Nucleating agent for polyolefin resin, nucleating agent composition for polyolefin resin, masterbatch and polyolefin resin composition

Abstract

The present invention relates to a nucleating agent for polyolefin resins, a nucleating agent composition for polyolefin resins, a masterbatch, and a polyolefin resin composition. The nucleating agent for polyolefin resins comprises a compound represented by the following general formula (1) (in the general formula (1), M represents a metal atom having a valence of 1 to 3 and a specific gravity of 4.0 or less, a represents 1 or 2, b represents 1 or 3, and x represents an integer of 1 to 3, satisfying ax=2b. Z represents a group represented by the following general formula (2) or (3). (In the general formulas (2) and (3), * represents a position connected to Z of the general formula (1), Y represents a direct bond or an alkylene group having 1 to 4 carbon atoms, and R1 to R 10 Each independently represents a hydrogen atom, a hydroxyl group, a halogen atom, an alkyl group having 1 to 10 carbon atoms, etc.

Description

[0001] This application is a divisional application of an application with an application date of November 6, 2019, application number 201980006822.1, and invention name “Nucleating agent for polyolefin-based resin, nucleating agent composition for polyolefin-based resin containing the same, and polyolefin-based resin composition”. Technical Field

[0002] The present invention relates to a nucleating agent for a polyolefin-based resin, a nucleating agent composition for a polyolefin-based resin containing the same, a masterbatch for a polyolefin-based resin, a polyolefin-based resin composition, a molded article thereof, a film thereof, a method for producing a porous film thereof, and a packaging body (hereinafter also referred to as a "nucleating agent," "nucleating agent composition," "masterbatch," and "resin composition"). Specifically, it relates to a nucleating agent for a polyolefin-based resin having an excellent β-crystal-forming effect, a nucleating agent composition for a polyolefin-based resin containing the same, a masterbatch for a polyolefin-based resin, a polyolefin-based resin composition, a molded article thereof, a film thereof, a method for producing a porous film thereof, and a packaging body. Background Art

[0003] Polyolefin resins are among the most widely used plastic materials among various general-purpose thermoplastic resins, particularly in terms of physical properties, moldability, and price. Polyolefin resins are particularly well-suited for a wide range of applications, as they can impart excellent heat resistance, transparency, impact resistance, rigidity, and gas barrier properties to molded products. Therefore, they are expected to be used in a variety of fields.

[0004] Polyolefin resins are crystalline resins. Besides the thermodynamically most stable α crystal (monoclinic), it is known that β crystals (trigonal) can be formed by crystallization in the presence of specific nucleating agents. Compared to α crystals, β crystals of polyolefin resins have characteristics such as a lower melting point, lower specific gravity, higher impact resistance, excellent stretchability, and superior heat resistance. Patent Document 1 discloses a nucleating agent composed of N,N'-dicyclohexyl-2,6-naphthalenedicarboxylic acid amide as a nucleating agent that preferentially forms β crystals in polyolefin resins.

[0005] Prior art literature

[0006] Patent Literature

[0007] Patent Document 1: Japanese Patent Application Laid-Open No. 5-310665 Summary of the Invention

[0008] Problems to be solved by the invention

[0009] However, the nucleating agent proposed in Patent Document 1 is not necessarily sufficient for the β-crystal forming effect, and a new nucleating agent having an excellent β-crystal forming effect is currently desired.

[0010] Therefore, the object of the present invention is to provide: a nucleating agent for a polyolefin-based resin having an excellent β-crystal-forming effect, a nucleating agent composition for a polyolefin-based resin containing the nucleating agent, a masterbatch for a polyolefin-based resin, a polyolefin-based resin composition, a molded article thereof, a film thereof, a method for producing a porous film, and a packaging body.

[0011] Solutions for solving problems

[0012] The present inventors have conducted intensive studies to solve the above-mentioned problems and, as a result, have found that a specific compound containing an aspartic acid structure exhibits an excellent β-crystal-forming effect on a polyolefin-based resin, thereby completing the present invention.

[0013] That is, the nucleating agent for polyolefin resin of the present invention is characterized by comprising a compound represented by the following general formula (1):

[0014]

[0015] (In the general formula (1), M represents a metal atom having a valence of 1 to 3 and a specific gravity of 4.0 or less, or a metal atom having a valence of 2 to 3 and a specific gravity of 4.0 or less and bonded to a hydroxyl group, a represents 1 or 2, b represents 1 or 3, and x represents an integer of 1 to 3 satisfying ax = 2b. Z represents a group represented by the following general formula (2) or (3).

[0016]

[0017] (In general formulae (2) and (3), * represents the position of connection with Z in general formula (1), Y represents a direct bond or an alkylene group having 1 to 4 carbon atoms, R1 to R 10 Each independently represents a hydrogen atom, a hydroxyl group, a halogen atom, an alkyl group having 1 to 10 carbon atoms, a haloalkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or an alkenyl group having 2 to 10 carbon atoms.

[0018] In the nucleating agent of the present invention, it is preferred that the aforementioned M is lithium, sodium, potassium, magnesium, calcium, barium, aluminum, hydroxyaluminum, or dihydroxyaluminum.

[0019] In addition, the nucleating agent composition for polyolefin resin of the present invention is characterized in that it contains the nucleating agent for polyolefin resin of the present invention and an additive, wherein the additive is selected from at least one of the group consisting of phenolic antioxidants, phosphorus antioxidants, sulfur antioxidants, other antioxidants, hindered amine compounds, ultraviolet absorbers, nucleating agents other than the compound represented by general formula (1), flame retardants, flame retardant aids, lubricants, fillers, hydrotalcites, fatty acid metal salts, antistatic agents, fluorescent whitening agents, pigments and dyes.

[0020] Furthermore, the masterbatch for polyolefin-based resins of the present invention is characterized by comprising a polyolefin-based resin and the nucleating agent for polyolefin-based resins of the present invention.

[0021] Furthermore, the polyolefin resin composition of the present invention comprises a polyolefin resin and the polyolefin resin nucleating agent of the present invention, wherein the content of the polyolefin resin nucleating agent is 0.001 to 10 parts by mass based on 100 parts by mass of the polyolefin resin.

[0022] In the resin composition of the present invention, the polyolefin-based resin is preferably a polypropylene-based resin. Furthermore, in the resin composition of the present invention, the polyolefin-based resin preferably comprises an ethylene-propylene copolymer. Furthermore, the resin composition of the present invention preferably comprises an elastomer. Furthermore, the resin composition of the present invention preferably comprises a filler.

[0023] Furthermore, the molded article of the present invention is characterized in that it is formed from the polyolefin-based resin composition of the present invention.

[0024] The molded article of the present invention is preferably an automobile exterior part, an automobile interior part, a housing, a container, and a pipe.

[0025] The film of the present invention is characterized in that it is formed from the polyolefin-based resin composition of the present invention.

[0026] The film of the present invention is preferably a porous film containing voids therein, and is suitable for light-reflecting films and battery separators.

[0027] In addition, the method for manufacturing the porous film of the present invention is characterized in that the method includes: a molding process, in which a polyolefin resin composition is molded to obtain a film; and a heating and stretching process, in which the film obtained by the aforementioned molding process is heated and stretched, and the aforementioned polyolefin resin composition is the polyolefin resin composition of the present invention.

[0028] Furthermore, the packaging body of the present invention is characterized by comprising the film of the present invention.

[0029] Effects of the Invention

[0030] According to the present invention, there can be provided: a nucleating agent for a polyolefin resin having an excellent β-crystal-forming effect, a nucleating agent composition for a polyolefin resin containing the nucleating agent, a masterbatch for a polyolefin resin, a polyolefin resin composition, a molded article thereof, a film thereof, a method for producing a porous film, and a packaging body. DETAILED DESCRIPTION

[0031] Hereinafter, embodiments of the present invention will be described in detail. First, the nucleating agent for polyolefin resin of the present invention will be described.

[0032] <Nucleating Agent for Polyolefin Resins>

[0033] The nucleating agent for a polyolefin resin of the present invention comprises a compound represented by the following general formula (1) and has an excellent β-crystal-forming effect.

[0034]

[0035] Here, in general formula (1), M represents a monovalent to trivalent metal atom with a specific gravity of 4.0 or less, or a divalent to trivalent metal atom with a specific gravity of 4.0 or less to which a hydroxyl group is bonded, a represents 1 or 2, b represents 1 or 3, and x represents an integer from 1 to 3 satisfying ax = 2b. Furthermore, Z represents a group represented by the following general formula (2) or (3).

[0036]

[0037] Here, in the general formulae (2) and (3), * represents the position of connection to Z in the general formula (1), Y represents a direct bond or an alkylene group having 1 to 4 carbon atoms, and R1 to R 10 Each independently represents a hydrogen atom, a hydroxyl group, a halogen atom, an alkyl group having 1 to 10 carbon atoms, a haloalkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or an alkenyl group having 2 to 10 carbon atoms.

[0038] Examples of the alkylene group having 1 to 4 carbon atoms represented by Y in general formulae (2) and (3) include methylene, ethylene, propylene, butylene, and isobutylene. Y is preferably a direct bond or a methylene group from the viewpoint of excellent β-crystal forming effect.

[0039] As R1 to R in the general formulas (2) and (3) 10 Examples of the halogen atom include fluorine, chlorine, bromine and iodine, among which chlorine is particularly preferred.

[0040] As R1 to R in the general formulas (2) and (3) 10 The alkyl group having 1 to 10 carbon atoms as shown in the formula (a) includes, for example, a linear or branched alkyl group, or a cycloalkyl group having 3 to 10 carbon atoms. Specifically, examples include methyl, ethyl, n-propyl, isopropyl, cyclopropyl, n-butyl, sec-butyl, tert-butyl, isobutyl, cyclobutyl, n-pentyl, tert-pentyl, cyclopentyl, n-hexyl, cyclohexyl, n-heptyl, cycloheptyl, n-octyl, isooctyl, tert-octyl, 2-ethylhexyl, n-nonyl, isononyl, and n-decyl.

[0041] As R1 to R in the general formulas (2) and (3) 10Examples of the halogenated alkyl group having 1 to 10 carbon atoms include those obtained by substituting a part or all of the hydrogen atoms of the above alkyl groups with halogen atoms. Examples of the halogenated alkyl group include fluorine, chlorine, bromine and iodine.

[0042] As R1 to R in the general formulas (2) and (3) 10 Examples of the alkoxy group having 1 to 10 carbon atoms include linear or branched alkoxy groups and cycloalkoxy groups having 5 to 10 carbon atoms. Specific examples include methoxy, ethoxy, n-propoxy, n-butoxy, n-hexoxy, 1-methylethoxy, 2-methylpropoxy, 1-methylbutoxy, 4-methylpentyloxy, and cyclohexyloxy groups.

[0043] As R1 to R in the general formulas (2) and (3) 10 Examples of the alkenyl group having 2 to 10 carbon atoms include ethenyl, propenyl, butenyl, hexenyl, octenyl, decenyl, etc. The double bond may be located at the α-position, internal position, or ω-position.

[0044] As R1 to R 10 , preferably a hydrogen atom or a halogen atom, particularly preferably a hydrogen atom.

[0045] Examples of M in the general formula (1) include metal atoms such as lithium, sodium, potassium, magnesium, calcium, barium, and aluminum. A divalent to trivalent metal atom may be bonded to a hydroxyl group. Examples of the divalent to trivalent metal atom bonded to a hydroxyl group include hydroxyaluminum and dihydroxyaluminum. From the perspective of obtaining a nucleating agent having an excellent β-crystal-forming effect, M in the general formula (1) is preferably lithium, sodium, potassium, magnesium, calcium, barium, aluminum, hydroxyaluminum, or dihydroxyaluminum, further preferably lithium, sodium, potassium, calcium, and hydroxyaluminum, and particularly preferably sodium.

[0046] In the general formula (1), b is preferably 1. Furthermore, x is preferably 1 or 2.

[0047] Z in the general formula (1) is preferably a group represented by the general formula (3). In the above case, the nucleating agent of the present invention exhibits a further excellent β-crystal forming effect.

[0048] Specific examples of the compound represented by the general formula (1) include the following compounds: However, the nucleating agent of the present invention is not limited to these.

[0049]

[0050] The compound represented by the general formula (1) can be produced, for example, by reacting a metal salt of aspartic acid with a carboxylic acid chloride such as benzoyl chloride or cyclohexanecarboxylic acid chloride in the presence of a base.

[0051] <Nucleating agent composition for polyolefin resin>

[0052] Next, embodiments of the nucleating agent composition for a polyolefin resin of the present invention are described. The nucleating agent composition of the present invention comprises the nucleating agent of the present invention and an additive, wherein the additive is at least one selected from the group consisting of a phenolic antioxidant, a phosphorus antioxidant, a sulfur antioxidant, other antioxidants, a hindered amine compound, an ultraviolet absorber, a nucleating agent other than the compound represented by general formula (1), a flame retardant, a flame retardant aid, a lubricant, a filler, hydrotalcites, a fatty acid metal salt, an antistatic agent, a fluorescent brightener, a pigment, and a dye. The nucleating agent composition of the present invention exhibits an excellent β-crystal-forming effect.

[0053] Examples of the phenolic antioxidant include 2,6-di-tert-butyl-4-ethylphenol, 2-tert-butyl-4,6-dimethylphenol, styrenated phenol, 2,2'-methylenebis(4-ethyl-6-tert-butylphenol), 2,2'-thiobis-(6-tert-butyl-4-methylphenol), 2,2'-thiodiethylenebis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], 2-methyl-4,6-bis(octylsulfanylmethyl)phenol, 2,2'-isobutylidenebis(4,6-dimethylphenol), isooctyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, N,N'-hexane-1,6-diylbis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionamide], 2,2'-oxalamide-bis[ethyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], 2-ethylhexyl-3-(3',5'-di-tert-butyl-4'-hydroxyphenyl)propionate, 2,2'-ethylenebis(4,6-di-tert-butylphenol), esters of 3,5-di-tert-butyl-4-hydroxyphenylpropionic acid and C13-15 alkyl, 2,5-di-tert-amylhydroquinone, polymers of hindered phenols (ADEKA POLYMER ADDITIVES EUROPE SAS company trade name "AO.OH.98"), 2,2'-methylenebis[6-(1-methylcyclohexyl)-p-cresol], 2-tert-butyl-6-(3-tert-butyl-2-hydroxy-5-methyl)-4-methylphenyl acrylate, 2-[1-(2-hydroxy-3,5-di-tert-pentylphenyl)ethyl]-4,6-di-tert-pentylphenyl acrylate, 6-[3-(3-tert-butyl-4-hydroxy- [5-methyl) propoxy]-2,4,8,10-tetra-tert-butylbenzo[d,f][1,3,2]-dioxaphosphine, hexamethylenebis[3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate], bis[monoethyl(3,5-di-tert-butyl-4-hydroxybenzyl)phosphonate] calcium salt, 5,7-bis(1,1-dimethylethyl)-3-hydroxy-2(3H)-benzofuranone and o-xylene] Reaction products, 2,6-di-tert-butyl-4-(4,6-bis(octylthio)-1,3,5-triazin-2-ylamino)phenol, DL-a-tocopherol (vitamin E), 2,6-bis(α-methylbenzyl)-4-methylphenol, bis[3,3-bis-(4'-hydroxy-3'-tert-butyl-phenyl)butyric acid]diol ester, 2,6-di-tert-butyl-p-cresol, 2,6-diphenyl-4-octadecyloxy phenol, stearyl (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, distearyl (3,5-di-tert-butyl-4-hydroxybenzyl) phosphonate, tridecyl-3,5-tert-butyl-4-hydroxybenzylthioacetate, thiodiethylene bis [(3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 4,4'-thiobis (6-tert-butyl-m-cresol), 2-octylthio-4,6-di(3,5-di-tert-butyl-4-hydroxyphenoxy)-s-triazine, 2,2'-methylenebis(4-methyl-6-tert-butylphenol), bis[3,3-bis(4-hydroxy-3-tert-butylphenyl)butyric acid] diol ester, 4,4'-butylidenebis(2,6-di-tert-butylphenol), 4,4'-butylidenebis(6-tert-butyl-3-methylphenol), 2,2'-ethylidenebis(4,6-di-tert-butylphenol), 1,1,3-tris(2-methyl-4-hydroxy-5-tert-butyl) phenyl) butane, bis[2-tert-butyl-4-methyl-6-(2-hydroxy-3-tert-butyl-5-methylbenzyl)phenyl] terephthalate, 1,3,5-tris(2,6-dimethyl-3-hydroxy-4-tert-butylbenzyl) isocyanurate, 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-2,4,6-trimethylbenzene, 1,3,5-tris[(3,5- di-tert-butyl-4-hydroxyphenyl)propionyloxyethyl] isocyanurate, tetrakis[methylene-3-(3',5'-tert-butyl-4'-hydroxyphenyl)propionate]methane, 2-tert-butyl-4-methyl-6-(2-acryloyloxy-3-tert-butyl-5-methylbenzyl)phenol, 3,9-bis[2-(3-tert-butyl-4-hydroxy-5-methylhydrocinnamoyloxy)-1,1-dimethylethyl]-2,4,8,10-tetraoxaspiro[5.5]undecane, triethylamine 3-(3,5-dialkyl-4-hydroxyphenyl) propionic acid derivatives such as diol bis[β-(3-tert-butyl-4-hydroxy-5-methylphenyl) propionate], stearyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionamide, palmityl-3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionamide, myristyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionamide, and lauryl-3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionamide. These can be used alone or in combination of two or more. When the nucleating agent composition of the present invention contains a phenolic antioxidant, the content of the phenolic antioxidant can be set to 0.001 to 5 parts by mass relative to 100 parts by mass of the polyolefin resin when the nucleating agent composition of the present invention is mixed with the polyolefin resin.

[0054] Examples of the phosphorus-based antioxidant include triphenyl phosphite, diisooctyl phosphite, heptadecanyl phosphite, triisodecyl phosphite, diphenylisooctyl phosphite, diisooctylphenyl phosphite, diphenyltridecyl phosphite, triisooctyl phosphite, trilauryl phosphite, diphenyl phosphite, tri(dipropylene glycol) phosphite, dioleyl hydrogen phosphite, trilauryl trithiophosphite, bis(tridecyl) phosphite, tri(isodecyl) phosphite, tri(tridecyl) phosphite, diphenyldecyl phosphite, dinonylphenyl bis(nonylphenyl) phosphite, poly(dipropylene glycol) phenyl phosphite, tetraphenyldipropyl glycol diphosphite, trinonylphenyl phosphite, tris(2,4-di-tert-butylphenyl) ) phosphite, tris(2,4-di-tert-butyl-5-methylphenyl) phosphite, tris[2-tert-butyl-4-(3-tert-butyl-4-hydroxy-5-methylphenylthio)-5-methylphenyl] phosphite, tris(decyl) phosphite, octyl diphenyl phosphite, di(decyl) monophenyl phosphite, mixture of distearyl pentaerythritol and calcium stearate, alkyl(C10) bisphenol A phosphite, tetraphenyl-tetra(tridecyl) pentaerythritol tetraphosphite, bis(2,4-di-tert-butyl-6-methylphenyl) ethyl phosphite, tetra(tridecyl) isopropylidene diphenol diphosphite, tetra(tridecyl)-4,4'-n-butylidene bis(2-tert-butyl-5-methylphenol) diphosphite, hexa(tridecyl) 1-Methyl-1-propenyl-3-ylidene)tris(1,1-dimethylethyl)-5-methyl-4,1-phenylene)hexatridecylphosphite, 2,2'-methylenebis(4,6-di-tert-butylphenyl)-2-ethylhexylphosphite, 2,2'-methylenebis(4,6-di-tert-butylphenyl)-octadecylphosphite, 2,2'-ethylidenebis(4,6-di-tert-butylphenyl)fluorophosphite, 4,4'-butylidenebis(3-methyl- 6-tert-Butylphenyl di(tridecyl)) phosphite, tris(2-[(2,4,8,10-tetra-tert-butyldibenzo[d,f][1,3,2]dioxaphosphin-6-yl)oxy]ethyl)amine, 3,9-bis(4-nonylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5,5]undecane, 2,4,6-tri-tert-butylphenyl-2-butyl-2-ethyl-1,3-propanediol phosphite, poly-4,4'-isopropylidene diphenol C12-15 alcohol phosphite, bis(diisodecyl)pentaerythritol diphosphite, bis(tridecyl)pentaerythritol diphosphite, bis(octadecyl)pentaerythritol diphosphite, bis(nonylphenyl)pentaerythritol diphosphite, bis(2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis(2,4,6-tri-tert-butylphenyl) pentaerythritol diphosphite, bis(2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, bis(2,4-dicumylphenyl) pentaerythritol diphosphite, etc. These can be used alone or in combination of two or more. When the nucleating agent composition of the present invention contains a phosphorus-based antioxidant, the content of the phosphorus-based antioxidant can be set to 0.001 to 5 parts by mass relative to 100 parts by mass of the polyolefin-based resin when the nucleating agent composition of the present invention is mixed with the polyolefin-based resin.

[0055] Examples of sulfur-based antioxidants include tetrakis[methylene-3-(laurylthio)propionate]methane, bis(methyl-4-[3-n-alkyl(C12 / C14)thiopropionyloxy]5-tert-butylphenyl)sulfide, ditridecyl-3,3'-thiodipropionate, dilauryl-3,3'-thiodipropionate, dimyristyl-3,3'-thiodipropionate, distearyl-3,3'-thiodipropionate, lauryl / stearylthiodipropionate, 4,4'-thiobis(6-tert-butyl-m-cresol), 2,2'-thiobis(6-tert-butyl-p-cresol), and distearyl disulfide. These may be used alone or in combination of two or more. When the nucleating agent composition of the present invention contains a sulfur-based antioxidant, the content of the sulfur-based antioxidant can be adjusted to 0.001 to 10 parts by mass relative to 100 parts by mass of the polyolefin-based resin when the nucleating agent composition of the present invention is blended with the polyolefin-based resin.

[0056] Examples of other antioxidants include nitrone compounds such as N-benzyl-α-phenylnitrone, N-ethyl-α-methylnitrone, N-octyl-α-heptylnitrone, N-lauryl-α-undecylnitrone, N-tetradecyl-α-tridecylnitrone, N-hexadecyl-α-pentadecylnitrone, N-octyl-α-heptadecylnitrone, N-hexadecyl-α-heptadecylnitrone, N-octadecyl-α-pentadecylnitrone, N-heptadecyl-α-heptadecylnitrone, and N-octadecyl-α-heptadecylnitrone; 3-arylbenzofuran-2(3H)-ones; 3-(alkoxyphenyl)benzofuran-2-ones; 3-(acyloxyphenyl)benzofuran-2(3H)-ones; 5,7-dimethylbenzyl ... Benzofuran compounds such as di-tert-butyl-3-(3,4-dimethylphenyl)-benzofuran-2(3H)-one, 5,7-di-tert-butyl-3-(4-hydroxyphenyl)-benzofuran-2(3H)-one, 5,7-di-tert-butyl-3-{4-(2-hydroxyethoxy)phenyl}-benzofuran-2(3H)-one, 6-(2-(4-(5,7-di-tert-2-oxo-2,3-dihydrobenzofuran-3-yl)phenoxy)ethoxy)-6-oxohexyl-6-((6-hydroxyhexanoyl)oxy)hexanoate, and 5-di-tert-butyl-3-(4-((15-hydroxy-3,6,9,13-tetraoxopentadecyl)oxy)phenyl)benzofuran-2(3H)-one may be used alone or in combination of two or more. When the nucleating agent composition of the present invention contains other antioxidants, the content of the other antioxidants can be adjusted to 0.001 to 20 parts by mass relative to 100 parts by mass of the polyolefin resin when the nucleating agent composition of the present invention is blended with the polyolefin resin.

[0057] Examples of the hindered amine compound include 2,2,6,6-tetramethyl-4-piperidyl stearate, 1,2,2,6,6-pentamethyl-4-piperidyl stearate, 2,2,6,6-tetramethyl-4-piperidyl benzoate, bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate, tetrakis(2,2,6,6-tetramethyl-4-piperidyl)-1,2,3,4-butanetetracarboxylate, tetrakis(1,2,2,6,6-pentamethyl-4-piperidyl)-1,2,3,4-butanetetracarboxylate, bis(2,2,6,6-tetramethyl-4-piperidyl) 1-(2-Hydroxyethyl)-2,2,6,6-tetramethyl-4-piperidinyl)-di(tridecyl)-1,2,3,4-butanetetracarboxylate, bis(1,2,2,6,6-pentamethyl-4-piperidinyl)-di(tridecyl)-1,2,3,4-butanetetracarboxylate, bis(1,2,2,4,4-pentamethyl-4-piperidinyl)-2-butyl-2-(3,5-di-tert-butyl-4-hydroxybenzyl)malonate, 1-(2-hydroxyethyl)-2,2,6,6-tetramethyl-4-hydroxypiperidine / diethyl succinate polycondensate, 1,6-bis(2,2,6,6-tetramethyl-4-piperidinylamino)hexane / 2,4-dimethyl- Chloro-6-morpholinyl-s-triazine polycondensate, 1,6-bis(2,2,6,6-tetramethyl-4-piperidinylamino)hexane / 2,4-dichloro-6-tert-octylamino-s-triazine polycondensate, 1,5,8,12-tetrakis[2,4-bis(N-butyl-N-(2,2,6,6-tetramethyl-4-piperidinyl)amino)-s-triazin-6-yl]-1,5,8,12-tetraazadodecane, 1,5,8,12-tetrakis[2,4-bis(N-butyl-N-(1,2,2,6,6-pentamethyl-4-piperidinyl)amino)-s-triazin-6-yl]-1,5 ,8-12-tetraazadodecane, 1,6,11-tris[2,4-bis(N-butyl-N-(2,2,6,6-tetramethyl-4-piperidinyl)amino)-s-triazin-6-yl]aminoundecane, 1,6,11-tris[2,4-bis(N-butyl-N-(1,2,2,6,6-pentamethyl-4-piperidinyl)amino)-s-triazin-6-yl]aminoundecane, bis{4-(1-octyloxy-2,2,6,6-tetramethyl)piperidinyl}sebacate, bis{4-(2,2,6,6-tetramethyl-1-undecyloxy)piperidinyl}carbonate, etc. These may be used alone or in combination of two or more. When the nucleating agent composition of the present invention contains a hindered amine compound, the content of the hindered amine compound can be adjusted to 0.001 to 20 parts by mass relative to 100 parts by mass of the polyolefin resin when the nucleating agent composition of the present invention is blended with the polyolefin resin.

[0058] Examples of the ultraviolet absorber include 2-hydroxybenzophenones such as 2,4-dihydroxybenzophenone and 5,5'-methylenebis(2-hydroxy-4-methoxybenzophenone); 2-(2-hydroxy-5-methylphenyl)benzotriazole, 2-(2-hydroxy-5-tert-octylphenyl)benzotriazole, 2-(2-hydroxy-3,5-di-tert-butylphenyl)-5-chlorobenzotriazole, 2-(2-hydroxy-3-tert-butyl-5-methylphenyl)-5-chlorobenzotriazole, 2-(2-hydroxy-3,5-dicumylphenyl)benzotriazole, 2,2'-methylenebis(4-tert-octyl-6-benzotriazolylphenol), and 2-(2-hydroxy-3-tert-butyl-5-carboxyphenyl)benzotriazole. Polyethylene glycol esters of triazoles, 2-[2-hydroxy-3-(2-acryloyloxyethyl)-5-methylphenyl]benzotriazole, 2-[2-hydroxy-3-(2-methacryloyloxyethyl)-5-tert-butylphenyl]benzotriazole, 2-[2-hydroxy-3-(2-methacryloyloxyethyl)-5-tert-octylphenyl]benzotriazole, 2-[2-hydroxy-3-(2-methacryloyloxyethyl)-5-tert-butylphenyl]-5-chlorobenzotriazole, 2-[2-hydroxy-5-(2-methacryloyloxyethyl)phenyl]benzotriazole, 2-[2-hydroxy-3-tert-butyl-5-(2-methacryloyloxyethyl)phenyl]benzotriazole, 2-[2-hydroxy-3-tert-butyl-5-(2-methacryloyloxyethyl)phenyl]benzotriazole, 2-(2-Hydroxyphenyl)benzotriazoles such as amyl-5-(2-methacryloyloxyethyl)phenylbenzotriazole, 2-[2-hydroxy-3-tert-butyl-5-(3-methacryloyloxypropyl)phenyl]-5-chlorobenzotriazole, 2-[2-hydroxy-4-(2-methacryloyloxymethyl)phenyl]benzotriazole, 2-[2-hydroxy-4-(3-methacryloyloxy-2-hydroxypropyl)phenyl]benzotriazole, and 2-[2-hydroxy-4-(3-methacryloyloxypropyl)phenyl]benzotriazole; phenyl salicylate, resorcinol monobenzoate, 2,4-di-tert-butylphenyl-3,5-di-tert-butyl-4-hydroxybenzoate, octyl (3,5-di-tert-butyl) Benzoates such as benzoate, benzoyl (3,5-di-tert-butyl-4-hydroxy) benzoate, dodecyl (3,5-di-tert-butyl-4-hydroxy) benzoate, tetradecyl (3,5-di-tert-butyl-4-hydroxy) benzoate, hexadecyl (3,5-di-tert-butyl-4-hydroxy) benzoate, octadecyl (3,5-di-tert-butyl-4-hydroxy) benzoate, and behenyl (3,5-di-tert-butyl-4-hydroxy) benzoate; substituted oxalanilides such as 2-ethyl-2'-ethoxyoxalanilide and 2-ethoxy-4'-dodecyloxalanilide; cyanoacrylates such as ethyl-α-cyano-β,β-diphenylacrylate and methyl-2-cyano-3-methyl-3-(p-methoxyphenyl)acrylate;2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-hexyloxyphenol, 2-(2-hydroxy-4-octyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, trioctyl-2,2',2"-((1,3,5-triazine-2,4,6-triyl)tris(3-hydroxybenzene-4-,1-diyl)tripronate), 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-[2-(2-ethylhexanoyloxy)ethoxy]phenol, 2,4,6-tris(2-hydroxy-4-hexyloxy-3-methylphenyl)-1,3,5-triazine, Triazines such as 1,12-bis[2-[4-(4,6-diphenyl-1,3,5-triazin-2-yl)-3-hydroxyphenoxy]ethyl]dodecanedioate; various metal salts or metal chelates, particularly nickel or chromium salts or chelates. These may be used alone or in combination of two or more. When the nucleating agent composition of the present invention contains a UV absorber, the content of the UV absorber can be adjusted to 0.001 to 20 parts by mass relative to 100 parts by mass of the polyolefin resin when the nucleating agent composition of the present invention is blended with the polyolefin resin.

[0059] Examples of other nucleating agents other than the compound represented by the general formula (1) include sodium 2,2'-methylenebis(4,6-di-tert-butylphenyl) phosphate, lithium 2,2'-methylenebis(4,6-di-tert-butylphenyl) phosphate, bis[2,2'-methylenebis(4,6-di-tert-butylphenyl) phosphate]hydroxyaluminum, sodium benzoate, aluminum 4-tert-butylbenzoate, sodium adipate, disodium bicyclo[2.2.1]heptane-2,3-dicarboxylate, calcium cyclohexane-1,2-dicarboxylate and other carboxylic acid metal salts, dibenzylidene sorbitol, bis(methylbenzylidene)hexanes, and the like. Polyol derivatives such as sorbitol, bis(3,4-dimethylbenzylidene)sorbitol, bis(p-ethylbenzylidene)sorbitol, bis(dimethylbenzylidene)sorbitol, 1,2,3-trideoxy-4,6:5,7-bis-O-((4-propylphenyl)methylene)nonanol, and amide compounds such as N,N',N"-tris[2-methylcyclohexyl]-1,2,3-propanetricarboxamide, N,N',N"-tricyclohexyl-1,3,5-benzenetricarboxamide, N,N'-dicyclohexylnaphthalene dicarboxamide, and 1,3,5-tris(dimethylisopropylamino)benzene. These may be used alone or in combination of two or more. When the nucleating agent composition of the present invention contains other nucleating agents different from the compound represented by general formula (1), the content of the other nucleating agent can be set to 0.001 to 10 parts by mass relative to 100 parts by mass of the polyolefin resin when the nucleating agent composition of the present invention is mixed with the polyolefin resin.

[0060] Examples of flame retardants include triphenyl phosphate, tricresyl phosphate, trixylyl phosphate, cresyl diphenyl phosphate, cresyl-2,6-dixylyl phosphate, resorcinol bis(diphenyl phosphate), (1-methylethylidene)-4,1-phenylenetetraphenyl diphosphate, 1,3-phenylenetetrakis(2,6-dimethylphenyl)phosphate, and ADEKA Corporation's trade names "ADEKASTAB FP-500," "ADEKASTAB FP-600," and "ADEKASTAB Phosphates such as aromatic phosphates of FP-800, divinyl phenylphosphonate, diallyl phenylphosphonate, (1-butenyl) phenylphosphonate, phenyl diphenylphosphinate, methyl diphenylphosphinate, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide derivatives, phosphazenes such as bis(2-allylphenoxy)phosphazene and ditolylphosphazene, melamine phosphate, melamine pyrophosphate, melamine polyphosphate, melam polyphosphate, ammonium polyphosphate, piperazine phosphate, piperazine pyrophosphate, piperazine polyphosphate, phosphorus-containing vinylbenzyl compounds, red phosphorus and other phosphorus-based flame retardants, magnesium hydroxide, aluminum hydroxide and other metals Brominated flame retardants include hydroxides, brominated bisphenol A epoxy resins, brominated phenol novolac epoxy resins, hexabromobenzene, pentabromotoluene, ethylenebis(pentabromobenzene), ethylenebis(tetrabromophthalimide), 1,2-dibromo-4-(1,2-dibromoethyl)cyclohexane, tetrabromocyclooctane, hexabromocyclododecane, bis(tribromophenoxy)ethane, brominated polyphenylene ether, brominated polystyrene, 2,4,6-tris(tribromophenoxy)-1,3,5-triazine, tribromophenylmaleimide, tribromophenyl acrylate, tribromophenyl methacrylate, tetrabromobisphenol A dimethacrylate, pentabromobenzyl acrylate, and brominated styrene. These flame retardants are preferably used in combination with anti-drip agents such as fluororesins, polyols, and flame retardant additives such as hydrotalcite. These flame retardants can be used alone or in combination of two or more. When the nucleating agent composition of the present invention contains a flame retardant, the content of the flame retardant can be adjusted to 1 to 100 parts by mass relative to 100 parts by mass of the polyolefin resin when the nucleating agent composition of the present invention is blended with the polyolefin resin.

[0061] Lubricants are added to impart slip properties to the surface of molded articles and enhance their anti-scratch properties. Examples of lubricants include unsaturated fatty acid amides such as oleamide and erucamide; saturated fatty acid amides such as behenamide and stearamide; butyl stearate, stearyl alcohol, stearic acid monoglyceride, sorbitan monopalmitate, sorbitan monostearate, mannitol, stearic acid, hydrogenated castor oil, stearamide, oleamide, and ethylene bisstearamide. These lubricants can be used alone or in combination of two or more. When the nucleating agent composition of the present invention contains a lubricant, the lubricant content can be adjusted to 0.01 to 2 parts by mass per 100 parts by mass of the polyolefin resin when the nucleating agent composition of the present invention is blended with the polyolefin resin.

[0062] As fillers, for example, talc, mica, calcium carbonate, calcium oxide, calcium hydroxide, magnesium carbonate, magnesium hydroxide, magnesium oxide, magnesium sulfate, aluminum hydroxide, barium sulfate, glass powder, glass fiber, clay, dolomite, silica, aluminum oxide, potassium titanate whisker, wollastonite, fibrous magnesium oxysulfate, etc. can be cited, and the particle size (in the case of fibrous, fiber diameter, fiber length and aspect ratio) can be appropriately selected and used. Among these fillers, talc is particularly preferably used from the aspect that it can impart particularly excellent rigidity to the molded article and is easy to obtain. In addition, fillers can be used that have been surface-treated as needed. They can be used alone or in combination of two or more. When the nucleating agent composition of the present invention contains a filler, the content of the filler can be set to 0.01 to 80 parts by mass relative to 100 parts by mass of the polyolefin resin when the nucleating agent composition of the present invention is mixed with the polyolefin resin.

[0063] As the fatty acid metal salt, a compound represented by the following general formula (4) is preferred from the viewpoint of heat resistance and the ability to obtain a dispersion effect of the nucleating agent in the resin.

[0064]

[0065] Here, in the general formula (4), R 11 represents a linear or branched fatty acid residue having 12 to 20 carbon atoms, which may be substituted with a hydroxyl group; M2 represents a monovalent to trivalent metal atom, which may be bonded to the hydroxyl group; and m represents an integer of 1 to 3.

[0066] When the nucleating agent composition of the present invention contains a fatty acid metal salt, the content of the fatty acid metal salt can be adjusted to 0.001 to 10 parts by mass relative to 100 parts by mass of the polyolefin resin when the nucleating agent composition of the present invention is blended with the polyolefin resin.

[0067] In the general formula (4), specific examples of M2 include sodium, potassium, lithium, calcium, zinc, barium, magnesium, and hydroxyaluminum. Among them, sodium, potassium, and lithium are particularly preferred.

[0068] Hydrotalcites are complex salt compounds known as natural or synthetic products containing magnesium, aluminum, hydroxyl groups, carbonate groups, and any water of crystallization. Examples include those in which a portion of the magnesium or aluminum is substituted with an alkali metal, zinc, or other metal, and those in which the hydroxyl groups or carbonate groups are substituted with other anionic groups. Specifically, examples include hydrotalcites represented by the following general formula (5) in which the metal is substituted with an alkali metal. Furthermore, compounds represented by the following general formula (6) can also be used as Al-Li-based hydrotalcites.

[0069] Mg z1 Zn z2 Al2(OH) 2(z1+z2)+4 (CO3)pH2O (5)

[0070] Here, in the general formula (5), z1 and z2 each represent a number that satisfies the conditions shown in the following formula, and p represents 0 or a positive number.

[0071] 0≤z2 / z1<10

[0072] 2≤z1+z2≤20

[0073] [Li 1 / 3 Al 2 / 3 (OH)2]·[A q- 1 / 3q pH2O] (6)

[0074] Here, in general formula (6), A q- represents an anion with a valence of q, and p represents 0 or a positive number. In addition, the carbonate anion in the hydrotalcites may be partially substituted with other anions.

[0075] Hydrotalcites may be obtained by dehydrating the crystal water, or may be coated with higher fatty acids such as stearic acid, higher fatty acid metal salts such as oleic acid alkali metal salts, organic sulfonic acid metal salts such as dodecylbenzenesulfonic acid alkali metal salts, higher fatty acid amides, higher fatty acid esters, or waxes.

[0076] Hydrotalcites can be natural or synthetic. As methods for synthesizing hydrotalcites, known methods described in Japanese Patent Publication No. 46-2280, Japanese Patent Publication No. 50-30039, Japanese Patent Publication No. 51-29129, Japanese Patent Publication No. 3-36839, Japanese Patent Application Laid-Open No. 61-174270, and Japanese Patent Application Laid-Open No. 5-179052 can be cited. In addition, hydrotalcites can be used without being restricted by their crystal structure, crystal grains, etc. One type of hydrotalcite can be used alone or in combination of two or more types. When the nucleating agent composition of the present invention contains hydrotalcites, the content of the hydrotalcites can be set to 0.001 to 5 parts by mass relative to 100 parts by mass of the polyolefin resin when the nucleating agent composition of the present invention is mixed with the polyolefin resin.

[0077] Examples of antistatic agents include low-molecular-weight antistatic agents based on nonionic, anionic, cationic, or amphoteric surfactants, and high-molecular-weight antistatic agents based on polymeric compounds. Nonionic surfactants include polyethylene glycol-type nonionic surfactants such as higher alcohol ethylene oxide adducts, fatty acid ethylene oxide adducts, higher alkylamine ethylene oxide adducts, and polyolefin glycol ethylene oxide adducts; polyol-type nonionic surfactants such as polyethylene oxide, fatty acid esters of glycerol, fatty acid esters of pentaerythritol, fatty acid esters of sorbitol or sorbitan, alkyl ethers of polyols, and fatty amides of alkanolamines; anionic surfactants include carboxylates such as alkali metal salts of higher fatty acids; sulfates such as higher alcohol sulfates and higher alkyl ether sulfates; sulfonates such as alkylbenzenesulfonates, alkylsulfonates, and paraffinsulfonates; and phosphates such as higher alcohol phosphates. Cationic surfactants include quaternary ammonium salts such as alkyltrimethylammonium salts. As amphoteric surfactants, amino acid-type amphoteric surfactants such as higher alkylaminopropionates, betaine-type amphoteric surfactants such as higher alkyldimethyl betaine and higher alkyldihydroxyethyl betaine can be cited. In the polyolefin resin composition, anionic surfactants are preferred, and sulfonates such as alkylbenzenesulfonates, alkylsulfonates, and paraffinsulfonates are particularly preferred. These can be used alone or in combination of two or more. When the nucleating agent composition of the present invention contains a low-molecular antistatic agent, the content of the low-molecular antistatic agent can be set to 0.1 to 10 parts by mass relative to 100 parts by mass of the polyolefin resin when the nucleating agent composition of the present invention is mixed with the polyolefin resin.

[0078] As polymeric antistatic agents, ionomers, block polymers with polyethylene glycol as the hydrophilic portion, etc. can be mentioned. As ionomers, ionomers described in Japanese Patent Application Laid-Open No. 2010-132927 can be mentioned. As polymers with polyethylene glycol as the hydrophilic portion, for example, polyetheresteramides described in Japanese Patent Application Laid-Open No. 7-10989, polymers formed by polyolefins and polyethylene glycol described in U.S. Patent No. 6552131, polymers formed by polyesters and polyethylene glycol described in Japanese Patent Application Laid-Open No. 2016-023254, etc. can be mentioned. They can be used alone or in combination of two or more. When the nucleating agent composition of the present invention includes a polymeric antistatic agent, the content of the polymeric antistatic agent can be set to an amount of 3 to 60 parts by mass relative to 100 parts by mass of the polyolefin resin when the nucleating agent composition of the present invention is mixed with the polyolefin resin.

[0079] Fluorescent whitening agents are compounds that absorb ultraviolet light from sunlight or artificial light, convert it into violet to blue visible light, and radiate it through fluorescence, thereby contributing to the whiteness and blue hue of the molded article. Examples of fluorescent whitening agents include benzoxazole-based compounds CIFluorescent Brightner 184; coumarin-based compounds CIFluorescent Brightner 52; and diaminostilbene disulfonic acid-based compounds CIFluorescent Brightner 24, 85, and 71. These can be used alone or in combination of two or more. When the nucleating agent composition of the present invention contains a fluorescent whitening agent, the content of the fluorescent whitening agent can be set to 0.00001 to 0.1 parts by mass relative to 100 parts by mass of the polyolefin-based resin when the nucleating agent composition of the present invention is mixed with the polyolefin-based resin.

[0080] The pigment is not particularly limited, and commercially available pigments may be used. Specific examples of the pigment include Pigment Red 1, 2, 3, 9, 10, 17, 22, 23, 31, 38, 41, 48, 49, 88, 90, 97, 112, 119, 122, 123, 144, 149, 166, 168, 169, 170, 171, 177, 179, 180, 184, 185, 19 2, 200, 202, 209, 215, 216, 217, 220, 223, 224, 226, 227, 228, 240, 254; Pigment Orange 13, 31, 34, 36, 38, 43, 46, 48, 49, 51, 52, 55, 59, 60, 61, 62, 64, 65, 71; Pigment Yellow 1, 3, 12, 1 3, 14, 16, 17, 20, 24, 55, 60, 73, 81, 83, 86, 93, 95, 97, 98, 100, 109, 110, 113, 114, 117, 120, 125, 126, 127, 129, 137, 138, 139, 147, 148, 150, 151, 152, 153, 154 4, 166, 168, 175, 180, 185; Pigment Green 7, 10, 36; Pigment Blue 15, 15:1, 15:2, 15:3, 15:4, 15:5, 15:6, 22, 24, 29, 56, 60, 61, 62, 64; Pigment Violet 1, 15, 19, 23, 27, 29, 30, 32, 37, 40, 50, etc.

[0081] Examples of the dye include azo dyes, anthraquinone dyes, indigo dyes, triarylmethane dyes, xanthene dyes, alizarin dyes, acridine dyes, stilbene dyes, thiazole dyes, naphthol dyes, quinoline dyes, nitro dyes, indamine dyes, oxazine dyes, phthalocyanine dyes, and cyanine dyes. These may be used alone or in combination of two or more.

[0082] The method for manufacturing the nucleating agent composition of the present invention is not particularly limited, and for example, any method of mixing the nucleating agent of the present invention with other additives may be used. In addition, other methods for manufacturing the nucleating agent composition of the present invention include: mixing the nucleating agent of the present invention and other additives with a binder comprising a polymer compound or a petroleum resin under heating, homogenizing the mixture in the presence of a molten binder, and then processing the mixture into a pellet shape. According to this method, a nucleating agent composition of the present invention that is uniform and has excellent operability can be manufactured. There is no limitation on the processing conditions in this method. Moreover, the processing equipment used in this method is also not limited, and may be any known general processing equipment such as an extruder and a disc pelletizer.

[0083] <Polyolefin-based resin composition>

[0084] Next, the polyolefin resin composition of the present invention will be described. The resin composition of the present invention comprises a polyolefin resin and a compound represented by general formula (1), wherein the content of the nucleating agent of the present invention is 0.001 to 10 parts by mass per 100 parts by mass of the polyolefin resin. The resin composition of the present invention can preferentially form β crystals in the polyolefin resin.

[0085] Examples of the polyolefin resin contained in the resin composition of the present invention include low-density polyethylene (LDPE), linear low-density polyethylene (L-LDPE), high-density polyethylene (HDPE), isotactic polypropylene, syndiotactic polypropylene, hemi-isotactic polypropylene, cycloolefin polymers, stereoblock polypropylene, poly-3-methyl-1-butene, poly-3-methyl-1-pentene, poly-4-methyl-1-pentene and other α-olefin polymers, ethylene / propylene copolymers, impact copolymer polypropylene, ethylene-methyl methacrylate copolymers, ethylene-methyl acrylate copolymers, ethylene-ethyl acrylate copolymers, ethylene-butyl acrylate copolymers, ethylene-vinyl acetate copolymers, ethylene-vinyl alcohol resin (EVOH) and their chlorides. The polyolefin resin may be a blend of two or more of these or an alloy thereof.

[0086] Polyolefin resin is preferably polypropylene resin.As polypropylene resin, can enumerate propylene homopolymer, ethylene-propylene copolymer (such as ethylene-propylene random copolymer etc.), ethylene-propylene-1-butene terpolymer, propylene and other α-olefin (such as 1-butene, 1-hexene, 1-octene, 4-methyl-1-pentene etc.) copolymer, the ethylene-propylene block copolymer (such as impact copolymer polypropylene, TPO etc.) comprising ethylene-propylene copolymer and their chloride etc..Polypropylene resin can be for blending these 2 or more and form person, can also be for resin through alloying and form person, can also be for block copolymer.

[0087] In addition, the polyolefin resin used in the resin combination of the present invention and then preferably comprises ethylene-propylene copolymer.In the above case, it is possible to give particularly excellent impact resistance to molded articles.As such polyolefin resin, for example, above-mentioned ethylene-propylene copolymer (for example ethylene-propylene random copolymer etc.) etc., ethylene-propylene block copolymer (for example impact copolymer polypropylene, TPO etc.) etc. can be enumerated.

[0088] In the resin composition of the present invention, the polyolefin resin can be used independently of the type, presence or absence, stereoregularity, average molecular weight, molecular weight distribution, presence or absence of specific molecular weight components, ratio, specific gravity, viscosity, solubility in various solvents, elongation, impact strength, crystallinity, X-ray diffraction, modification and crosslinking treatment based on unsaturated carboxylic acids (maleic acid, itaconic acid, fumaric acid, etc.) and their derivatives (maleic anhydride, maleic acid monoester, maleic acid diester, etc.), organic peroxides or energy ray irradiation and combinations of these treatments, etc.

[0089] As described above, in the resin composition of the present invention, the content of the nucleating agent of the present invention is 0.001 to 10 parts by mass per 100 parts by mass of the polyolefin resin. To further enhance the β-crystal formation effect, the content of the nucleating agent of the present invention is preferably 0.005 parts by mass or greater, and more preferably 0.02 parts by mass or greater, per 100 parts by mass of the polyolefin resin. Furthermore, to suppress blooming and enhance extractability of the nucleating agent, the content of the nucleating agent of the present invention is preferably 1 part by mass or less, more preferably 0.5 parts by mass or less, and even more preferably 0.3 parts by mass or less, per 100 parts by mass of the polyolefin resin.

[0090] The resin composition of the present invention preferably further contains an elastomer. In this case, excellent impact resistance can be imparted to the molded article.

[0091] The elastomer is not particularly limited, but is preferably a copolymer of ethylene and a monomer other than ethylene because of its excellent compatibility with the polyolefin-based resin.

[0092] Examples of the monomers other than ethylene include linear or branched α-olefins having 3 to 20 carbon atoms, aromatic vinyl compounds having 8 to 20 carbon atoms, other vinyl compounds, conjugated dienes, alkyl (meth)acrylates, and alkyl alkoxyacrylates. The term "alkyl (meth)acrylate" herein refers to alkyl acrylates or alkyl methacrylates. These monomers other than ethylene may be used alone or in combination of two or more.

[0093] Examples of the α-olefins having 3 to 20 carbon atoms include propylene, 1-butene, 3-methyl-1-butene, 3-ethyl-1-butene, 1-pentene, 3-methyl-1-pentene, 3-ethyl-1-pentene, 4,4-dimethyl-1-pentene, 1-hexene, 4-methyl-1-hexene, 4,4-dimethyl-1-hexene, 4-ethyl-1-hexene, 3-ethyl-1-hexene, 1-octene, 1-decene, 1-undecene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, and 1-eicosene. Preferred examples include propylene, 1-butene, 1-pentene, 1-hexene, and 1-octene.

[0094] Examples of the aromatic vinyl compound having 8 to 20 carbon atoms include styrene, o-methylstyrene, p-methylstyrene, m-methylstyrene, o-ethylstyrene, m-ethylstyrene, p-ethylstyrene, p-tert-butylstyrene, chloromethylstyrene, and vinyltoluene, and preferably monoalkylstyrene or polyalkylstyrene.

[0095] Examples of other vinyl compounds include halogenated olefins, unsaturated amines, unsaturated carboxylic acids, vinyl esters, unsaturated epoxy compounds, and ethylenically unsaturated silane compounds.

[0096] Here, the halogenated olefin refers to an α-olefin to which a halogen atom such as chlorine, bromine, or iodine is added.

[0097] Examples of the unsaturated amine include allylamine, 5-hexenamine, and 6-heptenamine.

[0098] Examples of the unsaturated carboxylic acid include (meth)acrylic acid, 3-butenoic acid, 4-pentenoic acid, 5-hexenoic acid, 6-heptenoic acid, 7-octenoic acid, 8-nonenoic acid, 9-decenoic acid, and 10-undecenoic acid. These may be substituted with a halogen atom.

[0099] Examples of the vinyl ester include aliphatic vinyl esters such as vinyl formate, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl isobutyrate, vinyl trimethylacetate, vinyl valerate, vinyl decanoate, vinyl undecanoate, vinyl laurate, vinyl myristate, vinyl pentadecanoate, vinyl palmitate, vinyl stearate, and vinyl neodecanoate (a mixture of carboxylic acids having 9 to 11 carbon atoms); and aromatic vinyl esters such as vinyl benzoate. Preferred vinyl esters include those having 3 to 20 carbon atoms, more preferably those having 4 to 10 carbon atoms, and even more preferably, vinyl acetate.

[0100] Examples of the unsaturated epoxy compound include 4-epoxy-1-butene, 5-epoxy-1-pentene, 6-epoxy-1-hexene, 7-epoxy-1-heptene, 8-epoxy-1-octene, 9-epoxy-1-nonene, 10-epoxy-1-decene, and 11-epoxy-1-undecene.

[0101] Examples of the ethylenically unsaturated silane compound include vinyltriethoxysilane, vinyltrimethoxysilane, 3-acryloxypropyltrimethoxysilane, and γ-methacryloxypropyltrimethoxysilane.

[0102] Examples of the conjugated diene include 1,3-butadiene, isoprene, 1,3-pentadiene, 2-ethyl-1,3-butadiene, 2,3-dimethylbutadiene, 2-methylpentadiene, 4-methylpentadiene, 2,4-hexadiene, and 1,3-octadiene.

[0103] Examples of the alkyl (meth)acrylate include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, n-pentyl (meth)acrylate, isopentyl (meth)acrylate, n-hexyl (meth)acrylate, 2-methylpentyl (meth)acrylate, n-octyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, n-decyl (meth)acrylate, n-dodecyl (meth)acrylate, and n-octadecyl (meth)acrylate.

[0104] Examples of the alkyl alkoxyacrylate include 2-methoxyethyl acrylate, 2-ethoxyethyl acrylate, 2-(n-propoxy)ethyl acrylate, 2-(n-butoxy)ethyl acrylate, 3-methoxypropyl acrylate, 3-ethoxypropyl acrylate, 2-(n-propoxy)propyl acrylate, and 2-(n-butoxy)propyl acrylate.

[0105] The elastomer may be obtained by copolymerizing these monomers alone with ethylene, or by copolymerizing two or more monomers in combination with ethylene.

[0106] Among elastomers that are copolymers of ethylene and monomers other than ethylene, ethylene-α-olefin copolymers are preferred due to their excellent compatibility with olefin resins. Copolymers of ethylene and vinyl esters are also preferred.

[0107] Specific examples of elastomers which are copolymers of ethylene and monomers other than ethylene include block or random copolymers such as ethylene-propylene copolymers, ethylene-butene copolymers, and ethylene-octene copolymers, ethylene-methyl methacrylate copolymers, ethylene-methyl acrylate copolymers, ethylene-ethyl acrylate copolymers, ethylene-butyl acrylate copolymers, styrene-ethylene-butene copolymers, styrene-ethylene-butylene-styrene copolymers, and ethylene-vinyl acetate copolymers.

[0108] Examples of elastomers other than elastomers which are copolymers of ethylene and monomers other than ethylene include thermoplastic polyesters and thermoplastic polyurethanes.

[0109] The elastomer can be used independently of the molecular weight, degree of polymerization, density, softening point, ratio of insoluble matter to solvent, degree of stereoregularity, presence or absence of catalyst residues, type of monomers used as raw materials, blending ratio, type of polymerization catalyst (e.g., Ziegler catalyst, metallocene catalyst, etc.), etc.

[0110] The content of the elastomer is preferably 1 to 80 parts by mass relative to 100 parts by mass of the polyolefin resin. In this case, the resin composition of the present invention can impart further excellent impact resistance to the molded article. The content of the elastomer is preferably 3 parts by mass or more, particularly preferably 5 parts by mass or more, relative to 100 parts by mass of the polyolefin resin. In addition, from the viewpoint of achieving excellent impact resistance of the molded article in a low-temperature environment, the content of the elastomer is further preferably 50 parts by mass or less, particularly preferably 40 parts by mass or less, relative to 100 parts by mass of the polyolefin resin.

[0111] The resin composition of the present invention preferably further comprises a filler. In the above case, excellent rigidity can be imparted to the molded article. As the filler, the same filler as that used in the above-mentioned nucleating agent composition can be cited. Among the fillers, talc is particularly preferred because it can impart particularly excellent rigidity to the molded article and is easily available. The content of the filler is preferably 0.01 to 80 parts by mass relative to 100 parts by mass of the polyolefin resin. In addition, the blending amount of the filler is more preferably 1 part by mass or more relative to 100 parts by mass of the polyolefin resin. Furthermore, the blending amount of the filler is more preferably 50 parts by mass or less relative to 100 parts by mass of the polyolefin resin.

[0112] In the polyolefin resin composition, as long as its performance is not greatly impaired, additives commonly used in polyolefin resins, such as phenolic antioxidants, phosphorus antioxidants, sulfur antioxidants, other antioxidants, hindered amine compounds, ultraviolet absorbers, other nucleating agents other than the compound represented by general formula (1), flame retardants, flame retardant aids, lubricants, hydrotalcites, fatty acid metal salts, antistatic agents, fluorescent whitening agents, pigments, dyes, etc. can be further mixed. As these additives, the same additives as those used in the above-mentioned nucleating agent composition can be cited. The mixing amount of these additives is not particularly limited, and these additives can be mixed in a manner such that they are present in the polyolefin resin at an appropriate concentration.

[0113] The method for producing the resin composition of the present invention is not particularly limited, and examples thereof include the following methods: a method of dry-mixing a polyolefin resin powder or pellets with the nucleating agent of the present invention and other additives; a method of melt-kneading a mixture obtained by dry-mixing a polyolefin resin powder or pellets with the nucleating agent of the present invention and other additives; a method of processing the nucleating agent of the present invention and other additives into a pellet shape and adding the pellets to the polyolefin resin; etc. In addition, the nucleating agent of the present invention and other additives may be added to the polyolefin resin simultaneously or separately. Furthermore, the method for producing the resin composition of the present invention may be a method of mixing the nucleating agent composition of the present invention with a polyolefin resin.

[0114] <Masterbatch for polyolefin resin>

[0115] As another method for producing the resin composition of the present invention, the following method can be mentioned: preparing the masterbatch of the present invention and mixing it with a polyolefin resin. Here, the masterbatch of the present invention contains: a polyolefin resin; and, the above-mentioned nucleating agent of the present invention. The masterbatch of the present invention can make the polyolefin resin preferentially form β crystals. The masterbatch of the present invention can further contain other additives as needed. The polyolefin resin contained in the masterbatch of the present invention is not particularly limited, and examples thereof include the above-mentioned polyolefin resins. The method for producing the masterbatch of the present invention is not particularly limited, and examples thereof include: a method of dry-mixing a polyolefin resin powder or pellets with the nucleating agent of the present invention and other additives to obtain a mixture, and melt-kneading the obtained mixture.

[0116] <Molded products>

[0117] Next, the molded article of the present invention will be described. The molded article of the present invention is formed from the resin composition of the present invention. The resin composition of the present invention can preferentially form β crystals in the polyolefin resin, and thus the molded article of the present invention contains β crystals of the polyolefin resin.

[0118] Examples of the molded article of the present invention include injection molded articles, fibers, flat yarns, biaxially stretched films, uniaxially stretched films, unstretched films, sheets, thermoformed articles, extrusion blow molded articles, injection blow molded articles, injection stretch blow molded articles, profile extrusion molded articles, and rotational molded articles. Specific examples of the molded article of the present invention include automotive exterior parts, automotive interior parts, housings, containers, and piping.

[0119] The molding method of the molded article of the present invention is not particularly limited, and examples thereof include injection molding, extrusion molding, blow molding, rotational molding, vacuum molding, inflation molding, calendering molding, solidification molding, dipping molding, and thermoforming.

[0120] Next, the automobile exterior part, automobile interior part, housing, container, and pipe of the present invention will be described.

[0121] <Automotive exterior parts>

[0122] The resin composition of the present invention can preferentially form β crystals in a polyolefin-based resin. Consequently, automotive exterior parts formed from the resin composition of the present invention exhibit excellent impact resistance. Examples of automotive exterior parts include bumpers, radiator grilles, front grilles, front windshields, fenders, pillars, pillar covers, rearview mirror bracket covers, window run channels, rearview mirror housings, lamp housings, wheel covers, spoilers, air spoilers, moldings, window moldings, seatbelt moldings, sunroofs, front modules, door modules, rear door modules, and exterior panels. Examples of methods for molding automotive exterior parts include injection molding, thermoforming, and blow molding.

[0123] <Automotive interior parts>

[0124] The resin composition of the present invention can preferentially form β crystals in a polyolefin-based resin. Consequently, automotive interior parts formed from the resin composition of the present invention exhibit excellent impact resistance. Examples of automotive interior parts include instrument panels, door trims, pillar moldings, door moldings, pillar trims, storage trays, rear storage trays, armrest boxes, and air conditioning ducts. Methods for molding automotive interior parts include injection molding, thermoforming, and blow molding.

[0125] <Case>

[0126] The resin composition of the present invention can preferentially form β crystals in a polyolefin-based resin. Therefore, a housing formed from the resin composition of the present invention has excellent impact resistance. Examples of the housing include housings for household appliances, large-scale game consoles, home game consoles, portable game consoles, cameras, mobile phones, smartphones, electronic equipment, batteries, and safety circuit breakers. Examples of methods for forming the housing include injection molding, thermoforming, and blow molding.

[0127] <Container>

[0128] The resin composition of the present invention can preferentially form β crystals in polyolefin resins, resulting in containers formed from the resin composition having excellent impact resistance. Examples of containers include: food containers such as tableware, side dish containers, frozen food containers, microwave-safe containers, freezer containers, retort pouch containers, cups, and frozen dessert cups; bottle containers such as beverage bottles, infusion bottles, and hollow medical bottles; containers for physical and chemical testing such as beakers and graduated cylinders; and pharmaceutical containers, medical containers, lotion containers, cosmetic containers, perfume containers, and toner containers. Examples of methods for forming the containers include blow molding, inflation molding, and thermoforming.

[0129] <Piping>

[0130] The resin composition of the present invention can preferentially form β crystals in polyolefin resins, resulting in excellent impact resistance in pipes formed from the resin composition. Examples of pipes include various types of pipes, such as water pipes, gas pipes, infrastructure pipes, factory facility pipes, vehicle fuel pipes, and vehicle air intake pipes; various types of tubes, such as cosmetic / perfume spray tubes, medical tubes, and infusion tubes; and various types of hoses, such as water hoses and vehicle air ducts. Methods for molding the pipes include injection molding, extrusion molding, and rotational molding.

[0131] <Film>

[0132] Next, the film will be described. The film of the present invention is formed from the resin composition of the present invention. The resin composition of the present invention can preferentially form β crystals in the polyolefin resin, thereby improving the stretchability of the film of the present invention. Furthermore, β crystals of the polyolefin resin have a lower melting point than α crystals, thereby improving the heat sealability of the film of the present invention. Examples of film forming methods include extrusion molding, inflation molding, and casting molding.

[0133] <Porous film>

[0134] The β crystals of polyolefin resins undergo a phase transformation into α crystals by heating. Moreover, the density of the β crystals of polyolefin resins is lower than that of the α crystals. Therefore, the porous film of the present invention can be produced by a manufacturing method comprising the following steps: a molding step of molding the resin composition of the present invention to obtain a film; and a step of heating and stretching the film obtained by the molding step. The porous film of the present invention has fine and uniform voids. The porous film of the present invention can be used, for example, as a light reflective film, a battery separator, etc. The heating temperature when the film is heated and stretched is not particularly limited, and can be, for example, 80 to 120°C. In addition, the stretching can be either uniaxial stretching or biaxial stretching. Furthermore, the stretching ratio is not particularly limited, and can be, for example, 1.1 to 10 times.

[0135] <Light-reflective film>

[0136] The porous film of the present invention contains fine and uniform voids, and therefore, the light-reflecting film of the present invention formed from the film of the present invention has excellent light reflectivity. The light-reflecting film of the present invention can be suitably used, for example, as a plate-shaped material incorporated into a backlight of a liquid crystal display, specifically as a reflector for edge illumination of a liquid crystal screen, a reflector for a direct-lit backlight, and as a reflector around a cold cathode ray tube.

[0137] <Battery separator>

[0138] The porous film of the present invention has fine and uniform pores, so the battery separator formed from the porous film of the present invention has excellent permeability. Such a battery separator can be suitably used in, for example, lithium secondary batteries, nickel-hydrogen batteries, nickel-cadmium batteries, polymer batteries, etc.

[0139] <Packaging>

[0140] Next, the packaging body of the present invention will be described. The packaging body of the present invention comprises the film of the present invention. The film of the present invention has excellent heat sealing properties, and therefore, the packaging body of the present invention has excellent heat sealing properties. The packaging body of the present invention can be formed solely by the film of the present invention, or can be formed by a laminate in which the film of the present invention is laminated on a substrate. In addition, in the laminate, the film of the present invention can also be laminated on the substrate via an intermediate layer formed by a polyolefin film or the like. Examples of substrates constituting the laminate include: films of polyolefin resins, styrene resins, polyesters or polyamides, stretched films thereof, laminated films of these films with polyamide films, resin films having gas barrier properties such as ethylene-vinyl alcohol copolymer films, metal foils such as aluminum, or vapor-deposited films with aluminum, silicon dioxide, etc., paper, etc. In addition, examples of methods for manufacturing the laminate include dry lamination, co-extrusion, and the like. The packaging body of the present invention can be suitably used for packaging of food, electronic materials, etc., in particular, retort packaging, and packaging using an automatic packaging machine.

[0141] Example

[0142] Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to the following examples and the like.

[0143] [Examples 1-1 to 1-10, Comparative Examples 1-1 to 1-4]

[0144] For homopolypropylene (MFR = 8 g / 10 minutes at 230°C and a load of 2.16 kg), 200 g of a phenolic antioxidant (tetrakis [methylene-3-(3', 5'-tert-butyl-4'-hydroxyphenyl) propionate] methane) 0.05% by mass, a phosphorus antioxidant (tris (2,4-di-tert-butylphenyl) phosphite) 0.1% by mass, 0.05% by mass of a calcium stearate, and 0.1% by mass of a polyolefin resin nucleating agent described in Table 1 were mixed and blended by hand for 3 minutes. The mixture was then fed into a single-screw extruder (device: Labo Plastomill Micro manufactured by Toyo Seiki Co., Ltd.) and granulated at a melt temperature of 230°C. It should be noted that in Comparative Example 1-1, a polyolefin resin nucleating agent was not mixed. Except for this, granulation was performed in the same manner as in Example 1-1. The granulated pellets were dried at 80°C for 8 hours and evaluated under the following conditions. In Table 1, the "steric structure" of the nucleating agent for a polyolefin-based resin refers to the steric structure of an aspartic acid residue, and Z represents the following group.

[0145]

[0146] <Crystallization temperature Tc[°C]>

[0147] The resulting pellets were used to measure the crystallization temperature (Tc) using a differential scanning calorimeter (Diamond, manufactured by PerkinElmer). The crystallization temperature was determined by raising the temperature from room temperature to 230°C at a rate of 50°C / minute, holding the temperature for 5 minutes, and then cooling the pellets to 50°C at a rate of 10°C / minute. The crystallization temperature was determined as the temperature (°C) of the exothermic peak observed during the cooling process. The results are shown in Table 1.

[0148] <β crystal ratio>

[0149] The pellets were used to determine the presence of β crystals and the β crystal ratio using a differential scanning calorimeter (Diamond, manufactured by Perkin Elmer). Specifically, the temperature was raised from room temperature to 230°C at a rate of 50°C / min, held for 20 minutes, cooled to 50°C at a rate of 10°C / min, held for a further 5 minutes, and then raised to 230°C at a rate of 10°C / min. If an endothermic peak with a peak near 150°C and an endothermic peak with a peak near 165°C were observed during the second heating step, the presence of β crystals was determined, while the absence of β crystals was determined if only the endothermic peak with a peak near 165°C was observed. If β crystals were determined to be present, the area of ​​the endothermic peak with a peak near 150°C was defined as the β crystal area, and the area of ​​the endothermic peak with a peak near 165°C was defined as the α crystal area. The β crystal ratio was calculated using the following formula.

[0150] β crystal ratio = β crystal area / (α crystal area + β crystal area) × 100 (%)

[0151] The results are shown in Table 1.

[0152] <Coloring>

[0153] The obtained pellets were injection molded at 200° C., and the presence or absence of coloration of the obtained test pieces having a thickness of 1 mm was visually determined.

[0154] [Table 1]

[0155]

[0156] [Examples 2-1 to 2-10, Comparative Examples 2-1 to 2-5]

[0157] 200 g of homopolypropylene (MFR = 8 g / 10 minutes at 230°C and a load of 2.16 kg) was mixed with 0.05% by mass of a phenolic antioxidant (tetrakis(methylene-3-(3',5'-tert-butyl-4'-hydroxyphenyl)propionate]methane), 0.1% by mass of a phosphorus antioxidant (tris(2,4-di-tert-butylphenyl)phosphite), 0.05% by mass of a calcium stearate, and 0.1% by mass of the compound listed in Table 2. These were blended by hand for 3 minutes and then fed into a single-screw extruder (equipment: Labo Plastomill Micro, manufactured by Toyo Seiki Seisaku-sho, Ltd.) and pelletized at a melt temperature of 230°C. In Table 2, the "stereostructure" of the nucleating agent for a polyolefin resin refers to the stereostructure of the aspartic acid residue, and Z represents the aforementioned group.

[0158] The pellets were dried at 80°C for 8 hours, and then evaluated for crystallization temperature Tc [°C], β crystal ratio, and coloration in the same manner as in Example 1-1.

[0159] [Table 2]

[0160]

[0161] * Quinacridone is severely colored, so the presence of Tc and β crystals was not evaluated.

[0162] [Comparative Examples 3-1 to 3-6]

[0163] 200 g of homopolypropylene (MFR = 8 g / 10 minutes at 230°C and a load of 2.16 kg) were mixed with 0.05% by mass of a phenolic antioxidant (tetrakis[methylene-3-(3',5'-tert-butyl-4'-hydroxyphenyl)propionate]methane), 0.1% by mass of a phosphorus antioxidant (tris(2,4-di-tert-butylphenyl)phosphite), 0.05% by mass of a calcium stearate, and 0.1% by mass of a comparative compound represented by the following general formula (7) and having Z as shown in Table 3. These were blended by hand for 3 minutes and then fed into a single-screw extruder (device: Labo Plastomill Micro manufactured by Toyo Seiki Seisaku-sho, Ltd.) and pelletized at a melt temperature of 230°C. In Table 3 and the general formula (7), Z represents the above-mentioned group. After drying the pellets at 80°C for 8 hours, the crystallization temperature Tc [°C] and the β-crystal ratio were evaluated in the same manner as in Example 1-1. The results are shown in Table 3.

[0164]

[0165] [Table 3]

[0166]

[0167] [Examples 4-1 to 4-9, Comparative Examples 4-1 to 4-4]

[0168] 70 parts by mass of impact copolymer polypropylene (Prime Polypro J707G manufactured by Prime Polymer Co., Ltd.), 10 parts by mass of ethylene-octene copolymer elastomer (Engage 8842 manufactured by Dow Chemical Co., Ltd.), talc (water content 0.1% by mass, particle size D based on laser diffraction method) were blended. 50=14.0 μm, bulk specific gravity 0.32 g / mL according to the measurement method described in JIS K5101) were prepared by adding 20 parts by mass of a phenolic antioxidant (tetrakis[methylene-3-(3',5'-tert-butyl-4'-hydroxyphenyl)propionate]methane) 0.05 mass%; a phosphorus antioxidant (tris(2,4-di-tert-butylphenyl)phosphite) 0.1 mass%; 0.05 mass% of calcium stearate; and a polyolefin resin nucleating agent described in Table 4 or Table 5 in the amount described in Table 4 or Table 5. The mixture was blended for 30 minutes using a Rocking Mixer (manufactured by Aichi Electric Co., Ltd.) and then fed into a twin-screw extruder (TEX-25αIII manufactured by The Japan Steel Works, Ltd.) and pelletized at a melt temperature of 230°C. Note that in Comparative Example 4-1, granulation was performed in the same manner as in Example 4-1, except that no polyolefin resin nucleating agent was added. In Tables 4 and 5, the "steric structure" of the polyolefin resin nucleating agent refers to the steric structure of the aspartic acid residue, and Z represents the aforementioned group.

[0169] [Table 4]

[0170]

[0171] [Table 5]

[0172]

[0173] [Examples 5-1 to 5-9, Comparative Examples 5-1 to 5-4]

[0174] 60 parts by mass of impact copolymer polypropylene (Prime Polypro J707G manufactured by Prime Polymer), 20 parts by mass of ethylene-octene copolymer elastomer (Engage 8842 manufactured by Dow Chemical Company), talc (water content 0.1% by mass, particle size D based on laser diffraction method) were blended. 50=14.0 μm, bulk specific gravity 0.32 g / mL according to the measurement method described in JIS K5101) were prepared by adding 20 parts by mass of a phenolic antioxidant (tetrakis[methylene-3-(3',5'-tert-butyl-4'-hydroxyphenyl)propionate]methane) 0.05 mass%; a phosphorus antioxidant (tris(2,4-di-tert-butylphenyl)phosphite) 0.1 mass%; 0.05 mass% of calcium stearate; and a polyolefin resin nucleating agent described in Tables 6 or 7 in the amounts described in Tables 6 or 7. The mixture was blended in a Rocking Mixer (manufactured by Aichi Electric Co., Ltd.) for 30 minutes, then fed into a twin-screw extruder (TEX-25αIII manufactured by The Japan Steel Works, Ltd.) and pelletized at a melt temperature of 230°C. In Tables 6 and 7, the "steric structure" of the polyolefin resin nucleating agent refers to the steric structure of the aspartic acid residue, and Z represents the aforementioned group. In Comparative Example 5-1, granulation was performed in the same manner as in Example 5-1, except that no polyolefin resin nucleating agent was added.

[0175] [Table 6]

[0176]

[0177] [Table 7]

[0178]

[0179] [Examples 6-1 to 6-4, Comparative Examples 6-1 and 6-2]

[0180] 2 kg of impact copolymer polypropylene (Prime Polypro J707G, manufactured by Prime Polymer Co., Ltd.) was blended with 0.05% by mass of a phenolic antioxidant (tetrakis(methylene-3-(3',5'-tert-butyl-4'-hydroxyphenyl)propionate]methane), 0.1% by mass of a phosphorus antioxidant (tris(2,4-di-tert-butylphenyl)phosphite), 0.05% by mass of a calcium stearate, and the polyolefin resin nucleating agent listed in Table 8 in the amounts listed in Table 8. The mixture was blended for 30 minutes using a Rocking Mixer (manufactured by Aichi Electric Co., Ltd.), then introduced into a twin-screw extruder (equipment: TEX-25αIII, manufactured by The Japan Steel Works, Ltd.) and pelletized at a melt temperature of 230°C. In Table 8, the "stereostructure" of the polyolefin resin nucleating agent refers to the stereostructure of the aspartic acid residue, and Z represents the aforementioned group. In addition, in Comparative Example 6-1, granulation was carried out in the same procedure as in Example 6-1 except that no nucleating agent for polyolefin resin was compounded.

[0181] [Table 8]

[0182]

[0183] The polyolefin resin composition pellets of Examples 4-1 to 4-9, Comparative Examples 4-1 to 4-4, Examples 5-1 to 5-9, Comparative Examples 5-1 to 5-4, Examples 6-1 to 6-4, and Comparative Examples 6-1 to 6-2, which had been pelletized as described above, were dried at 80°C for 8 hours. The dried polyolefin resin composition pellets were used to evaluate the crystallization temperature using the same procedure as in Example 1-1. Furthermore, the β-crystal ratio and Charpy impact strength were evaluated using the following procedures. The results are shown in Tables 4 to 8.

[0184] <β crystal ratio>

[0185] The obtained pellets were used with a differential scanning calorimeter (Diamond, manufactured by Perkin Elmer) to determine the presence of β crystals and the β crystal ratio. Specifically, the temperature was raised from room temperature to 230°C at a rate of 50°C / min, held for 20 minutes, cooled to 50°C at a rate of 10°C / min, held for a further 5 minutes, and then raised to 230°C at a rate of 30°C / min. If an endothermic peak with a peak near 150°C and an endothermic peak with a peak near 165°C were observed during the second heating process, β crystals were determined to be present. If only an endothermic peak with a peak near 165°C was observed, β crystals were determined to be absent. If β crystals were determined to be present, the area of ​​the endothermic peak with a peak near 150°C was defined as the β crystal area, and the area of ​​the endothermic peak with a peak near 165°C was defined as the α crystal area. The β crystal ratio was calculated using the following formula.

[0186] β crystal ratio = β crystal area / (α crystal area + β crystal area) × 100 (%)

[0187] <Charpy impact strength>

[0188] The obtained pellets were molded by an injection molding machine (device; horizontal injection molding machine NEX80 manufactured by Nissei Plastic Industry Co., Ltd.) under processing conditions of a resin temperature of 230°C and a mold temperature of 50°C to produce a test piece (80 mm × 10 mm × 4 mm) for Charpy impact strength measurement. The obtained test piece was allowed to stand in a constant temperature and humidity chamber at 23°C and a humidity of 60% RH for 7 days, and then a notch was given to the test piece. The notched test piece was allowed to stand in a constant temperature and humidity chamber at a temperature of 23°C and a humidity of 60% RH for 5 days, and then the test piece was taken out from the constant temperature and humidity chamber, and the Charpy impact strength (kJ / m 2 ).

[0189] [Examples 7-1 to 7-4, Comparative Examples 7-1 to 7-3]

[0190] 2 kg of homopolypropylene (MFR = 3 g / 10 minutes at 230°C and a load of 2.16 kg) was mixed with 0.05% by mass of a phenolic antioxidant (tetrakis(methylene-3-(3',5'-tert-butyl-4'-hydroxyphenyl)propionate]methane), 0.1% by mass of a phosphorus antioxidant (tris(2,4-di-tert-butylphenyl)phosphite), 0.05% by mass of a calcium stearate, and the polyolefin resin nucleating agent described in Table 9 in the amounts described in Table 9. These were blended by hand for 3 minutes and then fed into a twin-screw extruder (equipment: TEX-25αIII manufactured by The Japan Steel Works, Ltd.) and pelletized at a melt temperature of 230°C. In Table 9, the "stereostructure" of the polyolefin resin nucleating agent refers to the stereostructure of the aspartic acid residue, and Z represents the aforementioned group. In addition, in Comparative Example 7-1, no nucleating agent for polyolefin resin is added, and granulation is carried out in the same steps as in Example 7-1. After the granulated pellets are dried at 80°C for 8 hours, they are put into a single-screw extruder equipped with a T-die and a roller, and formed into a film with a thickness of 100 μm under the conditions of a barrel temperature of 200°C and a roller temperature of 120°C. The film thus obtained is heated and stretched at a ratio of 5 times in the MD direction under the conditions of a heating temperature of 100°C and a stretching speed of 1000 mm / min. Furthermore, the film is heated and stretched at a ratio of 2 times in the TD direction under the same conditions to obtain a stretched film. Then, the stretchability of the film and the void characteristics of the obtained stretched film are evaluated according to the following steps. The results are shown in Table 9.

[0191] <Stretchability>

[0192] The surface of the stretched film obtained as described above was visually observed, and stretchability was evaluated based on the following evaluation criteria.

[0193] ○: The entire surface is stretched uniformly

[0194] ×: The entire surface is not stretched uniformly, and unevenness exists in the stretched state.

[0195] <Void Characteristics>

[0196] The surface of the stretched film obtained as described above was observed at a magnification of 5000 times using a scanning electron microscope, and the void characteristics were evaluated according to the following evaluation criteria.

[0197] ○: Fine voids were observed throughout the film

[0198] △: Fine voids were observed in part of the film

[0199] ×: No gap was found

[0200] [Table 9]

[0201]

[0202] From the above, it was confirmed that the nucleating agent for polyolefin resin of the present invention has an excellent β-crystal forming effect.

Claims

1. A nucleating agent for polyolefin resin, characterized in that Contains a compound represented by the following general formula (1), In the general formula (1), M represents a monovalent to trivalent metal atom with a specific gravity of 4.0 or less or a divalent to trivalent metal atom with a specific gravity of 4.0 or less to which a hydroxyl group is bonded, a represents 1 or 2, b represents 1 or 3, x represents an integer of 1 to 3 satisfying ax=2b, and Z represents a group represented by the following general formula (2) or (3), In the general formulae (2) and (3), * represents the position of connection with Z in the general formula (1), Y represents a direct bond or an alkylene group having 1 to 4 carbon atoms, R1 to R5, R7, and R9 each independently represent a hydrogen atom, a hydroxyl group, a halogen atom, an alkyl group having 1 to 10 carbon atoms, a haloalkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or an alkenyl group having 2 to 10 carbon atoms; R6, R8, and R 10 Each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, a haloalkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or an alkenyl group having 2 to 10 carbon atoms.

2. The nucleating agent for polyolefin resin according to claim 1, wherein The M is lithium, sodium, potassium, magnesium, calcium, barium, aluminum, hydroxyaluminum, or dihydroxyaluminum.

3. A nucleating agent composition for polyolefin resin, characterized in that The invention comprises a nucleating agent for a polyolefin resin according to claim 1 or 2 and an additive, wherein the additive is selected from at least one of the group consisting of a phenolic antioxidant, a phosphorus antioxidant, a sulfur antioxidant, other antioxidants, an ultraviolet absorber, a nucleating agent other than the compound represented by the general formula (1), a flame retardant, a flame retardant aid, a lubricant, a filler, an antistatic agent, a pigment and a dye.

4. A masterbatch for polyolefin resin, characterized in that: The invention comprises a polyolefin resin and the nucleating agent for a polyolefin resin according to claim 1 or 2.

5. A polyolefin resin composition, characterized in that It comprises a polyolefin resin and the nucleating agent for polyolefin resin according to claim 1 or 2, The content of the nucleating agent for the polyolefin-based resin is 0.001 to 10 parts by mass based on 100 parts by mass of the polyolefin-based resin. The polyolefin resin composition according to claim 5, wherein The polyolefin resin is a polypropylene resin.

7. The polyolefin resin composition according to claim 5 or 6, wherein The polyolefin-based resin includes an ethylene-propylene copolymer. The polyolefin-based resin composition according to claim 5 or 6, comprising an elastomer. 9 . The polyolefin-based resin composition according to claim 5 , further comprising a filler.

10. A molded article, characterized in that: The polyolefin resin composition is formed from the polyolefin resin composition according to any one of claims 5 to 9. The molded article according to claim 10 , which is an automobile exterior part.

12. The molded article according to claim 10, which is an automobile interior part. The molded article according to claim 10 , which is a housing. The molded article according to claim 10 , which is a container. The molded article according to claim 10 , which is a pipe.

16. A film, characterized in that The polyolefin resin composition is formed from the polyolefin resin composition according to any one of claims 5 to 9. The film according to claim 16 , which is a porous film containing voids therein. The film according to claim 17 , which is a light reflecting film.

19. The film of claim 17, which is a battery separator.

20. A method for manufacturing a porous film, characterized in that: The method comprises: a molding step in which a polyolefin resin composition is molded into a film; and a heat-stretching step in which the film obtained by the molding step is heat-stretched. The polyolefin-based resin composition is the polyolefin-based resin composition according to any one of claims 5 to 9.

21. A packaging body, characterized in that: A film according to claim 16 is provided.

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