2), more than 0 to 30 parts by weight of hydrophilic resin (B), and 3 to 25 parts by weight of compatibilizer (C), wherein the hydrophilic resin (B) is a water-soluble resin or a water-absorbent resin having a water absorption capacity of 0.01 to 100 g / g, and the total of (A2), (B), and (C) is 100 parts by weight, dyed with dye (D).

33. The polypropylene fiber according to claim 32, comprising 3 to 20 parts by weight of a compatibilizer (C).

34. The polypropylene-based fiber according to claim 32, comprising 50 to 96 parts by weight of a polypropylene-based resin (A2), 1 to 30 parts by weight of a hydrophilic resin (B), and 3 to 25 parts by weight of a compatibilizer (C).

35. The polypropylene-based fiber according to claim 34, comprising 3 to 20 parts by weight of a compatibilizer (C).

36. Dyed polypropylene fiber comprising 50 parts by weight or more and less than 97 parts by weight of polypropylene resin (A2), more than 0 parts by weight and not more than 30 parts by weight of hydrophilic resin (B), 3 to 25 parts by weight of compatibilizer (C), and more than 0 parts by weight and not more than 10 parts by weight of compound (G) that crosslinks hydroxyl groups, wherein the hydrophilic resin (B) is a water-soluble resin or a water-absorbent resin having a water absorption capacity of 0.01 to 100 g / g, and the total of (A2), (B), (C), and (G) is 100 parts by weight, dyed with dye (D) of the polypropylene resin composition.

37. Polypropylene-based fibers according to any one of claims 32 to 36, in which the compatibilizer (C) is a modified polyolefin, the modifying group of which is one type of modifying group selected from maleic anhydride and a hydroxyl group.

38. Polypropylene-based fiber according to any one of claims 32 to 36, wherein the compatibilizer (C) is a modified polypropylene, and the modifying group of the modified polypropylene is one type of modifying group selected from maleic anhydride and a hydroxyl group.

39. Polypropylene-based fiber according to any one of claims 32 to 36, wherein the hydrophilic resin (B) is at least one resin having a hydroxyl group.

40. Polypropylene-based fiber according to any one of claims 32 to 36, wherein the hydrophilic resin (B) is at least one partially saponified polyvinyl alcohol.

41. The polypropylene fiber according to claim 36, wherein the compound (G) that crosslinks hydroxyl groups is a carbodiimide resin.

42. A polypropylene-based fiber according to any one of claims 25 or 26 or claims 32 to 36, wherein the dye (D) is a water-based dye.

43. Polypropylene-based fiber according to any one of claims 25 or 26 or claims 32 to 36, wherein dye (D) is a reactive dye.

44. A polypropylene-based fiber according to any one of claims 25 or 26 or claims 32 to 36, wherein the dye (D) is an acid dye.

45. Polypropylene-based fiber according to any one of claims 25 or 26 or claims 32 to 36, wherein the dye (D) is a disperse dye.

46. ​​Polypropylene-based fiber according to any one of claims 25 or 26 or claims 32 to 36, wherein the dye (D) is a direct dye.

47. A method for producing polypropylene-based fibers dyed with dye (D), comprising melt-spinning a composition containing a polypropylene-based resin (A2) and a hydrophilic resin (B) into a fiber shape, and then dyeing the fiber with dye (D) using water as a medium.

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