WO2020138205A1 - Nucleating agent for polyolefin-based resin, nucleating agent composition for polyolefin-based resin containing same, polyolefin-based resin composition, and molded product thereof - Google Patents

Nucleating agent for polyolefin-based resin, nucleating agent composition for polyolefin-based resin containing same, polyolefin-based resin composition, and molded product thereof Download PDF

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WO2020138205A1
WO2020138205A1 PCT/JP2019/050920 JP2019050920W WO2020138205A1 WO 2020138205 A1 WO2020138205 A1 WO 2020138205A1 JP 2019050920 W JP2019050920 W JP 2019050920W WO 2020138205 A1 WO2020138205 A1 WO 2020138205A1
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nucleating agent
polyolefin
tert
based resin
polyolefin resin
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PCT/JP2019/050920
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French (fr)
Japanese (ja)
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満 友田
直人 上田
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株式会社Adeka
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • C08L77/06—Polyamides derived from polyamines and polycarboxylic acids

Definitions

  • the present invention relates to a nucleating agent for a polyolefin resin, a nucleating agent composition for a polyolefin resin containing the same, a polyolefin resin composition (hereinafter, simply “nucleating agent”, “nucleating agent composition”, “resin composition”, respectively).
  • Nucleating agent and molded products thereof, specifically, a versatile nucleating agent for a polyolefin resin that does not require a special addition method and has an excellent nucleating effect, and a polyolefin resin containing the same.
  • TECHNICAL FIELD The present invention relates to a nucleating agent composition, a polyolefin resin composition, and a molded article thereof.
  • Olefin resin has the advantages of excellent moldability, heat resistance, mechanical properties and low specific gravity, and is widely used in general sundries, medical equipment, food packaging, etc. However, in order to enable such a wide range of use, it is necessary for the polyolefin resin to satisfy the required physical properties. It is known that a polyolefin-based resin can control crystallization during molding of the polyolefin-based resin by adding a specific compound or composition. In general, a olefin-based resin having a promoted crystallization effect has a shortened molding cycle time, improves the transparency of a molded product of the polyolefin-based resin, and improves heat resistance and physical properties. You can get the benefits.
  • Patent Document 1 proposes a method for producing a polypropylene copolymer having excellent crystallinity.
  • This method uses a catalyst system consisting of a titanium compound and an organoaluminum compound to carry out multi-stage polymerization of vinyl cycloalkane having 6 or more carbon atoms, particularly polyvinyl cyclohexane and homopolymerization of propylene or copolymerization with ethylene.
  • the content of vinylcycloalkane units in all polymers is set to a predetermined value.
  • Patent Document 1 the method for producing a propylene copolymer proposed in Patent Document 1 has a problem of low versatility because it requires a special polymerization step.
  • the stereocontrol of polyvinyl cyclohexane is important, and it also has a problem of lacking versatility.
  • an object of the present invention is a versatile, which does not require a special addition method, and a nucleating agent for a polyolefin resin having an excellent nucleating effect, a nucleating agent composition for a polyolefin resin containing the same, and a polyolefin.
  • a resin composition and a molded product thereof To provide a resin composition and a molded product thereof.
  • the polyolefin resin nucleating agent of the present invention is a polyolefin resin nucleating agent containing a polyamide
  • the polyamide has a structure in which dicarboxylic acid and diamine are dehydrated and condensed, At least one of the dicarboxylic acid and the diamine has a ring structure.
  • the dicarboxylic acid is preferably an aromatic dicarboxylic acid.
  • the diamine is alkylenediamine, the following general formula (1) or (2), An alicyclic diamine represented by (wherein Z 2 , Z 3 , Z 4 , Z 5 and Z 6 represent a direct bond, an alkylene group having 1 to 10 carbon atoms, and a hydrogen atom bonded to the ring is Optionally substituted with an alkyl group having 1 to 10 carbon atoms), and the following general formula (3) or (4), (Wherein Z 7 , Z 8 , Z 9 , Z 10 and Z 11 represent a direct bond or an alkylene group having 1 to 10 carbon atoms, and the hydrogen atom bonded to the ring is a carbon atom).
  • the melting point or decomposition point of the polyamide is preferably 250° C. or higher.
  • the weight average molecular weight of the polyamide is preferably 20,000 or less.
  • the polyolefin-based resin nucleating agent composition of the present invention includes the polyolefin-based resin nucleating agent of the present invention, a phenol-based antioxidant, a phosphorus-based antioxidant, a sulfur-based antioxidant, another antioxidant, and a hindered amine compound.
  • the polyolefin-based resin composition of the present invention comprises a polyolefin-based resin and a nucleating agent for the polyolefin-based resin of the present invention,
  • the content of the polyamide with respect to 100 parts by mass of the polyolefin resin is 0.001 to 10 parts by mass.
  • the molded article of the present invention is characterized by comprising the polyolefin resin composition of the present invention.
  • a general-purpose nucleating agent for a polyolefin-based resin that does not require a special addition method and has an excellent nucleating agent effect
  • a nucleating agent composition for a polyolefin-based resin containing the same a nucleating agent composition for a polyolefin-based resin containing the same
  • a polyolefin-based resin A composition and a molded article thereof can be provided.
  • the polyolefin resin nucleating agent of the present invention is a polyolefin resin nucleating agent containing a polyamide, wherein the polyamide has a structure in which a dicarboxylic acid and a diamine are dehydrated and condensed, and at least one of the dicarboxylic acid and the diamine is It has a ring structure.
  • the nucleating agent of the present invention is a dispersion-type nucleating agent, and the dispersion-type nucleating agent needs to maintain a solid state during resin molding. Therefore, the polyamide contained in the nucleating agent of the present invention preferably has a melting point or a decomposition point of 250° C. or higher.
  • the melting point or decomposition point of the polyamide contained in the nucleating agent of the present invention is more preferably 260°C or higher, further preferably 280°C or higher. It is difficult to produce a compound having a melting point or decomposition point of more than 500°C.
  • the melting point of the polyamide is the temperature when the polyamide is heated at a heating rate of 10° C./min under a nitrogen stream using a TG-DTA measuring instrument (Thermo plus Evo, TG8120) manufactured by Rigaku Corporation. It is the peak top temperature of the endothermic peak.
  • the decomposition point is the peak top temperature of the exothermic peak when the polyamide is heated under the same conditions.
  • At least one of the dicarboxylic acid and the diamine constituting the polyamide contained in the nucleating agent of the present invention has a ring structure.
  • the dicarboxylic acid having a ring structure include alicyclic dicarboxylic acid and aromatic dicarboxylic acid.
  • diamines having a ring structure include alicyclic diamines and aromatic diamines.
  • the alicyclic dicarboxylic acid is not particularly limited, but examples thereof include alicyclic dicarboxylic acids having 7 to 20 carbon atoms. Examples thereof include 1,3-cyclopentanedicarboxylic acid and 1,2-cyclopentanedicarboxylic acid. Acid, 1,4-cyclohexanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanediacetic acid, 1,3-cyclohexanediacetic acid, 1,2-cyclohexanediacetic acid and 4,4'-bicyclohexyldicarboxylic acid and the like can be mentioned.
  • the alicyclic dicarboxylic acid serving as the constitutional unit of the polyamide may be one type or two or more types.
  • the aromatic dicarboxylic acid is not particularly limited, but preferably is an aromatic dicarboxylic acid having 8 to 20 carbon atoms, and examples thereof include terephthalic acid, isophthalic acid, phthalic acid, phenylmalonic acid, homophthalic acid and phenylsuccinic acid. Acid, ⁇ -phenylglutaric acid, ⁇ -phenyladipic acid, ⁇ -phenyladipic acid, 2,2′-biphenyldicarboxylic acid, 4,4′-biphenyldicarboxylic acid, naphthalenedicarboxylic acid, sodium 5-sulfoisophthalate and 5 -Examples include potassium sulfoisophthalate.
  • terephthalic acid, isophthalic acid, and phthalic acid are more preferable from the viewpoint of obtaining a polyamide having a high melting point, and terephthalic acid is particularly preferable because a particularly excellent nucleating agent effect can be obtained.
  • the aromatic dicarboxylic acid serving as the constituent unit of the polyamide may be one type or two or more types.
  • the alicyclic diamine is not particularly limited, but examples thereof include compounds represented by the following general formulas (1) and (2).
  • Z 2 , Z 3 , Z 4 , Z 5 , and Z 6 represent a direct bond or an alkylene group having 1 to 10 carbon atoms, and the hydrogen atom bonded to the ring is an alkyl group having 1 to 10 carbon atoms. May be replaced with.
  • Examples of the alkylene group having 1 to 10 carbon atoms represented by Z 2 , Z 3 , Z 4 , Z 5 and Z 6 include methylene, ethylene, propylene, methylethylene, butylene, 1-methylpropylene, 2- Examples include methylpropylene, 1,2-dimethylpropylene, 1,3-dimethylpropylene, 1-methylbutylene, 2-methylbutylene, 3-methylbutylene, 1,3-dimethylbutylene, pentylene, hexylene, heptylene, octylene and the like. , And preferably an alkylene group having 1 to 4 carbon atoms.
  • alkyl group having 1 to 10 carbon atoms which may be substituted with the hydrogen atom bonded to the ring include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, Examples thereof include sec-pentyl, tert-pentyl, hexyl, heptyl, octyl, isooctyl, 2-ethylhexyl, tert-octyl, nonyl, isononyl and decyl, and an alkyl group having 1 to 4 carbon atoms is preferable.
  • the alicyclic diamine include the following compounds.
  • the alicyclic diamine that serves as a constituent unit of the polyamide may be one type or two or more types.
  • the aromatic diamine is not particularly limited, and examples thereof include diamines represented by the following general formulas (3) and (4).
  • Z 7 , Z 8 , Z 9 , Z 10 , and Z 11 represent a direct bond or an alkylene group having 1 to 10 carbon atoms
  • the hydrogen atom bonded to the ring is an alkyl group having 1 to 10 carbon atoms. May be replaced with.
  • Examples of the alkylene group having 1 to 10 carbon atoms and the alkyl group having 1 to 10 carbon atoms include the same ones as Z 2 , Z 3 , Z 4 , Z 5 and Z 6 .
  • Specific examples of the aromatic diamine include the following compounds.
  • the aromatic diamine which is a constituent unit of the polyamide may be one kind or two or more kinds.
  • At least one of the dicarboxylic acid and the diamine, which are the constituent units of the polyamide, has a ring structure, and when a dicarboxylic acid having a ring structure is used, it does not have a ring structure.
  • a diamine may be used, and when a diamine having a ring structure is used, a dicarboxylic acid having no ring structure may be used.
  • the dicarboxylic acid having no ring structure is not particularly limited, and examples thereof include malonic acid, oxalic acid, dimethylmalonic acid, succinic acid, fumaric acid, glutaric acid, adipic acid, muconic acid, 2-methyladipic acid, trimethyl.
  • the dicarboxylic acid having no ring structure which is a constituent unit of polyamide, may be one type or two or more types.
  • Examples of the diamine having no ring structure include alkylenediamine and the like.
  • the alkylenediamine is not particularly limited, but examples thereof include those having 2 to 20 carbon atoms, and preferably those having 2 to 12 carbon atoms.
  • Specific examples of the alkylenediamine include ethylenediamine, trimethylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, nonamethylenediamine, decamethylenediamine, undecamethylenediamine, dodecamethylenediamine.
  • Tridecamethylenediamine Tridecamethylenediamine, tetradecamethylenediamine, pentadecamethylenediamine, hexadecamethylenediamine, heptadecamethylenediamine, octadecamethylenediamine, nonadecamethylenediamine, eicosamethylenediamine, 2-/3-methyl-1
  • Examples include 5-pentanediamine, 2-methyl-1,8-octanediamine, 2,2,4-/2,4,4-trimethylhexamethylenediamine, 5-methyl-1,9-nonanediamine and the like.
  • nucleating agent of the present invention one type or two or more types of diamine having no ring structure, which is a constituent unit of polyamide, may be used.
  • the dicarboxylic acid serving as the constituent unit of the polyamide has a high melting point, and an especially excellent nucleating agent effect is obtained, so that it is preferably an aromatic dicarboxylic acid.
  • the diamine which is a constituent unit of the polyamide is preferably an alkylenediamine because a particularly excellent nucleating agent effect can be obtained.
  • the polyamide contained in the nucleating agent of the present invention may be copolymerized with lactam or diol.
  • lactam is not particularly limited, and examples thereof include ⁇ -caprolactam, ⁇ -heptalactam, undecanelactam, and lauryllactam.
  • the diol is not particularly limited, and examples thereof include aliphatic glycol, alicyclic glycol and aromatic glycol.
  • Examples of the aliphatic glycol include ethylene glycol, 1,2-propylene glycol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,3- Hexanediol, 1,4-hexanediol, 1,6-hexanediol, 2,5-hexanediol, 1,2-octanediol, 1,8-octanediol, 1,10-decanediol, 1,18-octadecane Examples thereof include diol, 1,20-eicosane diol, diethylene glycol, triethylene glycol and thiodiethylene glycol.
  • Examples of the alicyclic glycol include 1-hydroxymethyl-1-cyclobutanol, 1,2-cyclohexanediol, 1,3-cyclohexanediol, 1,4-cyclohexanediol, 1-methyl-3,4-cyclohexanediol. , 2-hydroxymethylcyclohexanol, 4-hydroxymethylcyclohexanol, 1,4-cyclohexanedimethanol and 4,4′-bicyclohexanediol.
  • aromatic glycols examples include dihydroxymethylbenzene, 1,4-bis( ⁇ -hydroxyethoxy)benzene, 2-phenyl-1,3-propanediol, 2-phenyl-1,4-butanediol, 2-benzyl.
  • aromatic glycols include dihydroxymethylbenzene, 1,4-bis( ⁇ -hydroxyethoxy)benzene, 2-phenyl-1,3-propanediol, 2-phenyl-1,4-butanediol, 2-benzyl.
  • 1,3-propanediol triphenylethylene glycol
  • tetraphenylethylene glycol examples include benzopinacol.
  • the weight average molecular weight of the polyamide is preferably 20,000 or less.
  • the weight average molecular weight of the polyamide is more preferably 10,000 or less.
  • the weight average molecular weight of the polyamide refers to the weight average molecular weight measured by GPC in a hexafluoroisopropanol (HFIP) solvent and calculated in terms of polymethylmethacrylate (PMMA).
  • the polyamide contained in the nucleating agent of the present invention can be produced by using any method known as a method for producing polyamide.
  • the polyamide contained in the nucleating agent of the present invention is specifically, for example, a melt polymerization method using dicarboxylic acid and diamine as raw materials, a solid phase polymerization method, a melt extrusion polymerization method, a dicarboxylic acid or an acid halide thereof and a diamine. It can be produced by a method such as a solution polymerization method or an interfacial polymerization method using as a raw material.
  • the nucleating agent of the present invention is an additive to be added to the polyolefin resin, and can be used in combination with other additives to be added to the polyolefin resin.
  • the nucleating agent and other additives of the present invention may be added separately to the polyolefin resin, or by mixing the nucleating agent of the present invention and other additives, as a nucleating agent composition for polyolefin May be used.
  • the nucleating agent of the present invention may be used as a masterbatch further containing a polyolefin resin.
  • additives that can be used in combination with the nucleating agent of the present invention are not particularly limited as long as the nucleating agent effect of the nucleating agent of the present invention is not significantly impaired or the performance of the obtained resin composition is not significantly impaired. There is no.
  • additives generally used for polyolefin resins for example, phenolic antioxidants, phosphorus antioxidants, sulfur antioxidants, other antioxidants, hindered amine compounds , UV absorbers, other nucleating agents different from the nucleating agent of the present invention, flame retardants, flame retardant aids, lubricants, fillers, hydrotalcites, antistatic agents, optical brighteners, pigments, dyes, etc. Can be mentioned.
  • the amount of other additives used in combination with the nucleating agent of the present invention can be used without particular limitation, but the nucleating agent of the present invention and the other additives may be present in the polyolefin resin at an appropriate concentration. It is preferable that it is blended with.
  • Phenolic antioxidants include, for example, 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'-isobutylidene bis(4,6-dimethylphenol), isooctyl-3-(3,3 5-di-tert-butyl-4-hydroxyphenyl)propionate, N,N′-hexane-1,6-diylbis[3-(3,5-di-tert-buty
  • Phosphorus-based antioxidants include, for example, triphenyl phosphite, diisooctyl phosphite, heptakis (dipropylene glycol) triphosphite, triisodecyl phosphite, diphenylisooctyl phosphite, diisooctyl phenyl phosphite, diphenyl triphenyl phosphite.
  • Decyl phosphite triisooctyl phosphite, trilauryl phosphite, diphenyl phosphite, tris(dipropylene glycol) phosphite, dioleyl hydrogen phosphite, trilauryl trithiophosphite, bis(tridecyl) phosphite, tris( Isodecyl)phosphite, tris(tridecyl)phosphite, diphenyldecylphosphite, dinonylphenylbis(nonylphenyl)phosphite, poly(dipropyleneglycol)phenylphosphite, tetraphenyldipropylglycol diphosphite, trisnonylphenyl Phosphite, tris(2,4-di-tert-butylphenyl)phosphite,
  • sulfur-based antioxidant examples 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/stearyl thiodipropionate, 4,4'-thiobis(6-tert-butyl-m-cresol), 2,2'-thiobis(6-tert-butyl-p-cresol), distearyl-disulfide Are listed. When the sulfur-based antioxidant is blended, the blending amount is adjusted to be 0.001 to 10 parts by mass, more preferably 0.
  • 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), polyethylene glycol ester of 2-(2-hydroxy-3-tert-butyl-5-carboxyphenyl)benzotriazole, 2-[2-hydroxy-3-(2-acryloyloxy
  • antioxidants include N-benzyl- ⁇ -phenyl nitrone, N-ethyl- ⁇ -methyl nitrone, N-octyl- ⁇ -heptyl nitrone, N-lauryl- ⁇ -undecyl nitrone, N-tetradecyl- ⁇ .
  • hindered amine compound examples include 2,2,6,6-tetramethyl-4-piperidyl stearate, 1,2,2,6,6-pentamethyl-4-piperidyl stearate and 2,2,6,6-tetra Methyl-4-piperidyl benzoate, bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate, tetrakis(2,2,6,6-tetramethyl-4-piperidyl)-1,2,3 4-butane tetracarboxylate, tetrakis(1,2,2,6,6-pentamethyl-4-piperidyl)-1,2,3,4-butane tetracarboxylate, bis(2,2,6,6-tetra Methyl-4-piperidyl)-di(tridecyl)-1,2,3,4-butanetetracarboxylate, bis(1,2,2,6,6-pentamethyl-4-piperidyl)-di(tridecyl)-1,2,
  • nucleating agents include, for example, sodium-2,2'-methylenebis(4,6-di-tert-butylphenyl)phosphate, lithium-2,2'-methylenebis(4,6-di-tert-butylphenyl).
  • Phosphate aluminum hydroxybis[2,2'-methylenebis(4,6-di-tert-butylphenyl)phosphate], sodium benzoate, 4-tert-butylbenzoic acid aluminum salt, sodium adipate and disodium bicyclo
  • Carboxylic acid metal salts such as heptane-2,3-dicarboxylate, dibenzylidene sorbitol, bis(methylbenzylidene)sorbitol, bis(3,4-dimethylbenzylidene)sorbitol, bis(p-ethylbenzylidene) ) Sorbitol, and polyol derivatives such as bis(dimethylbenzylidene)sorbitol, 1,2,3-trideoxy-4,6:5,7-bis-O-((4-propylphenyl)methylene)nonitol, N,N'.
  • N"-tris[2-methylcyclohexyl]-1,2,3-propanetricarboxamide, N,N',N"-tricyclohexyl-1,3,5-benzenetricarboxamide, N,N'-dicyclohexylnaphthalene examples thereof include amide compounds such as dicarboxamide and 1,3,5-tri(dimethylisopropoylamino)benzene.
  • the blending amount is preferably 0.001 to 10 parts by mass, and more preferably 0.01 to 5 parts by mass with respect to 100 parts by mass of the polyolefin resin.
  • Flame retardants include, for example, triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, cresyl diphenyl phosphate, cresyl-2,6-dixylenyl phosphate, resorcinol bis(diphenyl phosphate), (1-methylethylidene)- 4,1-phenylenetetraphenyldiphosphate, 1,3-phenylenetetrakis(2,6-dimethylphenyl)phosphate, trade names "ADEKA STAB FP-500", "ADEKA STAB FP-600", “ADEKA STAB FP-” manufactured by ADEKA Co., Ltd.
  • aromatic phosphoric acid ester phenylphosphonic acid divinyl, phenylphosphonic acid diallyl, phosphonic acid ester such as phenylphosphonic acid (1-butenyl), phenyl diphenylphosphinate, methyl diphenylphosphinate, 9,10-dihydro-9 -Phosphinic acid ester such as oxa-10-phosphaphenanthrene-10-oxide derivative, phosphazene compound such as bis(2-allylphenoxy)phosphazene, dicresylphosphazene, melamine phosphate, melamine pyrophosphate, melamine polyphosphate, polyphosphate Melum, ammonium polyphosphate, piperazine phosphate, piperazine pyrophosphate, piperazine polyphosphate, phosphorus-containing vinylbenzyl compounds and phosphorus flame retardants such as red phosphorus, metal hydroxides such as magnesium hydroxide and aluminum hydroxide, brominated bisphenol
  • flame retardants are preferably used in combination with anti-dripping agents such as fluororesins and flame retardant aids such as polyhydric alcohols and hydrotalcite.
  • anti-dripping agents such as fluororesins and flame retardant aids such as polyhydric alcohols and hydrotalcite.
  • the blending amount is preferably adjusted to 1 to 100 parts by mass, more preferably 10 to 70 parts by mass with respect to 100 parts by mass of the polyolefin resin.
  • Lubricant is added for the purpose of imparting lubricity to the surface of the molded product and enhancing the scratch prevention effect.
  • the lubricant include unsaturated fatty acid amides such as oleic acid amide and erucic acid amide; saturated fatty acid amides such as behenic acid amide and stearic acid amide, butyl stearate, stearyl alcohol, stearic acid monoglyceride, sorbitan monopalmitate, Examples thereof include sorbitan monostearate, mannitol, stearic acid, hydrogenated castor oil, stearin amide, oleic acid amide, and ethylenebisstearic acid amide.
  • the blending amount is preferably adjusted to 0.01 to 2 parts by mass, more preferably 0.03 to 0.5 part by mass, relative to 100 parts by mass of the polyolefin resin. ..
  • the filler examples include 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 and dolomite. , Silica, alumina, potassium titanate whiskers, wollastonite, fibrous magnesium oxysulfate, and the like, and the particle diameter (in the fibrous shape, the fiber diameter, the fiber length, and the aspect ratio) can be appropriately selected and used. .. These may be used alone or in combination of two or more.
  • the filler may be surface-treated if necessary.
  • the compounding amount is 1 to 80 parts by mass, more preferably 3 to 50 parts by mass, and further preferably 5 to 40 parts by mass with respect to 100 parts by mass of the polyolefin resin.
  • Hydrotalcites are complex salt compounds composed of magnesium, aluminum, hydroxyl groups, carbonic acid groups and arbitrary crystal water, which are known as natural products or synthetic products, and a part of magnesium or aluminum is mixed with other metals such as alkali metals and zinc. And a hydroxyl group or a carbonate group substituted with another anion group.
  • the metal of hydrotalcite represented by the following general formula (5) is substituted with an alkali metal.
  • the Al-Li-based hydrotalcites a compound represented by the following general formula (6) can also be used.
  • x1 and x2 are respectively the following formulas, 0 ⁇ x2/x1 ⁇ 10, 2 ⁇ x1+x2 ⁇ 20 Represents a number satisfying the condition represented by, and p represents 0 or a positive number.
  • a q ⁇ represents a q-valent anion
  • p represents 0 or a positive number.
  • the carbonate anion in hydrotalcites may be partially replaced with another anion.
  • the hydrotalcites may be those obtained by dehydrating water of crystallization, higher fatty acids such as stearic acid, higher fatty acid metal salts such as alkali metal salts of oleic acid, organic sulfonic acid metal salts such as alkali metal salts of dodecylbenzene sulfonic acid. It may be coated with a salt, higher fatty acid amide, higher fatty acid ester, wax or the like.
  • Hydrotalcites may be natural products or synthetic products.
  • Japanese Patent Publication No. 46-2280 Japanese Patent Publication No. 50-30039, Japanese Patent Publication No. 51-29129, Japanese Patent Publication No. 3-36839, and Japanese Patent Publication No. 61-174270.
  • Known methods are described in, for example, JP-A-5-179052.
  • hydrotalcites can be used without being limited by their crystal structure, crystal particles and the like.
  • the compounding amount thereof may be adjusted to 0.001 to 5 parts by mass, more preferably 0.01 to 3 parts by mass, relative to 100 parts by mass of the polyolefin resin. preferable.
  • antistatic agent examples include low molecular type antistatic agents such as nonionic, anionic, cationic or amphoteric surfactants and high molecular type antistatic agents such as polymer 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, polypropylene glycol ethylene oxide adducts; polyethylene oxide, fatty acid esters of glycerin.
  • carboxylic acid salts such as alkali metal salts of higher fatty acids
  • sulfuric acid ester salts such as higher alcohol sulfate ester salts and higher alkyl ether sulfate ester salts
  • alkylbenzene sulfonates alkyl sulfonates, paraffin sulfonates, etc.
  • amphoteric surfactant include amino acid type amphoteric surfactants such as higher alkylaminopropionate, higher alkyldimethyl betaine, betaine type amphoteric surfactants such as higher alkyldihydroxyethyl betaine, and the like, and the resin composition of the present invention.
  • anionic surfactants are preferable, and sulfonates such as alkylbenzene sulfonate, alkyl sulfonate and paraffin sulfonate are particularly preferable.
  • the compounding amount is adjusted to be 0.1 to 10 parts by mass, more preferably 0.5 to 5 parts by mass with respect to 100 parts by mass of the polyolefin resin. It is preferable.
  • Examples of high molecular type antistatic agents include ionomers and block polymers having polyethylene glycol as a hydrophilic part.
  • Examples of the ionomer include the ionomer described in JP 2010-132927 A.
  • Examples of the polymer having polyethylene glycol as a hydrophilic part include polyether ester amide described in JP-A-7-10989, a polymer composed of polyolefin and polyethylene glycol described in US Pat. No. 6,552,131, and JP-A-2016-023254. Examples thereof include polymers composed of polyester and polyethylene glycol.
  • the blending amount is 3 to 60 parts by mass, more preferably 5 to 25 parts by mass, and further preferably 7 to 20 parts by mass with respect to 100 parts by mass of the polyolefin resin. It is preferable to adjust so that
  • Fluorescent whitening agent is a compound that promotes the whiteness and bluishness of the molded product by absorbing the ultraviolet rays of sunlight and artificial light, converting it into visible light of purple to blue and radiating it.
  • the fluorescent whitening agent include benzoxazole-based compounds C.I. I. Fluorescent Brightner 184; coumarin-based compound C.I. I. Fluorescent Brightner 52; diaminostilbene disulphonic acid compound C.I. I. Fluorescent Brightner 24, 85, 71 and the like.
  • the compounding amount is adjusted to be 0.00001 to 0.1 part by mass, more preferably 0.00005 to 0.05 part by mass, relative to 100 parts by mass of the polyolefin resin. Preferably.
  • the pigment may be a commercially available pigment, for example, 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, 192, 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, 13, 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,
  • the dye examples include azo dye, anthraquinone dye, indigoid dye, triarylmethane dye, xanthene dye, alizarin dye, acridine dye, stilbene dye, thiazole dye, naphthol dye, quinoline dye, nitro dye, indamine dye, oxazine dye, phthalocyanine dye. , Dyes such as cyanine dyes, and the like, and a plurality of these may be mixed and used.
  • the polyolefin-based resin composition of the present invention contains the polyolefin-based resin and the nucleating agent of the present invention, and the content of the polyamide is 0.001 to 10 parts by mass based on 100 parts by mass of the polyolefin-based resin.
  • the polyolefin resin used in the present invention include low density polyethylene, linear low density polyethylene, high density polyethylene, isotactic polypropylene, syndiotactic polypropylene, hemiisotactic polypropylene, cycloolefin polymer, stereoblock.
  • ⁇ -olefin polymers such as polypropylene, poly-3-methyl-1-butene, poly-3-methyl-1-pentene, poly-4-methyl-1-pentene, ethylene/propylene block or random copolymers, etc.
  • ⁇ -olefin copolymers examples include ⁇ -olefin copolymers.
  • polypropylene-based resins which have a remarkable effect of using the nucleating agent of the present invention, are preferable.
  • polypropylene resin examples include propylene homopolymer, ethylene-propylene random copolymer, ethylene-propylene block copolymer, propylene and other ⁇ -olefins (eg, 1-butene, 1-hexene, 4-methyl-1-).
  • examples include a copolymer with a small amount (1 to 10% by mass) such as pentene, a copolymer of propylene and ethylene propylene (TPO), and the like.
  • polystyrene resin composition of the present invention stereoregularity, specific gravity, type of polymerization catalyst, presence/absence or degree of removal of polymerization catalyst, degree of crystallization, polymerization conditions such as temperature and pressure, type of crystal, X-ray Lamela size measured by small angle scattering, crystal aspect ratio, solubility in aromatic or aliphatic solvent, solution viscosity, melt viscosity, average molecular weight, degree of molecular weight distribution, number of peaks in molecular weight distribution,
  • the copolymer may be block or random, or the expression of the stabilizing effect may differ depending on the compounding ratio of each monomer, but it is applicable to any resin selected.
  • the method of blending the nucleating agent of the present invention with the polyolefin-based resin is not particularly limited and is a commonly used method, for example, a method of dry blending the nucleating agent of the present invention with a polyolefin-based resin powder or pellets, A method of preparing a masterbatch containing a nucleating agent at a high concentration and adding it to a polyolefin-based resin, a method of processing the nucleating agent of the present invention and other additives into a pellet shape and adding them to the polyolefin-based resin are mentioned.
  • the nucleating agent of the present invention and other additives may be added to the polyolefin resin at the same time, or may be added separately.
  • a mixture of the nucleating agent of the present invention, a phenolic antioxidant, a polymer compound, a binder such as a petroleum resin, and an additive optionally contained as necessary is melted. It can be prepared by mixing in the presence of a binder in the state.
  • the processing conditions, processing equipment, etc. are not particularly limited, and well-known general processing methods and processing equipment can be used. Specific examples of the manufacturing method include a disk pelleter method and an extrusion method.
  • the content of the polyamide is 0.001 to 10 parts by mass with respect to 100 parts by mass of the polyolefin resin.
  • the content of polyamide with respect to 100 parts by mass of the polyolefin resin is preferably 0.005 parts by mass or more, and more preferably 0.05 parts by mass, because a more excellent nucleating agent effect can be obtained.
  • the content of the polyamide based on 100 parts by mass of the polyolefin-based resin is preferably 1 part by mass or less from the viewpoint of sufficiently dispersing the polyamide in the polyolefin-based resin and obtaining a molded article having particularly excellent physical properties and appearance. More preferably 0.5 parts by mass or less.
  • any known additives for example, phenolic antioxidants, phosphorus antioxidants, thioether antioxidants, other antioxidants, etc.
  • these additives include the same as those used in the nucleating agent composition of the present invention.
  • the molded article of the present invention comprises the resin composition of the present invention.
  • the resin composition of the present invention can be molded using a known molding method. For example, it is possible to obtain a molded product by using an injection molding method, an extrusion molding method, a blow molding method, a vacuum molding method, an inflation molding method, a calender molding method, a slush molding method, a dip molding method, a foam molding method, or the like. ..
  • the resin composition of the present invention is used for various purposes such as building materials, agricultural materials, automobiles, trains, ships, aircraft parts, packaging materials, miscellaneous goods, toys, home appliances, medical products, etc. be able to.
  • automotive parts such as bumpers, dashboards, instrument panels, battery cases, luggage cases, door panels, door trims, and fender liners
  • resin parts for home appliances such as refrigerators, washing machines, and vacuum cleaners
  • tableware bottles Household products such as caps, buckets, bath products, etc.
  • resin parts for connecting connectors, etc. miscellaneous goods such as toys, storage containers, synthetic paper
  • Medical products such as containers, medicine containers, individual packaging for medicines; building materials such as wall materials, floor materials, window frames, wallpaper, windows; electric wire coating materials; agricultural materials such as houses, tunnels, flat yarn mesh bags, etc.
  • Industrial materials such as pallets, pail cans, back grind tapes, liquid crystal protection tapes, pipes, modified silicone polymers for sealing materials; food packaging materials such as wraps, trays, cups, films, bottles, caps, storage containers, etc. Examples thereof include 3D printer materials and battery separator films.
  • Example 1 Methylenebiscyclohexylamine (2.09 g, 0.0098 mol), dimethylformamide (DMF, 40 g), and triethylamine (4.89 g) were added to a 200 mL five-necked flask equipped with a stirring blade. While maintaining the flask at room temperature, a solution of terephthaloyl chloride (2.00 g, 0.0098 mol) in DMF (10 g) was added dropwise to the reaction solution over 30 minutes, and the reaction was further continued for 2 hours. The reaction solution was poured into a beaker containing distilled water (50 g), stirred for 1 hour, and then suction-filtered to obtain a polyamide powder. The target polyamide powder was obtained by vacuum-drying the obtained powder at 120°C.
  • Example 2 to 22 Comparative Examples 1 to 2
  • polyamide powder was obtained by the same procedure as in Example 1 except that the diamine and dicarboxylic acid chloride shown in Table 1 were used.
  • the weight average molecular weight of the obtained polyamide was measured. The obtained results are also shown in Table 1. The weight average molecular weight was calculated by the method described below.
  • the sample solution was analyzed by a gel permeation chromatography device (model number: HLC-8320GPC) manufactured by Tosoh Corporation equipped with a differential refractive index detector.
  • HFIP containing 5 mM sodium trifluoroacetate was used as an eluent.
  • the analysis conditions were a flow rate of 0.25 mL/min and a temperature of 40°C.
  • the weight average molecular weight was determined using a calibration curve prepared using PMMA (manufactured by Showa Denko KK) as a standard sample.
  • ⁇ Crystallization temperature Tc [°C]> Using the obtained pellets, the crystallization temperature (Tc) was measured using a differential scanning calorimeter (apparatus: Diamond manufactured by Perkiermer Co., Ltd.). As the measuring method, the temperature was raised from room temperature to 230° C. at a rate of 50° C./min, held for 20 minutes, and then cooled to 50° C. at ⁇ 10° C./min. In the obtained chart, the peak top temperature of the exothermic peak in the cooling process was defined as the crystallization temperature (°C).
  • the nucleating agent of the present invention exerts an excellent nucleating agent effect on the polyolefin resin.

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Abstract

Provided are: a nucleating agent for a polyolefin-based resin; a nucleating agent composition for a polyolefin-based resin containing the same; a polyolefin-based resin composition; and a molded product thereof, which has high versatility without requiring a special method for adding and has excellent effects of a nucleating agent. The nucleating agent for a polyolefin-based resin contains polyamide, wherein the polyamide has a structure in which a dicarboxylic acid and a diamine are dehydrated and condensed, and at least one among the dicarboxylic acid and the diamine has a ring structure. An aromatic dicarboxylic acid is preferable as the dicarboxylic acid.

Description

ポリオレフィン系樹脂用核剤、これを含有するポリオレフィン系樹脂用核剤組成物、ポリオレフィン系樹脂組成物、およびその成形品Nucleating agent for polyolefin resin, nucleating agent composition for polyolefin resin containing the same, polyolefin resin composition, and molded article thereof
　本発明は、ポリオレフィン系樹脂用核剤、これを含有するポリオレフィン系樹脂用核剤組成物、ポリオレフィン系樹脂組成物（以下、それぞれ、単に「核剤」、「核剤組成物」、「樹脂組成物」とも称す）、およびその成形品に関し、詳しくは、特殊な添加方法を要しない汎用性の高い、かつ、優れた核剤効果を有するポリオレフィン系樹脂用核剤、これを含有するポリオレフィン系樹脂用核剤組成物、ポリオレフィン系樹脂組成物、およびその成形品に関する。 The present invention relates to a nucleating agent for a polyolefin resin, a nucleating agent composition for a polyolefin resin containing the same, a polyolefin resin composition (hereinafter, simply “nucleating agent”, “nucleating agent composition”, “resin composition”, respectively). Nucleating agent) and molded products thereof, specifically, a versatile nucleating agent for a polyolefin resin that does not require a special addition method and has an excellent nucleating effect, and a polyolefin resin containing the same. TECHNICAL FIELD The present invention relates to a nucleating agent composition, a polyolefin resin composition, and a molded article thereof.
　ポリオレフィン系樹脂は、その成形加工性、耐熱性、力学的特性および低比重等に優れている利点があり、一般雑貨、医療器具、食品包装等広範囲に使用されている。しかし、そのような広範囲の使用を可能にするためには、ポリオレフィン系樹脂が要求されている物理的特性を満たす必要がある。ポリオレフィン系樹脂は、特定の化合物または組成物を添加することによって、ポリオレフィン系樹脂の成形加工時の結晶化を制御可能にすることは知られている。一般に、結晶化作用が促進されたポリオレフィン系樹脂は、成形加工サイクル時間が短縮されたり、ポリオレフィン系樹脂の成形品の透明性を改善したり、耐熱性や物理的特性が向上したりする等の利点を得ることができる。 Olefin resin has the advantages of excellent moldability, heat resistance, mechanical properties and low specific gravity, and is widely used in general sundries, medical equipment, food packaging, etc. However, in order to enable such a wide range of use, it is necessary for the polyolefin resin to satisfy the required physical properties. It is known that a polyolefin-based resin can control crystallization during molding of the polyolefin-based resin by adding a specific compound or composition. In general, a olefin-based resin having a promoted crystallization effect has a shortened molding cycle time, improves the transparency of a molded product of the polyolefin-based resin, and improves heat resistance and physical properties. You can get the benefits.
　このような中、特許文献１では、結晶性に優れたポリプロピレン共重合体の製造方法が提案されている。この方法は、チタン化合物と有機アルミニウム化合物とからなる触媒系を用いて、炭素原子数６以上のビニルシクロアルカン、特にポリビニルシクロヘキサンの重合とプロピレンの単独またはエチレンとの共重合とを多段で行い、かつ、全重合体中のビニルシクロアルカン単位の含有量を所定のものとするものである。 Under such circumstances, Patent Document 1 proposes a method for producing a polypropylene copolymer having excellent crystallinity. This method uses a catalyst system consisting of a titanium compound and an organoaluminum compound to carry out multi-stage polymerization of vinyl cycloalkane having 6 or more carbon atoms, particularly polyvinyl cyclohexane and homopolymerization of propylene or copolymerization with ethylene. In addition, the content of vinylcycloalkane units in all polymers is set to a predetermined value.
特開昭６０－１３９７１０号公報JP-A-60-139710
　しかしながら、特許文献１で提案されているプロピレン共重合体の製造方法では、特殊な重合工程を要するため、汎用性が低いという問題を有している。また、ポリビニルシクロヘキサンの立体制御が重要であり、やはり、汎用性に欠けるという問題も有していた。 However, the method for producing a propylene copolymer proposed in Patent Document 1 has a problem of low versatility because it requires a special polymerization step. In addition, the stereocontrol of polyvinyl cyclohexane is important, and it also has a problem of lacking versatility.
　そこで、本発明の目的は、特殊な添加方法を要しない汎用性の高い、かつ、優れた核剤効果を有するポリオレフィン系樹脂用核剤、これを含有するポリオレフィン系樹脂用核剤組成物、ポリオレフィン系樹脂組成物、およびその成形品を提供することにある。 Therefore, an object of the present invention is a versatile, which does not require a special addition method, and a nucleating agent for a polyolefin resin having an excellent nucleating effect, a nucleating agent composition for a polyolefin resin containing the same, and a polyolefin. To provide a resin composition and a molded product thereof.
　本発明者らは、上記課題を解決すべく鋭意検討した結果、所定の構造を有するポリアミドが優れた核剤効果を示すことを見出し、本発明を完成するに至った。 As a result of intensive studies to solve the above problems, the present inventors have found that a polyamide having a predetermined structure exhibits an excellent nucleating agent effect, and have completed the present invention.
　すなわち、本発明のポリオレフィン系樹脂用核剤は、ポリアミドを含むポリオレフィン系樹脂用核剤であって、
　前記ポリアミドが、ジカルボン酸とジアミンとが脱水縮合した構造を有し、
　前記ジカルボン酸および前記ジアミンのうち少なくとも一方が環構造を有することを特徴とするものである。 That is, the polyolefin resin nucleating agent of the present invention is a polyolefin resin nucleating agent containing a polyamide,
The polyamide has a structure in which dicarboxylic acid and diamine are dehydrated and condensed,
At least one of the dicarboxylic acid and the diamine has a ring structure.
　本発明のポリオレフィン系樹脂用核剤においては、前記ジカルボン酸は、芳香族ジカルボン酸であることが好ましい。また、本発明の核剤においては、前記ジアミンが、アルキレンジアミン、下記一般式（１）または（２）、       
Figure JPOXMLDOC01-appb-I000003
で表される脂環式ジアミン（ここで、Ｚ２、Ｚ３、Ｚ４、Ｚ５、Ｚ６は、直接結合、炭素原子数１～１０のアルキレン基を表し、環に結合する水素原子は炭素原子数１～１０のアルキル基で置換されていてもよい。）、並びに、下記一般式（３）または（４）、       
Figure JPOXMLDOC01-appb-I000004
で表される芳香族ジアミン（ここで、Ｚ７、Ｚ８、Ｚ９、Ｚ１０、Ｚ１１は、直接結合、炭素原子数１～１０のアルキレン基を表し、環に結合する水素原子は炭素原子数１～１０のアルキル基で置換されていてもよい。）からなる群から選ばれる少なくとも１種であることが好ましい。さらに、本発明の核剤においては、前記ポリアミドの融点または分解点が、２５０℃以上であることが好ましい。さらにまた、本発明の核剤においては、前記ポリアミドの重量平均分子量が、２０，０００以下であることが好ましい。 In the nucleating agent for polyolefin resin of the present invention, the dicarboxylic acid is preferably an aromatic dicarboxylic acid. In the nucleating agent of the present invention, the diamine is alkylenediamine, the following general formula (1) or (2),
Figure JPOXMLDOC01-appb-I000003
An alicyclic diamine represented by (wherein Z 2 , Z 3 , Z 4 , Z 5 and Z 6 represent a direct bond, an alkylene group having 1 to 10 carbon atoms, and a hydrogen atom bonded to the ring is Optionally substituted with an alkyl group having 1 to 10 carbon atoms), and the following general formula (3) or (4),
Figure JPOXMLDOC01-appb-I000004
(Wherein Z 7 , Z 8 , Z 9 , Z 10 and Z 11 represent a direct bond or an alkylene group having 1 to 10 carbon atoms, and the hydrogen atom bonded to the ring is a carbon atom). It may be substituted with an alkyl group having 1 to 10 atoms). Further, in the nucleating agent of the present invention, the melting point or decomposition point of the polyamide is preferably 250° C. or higher. Furthermore, in the nucleating agent of the present invention, the weight average molecular weight of the polyamide is preferably 20,000 or less.
　本発明のポリオレフィン系樹脂用核剤組成物は、本発明のポリオレフィン系樹脂用核剤と、フェノール系酸化防止剤、リン系酸化防止剤、硫黄系酸化防止剤、その他の酸化防止剤、ヒンダードアミン化合物、紫外線吸収剤、その他の核剤、難燃剤、難燃助剤、滑剤、充填剤、ハイドロタルサイト類、帯電防止剤、顔料および染料からなる群から選ばれる１種以上と、を含有することを特徴とするものである。 The polyolefin-based resin nucleating agent composition of the present invention includes the polyolefin-based resin nucleating agent of the present invention, a phenol-based antioxidant, a phosphorus-based antioxidant, a sulfur-based antioxidant, another antioxidant, and a hindered amine compound. , An ultraviolet absorber, other nucleating agent, a flame retardant, a flame retardant aid, a lubricant, a filler, a hydrotalcite, an antistatic agent, and one or more selected from the group consisting of pigments and dyes. It is characterized by.
　本発明のポリオレフィン系樹脂組成物は、ポリオレフィン系樹脂と、本発明のポリオレフィン系樹脂用核剤と、を含み、
　前記ポリオレフィン系樹脂１００質量部に対する前記ポリアミドの含有量が、０．００１～１０質量部であることを特徴とするものである。 The polyolefin-based resin composition of the present invention comprises a polyolefin-based resin and a nucleating agent for the polyolefin-based resin of the present invention,
The content of the polyamide with respect to 100 parts by mass of the polyolefin resin is 0.001 to 10 parts by mass.
　本発明の成形品は、本発明のポリオレフィン系樹脂組成物からなることを特徴とするものである。 The molded article of the present invention is characterized by comprising the polyolefin resin composition of the present invention.
　本発明によれば、特殊な添加方法を要しない汎用性の高い、かつ、優れた核剤効果を有するポリオレフィン系樹脂用核剤、これを含有するポリオレフィン系樹脂用核剤組成物、ポリオレフィン系樹脂組成物、およびその成形品を提供することができる。 According to the present invention, a general-purpose nucleating agent for a polyolefin-based resin that does not require a special addition method and has an excellent nucleating agent effect, a nucleating agent composition for a polyolefin-based resin containing the same, and a polyolefin-based resin A composition and a molded article thereof can be provided.
　以下、本発明の実施形態について詳細に説明する。
　本発明のポリオレフィン系樹脂用核剤は、ポリアミドを含むポリオレフィン系樹脂用核剤であって、ポリアミドが、ジカルボン酸とジアミンとが脱水縮合した構造を有し、ジカルボン酸およびジアミンのうち少なくとも一方が環構造を有する。 Hereinafter, embodiments of the present invention will be described in detail.
The polyolefin resin nucleating agent of the present invention is a polyolefin resin nucleating agent containing a polyamide, wherein the polyamide has a structure in which a dicarboxylic acid and a diamine are dehydrated and condensed, and at least one of the dicarboxylic acid and the diamine is It has a ring structure.
　本発明の核剤は、分散型核剤であり、分散型核剤は樹脂の成形加工時に固体状態を維持する必要がある。そのため、本発明の核剤に含まれるポリアミドは、融点または分解点が２５０℃以上であることが好ましい。本発明の核剤に含まれるポリアミドの融点または分解点は、より好ましくは２６０℃以上であり、さらに好ましくは２８０℃以上である。なお、融点または分解点が５００℃を超える化合物の製造は困難である。ここで、ポリアミドの融点とは、株式会社リガク社製ＴＧ－ＤＴＡ測定器（Ｔｈｅｒｍｏ　ｐｌｕｓ　Ｅｖｏ、ＴＧ８１２０）を用いて、窒素気流下において昇温速度１０℃／ｍｉｎの条件でポリアミドを加熱した際の吸熱ピークのピークトップ温度である。また、分解点は、同条件でポリアミドを加熱した際の発熱ピークのピークトップ温度である。 The nucleating agent of the present invention is a dispersion-type nucleating agent, and the dispersion-type nucleating agent needs to maintain a solid state during resin molding. Therefore, the polyamide contained in the nucleating agent of the present invention preferably has a melting point or a decomposition point of 250° C. or higher. The melting point or decomposition point of the polyamide contained in the nucleating agent of the present invention is more preferably 260°C or higher, further preferably 280°C or higher. It is difficult to produce a compound having a melting point or decomposition point of more than 500°C. Here, the melting point of the polyamide is the temperature when the polyamide is heated at a heating rate of 10° C./min under a nitrogen stream using a TG-DTA measuring instrument (Thermo plus Evo, TG8120) manufactured by Rigaku Corporation. It is the peak top temperature of the endothermic peak. The decomposition point is the peak top temperature of the exothermic peak when the polyamide is heated under the same conditions.
　また、本発明の核剤に含まれるポリアミドを構成するジカルボン酸およびジアミンのうち少なくとも一方が環構造を有している。環構造を有するジカルボン酸としては、例えば、脂環式ジカルボン酸、芳香族ジカルボン酸等が挙げられる。また、環構造を有するジアミンとしては、例えば、脂環式ジアミン、芳香族ジアミン等が挙げられる。 Further, at least one of the dicarboxylic acid and the diamine constituting the polyamide contained in the nucleating agent of the present invention has a ring structure. Examples of the dicarboxylic acid having a ring structure include alicyclic dicarboxylic acid and aromatic dicarboxylic acid. Examples of diamines having a ring structure include alicyclic diamines and aromatic diamines.
　脂環式ジカルボン酸としては、特に制限はないが、好ましくは炭素原子数７～２０の脂環式ジカルボン酸が挙げられ、例えば、１，３－シクロペンタンジカルボン酸、１，２－シクロペンタンジカルボン酸、１，４－シクロヘキサンジカルボン酸、１，２－シクロヘキサンジカルボン酸、１，３－シクロヘキサンジカルボン酸、１，４－シクロヘキサンジ酢酸、１，３－シクロヘキサンジ酢酸、１，２－シクロヘキサンジ酢酸および４、４’－ビシクロヘキシルジカルボン酸等を挙げることができる。本発明の核剤においては、ポリアミドの構成単位となる脂環式ジカルボン酸は、１種でもよく２種以上であってもよい。 The alicyclic dicarboxylic acid is not particularly limited, but examples thereof include alicyclic dicarboxylic acids having 7 to 20 carbon atoms. Examples thereof include 1,3-cyclopentanedicarboxylic acid and 1,2-cyclopentanedicarboxylic acid. Acid, 1,4-cyclohexanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanediacetic acid, 1,3-cyclohexanediacetic acid, 1,2-cyclohexanediacetic acid and 4,4'-bicyclohexyldicarboxylic acid and the like can be mentioned. In the nucleating agent of the present invention, the alicyclic dicarboxylic acid serving as the constitutional unit of the polyamide may be one type or two or more types.
　芳香族ジカルボン酸としては、特に制限はないが、好ましくは炭素原子数８～２０の芳香族ジカルボン酸が挙げられ、例えば、テレフタル酸、イソフタル酸、フタル酸、フェニルマロン酸、ホモフタル酸、フェニルコハク酸、β－フェニルグルタル酸、α－フェニルアジピン酸、β－フェニルアジピン酸、２，２’－ビフェニルジカルボン酸、４，４’－ビフェニルジカルボン酸、ナフタレンジカルボン酸、５－スルホイソフタル酸ナトリウムおよび５－スルホイソフタル酸カリウム等が挙げられる。これらの中では、高い融点を有するポリアミドを得る観点から、テレフタル酸、イソフタル酸、フタル酸がより好ましく、特に優れた核剤効果が得られることから、テレフタル酸が特に好ましい。本発明の核剤においては、ポリアミドの構成単位となる芳香族ジカルボン酸は、１種でもよく２種以上であってもよい。 The aromatic dicarboxylic acid is not particularly limited, but preferably is an aromatic dicarboxylic acid having 8 to 20 carbon atoms, and examples thereof include terephthalic acid, isophthalic acid, phthalic acid, phenylmalonic acid, homophthalic acid and phenylsuccinic acid. Acid, β-phenylglutaric acid, α-phenyladipic acid, β-phenyladipic acid, 2,2′-biphenyldicarboxylic acid, 4,4′-biphenyldicarboxylic acid, naphthalenedicarboxylic acid, sodium 5-sulfoisophthalate and 5 -Examples include potassium sulfoisophthalate. Among these, terephthalic acid, isophthalic acid, and phthalic acid are more preferable from the viewpoint of obtaining a polyamide having a high melting point, and terephthalic acid is particularly preferable because a particularly excellent nucleating agent effect can be obtained. In the nucleating agent of the present invention, the aromatic dicarboxylic acid serving as the constituent unit of the polyamide may be one type or two or more types.
　脂環式ジアミンとしては、特に制限はないが、例えば、下記一般式（１）、（２）で表される化合物が挙げられる。 The alicyclic diamine is not particularly limited, but examples thereof include compounds represented by the following general formulas (1) and (2).
Figure JPOXMLDOC01-appb-I000005
Figure JPOXMLDOC01-appb-I000005
　ここで、Ｚ２、Ｚ３、Ｚ４、Ｚ５、Ｚ６は、直接結合、炭素原子数１～１０のアルキレン基を表し、環に結合する水素原子は炭素原子数１～１０のアルキル基で置換されていてもよい。 Here, Z 2 , Z 3 , Z 4 , Z 5 , and Z 6 represent a direct bond or an alkylene group having 1 to 10 carbon atoms, and the hydrogen atom bonded to the ring is an alkyl group having 1 to 10 carbon atoms. May be replaced with.
　Ｚ２、Ｚ３、Ｚ４、Ｚ５、Ｚ６で表される炭素原子数１～１０のアルキレン基としては、例えば、メチレン、エチレン、プロピレン、メチルエチレン、ブチレン、１－メチルプロピレン、２－メチルプロピレン、１，２－ジメチルプロピレン、１，３－ジメチルプロピレン、１－メチルブチレン、２－メチルブチレン、３－メチルブチレン、１，３－ジメチルブチレン、ペンチレン、ヘキシレン、ヘプチレン、オクチレン等が挙げられ、好ましくは、炭素原子数１～４のアルキレン基である。 Examples of the alkylene group having 1 to 10 carbon atoms represented by Z 2 , Z 3 , Z 4 , Z 5 and Z 6 include methylene, ethylene, propylene, methylethylene, butylene, 1-methylpropylene, 2- Examples include methylpropylene, 1,2-dimethylpropylene, 1,3-dimethylpropylene, 1-methylbutylene, 2-methylbutylene, 3-methylbutylene, 1,3-dimethylbutylene, pentylene, hexylene, heptylene, octylene and the like. , And preferably an alkylene group having 1 to 4 carbon atoms.
　また、環に結合する水素原子と置換してもよい炭素原子数１～１０のアルキル基としては、例えば、メチル、エチル、プロピル、イソプロピル、ブチル、イソブチル、ｓｅｃ－ブチル、ｔｅｒｔ－ブチル、ペンチル、ｓｅｃ－ペンチル、ｔｅｒｔ－ペンチル、ヘキシル、ヘプチル、オクチル、イソオクチル、２－エチルヘキシル、ｔｅｒｔ－オクチル、ノニル、イソノニル、デシル等が挙げられ、好ましくは、炭素原子数１～４のアルキル基である。 Examples of the alkyl group having 1 to 10 carbon atoms which may be substituted with the hydrogen atom bonded to the ring include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, Examples thereof include sec-pentyl, tert-pentyl, hexyl, heptyl, octyl, isooctyl, 2-ethylhexyl, tert-octyl, nonyl, isononyl and decyl, and an alkyl group having 1 to 4 carbon atoms is preferable.
　脂環式ジアミンの具体例としては、以下の化合物等が挙げられる。なお、本発明の核剤においては、ポリアミドの構成単位となる脂環式ジアミンは、１種でもよく２種以上であってもよい。 Specific examples of the alicyclic diamine include the following compounds. In the nucleating agent of the present invention, the alicyclic diamine that serves as a constituent unit of the polyamide may be one type or two or more types.
Figure JPOXMLDOC01-appb-I000006
Figure JPOXMLDOC01-appb-I000006
　芳香族ジアミンとしては、特に制限はないが、下記一般式（３）、（４）で表されるジアミン等が挙げられる。 The aromatic diamine is not particularly limited, and examples thereof include diamines represented by the following general formulas (3) and (4).
Figure JPOXMLDOC01-appb-I000007
Figure JPOXMLDOC01-appb-I000007
　ここで、Ｚ７、Ｚ８、Ｚ９、Ｚ１０、Ｚ１１は、直接結合、炭素原子数１～１０のアルキレン基を表し、環に結合する水素原子は炭素原子数１～１０のアルキル基で置換されていてもよい。炭素原子数１～１０のアルキレン基および炭素原子数１～１０のアルキル基としては、Ｚ２、Ｚ３、Ｚ４、Ｚ５、Ｚ６と同じものが挙げられる。芳香族ジアミンの具体例としては、以下の化合物等が挙げられる。 Here, Z 7 , Z 8 , Z 9 , Z 10 , and Z 11 represent a direct bond or an alkylene group having 1 to 10 carbon atoms, and the hydrogen atom bonded to the ring is an alkyl group having 1 to 10 carbon atoms. May be replaced with. Examples of the alkylene group having 1 to 10 carbon atoms and the alkyl group having 1 to 10 carbon atoms include the same ones as Z 2 , Z 3 , Z 4 , Z 5 and Z 6 . Specific examples of the aromatic diamine include the following compounds.
Figure JPOXMLDOC01-appb-I000008
Figure JPOXMLDOC01-appb-I000008
　本発明の核剤においては、ポリアミドの構成単位となる芳香族ジアミンは、１種でもよく２種以上であってもよい。 In the nucleating agent of the present invention, the aromatic diamine which is a constituent unit of the polyamide may be one kind or two or more kinds.
　本発明の核剤においては、ポリアミドの構成単位となるジカルボン酸およびジアミンのうち少なくとも一方が環構造を有していればよく、環構造を有するジカルボン酸を用いた場合、環構造を有さないジアミンを用いてもよく、環構造を有するジアミンを用いた場合、環構造を有さないジカルボン酸を用いてもよい。 In the nucleating agent of the present invention, at least one of the dicarboxylic acid and the diamine, which are the constituent units of the polyamide, has a ring structure, and when a dicarboxylic acid having a ring structure is used, it does not have a ring structure. A diamine may be used, and when a diamine having a ring structure is used, a dicarboxylic acid having no ring structure may be used.
　環構造を有さないジカルボン酸としては、特に制限はなく、例えば、マロン酸、シュウ酸、ジメチルマロン酸、コハク酸、フマル酸、グルタル酸、アジピン酸、ムコン酸、２－メチルアジピン酸、トリメチルアジピン酸、ピメリン酸、２，２－ジメチルグルタル酸、３，３－ジエチルコハク酸、アゼライン酸、セバシン酸、スベリン酸、ウンデカン二酸、ドデカン二酸、トリデカン二酸、テトラデカンン二酸、ペンタデカン二酸、ヘキサデカン二酸等を挙げることができる。本発明の核剤においては、ポリアミドの構成単位となる環構造を有さないジカルボン酸は、１種でもよく２種以上であってもよい。 The dicarboxylic acid having no ring structure is not particularly limited, and examples thereof include malonic acid, oxalic acid, dimethylmalonic acid, succinic acid, fumaric acid, glutaric acid, adipic acid, muconic acid, 2-methyladipic acid, trimethyl. Adipic acid, pimelic acid, 2,2-dimethylglutaric acid, 3,3-diethylsuccinic acid, azelaic acid, sebacic acid, suberic acid, undecanedioic acid, dodecanedioic acid, tridecanedioic acid, tetradecanedioic acid, pentadecanedioic acid An acid, hexadecanedioic acid, etc. can be mentioned. In the nucleating agent of the present invention, the dicarboxylic acid having no ring structure, which is a constituent unit of polyamide, may be one type or two or more types.
　環構造を有さないジアミンとしては、例えば、アルキレンジアミン等を挙げることができる。アルキレンジアミンとしては、特に制限はないが、例えば、炭素原子数２～２０のもの、好ましくは炭素原子数が２～１２のものを挙げることができる。アルキレンジアミンの具体例としては、エチレンジアミン、トリメチレンジアミン、テトラメチレンジアミン、ペンタメチレンジアミン、ヘキサメチレンジアミン、ヘプタメチレンジアミン、オクタメチレンジアミン、ノナメチレンジアミン、デカメチレンジアミン、ウンデカメチレンジアミン、ドデカメチレンジアミン、トリデカメチレンジアミン、テトラデカメチレンジアミン、ペンタデカメチレンジアミン、ヘキサデカメチレンジアミン、ヘプタデカメチレンジアミン、オクタデカメチレンジアミン、ノナデカメチレンジアミン、エイコサメチレンジアミン、２－／３－メチル－１，５－ペンタンジアミン、２－メチル－１，８－オクタンジアミン、２，２，４－／２，４，４－トリメチルヘキサメチレンジアミン、５－メチル－１，９－ノナンジアミン等を挙げることができる。これらの中では、特に優れた核剤効果が得られることから、ペンタメチレンジアミン、ヘキサメチレンジアミン、ヘプタメチレンジアミン、オクタメチレンジアミン、ノナメチレンジアミン、デカメチレンジアミン、ウンデカメチレンジアミン、ドデカメチレンジアミンが好ましく、ヘキサメチレンジアミンが特に好ましい。本発明の核剤においては、ポリアミドの構成単位となる環構造を有さないジアミンは１種または２種以上であってもよい。 Examples of the diamine having no ring structure include alkylenediamine and the like. The alkylenediamine is not particularly limited, but examples thereof include those having 2 to 20 carbon atoms, and preferably those having 2 to 12 carbon atoms. Specific examples of the alkylenediamine include ethylenediamine, trimethylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, nonamethylenediamine, decamethylenediamine, undecamethylenediamine, dodecamethylenediamine. , Tridecamethylenediamine, tetradecamethylenediamine, pentadecamethylenediamine, hexadecamethylenediamine, heptadecamethylenediamine, octadecamethylenediamine, nonadecamethylenediamine, eicosamethylenediamine, 2-/3-methyl-1, Examples include 5-pentanediamine, 2-methyl-1,8-octanediamine, 2,2,4-/2,4,4-trimethylhexamethylenediamine, 5-methyl-1,9-nonanediamine and the like. Among these, since particularly excellent nucleating agent effect is obtained, pentamethylenediamine, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, nonamethylenediamine, decamethylenediamine, undecamethylenediamine, dodecamethylenediamine Hexamethylenediamine is particularly preferred. In the nucleating agent of the present invention, one type or two or more types of diamine having no ring structure, which is a constituent unit of polyamide, may be used.
　本発明の核剤において、ポリアミドの構成単位となるジカルボン酸は、高い融点を有し、かつ、特に優れた核剤効果が得られることから、芳香族ジカルボン酸であることが好ましい。また、ポリアミドの構成単位となるジアミンは、特に優れた核剤効果が得られることから、アルキレンジアミンであることが好ましい。 In the nucleating agent of the present invention, the dicarboxylic acid serving as the constituent unit of the polyamide has a high melting point, and an especially excellent nucleating agent effect is obtained, so that it is preferably an aromatic dicarboxylic acid. Further, the diamine which is a constituent unit of the polyamide is preferably an alkylenediamine because a particularly excellent nucleating agent effect can be obtained.
　本発明の核剤に含まれるポリアミドはラクタムやジオールと共重合してもよい。ラクタムとしては特に制限はなく、例えば、ε-カプロラクタム、ω-ヘプタラクタム、ウンデカンラクタム、ラウリルラクタム等を挙げることができる。 The polyamide contained in the nucleating agent of the present invention may be copolymerized with lactam or diol. The lactam is not particularly limited, and examples thereof include ε-caprolactam, ω-heptalactam, undecanelactam, and lauryllactam.
　ジオールとしては特に制限はなく、脂肪族グリコール、脂環式グリコールおよび芳香族グリコール等を挙げることができる。 The diol is not particularly limited, and examples thereof include aliphatic glycol, alicyclic glycol and aromatic glycol.
　脂肪族グリコールとしては、例えば、エチレングリコール、１，２－プロピレングリコール、１，３－プロパンジオール、１，２－ブタンジオール、１，３－ブタンジオール、１，４－ブタンジオール、１，３－ヘキサンジオール、１，４－ヘキサンジオール、１，６－ヘキサンジオール、２，５－ヘキサンジオール、１，２－オクタンジオール、１，８－オクタンジオール、１，１０－デカンジオール、１，１８－オクタデカンジオール、１，２０－エイコサンジオール、ジエチレングリコール、トリエチレングリコールおよびチオジエチレングリコール等が挙げられる。 Examples of the aliphatic glycol include ethylene glycol, 1,2-propylene glycol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,3- Hexanediol, 1,4-hexanediol, 1,6-hexanediol, 2,5-hexanediol, 1,2-octanediol, 1,8-octanediol, 1,10-decanediol, 1,18-octadecane Examples thereof include diol, 1,20-eicosane diol, diethylene glycol, triethylene glycol and thiodiethylene glycol.
　脂環式グリコールとしては、例えば、１－ヒドロキシメチル－１－シクロブタノール、１，２－シクロヘキサンジオール、１，３－シクロヘキサンジオール、１，４－シクロヘキサンジオール、１－メチル－３，４－シクロヘキサンジオール、２－ヒドロキシメチルシクロヘキサノール、４－ヒドロキシメチルシクロヘキサノール、１，４－シクロヘキサンジメタノールおよび４，４’－ビシクロヘキサンジオール等が挙げられる。 Examples of the alicyclic glycol include 1-hydroxymethyl-1-cyclobutanol, 1,2-cyclohexanediol, 1,3-cyclohexanediol, 1,4-cyclohexanediol, 1-methyl-3,4-cyclohexanediol. , 2-hydroxymethylcyclohexanol, 4-hydroxymethylcyclohexanol, 1,4-cyclohexanedimethanol and 4,4′-bicyclohexanediol.
　芳香族グリコールとしては、例えば、ジヒドロキシメチルベンゼン、１，４－ビス（β－ヒドロキシエトキシ）ベンゼン、２－フェニル－１，３－プロパンジオール、２－フェニル－１，４－ブタンジオール、２－ベンジル－１，３－プロパンジオール、トリフェニルエチレングリコール、テトラフェニルエチレングリコールおよびベンゾピナコール等が挙げられる。 Examples of aromatic glycols include dihydroxymethylbenzene, 1,4-bis(β-hydroxyethoxy)benzene, 2-phenyl-1,3-propanediol, 2-phenyl-1,4-butanediol, 2-benzyl. Examples thereof include 1,3-propanediol, triphenylethylene glycol, tetraphenylethylene glycol and benzopinacol.
　また、本発明の核剤においては、ポリアミドの重量平均分子量は、２０，０００以下であることが好ましい。この場合、核剤のポリオレフィン系樹脂への分散性が優れたものになるため、良好な核剤性能を示す核剤を得ることができる。ポリアミドの重量平均分子量は、より好ましくは１０，０００以下である。一方、ポリアミドの重量平均分子量を２００超とすることで分散性が高くなりすぎ、ポリアミドがポリオレフィン系樹脂中に溶解するのを抑制することができ、良好な核剤性能を示す核剤を得ることができる。なお、ポリアミドの重量平均分子量とは、ヘキサフルオロイソプロパノール（ＨＦＩＰ）溶媒中、ＧＰＣにより測定し、ポリメチルメタクリレート（ＰＭＭＡ）換算で求めた重量平均分子量をいう。 Further, in the nucleating agent of the present invention, the weight average molecular weight of the polyamide is preferably 20,000 or less. In this case, since the dispersibility of the nucleating agent in the polyolefin resin is excellent, it is possible to obtain a nucleating agent exhibiting good nucleating agent performance. The weight average molecular weight of the polyamide is more preferably 10,000 or less. On the other hand, when the weight average molecular weight of the polyamide is more than 200, the dispersibility becomes too high, the polyamide can be prevented from dissolving in the polyolefin resin, and a nucleating agent showing good nucleating agent performance can be obtained. You can The weight average molecular weight of the polyamide refers to the weight average molecular weight measured by GPC in a hexafluoroisopropanol (HFIP) solvent and calculated in terms of polymethylmethacrylate (PMMA).
　なお、本発明の核剤に含まれるポリアミドは、ポリアミドを製造する方法として知られている任意の方法を用いて製造することができる。本発明の核剤に含まれるポリアミドは、具体的には、例えば、ジカルボン酸とジアミンを原料とする溶融重合法、固相重合法、溶融押出重合法、ジカルボン酸またはその酸ハロゲン化物とジアミンとを原料とする溶液重合法または界面重合法などの方法により製造することができる。 The polyamide contained in the nucleating agent of the present invention can be produced by using any method known as a method for producing polyamide. The polyamide contained in the nucleating agent of the present invention is specifically, for example, a melt polymerization method using dicarboxylic acid and diamine as raw materials, a solid phase polymerization method, a melt extrusion polymerization method, a dicarboxylic acid or an acid halide thereof and a diamine. It can be produced by a method such as a solution polymerization method or an interfacial polymerization method using as a raw material.
　本発明の核剤は、ポリオレフィン系樹脂に配合するための添加剤であり、ポリオレフィン系樹脂に配合するその他の添加剤と組み合わせて用いることができる。この場合、本発明の核剤とその他の添加剤は、別々にポリオレフィン系樹脂に添加してもよく、本発明の核剤とその他の添加剤とを混合して、ポリオレフィン用核剤組成物として使用してもよい。また、本発明の核剤は、さらに、ポリオレフィン系樹脂を含むマスターバッチとして使用してもよい。 The nucleating agent of the present invention is an additive to be added to the polyolefin resin, and can be used in combination with other additives to be added to the polyolefin resin. In this case, the nucleating agent and other additives of the present invention may be added separately to the polyolefin resin, or by mixing the nucleating agent of the present invention and other additives, as a nucleating agent composition for polyolefin May be used. Further, the nucleating agent of the present invention may be used as a masterbatch further containing a polyolefin resin.
　本発明の核剤と組み合わせて用いることができるその他の添加剤は、本発明の核剤の核剤効果を大きく損なわない限り、または、得られる樹脂組成物の性能を大きく損なわない限り、特に制限はない。このようなその他の添加剤としては、ポリオレフィン系樹脂に一般的に用いられる添加剤、例えば、フェノール系酸化防止剤、リン系酸化防止剤、硫黄系酸化防止剤、その他の酸化防止剤、ヒンダードアミン化合物、紫外線吸収剤、本発明の核剤とは異なるその他の核剤、難燃剤、難燃助剤、滑剤、充填剤、ハイドロタルサイト類、帯電防止剤、蛍光増白剤、顔料、染料等が挙げられる。本発明の核剤と併用するその他の添加剤の配合量は、特に制限なく用いることができるが、本発明の核剤およびその他の添加剤が、ポリオレフィン系樹脂中で適度な濃度で存在するように配合されていることが好ましい。 Other additives that can be used in combination with the nucleating agent of the present invention are not particularly limited as long as the nucleating agent effect of the nucleating agent of the present invention is not significantly impaired or the performance of the obtained resin composition is not significantly impaired. There is no. As such other additives, additives generally used for polyolefin resins, for example, phenolic antioxidants, phosphorus antioxidants, sulfur antioxidants, other antioxidants, hindered amine compounds , UV absorbers, other nucleating agents different from the nucleating agent of the present invention, flame retardants, flame retardant aids, lubricants, fillers, hydrotalcites, antistatic agents, optical brighteners, pigments, dyes, etc. Can be mentioned. The amount of other additives used in combination with the nucleating agent of the present invention can be used without particular limitation, but the nucleating agent of the present invention and the other additives may be present in the polyolefin resin at an appropriate concentration. It is preferable that it is blended with.
　フェノール系酸化防止剤は、例えば、２，６－ジ－ｔｅｒｔ－ブチル－４－エチルフェノール、２－ｔｅｒｔ－ブチル－４，６－ジメチルフェノール、スチレン化フェノール、２，２’－メチレンビス（４－エチル－６－ｔｅｒｔ－ブチルフェノール）、２，２’－チオビス－（６－ｔｅｒｔ－ブチル－４－メチルフェノール）、２，２’－チオジエチレンビス［３－（３，５－ジ－ｔｅｒｔ－ブチル－４－ヒドロキシフェニル）プロピオネート］、２－メチル－４，６－ビス（オクチルスルファニルメチル）フェノール、２，２’－イソブチリデンビス（４，６－ジメチルフェノール）、イソオクチル－３－（３，５－ジ－ｔｅｒｔ－ブチル－４－ヒドロキシフェニル）プロピオネート、Ｎ，Ｎ’－ヘキサン－１，６－ジイルビス［３－（３，５－ジ－ｔｅｒｔ－ブチル－４－ヒドロキシフェニル）プロピオンアミド］、２，２’－オキサミド－ビス［エチル－３－（３，５－ジ－ｔｅｒｔ－ブチル－４－ヒドロキシフェニル）プロピオネート］、２－エチルヘキシル－３－（３’，５’－ジ－ｔｅｒｔ－ブチル－４’－ヒドロキシフェニル）プロピオネート、２，２’－エチレンビス（４，６－ジ－ｔｅｒｔ－ブチルフェノール）、３，５－ジ－ｔｅｒｔ－ブチル－４－ヒドロキシベンゼンプロパン酸およびＣ１３－１５アルキルのエステル、２，５－ジ－ｔｅｒｔ－アミルヒドロキノン、ヒンダードフェノールの重合物（ＡＤＥＫＡ　ＰＯＬＹＭＥＲ　ＡＤＤＩＴＩＶＥＳ　ＥＵＲＯＰＥ　ＳＡＳ社製　商品名「ＡＯ．ＯＨ．９８」）、２，２’－メチレンビス［６－（１－メチルシクロヘキシル）－ｐ－クレゾール］、２－ｔｅｒｔ－ブチル－６－（３－ｔｅｒｔ－ブチル－２－ヒドロキシ５－メチルベンジル）－４－メチルフェニルアクリレート、２－［１－（２－ヒドロキシ－３，５－ジ－ｔｅｒｔ－ペンチルフェニル）エチル］－４，６－ジ－ｔｅｒｔ－ペンチルフェニルアクリレート、６－［３－（３－ｔｅｒｔ－ブチル－４－ヒドロキシ－５－メチル）プロポキシ］－２，４，８，１０－テトラ－ｔｅｒｔ－ブチルベンズ［ｄ，ｆ］［１，３，２］－ジオキサホスフォビン、ヘキサメチレンビス［３－（３，５－ジ－ｔｅｒｔ－ブチル－４－ヒドロキシフェニル）プロピオネート］、ビス［モノエチル（３，５－ジ－ｔｅｒｔ－ブチル－４－ヒドロキシベンジル）ホスホネート］カルシウム塩、５，７－ビス（１，１－ジメチルエチル）－３－ヒドロキシ－２（３Ｈ）－ベンゾフラノンとｏ－キシレンとの反応生成物、２，６－ジ－ｔｅｒｔ－ブチル－４－（４，６－ビス（オクチルチオ）－１，３，５－トリアジン－２－イルアミノ）フェノール、ＤＬ－ａ－トコフェノール（ビタミンＥ）、２，６－ビス（α－メチルベンジル）－４－メチルフェノール、ビス［３，３－ビス－（４’－ヒドロキシ－３’－ｔｅｒｔ－ブチル－フェニル）ブタン酸］グリコールエステル、２，６－ジ－ｔｅｒｔ－ブチル－ｐ－クレゾール、２，６－ジフェニル－４－オクタデシロキシフェノール、ステアリル（３，５－ジ－ｔｅｒｔ－ブチル－４－ヒドロキシフェニル）プロピオネート、ジステアリル（３，５－ジ－ｔｅｒｔ－ブチル－４－ヒドロキシベンジル）ホスホネート、トリデシル－３，５－ｔｅｒｔ－ブチル－４－ヒドロキシベンジルチオアセテート、チオジエチレンビス［（３，５－ジ－ｔｅｒｔ－ブチル－４－ヒドロキシフェニル）プロピオネート］、４，４’－チオビス（６－ｔｅｒｔ－ブチル－ｍ－クレゾール）、２－オクチルチオ－４，６－ジ（３，５－ジ－ｔｅｒｔ－ブチル－４－ヒドロキシフェノキシ）－ｓ－トリアジン、２，２’－メチレンビス（４－メチル－６－ｔｅｒｔ－ブチルフェノール）、ビス［３，３－ビス（４－ヒドロキシ－３－ｔｅｒｔ－ブチルフェニル）ブチリックアシッド］グリコールエステル、４，４’－ブチリデンビス（２，６－ジ－ｔｅｒｔ－ブチルフェノール）、４，４’－ブチリデンビス（６－ｔｅｒｔ－ブチル－３－メチルフェノール）、２，２’－エチリデンビス（４，６－ジ－ｔｅｒｔ－ブチルフェノール）、１，１，３－トリス（２－メチル－４－ヒドロキシ－５－ｔｅｒｔ－ブチルフェニル）ブタン、ビス［２－ｔｅｒｔ－ブチル－４－メチル－６－（２－ヒドロキシ－３－ｔｅｒｔ－ブチル－５－メチルベンジル）フェニル］テレフタレート、１，３，５－トリス（２，６－ジメチル－３－ヒドロキシ－４－ｔｅｒｔ－ブチルベンジル）イソシアヌレート、１，３，５－トリス（３，５－ジ－ｔｅｒｔ－ブチル－４－ヒドロキシベンジル）イソシアヌレート、１，３，５－トリス（３，５－ジ－ｔｅｒｔ－ブチル－４－ヒドロキシベンジル）－２，４，６－トリメチルベンゼン、１，３，５－トリス［（３，５－ジ－ｔｅｒｔ－ブチル－４－ヒドロキシフェニル）プロピオニルオキシエチル］イソシアヌレート、テトラキス［メチレン－３－（３’，５’－ｔｅｒｔ－ブチル－４’－ヒドロキシフェニル）プロピオネート］メタン、２－ｔｅｒｔ－ブチル－４－メチル－６－（２－アクリロイルオキシ－３－ｔｅｒｔ－ブチル－５－メチルベンジル）フェノール、３，９－ビス［２－（３－ｔｅｒｔ－ブチル－４－ヒドロキシ－５－メチルヒドロシンナモイルオキシ）－１，１－ジメチルエチル］－２，４，８，１０－テトラオキサスピロ［５．５］ウンデカン、トリエチレングリコールビス［β－（３－ｔｅｒｔ－ブチル－４－ヒドロキシ－５－メチルフェニル）プロピオネート］、ステアリル－３－（３，５－ジ－ｔｅｒｔ－ブチル－４－ヒドロキシフェニル）プロピオン酸アミド、パルミチル－３－（３，５－ジ－ｔｅｒｔ－ブチル－４－ヒドロキシフェニル）プロピオン酸アミド、ミリスチル－３－（３，５－ジ－ｔｅｒｔ－ブチル－４－ヒドロキシフェニル）プロピオン酸アミド、ラウリル－３－（３，５－ジ－ｔｅｒｔ－ブチル－４－ヒドロキシフェニル）プロピオン酸アミド等の３－（３，５－ジアルキル－４－ヒドロキシフェニル）プロピオン酸誘導体等が挙げられる。フェノール系酸化防止剤を配合する場合の配合量は、ポリオレフィン系樹脂１００質量部に対して、０．００１～５質量部、より好ましくは、０．０３～３質量部になるように調整することが好ましい。 Phenolic antioxidants include, for example, 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'-isobutylidene bis(4,6-dimethylphenol), isooctyl-3-(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'-oxamido-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), 3,5-di-tert-butyl-4-hydroxybenzenepropanoic acid and C13-15 alkyl Polymer of ester, 2,5-di-tert-amylhydroquinone, and hindered phenol (ADEKA POLYMER ADDITIVES EUROPE SAS, product name "AO.OH.98"), 2,2'-methylenebis[6-(1- Methylcyclohexyl)-p-cresol], 2-tert-butyl-6-(3-tert-butyl-2-hydroxy-5-methylbenzyl)-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-butylbenz[d,f][1,3,2]-dioxaphosphobin, hexamethylenebis[3-(3,5-di-tert-butyl-4-hydroxy) Phenyl)propionate], bis[monoethyl(3,5-di-tert-butyl-4-hydroxybenzyl)phosphonate] calcium salt, 5,7 Reaction product of -bis(1,1-dimethylethyl)-3-hydroxy-2(3H)-benzofuranone and o-xylene, 2,6-di-tert-butyl-4-(4,6-bis( Octylthio)-1,3,5-triazin-2-ylamino)phenol, DL-a-tocophenol (vitamin E), 2,6-bis(α-methylbenzyl)-4-methylphenol, bis[3,3 -Bis-(4'-hydroxy-3'-tert-butyl-phenyl)butanoic acid]glycol ester, 2,6-di-tert-butyl-p-cresol, 2,6-diphenyl-4-octadecyloxyphenol , Stearyl (3,5-di-tert-butyl-4-hydroxyphenyl)propionate, distearyl (3,5-di-tert-butyl-4-hydroxybenzyl)phosphonate, tridecyl-3,5-tert-butyl- 4-hydroxybenzyl thioacetate, 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 3-bis(4-hydroxy-3-tert-butylphenyl)butyric acid]glycol ester, 4,4′-butylidene bis(2,6-di-tert-butylphenol), 4,4′-butylidene bis(6-tert) -Butyl-3-methylphenol), 2,2'-ethylidenebis(4,6-di-tert-butylphenol), 1,1,3-tris(2-methyl-4-hydroxy-5-tert-butylphenyl) ) 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-acryloyl) Oxy-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, triethylene glycol bis[β-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionate], stearyl-3-( 3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid amide, palmityl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid amide, myristyl-3-(3,3 3-(3,5-dialkyl such as 5-di-tert-butyl-4-hydroxyphenyl)propionic amide and lauryl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic amide Examples include -4-hydroxyphenyl)propionic acid derivatives. When blending the phenolic antioxidant, the blending amount should be adjusted to 0.001 to 5 parts by mass, and more preferably 0.03 to 3 parts by mass, relative to 100 parts by mass of the polyolefin resin. Is preferred.
　リン系酸化防止剤は、例えば、トリフェニルホスファイト、ジイソオクチルホスファイト、ヘプタキス（ジプロピレングリコール）トリホスファイト、トリイソデシルホスファイト、ジフェニルイソオクチルホスファイト、ジイソオクチルフェニルホスファイト、ジフェニルトリデシルホスファイト、トリイソオクチルホスファイト、トリラウリルホスファイト、ジフェニルホスファイト、トリス（ジプロピレングリコール）ホスファイト、ジオレイルヒドロゲンホスファイト、トリラウリルトリチオホスファイト、ビス（トリデシル）ホスファイト、トリス（イソデシル）ホスファイト、トリス（トリデシル）ホスファイト、ジフェニルデシルホスファイト、ジノニルフェニルビス（ノニルフェニル）ホスファイト、ポリ（ジプロピレングリコール）フェニルホスファイト、テトラフェニルジプロピルグリコールジホスファイト、トリスノニルフェニルホスファイト、トリス（２，４－ジ－ｔｅｒｔ－ブチルフェニル）ホスファイト、トリス（２，４－ジ－ｔｅｒｔ－ブチル－５－メチルフェニル）ホスファイト、トリス〔２－ｔｅｒｔ－ブチル－４－（３－ｔｅｒｔ－ブチル－４－ヒドロキシ－５－メチルフェニルチオ）－５－メチルフェニル〕ホスファイト、トリ（デシル）ホスファイト、オクチルジフェニルホスファイト、ジ（デシル）モノフェニルホスファイト、ジステアリルペンタエリスリトールとステアリン酸カルシウム塩との混合物、アルキル（Ｃ１０）ビスフェノールＡホスファイト、テトラフェニル－テトラ（トリデシル）ペンタエリスリトールテトラホスファイト、ビス（２，４－ジ－ｔｅｒｔ－ブチル－６－メチルフェニル）エチルホスファイト、テトラ（トリデシル）イソプロピリデンジフェノールジホスファイト、テトラ（トリデシル）－４，４’－ｎ－ブチリデンビス（２－ｔｅｒｔ－ブチル－５－メチルフェノール）ジホスファイト、ヘキサ（トリデシル）－１，１，３－トリス（２－メチル－４－ヒドロキシ－５－ｔｅｒｔ－ブチルフェニル）ブタントリホスファイト、テトラキス（２，４－ジ－ｔｅｒｔ－ブチルフェニル）ビフェニレンジホスホナイト、９，１０－ジハイドロ－９－オキサ－１０－ホスファフェナンスレン－１０－オキサイド、（１－メチル－１－プロペニル－３－イリデン）トリス（１，１－ジメチルエチル）－５－メチル－４，１－フェニレン）ヘキサトリデシルホスファイト、２，２’－メチレンビス（４，６－ジ－ｔｅｒｔ－ブチルフェニル）－２－エチルヘキシルホスファイト、２，２’－メチレンビス（４，６－ジ－ｔｅｒｔ－ブチルフェニル）－オクタデシルホスファイト、２，２’－エチリデンビス（４，６－ジ－ｔｅｒｔ－ブチルフェニル）フルオロホスファイト、４，４’－ブチリデンビス（３－メチル－６－ｔｅｒｔ－ブチルフェニルジトリデシル）ホスファイト、トリス（２－〔（２，４，８，１０－テトラキス－ｔｅｒｔ－ブチルジベンゾ〔ｄ，ｆ〕〔１，３，２〕ジオキサホスフェピン－６－イル）オキシ〕エチル）アミン、３，９－ビス（４－ノニルフェノキシ）－２，４，８，１０－テトラオキサ－３，９－ジホスフェススピロ［５，５］ウンデカン、２，４，６－トリ－ｔｅｒｔ－ブチルフェニル－２－ブチル－２－エチル－１，３－プロパンジオールホスファイト、ポリ４，４’－イソプロピリデンジフェノールＣ１２－１５アルコールホスファイト、ビス（ジイソデシル）ペンタエリスリトールジホスファイト、ビス（トリデシル）ペンタエリスリトールジホスファイト、ビス（オクタデシル）ペンタエリスリトールジホスファイト、ビス（ノニルフェニル）ペンタエリスリトールジホスファイト、ビス（２，４－ジ－ｔｅｒｔ－ブチルフェニル）ペンタエリスリトールジホスファイト、ビス（２，４，６－トリ－ｔｅｒｔ－ブチルフェニル）ペンタエリスリトールジホスファイト、ビス（２，６－ジ－ｔｅｒｔ－ブチル－４－メチルフェニル）ペンタエリスリトールジホスファイト、ビス（２，４－ジクミルフェニル）ペンタエリスリトールジホスファイト等が挙げられる。リン系酸化防止剤を配合する場合の配合量は、ポリオレフィン系樹脂１００質量部に対して、０．００１～１０質量部、より好ましくは、０．０１～０．５質量部になるように調整することが好ましい。 Phosphorus-based antioxidants include, for example, triphenyl phosphite, diisooctyl phosphite, heptakis (dipropylene glycol) triphosphite, triisodecyl phosphite, diphenylisooctyl phosphite, diisooctyl phenyl phosphite, diphenyl triphenyl phosphite. Decyl phosphite, triisooctyl phosphite, trilauryl phosphite, diphenyl phosphite, tris(dipropylene glycol) phosphite, dioleyl hydrogen phosphite, trilauryl trithiophosphite, bis(tridecyl) phosphite, tris( Isodecyl)phosphite, tris(tridecyl)phosphite, diphenyldecylphosphite, dinonylphenylbis(nonylphenyl)phosphite, poly(dipropyleneglycol)phenylphosphite, tetraphenyldipropylglycol diphosphite, trisnonylphenyl 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, tri(decyl)phosphite, octyldiphenylphosphite, di(decyl)monophenylphosphite, distearyl pentaerythritol And a mixture of calcium stearate, alkyl(C10)bisphenol A phosphite, tetraphenyl-tetra(tridecyl)pentaerythritol tetraphosphite, bis(2,4-di-tert-butyl-6-methylphenyl)ethylphosphite , Tetra(tridecyl)isopropylidene diphenol diphosphite, tetra(tridecyl)-4,4'-n-butylidene bis(2-tert-butyl-5-methylphenol) diphosphite, hexa(tridecyl)-1,1,3 -Tris(2-methyl-4-hydroxy-5-tert-butylphenyl)butane triphosphite, tetrakis(2,4-di-tert-butylphenyl)biphenylene diphosphonite, 9,10-dihydro-9-oxa- 10-phosphaphenanthrene-10-oxide, (1-methyl-1-propenyl-3-ylidene)tris(1,1-dimethylethyl)-5-methyl-4,1-phenylene)hexatride Sylphosphite, 2,2'-methylenebis(4,6-di-tert-butylphenyl)-2-ethylhexylphosphite, 2,2'-methylenebis(4,6-di-tert-butylphenyl)-octadecylphosphite Fight, 2,2'-ethylidene bis(4,6-di-tert-butylphenyl)fluorophosphite, 4,4'-butylidene bis(3-methyl-6-tert-butylphenylditridecyl)phosphite, tris( 2-[(2,4,8,10-tetrakis-tert-butyldibenzo[d,f][1,3,2]dioxaphosphepin-6-yl)oxy]ethyl)amine, 3,9- Bis(4-nonylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphesspiro[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. Are listed. When the phosphorus-based antioxidant is blended, the blending amount is adjusted to be 0.001 to 10 parts by mass, more preferably 0.01 to 0.5 parts by mass, relative to 100 parts by mass of the polyolefin resin. Preferably.
　硫黄系酸化防止剤は、例えば、テトラキス［メチレン－３－（ラウリルチオ）プロピオネート］メタン、ビス（メチル－４－［３－ｎ－アルキル（Ｃ１２／Ｃ１４）チオプロピオニルオキシ］５－ｔｅｒｔ－ブチルフェニル）スルファイド、ジトリデシル－３，３’－チオジプロピオネート、ジラウリル－３，３’－チオジプロピオネート、ジミリスチル－３，３’－チオジプロピオネート、ジステアリル－３，３’－チオジプロピオネート、ラウリル／ステアリルチオジプロピオネート、４，４’－チオビス（６－ｔｅｒｔ－ブチル－ｍ－クレゾール）、２，２’－チオビス（６－ｔｅｒｔ－ブチル－ｐ－クレゾール）、ジステアリル－ジサルファイドが挙げられる。硫黄系酸化防止剤を配合する場合の配合量は、ポリオレフィン系樹脂１００質量部に対して、０．００１～１０質量部、より好ましくは、０．０１～０．５質量部になるように調整することが好ましい。 Examples of the sulfur-based antioxidant 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/stearyl thiodipropionate, 4,4'-thiobis(6-tert-butyl-m-cresol), 2,2'-thiobis(6-tert-butyl-p-cresol), distearyl-disulfide Are listed. When the sulfur-based antioxidant is blended, the blending amount is adjusted to be 0.001 to 10 parts by mass, more preferably 0.01 to 0.5 parts by mass, based on 100 parts by mass of the polyolefin resin. Preferably.
　紫外線吸収剤としては、例えば、２，４－ジヒドロキシベンゾフェノン、５，５’－メチレンビス（２－ヒドロキシ－４－メトキシベンゾフェノン）等の２－ヒドロキシベンゾフェノン類；２－（２－ヒドロキシ－５－メチルフェニル）ベンゾトリアゾール、２－（２－ヒドロキシ－５－ｔｅｒｔ－オクチルフェニル）ベンゾトリアゾール、２－（２－ヒドロキシ－３，５－ジ－ｔｅｒｔ－ブチルフェニル）－５－クロロベンゾトリアゾール、２－（２－ヒドロキシ－３－ｔｅｒｔ－ブチル－５－メチルフェニル）－５－クロロベンゾトリアゾール、２－（２－ヒドロキシ－３，５－ジクミルフェニル）ベンゾトリアゾール、２，２’－メチレンビス（４－ｔｅｒｔ－オクチル－６－ベンゾトリアゾリルフェノール）、２－（２－ヒドロキシ－３－ｔｅｒｔ－ブチル－５－カルボキシフェニル）ベンゾトリアゾールのポリエチレングリコールエステル、２－〔２－ヒドロキシ－３－（２－アクリロイルオキシエチル）－５－メチルフェニル〕ベンゾトリアゾール、２－〔２－ヒドロキシ－３－（２－メタクリロイルオキシエチル）－５－ｔｅｒｔ－ブチルフェニル〕ベンゾトリアゾール、２－〔２－ヒドロキシ－３－（２－メタクリロイルオキシエチル）－５－ｔｅｒｔ－オクチルフェニル〕ベンゾトリアゾール、２－〔２－ヒドロキシ－３－（２－メタクリロイルオキシエチル）－５－ｔｅｒｔ－ブチルフェニル〕－５－クロロベンゾトリアゾール、２－〔２－ヒドロキシ－５－（２－メタクリロイルオキシエチル）フェニル〕ベンゾトリアゾール、２－〔２－ヒドロキシ－３－ｔｅｒｔ－ブチル－５－（２－メタクリロイルオキシエチル）フェニル〕ベンゾトリアゾール、２－〔２－ヒドロキシ－３－ｔｅｒｔ－アミル－５－（２－メタクリロイルオキシエチル）フェニル〕ベンゾトリアゾール、２－〔２－ヒドロキシ－３－ｔｅｒｔ－ブチル－５－（３－メタクリロイルオキシプロピル）フェニル〕－５－クロロベンゾトリアゾール、２－〔２－ヒドロキシ－４－（２－メタクリロイルオキシメチル）フェニル〕ベンゾトリアゾール、２－〔２－ヒドロキシ－４－（３－メタクリロイルオキシ－２－ヒドロキシプロピル）フェニル〕ベンゾトリアゾール、２－〔２－ヒドロキシ－４－（３－メタクリロイルオキシプロピル）フェニル〕ベンゾトリアゾール等の２－（２－ヒドロキシフェニル）ベンゾトリアゾール類；フェニルサリシレート、レゾルシノールモノベンゾエート、２，４－ジ－ｔｅｒｔ－ブチルフェニル－３，５－ジ－ｔｅｒｔ－ブチル－４－ヒドロキシベンゾエート、オクチル（３，５－ジ－ｔｅｒｔ－ブチル－４－ヒドロキシ）ベンゾエート、ドデシル（３，５－ジ－ｔｅｒｔ－ブチル－４－ヒドロキシ）ベンゾエート、テトラデシル（３，５－ジ－ｔｅｒｔ－ブチル－４－ヒドロキシ）ベンゾエート、ヘキサデシル（３，５－ジ－ｔｅｒｔ－ブチル－４－ヒドロキシ）ベンゾエート、オクタデシル（３，５－ジ－ｔｅｒｔ－ブチル－４－ヒドロキシ）ベンゾエート、ベヘニル（３，５－ジ－ｔｅｒｔ－ブチル－４－ヒドロキシ）ベンゾエート等のベンゾエート類；２－エチル－２’－エトキシオキザニリド、２－エトキシ－４’－ドデシルオキザニリド等の置換オキザニリド類；エチル－α－シアノ－β，β－ジフェニルアクリレート、メチル－２－シアノ－３－メチル－３－（ｐ－メトキシフェニル）アクリレート等のシアノアクリレート類；２－（４，６－ジフェニル－１，３，５－トリアジン－２－イル）－５－ヘキシルオキシフェノール、２－（２－ヒドロキシ－４－オクトキシフェニル）－４，６－ビス（２，４－ジメチルフェニル）－１，３，５－トリアジン、トリオクチル－２，２’，２”－（（１，３，５－トリアジン－２，４，６－トリイル）トリス（３－ヒドロシキベンゼン－４－，１－ジイル）トリプロピオネート）、２－（４，６－ジフェニル－１，３，５－トリアジン－２－イル）－５－［２－（２－エチルヘキサノイルオキシ）エトキシ］フェノール、２，４，６－トリス（２－ヒドロキシ－４－ヘキシルオキシ－３－メチルフェニル）－１，３，５－トリアジン、１，１２－ビス［２－［４－（４，６－ジフェニル－１，３，５－トリアジン－２－イル）－３－ヒドロキシフェノキシ］エチル］ドデカンジオエート等のトリアジン類；各種の金属塩、または金属キレート、特にニッケル、クロムの塩、またはキレート類等が挙げられる。紫外線吸収剤を配合する場合の配合量は、ポリオレフィン系樹脂１００質量部に対して、０．００１～１０質量部、より好ましくは、０．０１～０．５質量部になるように調整することが好ましい。 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), polyethylene glycol ester of 2-(2-hydroxy-3-tert-butyl-5-carboxyphenyl)benzotriazole, 2-[2-hydroxy-3-(2-acryloyloxy) Ethyl)-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-amyl-5-(2-methacryloyloxyethyl)phenyl]benzotriazole, 2-[2-hydroxy-3-tert-butyl-5-(3-methacryloyloxypropyl)phenyl]-5-chlorobenzo Triazole, 2-[2-hydroxy-4-(2-methacryloyloxymethyl)phenyl]benzotriazole, 2-[2-hydroxy-4-(3-methacryloyloxy-2-hydroxypropyl)phenyl]benzotriazole, 2- 2-(2-hydroxyphenyl)benzotriazoles such as [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-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- Benzoates such as 4-hydroxy)benzoate, octadecyl (3,5-di-tert-butyl-4-hydroxy)benzoate and behenyl (3,5-di-tert-butyl-4-hydroxy)benzoate; 2-ethyl- Substituted oxanilides such as 2'-ethoxyoxanilide and 2-ethoxy-4'-dodecyloxanilide; ethyl-α-cyano-β,β-diphenylacrylate, methyl-2-cyano-3-methyl-3- Cyanoacrylates such as (p-methoxyphenyl)acrylate; 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-hexyloxyphenol, 2-(2-hydroxy-4-) Octoxyphenyl)-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)tripropionate), 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, 1,12-bis Triazines such as [2-[4-(4,6-diphenyl-1,3,5-triazin-2-yl)-3-hydroxyphenoxy]ethyl]dodecanedioate; various metal salts or metal chelates, In particular, nickel, chromium salts, chelates and the like can be mentioned. When compounding the ultraviolet absorber, the compounding amount should be adjusted to 0.001 to 10 parts by mass, more preferably 0.01 to 0.5 parts by mass, relative to 100 parts by mass of the polyolefin resin. Is preferred.
　その他の酸化防止剤としては、Ｎ－ベンジル－α－フェニルニトロン、Ｎ－エチル－α－メチルニトロン、Ｎ－オクチル－α－ヘプチルニトロン、Ｎ－ラウリル－α－ウンデシルニトロン、Ｎ－テトラデシル－α－トリデシルニトロン、Ｎ－ヘキサデシル－α－ペンタデシルニトロン、Ｎ－オクチル－α－ヘプタデシルニトロン、Ｎ－ヘキサデシル－α－ヘプタデシルニトロン、Ｎ－オクタデシル－α－ペンタデシルニトロン、Ｎ－ヘプタデシル－α－ヘプタデシルニトロン、Ｎ－オクタデシル－α－ヘプタデシルニトロン等のニトロン化合物、３－アリールベンゾフラン－２（３Ｈ）－オン、３－（アルコキシフェニル）ベンゾフラン－２－オン、３－（アシルオキシフェニル）ベンゾフラン－２（３Ｈ）－オン、５，７－ジ－ｔｅｒｔ－ブチル－３－（３，４－ジメチルフェニル）－ベンゾフラン－２（３Ｈ）－オン、５，７－ジ－ｔｅｒｔ－ブチル－３－（４－ヒドロキシフェニル）－ベンゾフラン－２（３Ｈ）－オン、５，７－ジ－ｔｅｒｔ－ブチル－３－｛４－（２－ヒドロキシエトキシ）フェニル｝－ベンゾフラン－２（３Ｈ）－オン、６－（２－（４－（５，７－ジ－ｔｅｒｔ－２－オキソ－２，３－ジヒドロベンゾフラン－３－イル）フェノキシ）エトキシ）－６－オキソヘキシル－６－（（６－ヒドロキシヘキサノイル）オキシ）ヘキサノエート、５－ジ－ｔｅｒｔ－ブチル－３－（４－（（１５－ヒドロキシ－３，６，９，１３－テトラオキサペンタデシル）オキシ）フェニル）ベンゾフラン－２（３Ｈ）オン等のベンゾフラン化合物等が挙げられる。その他の酸化防止剤を配合する場合の配合量は、ポリオレフィン系樹脂１００質量部に対し、０．００１～２０質量部が好ましく、０．０１～５質量部がより好ましい。 Other antioxidants include N-benzyl-α-phenyl nitrone, N-ethyl-α-methyl nitrone, N-octyl-α-heptyl nitrone, N-lauryl-α-undecyl nitrone, N-tetradecyl-α. -Tridecyl nitrone, N-hexadecyl-α-pentadecyl nitrone, N-octyl-α-heptadecyl nitrone, N-hexadecyl-α-heptadecyl nitrone, N-octadecyl-α-pentadecyl nitrone, N-heptadecyl-α -Nitron compounds such as heptadecyl nitrone, N-octadecyl-α-heptadecyl nitrone, 3-arylbenzofuran-2(3H)-one, 3-(alkoxyphenyl)benzofuran-2-one, 3-(acyloxyphenyl)benzofuran -2(3H)-one, 5,7-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, 5-di-tert-butyl-3-(4-((15-hydroxy-3,6,9,13-tetraoxapentadecyl)oxy)phenyl)benzofuran-2(3H)one, etc. Examples thereof include benzofuran compounds. When the other antioxidant is blended, the blending amount is preferably 0.001 to 20 parts by mass, and more preferably 0.01 to 5 parts by mass with respect to 100 parts by mass of the polyolefin resin.
　ヒンダードアミン化合物は、例えば、２，２，６，６－テトラメチル－４－ピペリジルステアレート、１，２，２，６，６－ペンタメチル－４－ピペリジルステアレート、２，２，６，６－テトラメチル－４－ピペリジルベンゾエート、ビス（２，２，６，６－テトラメチル－４－ピペリジル）セバケート、テトラキス（２，２，６，６－テトラメチル－４－ピペリジル）－１，２，３，４－ブタンテトラカルボキシレート、テトラキス（１，２，２，６，６－ペンタメチル－４－ピペリジル）－１，２，３，４－ブタンテトラカルボキシレート、ビス（２，２，６，６－テトラメチル－４－ピペリジル）・ジ（トリデシル）－１，２，３，４－ブタンテトラカルボキシレート、ビス（１，２，２，６，６－ペンタメチル－４－ピペリジル）－ジ（トリデシル）－１，２，３，４－ブタンテトラカルボキシレート、ビス（１，２，２，４，４－ペンタメチル－４－ピペリジル）－２－ブチル－２－（３，５－ジ－ｔｅｒｔ－ブチル－４－ヒドロキシベンジル）マロネート、１－（２－ヒドロキシエチル）－２，２，６，６－テトラメチル－４－ピペリジノ－ル／コハク酸ジエチル重縮合物、１，６－ビス（２，２，６，６－テトラメチル－４－ピペリジルアミノ）ヘキサン／２，４－ジクロロ－６－モルホリノ－ｓ－トリアジン重縮合物、１，６－ビス（２，２，６，６－テトラメチル－４－ピペリジルアミノ）ヘキサン／２，４－ジクロロ－６－ｔｅｒｔ－オクチルアミノ－ｓ－トリアジン重縮合物、１，５，８，１２－テトラキス〔２，４－ビス（Ｎ－ブチル－Ｎ－（２，２，６，６－テトラメチル－４－ピペリジル）アミノ）－ｓ－トリアジン－６－イル〕－１，５，８，１２－テトラアザドデカン、１，５，８，１２－テトラキス〔２，４－ビス（Ｎ－ブチル－Ｎ－（１，２，２，６，６－ペンタメチル－４－ピペリジル）アミノ）－ｓ－トリアジン－６－イル〕－１，５，８－１２－テトラアザドデカン、１，６，１１－トリス〔２，４－ビス（Ｎ－ブチル－Ｎ－（２，２，６，６－テトラメチル－４－ピペリジル）アミノ）－ｓ－トリアジン－６－イル〕アミノウンデカン、１，６，１１－トリス〔２，４－ビス（Ｎ－ブチル－Ｎ－（１，２，２，６，６－ペンタメチル－４－ピペリジル）アミノ）－ｓ－トリアジン－６－イル〕アミノウンデカン、ビス｛４－（１－オクチルオキシ－２，２，６，６－テトラメチル）ピペリジル｝デカンジオナート、ビス｛４－（２，２，６，６－テトラメチル－１－ウンデシルオキシ）ピペリジル）カーボナート等が挙げられる。ヒンダードアミン化合物を配合する場合の配合量は、ポリオレフィン系樹脂１００質量部に対して、０．００１～１０質量部、より好ましくは、０．０１～０．５質量部になるように調整することが好ましい。 Examples of the hindered amine compound include 2,2,6,6-tetramethyl-4-piperidyl stearate, 1,2,2,6,6-pentamethyl-4-piperidyl stearate and 2,2,6,6-tetra Methyl-4-piperidyl benzoate, bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate, tetrakis(2,2,6,6-tetramethyl-4-piperidyl)-1,2,3 4-butane tetracarboxylate, tetrakis(1,2,2,6,6-pentamethyl-4-piperidyl)-1,2,3,4-butane tetracarboxylate, bis(2,2,6,6-tetra Methyl-4-piperidyl)-di(tridecyl)-1,2,3,4-butanetetracarboxylate, bis(1,2,2,6,6-pentamethyl-4-piperidyl)-di(tridecyl)-1 ,2,3,4-butane tetracarboxylate, bis(1,2,2,4,4-pentamethyl-4-piperidyl)-2-butyl-2-(3,5-di-tert-butyl-4- Hydroxybenzyl)malonate, 1-(2-hydroxyethyl)-2,2,6,6-tetramethyl-4-piperidinole/diethyl succinate polycondensate, 1,6-bis(2,2,6, 6-Tetramethyl-4-piperidylamino)hexane/2,4-dichloro-6-morpholino-s-triazine polycondensate, 1,6-bis(2,2,6,6-tetramethyl-4-piperidylamino) ) Hexane/2,4-dichloro-6-tert-octylamino-s-triazine polycondensate, 1,5,8,12-tetrakis[2,4-bis(N-butyl-N-(2,2,2 6,6-Tetramethyl-4-piperidyl)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-piperidyl)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-piperidyl)amino)-s-triazin-6-yl]aminoundecane, 1, 6,11-Tris[2,4-bis(N-butyl-N-(1,2,2,6,6-pentamethyl-4-piperidyl)amino)-s-triazin-6-yl]aminoundecane, bis {4-(1-octyloxy-2,2,6,6-teto Lamethyl)piperidyl}decandionate, bis{4-(2,2,6,6-tetramethyl-1-undecyloxy)piperidyl)carbonate and the like can be mentioned. When the hindered amine compound is blended, the blending amount may be adjusted to 0.001 to 10 parts by mass, more preferably 0.01 to 0.5 parts by mass, based on 100 parts by mass of the polyolefin resin. preferable.
　その他の核剤としては、例えば、ナトリウム－２，２’－メチレンビス（４，６－ジ－ｔｅｒｔ－ブチルフェニル）ホスフェート、リチウム－２，２’－メチレンビス（４，６－ジ－ｔｅｒｔ－ブチルフェニル）ホスフェート、アルミニウムヒドロキシビス［２，２’－メチレンビス（４，６－ジ－ｔｅｒｔ－ブチルフェニル）ホスフェート］、安息香酸ナトリウム、４－ｔｅｒｔ－ブチル安息香酸アルミニウム塩、アジピン酸ナトリウムおよび２ナトリウムビシクロ［２．２．１］ヘプタン－２，３－ジカルボキシレート等のカルボン酸金属塩、ジベンジリデンソルビトール、ビス（メチルベンジリデン）ソルビトール、ビス（３，４－ジメチルベンジリデン）ソルビトール、ビス（ｐ－エチルベンジリデン）ソルビトール、およびビス（ジメチルベンジリデン）ソルビトール、１，２，３－トリデオキシ－４，６：５，７－ビス－Ｏ－（（４－プロピルフェニル）メチレン）ノニトール等のポリオール誘導体、Ｎ，Ｎ’，Ｎ”－トリス［２－メチルシクロヘキシル］－１，２，３－プロパントリカルボキサミド、Ｎ，Ｎ’，Ｎ”－トリシクロヘキシル－１，３，５－ベンゼントリカルボキサミド、Ｎ，Ｎ’－ジシクロヘキシルナフタレンジカルボキサミド、１，３，５－トリ（ジメチルイソプロポイルアミノ）ベンゼン等のアミド化合物等を挙げることができる。その他の核剤を配合する場合の配合量は、ポリオレフィン系樹脂１００質量部に対して、０．００１～１０質量部であることが好ましく、０．０１～５質量部がより好ましい。 Other nucleating agents include, for example, sodium-2,2'-methylenebis(4,6-di-tert-butylphenyl)phosphate, lithium-2,2'-methylenebis(4,6-di-tert-butylphenyl). ) Phosphate, aluminum hydroxybis[2,2'-methylenebis(4,6-di-tert-butylphenyl)phosphate], sodium benzoate, 4-tert-butylbenzoic acid aluminum salt, sodium adipate and disodium bicyclo [ 2.2.1] Carboxylic acid metal salts such as heptane-2,3-dicarboxylate, dibenzylidene sorbitol, bis(methylbenzylidene)sorbitol, bis(3,4-dimethylbenzylidene)sorbitol, bis(p-ethylbenzylidene) ) Sorbitol, and polyol derivatives such as bis(dimethylbenzylidene)sorbitol, 1,2,3-trideoxy-4,6:5,7-bis-O-((4-propylphenyl)methylene)nonitol, N,N'. , N"-tris[2-methylcyclohexyl]-1,2,3-propanetricarboxamide, N,N',N"-tricyclohexyl-1,3,5-benzenetricarboxamide, N,N'-dicyclohexylnaphthalene Examples thereof include amide compounds such as dicarboxamide and 1,3,5-tri(dimethylisopropoylamino)benzene. When the other nucleating agent is blended, the blending amount is preferably 0.001 to 10 parts by mass, and more preferably 0.01 to 5 parts by mass with respect to 100 parts by mass of the polyolefin resin.
　難燃剤は、例えば、トリフェニルホスフェート、トリクレジルホスフェート、トリキシレニルホスフェート、クレジルジフェニルホスフェート、クレジル－２，６－ジキシレニルホスフェート、レゾルシノールビス（ジフェニルホスフェート）、（１－メチルエチリデン）－４，１－フェニレンテトラフェニルジホスフェート、１，３－フェニレンテトラキス（２，６－ジメチルフェニル）ホスフェート、株式会社ＡＤＥＫＡ製商品名「アデカスタブＦＰ－５００」、「アデカスタブＦＰ－６００」、「アデカスタブＦＰ－８００」の芳香族リン酸エステル、フェニルホスホン酸ジビニル、フェニルホスホン酸ジアリル、フェニルホスホン酸（１－ブテニル）等のホスホン酸エステル、ジフェニルホスフィン酸フェニル、ジフェニルホスフィン酸メチル、９，１０－ジヒドロ－９－オキサ－１０－ホスファフェナントレン－１０－オキシド誘導体等のホスフィン酸エステル、ビス（２－アリルフェノキシ）ホスファゼン、ジクレジルホスファゼン等のホスファゼン化合物、リン酸メラミン、ピロリン酸メラミン、ポリリン酸メラミン、ポリリン酸メラム、ポリリン酸アンモニウム、リン酸ピペラジン、ピロリン酸ピペラジン、ポリリン酸ピペラジン、リン含有ビニルベンジル化合物および赤リン等のリン系難燃剤、水酸化マグネシウム、水酸化アルミニウム等の金属水酸化物、臭素化ビスフェノールＡ型エポキシ樹脂、臭素化フェノールノボラック型エポキシ樹脂、ヘキサブロモベンゼン、ペンタブロモトルエン、エチレンビス（ペンタブロモフェニル）、エチレンビステトラブロモフタルイミド、１，２－ジブロモ－４－（１，２－ジブロモエチル）シクロヘキサン、テトラブロモシクロオクタン、ヘキサブロモシクロドデカン、ビス（トリブロモフェノキシ）エタン、臭素化ポリフェニレンエーテル、臭素化ポリスチレンおよび２，４，６－トリス（トリブロモフェノキシ）－１，３，５－トリアジン、トリブロモフェニルマレイミド、トリブロモフェニルアクリレート、トリブロモフェニルメタクリレート、テトラブロモビスフェノールＡ型ジメタクリレート、ペンタブロモベンジルアクリレート、および、臭素化スチレン等の臭素系難燃剤等を挙げることができる。これら難燃剤はフッ素樹脂等のドリップ防止剤や多価アルコール、ハイドロタルサイト等の難燃助剤と併用することが好ましい。難燃剤を配合する場合の配合量は、ポリオレフィン系樹脂１００質量部に対して、１～１００質量部、より好ましくは、１０～７０質量部になるように調整することが好ましい。 Flame retardants include, for example, triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, cresyl diphenyl phosphate, cresyl-2,6-dixylenyl phosphate, resorcinol bis(diphenyl phosphate), (1-methylethylidene)- 4,1-phenylenetetraphenyldiphosphate, 1,3-phenylenetetrakis(2,6-dimethylphenyl)phosphate, trade names "ADEKA STAB FP-500", "ADEKA STAB FP-600", "ADEKA STAB FP-" manufactured by ADEKA Co., Ltd. 800" aromatic phosphoric acid ester, phenylphosphonic acid divinyl, phenylphosphonic acid diallyl, phosphonic acid ester such as phenylphosphonic acid (1-butenyl), phenyl diphenylphosphinate, methyl diphenylphosphinate, 9,10-dihydro-9 -Phosphinic acid ester such as oxa-10-phosphaphenanthrene-10-oxide derivative, phosphazene compound such as bis(2-allylphenoxy)phosphazene, dicresylphosphazene, melamine phosphate, melamine pyrophosphate, melamine polyphosphate, polyphosphate Melum, ammonium polyphosphate, piperazine phosphate, piperazine pyrophosphate, piperazine polyphosphate, phosphorus-containing vinylbenzyl compounds and phosphorus flame retardants such as red phosphorus, metal hydroxides such as magnesium hydroxide and aluminum hydroxide, brominated bisphenol A type epoxy resin, brominated phenol novolac type epoxy resin, hexabromobenzene, pentabromotoluene, ethylenebis(pentabromophenyl), ethylenebistetrabromophthalimide, 1,2-dibromo-4-(1,2-dibromoethyl) ) Cyclohexane, tetrabromocyclooctane, hexabromocyclododecane, bis(tribromophenoxy)ethane, brominated polyphenylene ether, brominated polystyrene and 2,4,6-tris(tribromophenoxy)-1,3,5-triazine , Tribromophenyl maleimide, tribromophenyl acrylate, tribromophenyl methacrylate, tetrabromobisphenol A type dimethacrylate, pentabromobenzyl acrylate, and brominated flame retardants such as brominated styrene. These flame retardants are preferably used in combination with anti-dripping agents such as fluororesins and flame retardant aids such as polyhydric alcohols and hydrotalcite. When blending the flame retardant, the blending amount is preferably adjusted to 1 to 100 parts by mass, more preferably 10 to 70 parts by mass with respect to 100 parts by mass of the polyolefin resin.
　滑剤は、成形体表面に滑性を付与し傷つき防止効果を高める目的で加えられる。滑剤としては、例えば、オレイン酸アミド、エルカ酸アミド等の不飽和脂肪酸アミド；ベヘン酸アミド、ステアリン酸アミド等の飽和脂肪酸アミド、ブチルステアレート、ステアリルアルコール、ステアリン酸モノグリセライド、ソルビタンモノパルミチテート、ソルビタンモノステアレート、マンニトール、ステアリン酸、硬化ひまし油、ステアリンサンアマイド、オレイン酸アマイド、エチレンビスステアリン酸アマイド等が挙げられる。これらは１種を単独で用いてもよく、２種以上を併用して用いてもよい。滑剤を配合する場合の配合量は、ポリオレフィン系樹脂１００質量部に対して、０．０１～２質量部、より好ましくは、０．０３～０．５質量部になるように調整することが好ましい。 Lubricant is added for the purpose of imparting lubricity to the surface of the molded product and enhancing the scratch prevention effect. Examples of the lubricant include unsaturated fatty acid amides such as oleic acid amide and erucic acid amide; saturated fatty acid amides such as behenic acid amide and stearic acid amide, butyl stearate, stearyl alcohol, stearic acid monoglyceride, sorbitan monopalmitate, Examples thereof include sorbitan monostearate, mannitol, stearic acid, hydrogenated castor oil, stearin amide, oleic acid amide, and ethylenebisstearic acid amide. These may be used alone or in combination of two or more. When the lubricant is blended, the blending amount is preferably adjusted to 0.01 to 2 parts by mass, more preferably 0.03 to 0.5 part by mass, relative to 100 parts by mass of the polyolefin resin. ..
　充填剤としては、例えば、タルク、マイカ、炭酸カルシウム、酸化カルシウム、水酸化カルシウム、炭酸マグネシウム、水酸化マグネシウム、酸化マグネシウム、硫酸マグネシウム、水酸化アルミニウム、硫酸バリウム、ガラス粉末、ガラス繊維、クレー、ドロマイト、シリカ、アルミナ、チタン酸カリウムウィスカー、ワラステナイト、繊維状マグネシウムオキシサルフェート等を挙げることができ、粒子径（繊維状においては繊維径や繊維長およびアスペクト比）を適宜選択して用いることができる。これらは１種を単独で用いてもよく、２種以上を併用して用いてもよい。また、充填剤は、必要に応じて表面処理したものを用いることができる。充填剤を配合する場合の配合量は、ポリオレフィン系樹脂１００質量部に対して、１～８０質量部、より好ましくは、３～５０質量部、さらに好ましくは、５～４０質量部である。 Examples of the filler include 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 and dolomite. , Silica, alumina, potassium titanate whiskers, wollastonite, fibrous magnesium oxysulfate, and the like, and the particle diameter (in the fibrous shape, the fiber diameter, the fiber length, and the aspect ratio) can be appropriately selected and used. .. These may be used alone or in combination of two or more. The filler may be surface-treated if necessary. When compounding the filler, the compounding amount is 1 to 80 parts by mass, more preferably 3 to 50 parts by mass, and further preferably 5 to 40 parts by mass with respect to 100 parts by mass of the polyolefin resin.
　ハイドロタルサイト類は、天然物や合成物として知られるマグネシウム、アルミニウム、水酸基、炭酸基および任意の結晶水からなる複合塩化合物であり、マグネシウムまたはアルミニウムの一部をアルカリ金属や亜鉛等他の金属で置換したものや水酸基、炭酸基を他のアニオン基で置換したものが挙げられ、具体的には、例えば、下記一般式（５）で表されるハイドロタルサイトの金属をアルカリ金属に置換したものが挙げられる。また、Ａｌ－Ｌｉ系のハイドロタルサイト類としては、下記一般式（６）で表される化合物も用いることができる。 Hydrotalcites are complex salt compounds composed of magnesium, aluminum, hydroxyl groups, carbonic acid groups and arbitrary crystal water, which are known as natural products or synthetic products, and a part of magnesium or aluminum is mixed with other metals such as alkali metals and zinc. And a hydroxyl group or a carbonate group substituted with another anion group. Specifically, for example, the metal of hydrotalcite represented by the following general formula (5) is substituted with an alkali metal. There are things. Further, as the Al-Li-based hydrotalcites, a compound represented by the following general formula (6) can also be used.
Figure JPOXMLDOC01-appb-I000009
　ここで、一般式（５）中、ｘ１およびｘ２はそれぞれ下記式、
０≦ｘ２／ｘ１＜１０，２≦ｘ１＋ｘ２≦２０
で表される条件を満たす数を表し、ｐは０または正の数を表す。
Figure JPOXMLDOC01-appb-I000009
Here, in the general formula (5), x1 and x2 are respectively the following formulas,
0≦x2/x1<10, 2≦x1+x2≦20
Represents a number satisfying the condition represented by, and p represents 0 or a positive number.
Figure JPOXMLDOC01-appb-I000010
　ここで、一般式（６）中、Ａｑ－は、ｑ価のアニオンを表し、ｐは０または正の数を表す。また、ハイドロタルサイト類における炭酸アニオンは、一部を他のアニオンで置換したものでもよい。
Figure JPOXMLDOC01-appb-I000010
Here, in the general formula (6), A q− represents a q-valent anion, and p represents 0 or a positive number. The carbonate anion in hydrotalcites may be partially replaced with another anion.
　ハイドロタルサイト類は、結晶水を脱水したものであってもよく、ステアリン酸等の高級脂肪酸、オレイン酸アルカリ金属塩等の高級脂肪酸金属塩、ドデシルベンゼンスルホン酸アルカリ金属塩等の有機スルホン酸金属塩、高級脂肪酸アミド、高級脂肪酸エステルまたはワックス等で被覆されたものであってもよい。 The hydrotalcites may be those obtained by dehydrating water of crystallization, higher fatty acids such as stearic acid, higher fatty acid metal salts such as alkali metal salts of oleic acid, organic sulfonic acid metal salts such as alkali metal salts of dodecylbenzene sulfonic acid. It may be coated with a salt, higher fatty acid amide, higher fatty acid ester, wax or the like.
　ハイドロタルサイト類は、天然物であってもよく、また合成品であってもよい。ハイドロタルサイト類の合成方法としては、特公昭４６－２２８０号公報、特公昭５０－３００３９号公報、特公昭５１－２９１２９号公報、特公平３－３６８３９号公報、特開昭６１－１７４２７０号公報、特開平５－１７９０５２号公報等に記載されている公知の方法が挙げられる。また、ハイドロタルサイト類は、その結晶構造、結晶粒子等に制限されることなく使用することができる。ハイドロタルサイト類を配合する場合の配合量は、ポリオレフィン系樹脂１００質量部に対して、０．００１～５質量部、より好ましくは、０．０１～３質量部になるように調整することが好ましい。 Hydrotalcites may be natural products or synthetic products. As a method for synthesizing hydrotalcites, Japanese Patent Publication No. 46-2280, Japanese Patent Publication No. 50-30039, Japanese Patent Publication No. 51-29129, Japanese Patent Publication No. 3-36839, and Japanese Patent Publication No. 61-174270. Known methods are described in, for example, JP-A-5-179052. Further, hydrotalcites can be used without being limited by their crystal structure, crystal particles and the like. When the hydrotalcites are compounded, the compounding amount thereof may be adjusted to 0.001 to 5 parts by mass, more preferably 0.01 to 3 parts by mass, relative to 100 parts by mass of the polyolefin resin. preferable.
　帯電防止剤としては、例えば、非イオン性、アニオン性、カチオン性または両性の界面活性剤等による低分子型帯電防止剤、高分子化合物による高分子型帯電防止型が挙げられる。非イオン性界面活性剤としては、高級アルコールエチレンオキシド付加物、脂肪酸エチレンオキシド付加物、高級アルキルアミンエチレンオキシド付加物、ポリプロピレングリコールエチレンオキシド付加物等のポリエチレングリコール型非イオン界面活性剤；ポリエチレンオキシド、グリセリンの脂肪酸エステル、ペンタエリスリットの脂肪酸エステル、ソルビット若しくはソルビタンの脂肪酸エステル、多価アルコールのアルキルエーテル、アルカノールアミンの脂肪族アミド等の多価アルコール型非イオン界面活性剤等が挙げられ、アニオン性界面活性剤としては、例えば、高級脂肪酸のアルカリ金属塩等のカルボン酸塩；高級アルコール硫酸エステル塩、高級アルキルエーテル硫酸エステル塩等の硫酸エステル塩、アルキルベンゼンスルホン酸塩、アルキルスルホン酸塩、パラフィンスルホン酸塩等のスルホン酸塩；高級アルコールリン酸エステル塩等のリン酸エステル塩等が挙げられ、カチオン性界面活性剤としては、アルキルトリメチルアンモニウム塩等の第４級アンモニウム塩等が挙げられる。両性界面活性剤としては、高級アルキルアミノプロピオン酸塩等のアミノ酸型両性界面活性剤、高級アルキルジメチルベタイン、高級アルキルジヒドロキシエチルベタイン等のベタイン型両性界面活性剤等が挙げられ、本発明の樹脂組成物においては、アニオン性界面活性剤が好ましく、特に、アルキルベンゼンスルホン酸塩、アルキルスルホン酸塩、パラフィンスルホン酸塩等のスルホン酸塩が好ましい。低分子型帯電防止剤を配合する場合の配合量は、ポリオレフィン系樹脂１００質量部に対して、０．１～１０質量部、より好ましくは、０．５～５質量部になるように調整することが好ましい。 Examples of the antistatic agent include low molecular type antistatic agents such as nonionic, anionic, cationic or amphoteric surfactants and high molecular type antistatic agents such as polymer 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, polypropylene glycol ethylene oxide adducts; polyethylene oxide, fatty acid esters of glycerin. , Fatty acid esters of pentaerythritol, fatty acid esters of sorbit or sorbitan, alkyl ethers of polyhydric alcohols, polyhydric alcohol type nonionic surfactants such as aliphatic amides of alkanolamines, and the like, as anionic surfactants. Are, for example, carboxylic acid salts such as alkali metal salts of higher fatty acids; sulfuric acid ester salts such as higher alcohol sulfate ester salts and higher alkyl ether sulfate ester salts, alkylbenzene sulfonates, alkyl sulfonates, paraffin sulfonates, etc. Sulfonates; phosphoric acid ester salts such as higher alcohol phosphoric acid ester salts, and the like, and cationic surfactants include quaternary ammonium salts, such as alkyl trimethyl ammonium salts. Examples of the amphoteric surfactant include amino acid type amphoteric surfactants such as higher alkylaminopropionate, higher alkyldimethyl betaine, betaine type amphoteric surfactants such as higher alkyldihydroxyethyl betaine, and the like, and the resin composition of the present invention. In the present invention, anionic surfactants are preferable, and sulfonates such as alkylbenzene sulfonate, alkyl sulfonate and paraffin sulfonate are particularly preferable. When the low-molecular type antistatic agent is mixed, the compounding amount is adjusted to be 0.1 to 10 parts by mass, more preferably 0.5 to 5 parts by mass with respect to 100 parts by mass of the polyolefin resin. It is preferable.
　高分子型帯電防止剤としては、アイオノマーやポリエチレングリコールを親水部とするブロックポリマー等が挙げられる。アイオノマーとしては特開２０１０－１３２９２７号公報に記載のアイオノマーが挙げられる。ポリエチレングリコールを親水部とするポリマーとしては、例えば特開平７－１０９８９号公報に記載のポリエーテルエステルアミド、米国特許第６５５２１３１号公報記載のポリオレフィンとポリエチレングリコールからなるポリマー、特開２０１６－０２３２５４号公報記載のポリエステルとポリエチレングリコールからなるポリマー等が挙げられる。高分子型帯電防止剤を配合する場合の配合量は、ポリオレフィン系樹脂１００質量部に対して、３～６０質量部、より好ましくは、５～２５質量部、さらに好ましくは、７～２０質量部になるように調整することが好ましい。 Examples of high molecular type antistatic agents include ionomers and block polymers having polyethylene glycol as a hydrophilic part. Examples of the ionomer include the ionomer described in JP 2010-132927 A. Examples of the polymer having polyethylene glycol as a hydrophilic part include polyether ester amide described in JP-A-7-10989, a polymer composed of polyolefin and polyethylene glycol described in US Pat. No. 6,552,131, and JP-A-2016-023254. Examples thereof include polymers composed of polyester and polyethylene glycol. When the high molecular type antistatic agent is blended, the blending amount is 3 to 60 parts by mass, more preferably 5 to 25 parts by mass, and further preferably 7 to 20 parts by mass with respect to 100 parts by mass of the polyolefin resin. It is preferable to adjust so that
　蛍光増白剤とは、太陽光や人工光の紫外線を吸収し、これを紫～青色の可視光線に変えて輻射する蛍光作用によって、成形体の白色度や青味を助長させる化合物である。蛍光増白剤としては、ベンゾオキサゾール系化合物Ｃ．Ｉ．Ｆｌｕｏｒｅｓｃｅｎｔ　Ｂｒｉｇｈｔｎｅｒ１８４；クマリン系化合物Ｃ．Ｉ．Ｆｌｕｏｒｅｓｃｅｎｔ　Ｂｒｉｇｈｔｎｅｒ５２；ジアミノスチルベンジスルフォン酸系化合物Ｃ．Ｉ．Ｆｌｕｏｒｅｓｃｅｎｔ　Ｂｒｉｇｈｔｎｅｒ２４、８５、７１等が挙げられる。蛍光増白剤を用いる場合の配合量は、ポリオレフィン系樹脂１００質量部に対して、０．００００１～０．１質量部、より好ましくは、０．００００５～０．０５質量部になるように調整することが好ましい。 Fluorescent whitening agent is a compound that promotes the whiteness and bluishness of the molded product by absorbing the ultraviolet rays of sunlight and artificial light, converting it into visible light of purple to blue and radiating it. Examples of the fluorescent whitening agent include benzoxazole-based compounds C.I. I. Fluorescent Brightner 184; coumarin-based compound C.I. I. Fluorescent Brightner 52; diaminostilbene disulphonic acid compound C.I. I. Fluorescent Brightner 24, 85, 71 and the like. When using a fluorescent whitening agent, the compounding amount is adjusted to be 0.00001 to 0.1 part by mass, more preferably 0.00005 to 0.05 part by mass, relative to 100 parts by mass of the polyolefin resin. Preferably.
　顔料は、市販の顔料を用いることもでき、例えば、ピグメントレッド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、１９２、２００、２０２、２０９、２１５、２１６、２１７、２２０、２２３、２２４、２２６、２２７、２２８、２４０、２５４；ピグメントオレンジ１３、３１、３４、３６、３８、４３、４６、４８、４９、５１、５２、５５、５９、６０、６１、６２、６４、６５、７１；ピグメントイエロー１、３、１２、１３、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、１６６、１６８、１７５、１８０、１８５；ピグメントグリーン７、１０、３６；ピグメントブルー１５、１５：１、１５：２、１５：３、１５：４、１５：５、１５：６、２２、２４、２９、５６、６０、６１、６２、６４；ピグメントバイオレット１、１５、１９、２３、２７、２９、３０、３２、３７、４０、５０等が挙げられる。 The pigment may be a commercially available pigment, for example, 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, 192, 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, 13, 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, 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 and the like.
　染料としては、アゾ染料、アントラキノン染料、インジゴイド染料、トリアリールメタン染料、キサンテン染料、アリザリン染料、アクリジン染料、スチルベン染料、チアゾール染料、ナフトール染料、キノリン染料、ニトロ染料、インダミン染料、オキサジン染料、フタロシアニン染料、シアニン染料等の染料等が挙げられ、これらは複数を混合して用いてもよい。 Examples of the dye include azo dye, anthraquinone dye, indigoid dye, triarylmethane dye, xanthene dye, alizarin dye, acridine dye, stilbene dye, thiazole dye, naphthol dye, quinoline dye, nitro dye, indamine dye, oxazine dye, phthalocyanine dye. , Dyes such as cyanine dyes, and the like, and a plurality of these may be mixed and used.
　次に、本発明のポリオレフィン系樹脂組成物について説明する。本発明のポリオレフィン系樹脂組成物は、ポリオレフィン系樹脂と本発明の核剤とを含み、ポリオレフィン系樹脂１００質量部に対するポリアミドの含有量が、０．００１～１０質量部であるものである。本発明に用いられるポリオレフィン系樹脂としては、例えば、低密度ポリエチレン、直鎖状低密度ポリエチレン、高密度ポリエチレン、アイソタクチックポリプロピレン、シンジオタクチックポリプロピレン、ヘミアイソタクチックポリプロピレン、シクロオレフィンポリマー、ステレオブロックポリプロピレン、ポリ－３－メチル－１－ブテン、ポリ－３－メチル－１－ペンテン、ポリ－４－メチル－１－ペンテン等のα－オレフィン重合体、エチレン／プロピレンブロック又はランダム共重合体等のα－オレフィン共重合体等が挙げられる。上記のポリオレフィン系樹脂の中では、本発明の核剤の使用効果が顕著であるポリプロピレン系樹脂が好適である。ポリプロピレン系樹脂としては、プロピレンホモポリマー、エチレン－プロピレンランダム共重合体、エチレン－プロピレンブロック共重合体、プロピレンと他のα－オレフィン（例えば、１－ブテン、１－ヘキセン、４－メチル－１－ペンテン等）少量（１～１０質量％）との共重合体、プロピレンとエチレンプロピレンとの共重合体（ＴＰＯ）等が挙げられる。 Next, the polyolefin resin composition of the present invention will be described. The polyolefin-based resin composition of the present invention contains the polyolefin-based resin and the nucleating agent of the present invention, and the content of the polyamide is 0.001 to 10 parts by mass based on 100 parts by mass of the polyolefin-based resin. Examples of the polyolefin resin used in the present invention include low density polyethylene, linear low density polyethylene, high density polyethylene, isotactic polypropylene, syndiotactic polypropylene, hemiisotactic polypropylene, cycloolefin polymer, stereoblock. Α-olefin polymers such as polypropylene, poly-3-methyl-1-butene, poly-3-methyl-1-pentene, poly-4-methyl-1-pentene, ethylene/propylene block or random copolymers, etc. Examples include α-olefin copolymers. Among the above polyolefin-based resins, polypropylene-based resins, which have a remarkable effect of using the nucleating agent of the present invention, are preferable. Examples of the polypropylene resin include propylene homopolymer, ethylene-propylene random copolymer, ethylene-propylene block copolymer, propylene and other α-olefins (eg, 1-butene, 1-hexene, 4-methyl-1-). Examples include a copolymer with a small amount (1 to 10% by mass) such as pentene, a copolymer of propylene and ethylene propylene (TPO), and the like.
　本発明のポリオレフィン系樹脂組成物においては、立体規則性、比重、重合触媒の種類、重合触媒の除去の有無や程度、結晶化の度合い、温度や圧力などの重合条件、結晶の種類、Ｘ線小角散乱で測定したラメラ晶のサイズ、結晶のアスペクト比、芳香族系または脂肪族系溶媒への溶解度、溶液粘度、溶融粘度、平均分子量、分子量分布の程度、分子量分布におけるピークがいくつあるか、共重合体にあってはブロックであるかランダムであるか、各モノマーの配合比率などにより安定化効果の発現に差異が生じることはあるものの、いかなる樹脂を選択した場合においても適用可能である。 In the polyolefin resin composition of the present invention, stereoregularity, specific gravity, type of polymerization catalyst, presence/absence or degree of removal of polymerization catalyst, degree of crystallization, polymerization conditions such as temperature and pressure, type of crystal, X-ray Lamela size measured by small angle scattering, crystal aspect ratio, solubility in aromatic or aliphatic solvent, solution viscosity, melt viscosity, average molecular weight, degree of molecular weight distribution, number of peaks in molecular weight distribution, The copolymer may be block or random, or the expression of the stabilizing effect may differ depending on the compounding ratio of each monomer, but it is applicable to any resin selected.
　本発明の核剤をポリオレフィン系樹脂に配合する方法は、特に制限を受けず、一般に用いられる方法、例えば、ポリオレフィン系樹脂粉末若しくはペレットと、本発明の核剤をドライブレンドする方法、本発明の核剤を高濃度で含有するマスターバッチを作製し、これをポリオレフィン系樹脂に添加する方法、本発明の核剤とその他の添加剤をペレット形状に加工してポリオレフィン系樹脂に添加する方法が挙げられる。また、本発明の核剤とその他の添加剤は、同時にポリオレフィン系樹脂に添加してもよく、別々に添加するものであってもよい。 The method of blending the nucleating agent of the present invention with the polyolefin-based resin is not particularly limited and is a commonly used method, for example, a method of dry blending the nucleating agent of the present invention with a polyolefin-based resin powder or pellets, A method of preparing a masterbatch containing a nucleating agent at a high concentration and adding it to a polyolefin-based resin, a method of processing the nucleating agent of the present invention and other additives into a pellet shape and adding them to the polyolefin-based resin are mentioned. To be Further, the nucleating agent of the present invention and other additives may be added to the polyolefin resin at the same time, or may be added separately.
　ペレット形状に加工する方法としては、本発明の核剤と、フェノール系酸化防止剤、高分子化合物、石油樹脂等のバインダーおよび必要に応じて任意で含まれる添加剤の混合物を加熱して、融解状態のバインダーの存在下で混合することによって製造することができる。加工条件、加工機器等については何ら限定されることなく、周知一般の加工方法、加工機器を使用することができる。具体的な製造方法としては、ディスクペレッター法、押出法等が挙げられる。 As a method for processing into a pellet form, a mixture of the nucleating agent of the present invention, a phenolic antioxidant, a polymer compound, a binder such as a petroleum resin, and an additive optionally contained as necessary is melted. It can be prepared by mixing in the presence of a binder in the state. The processing conditions, processing equipment, etc. are not particularly limited, and well-known general processing methods and processing equipment can be used. Specific examples of the manufacturing method include a disk pelleter method and an extrusion method.
　本発明の樹脂組成物において、ポリオレフィン系樹脂１００質量部に対する、ポリアミドの含有量は、０．００１～１０質量部である。ポリオレフィン系樹脂１００質量部に対するポリアミドの含有量は、さらに優れた核剤効果が得られることから、０．００５質量部以上であることが好ましく、０．０５質量部であることがさらに好ましい。また、ポリオレフィン系樹脂１００質量部に対するポリアミドの含有量は、ポリオレフィン系樹脂中にポリアミドを十分に分散させ、物性および外観が特に優れた成形品を得る観点から、１質量部以下であることが好ましく、０．５質量部以下であることがより好ましい。 In the resin composition of the present invention, the content of the polyamide is 0.001 to 10 parts by mass with respect to 100 parts by mass of the polyolefin resin. The content of polyamide with respect to 100 parts by mass of the polyolefin resin is preferably 0.005 parts by mass or more, and more preferably 0.05 parts by mass, because a more excellent nucleating agent effect can be obtained. In addition, the content of the polyamide based on 100 parts by mass of the polyolefin-based resin is preferably 1 part by mass or less from the viewpoint of sufficiently dispersing the polyamide in the polyolefin-based resin and obtaining a molded article having particularly excellent physical properties and appearance. More preferably 0.5 parts by mass or less.
　本発明の樹脂組成物において、発明の効果を著しく損なわない範囲で、任意で公知の添加剤（例えば、フェノール系酸化防止剤、リン系酸化防止剤、チオエーテル系酸化防止剤、その他の酸化防止剤、ヒンダードアミン化合物、紫外線吸収剤、本発明のポリオレフィン系樹脂用核剤とは異なるその他の核剤、難燃剤、難燃助剤、滑剤、充填剤、ハイドロタルサイト類、帯電防止剤、蛍光増白剤、顔料、染料等）を含有させてもよい。これらの添加剤としては、本発明の核剤組成物に用いるものと同じものが挙げられる。 In the resin composition of the present invention, any known additives (for example, phenolic antioxidants, phosphorus antioxidants, thioether antioxidants, other antioxidants, etc.) are used as long as the effects of the invention are not significantly impaired. , Hindered amine compounds, ultraviolet absorbers, other nucleating agents different from the nucleating agent for polyolefin resin of the present invention, flame retardants, flame retardant aids, lubricants, fillers, hydrotalcites, antistatic agents, fluorescent whitening Agents, pigments, dyes, etc.) may be contained. Examples of these additives include the same as those used in the nucleating agent composition of the present invention.
　次に、本発明の成形品について説明する。本発明の成形品は、本発明の樹脂組成物からなる。本発明の樹脂組成物は、公知の成形方法を用いて成形することができる。例えば、射出成形法、押出成形法、ブロー成形法、真空成形法、インフレーション成形法、カレンダー成形法、スラッシュ成形法、ディップ成形法、発泡成形法等を用いて成形品を得ることが可能である。 Next, the molded product of the present invention will be described. The molded article of the present invention comprises the resin composition of the present invention. The resin composition of the present invention can be molded using a known molding method. For example, it is possible to obtain a molded product by using an injection molding method, an extrusion molding method, a blow molding method, a vacuum molding method, an inflation molding method, a calender molding method, a slush molding method, a dip molding method, a foam molding method, or the like. ..
　本発明の樹脂組成物の用途としては、建築資材、農業用資材、自動車、列車、船、航空機など乗り物用部品、包装用資材、雑貨、玩具、家電製品、医療品等、種々の用途に用いることができる。具体的には、バンパー、ダッシュボード、インスツルメントパネル、バッテリーケース、ラゲッジケース、ドアパネル、ドアトリム、フェンダーライナー等の自動車部品；冷蔵庫、洗濯機、掃除機等の家電製品用樹脂部品；食器、ボトルキャップ、バケツ、入浴用品等の家庭用品；コネクター等の接続用樹脂部品；玩具、収納容器、合成紙等の雑貨品；医療用パック、注射器、カテーテル、医療用チューブ、シリンジ製剤、輸液バッグ、試薬容器、飲み薬容器、飲み薬個包装等の医療用成形品；壁材、床材、窓枠、壁紙、窓等の建材；電線被覆材；ハウス、トンネル、フラットヤーンメッシュバッグ等の農業用資材；パレット、ペール缶、バックグラインドテープ、液晶プロテクト用テープ、パイプ、シーリング材用変性シリコーンポリマー等の工業用資材；ラップ、トレイ、カップ、フィルム、ボトル、キャップ、保存容器等の食品包装材、その他３Ｄプリンター材料、電池用セパレータ膜等が挙げられる。 The resin composition of the present invention is used for various purposes such as building materials, agricultural materials, automobiles, trains, ships, aircraft parts, packaging materials, miscellaneous goods, toys, home appliances, medical products, etc. be able to. Specifically, automotive parts such as bumpers, dashboards, instrument panels, battery cases, luggage cases, door panels, door trims, and fender liners; resin parts for home appliances such as refrigerators, washing machines, and vacuum cleaners; tableware, bottles Household products such as caps, buckets, bath products, etc.; resin parts for connecting connectors, etc.; miscellaneous goods such as toys, storage containers, synthetic paper; medical packs, syringes, catheters, medical tubes, syringe preparations, infusion bags, reagents Medical products such as containers, medicine containers, individual packaging for medicines; building materials such as wall materials, floor materials, window frames, wallpaper, windows; electric wire coating materials; agricultural materials such as houses, tunnels, flat yarn mesh bags, etc. Industrial materials such as pallets, pail cans, back grind tapes, liquid crystal protection tapes, pipes, modified silicone polymers for sealing materials; food packaging materials such as wraps, trays, cups, films, bottles, caps, storage containers, etc. Examples thereof include 3D printer materials and battery separator films.
　以下、実施例を挙げて、本発明をさらに具体的に説明するが、本発明は以下の実施例等によって何ら制限を受けるものではない。 Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to the following examples.
〔実施例１〕
　撹拌羽を備えた２００ｍＬの５つ口フラスコにメチレンビスシクロヘキシルアミン（２．０９ｇ、０．００９８ｍｏｌ）、ジメチルホルムアミド（ＤＭＦ、４０ｇ）、トリエチルアミン（４．８９ｇ）を加えた。フラスコを室温に保ちつつ、窒素を流しながら反応溶液に対してテレフタル酸クロリド（２．００ｇ、０．００９８ｍｏｌ）のＤＭＦ（１０ｇ）溶液を３０分かけて滴下し、さらに２時間反応させた。反応溶液を蒸留水（５０ｇ）が入ったビーカーに注ぎさらに１時間撹拌したのち、吸引ろ過によりポリアミドの粉末を得た。得られた粉末を１２０℃で真空乾燥することにより目的とするポリアミド粉末を得た。 [Example 1]
Methylenebiscyclohexylamine (2.09 g, 0.0098 mol), dimethylformamide (DMF, 40 g), and triethylamine (4.89 g) were added to a 200 mL five-necked flask equipped with a stirring blade. While maintaining the flask at room temperature, a solution of terephthaloyl chloride (2.00 g, 0.0098 mol) in DMF (10 g) was added dropwise to the reaction solution over 30 minutes, and the reaction was further continued for 2 hours. The reaction solution was poured into a beaker containing distilled water (50 g), stirred for 1 hour, and then suction-filtered to obtain a polyamide powder. The target polyamide powder was obtained by vacuum-drying the obtained powder at 120°C.
〔実施例２～２２、比較例１～２〕
　実施例２～２２は、表１に示すジアミンとジカルボン酸クロリドを用いたこと以外は実施例１と同じ手順でポリアミド粉末を得た。 [Examples 2 to 22, Comparative Examples 1 to 2]
In Examples 2 to 22, polyamide powder was obtained by the same procedure as in Example 1 except that the diamine and dicarboxylic acid chloride shown in Table 1 were used.
　得られたポリアミドにつき、重量平均分子量を測定した。得られた結果を表１に併記する。なお、重量平均分子量は、以下に示す方法で算出した。 The weight average molecular weight of the obtained polyamide was measured. The obtained results are also shown in Table 1. The weight average molecular weight was calculated by the method described below.
　ポリアミド１ｍｇに５ｍＭトリフルオロ酢酸ナトリウム含有ＨＦＩＰ２ｍＬを加えて溶解させて得られた溶解液を、メンブレンフィルターで濾過し、試料溶液を調製した。この試料溶液を、示差屈折率検出器を備えた東ソー株式会社製ゲル浸透クロマトグラフィ装置（型番：ＨＬＣ－８３２０ＧＰＣ）で分析した。溶離液として５ｍＭトリフルオロ酢酸ナトリウム含有ＨＦＩＰを用いた。分析条件は流速０．２５ｍＬ／ｍｉｎ、温度４０℃とした。そして、ＰＭＭＡ（昭和電工株式会社製）を標準試料として作成した検量線を用いて、重量平均分子量を求めた。 A solution obtained by adding 2 mL of HFIP containing 5 mM sodium trifluoroacetate to 1 mg of polyamide and dissolving the mixture was filtered with a membrane filter to prepare a sample solution. The sample solution was analyzed by a gel permeation chromatography device (model number: HLC-8320GPC) manufactured by Tosoh Corporation equipped with a differential refractive index detector. HFIP containing 5 mM sodium trifluoroacetate was used as an eluent. The analysis conditions were a flow rate of 0.25 mL/min and a temperature of 40°C. Then, the weight average molecular weight was determined using a calibration curve prepared using PMMA (manufactured by Showa Denko KK) as a standard sample.
〔実施例１～２２、比較例１～２およびコントロール〕
　ポリオレフィン系樹脂として、ホモポリプロピレン（ＭＦＲ＝８ｇ／１０ｍｉｎ）２００ｇに対し、フェノール系酸化防止剤（テトラキス［メチレン－３－（３’，５’―ｔｅｒｔ－ブチル－４’－ヒドロキシフェニル）プロピオネート］メタン）５００ｐｐｍ、リン系酸化防止剤（トリス（２，４－ジ－ｔｅｒｔ－ブチルフェニル）ホスファイト）１０００ｐｐｍ、ステアリン酸カルシウム塩５００ｐｐｍ、および、表１記載のポリアミドを１０００ｐｐｍとなるように配合して、手ブレンドで３分間これらをブレンド後、二軸押出機（装置：株式会社東洋精機製作所製ラボプラストミルマイクロ）に投入し、２３０℃で溶融混錬したのち、ペレットに造粒した。なお、コントロールは、ポリアミドを配合しなかった以外は実施例および比較例と同様の手順でペレットに造粒した。こうして得られたペレットを、８０℃で８時間乾燥させた後、下記の条件で結晶化温度Ｔｃ［℃］を評価した。なお、表１における括弧内の数値は分解点である。 [Examples 1 to 22, Comparative Examples 1 to 2 and control]
As a polyolefin resin, 200 g of homopolypropylene (MFR=8 g/10 min) was added to a phenolic antioxidant (tetrakis[methylene-3-(3′,5′-tert-butyl-4′-hydroxyphenyl)propionate]methane. ) 500 ppm, phosphorus-based antioxidant (tris(2,4-di-tert-butylphenyl)phosphite) 1000 ppm, calcium stearate salt 500 ppm, and the polyamides listed in Table 1 were blended to a concentration of 1000 ppm, and After blending for 3 minutes by blending, the mixture was charged into a twin-screw extruder (apparatus: Labo Plastomill Micro manufactured by Toyo Seiki Seisakusho Co., Ltd.), melt-kneaded at 230° C., and then granulated into pellets. As a control, pellets were granulated in the same procedure as in Examples and Comparative Examples except that polyamide was not added. The pellets thus obtained were dried at 80° C. for 8 hours, and then the crystallization temperature Tc [° C.] was evaluated under the following conditions. The values in parentheses in Table 1 are decomposition points.
＜結晶化温度Ｔｃ［℃］＞
　得られたペレットを用い、示差走査熱量測定器（装置；パーキエルマー社製ダイアモンド）を用いて結晶化温度（Ｔｃ）を測定した。測定方法は、室温から５０℃／ｍｉｎの速度で２３０℃まで昇温し、２０分間保持後、－１０℃／ｍｉｎで５０℃まで冷却した。得られたチャートにおいて、冷却過程における発熱ピークのピークトップ温度を結晶化温度（℃）とした。 <Crystallization temperature Tc [°C]>
Using the obtained pellets, the crystallization temperature (Tc) was measured using a differential scanning calorimeter (apparatus: Diamond manufactured by Perkiermer Co., Ltd.). As the measuring method, the temperature was raised from room temperature to 230° C. at a rate of 50° C./min, held for 20 minutes, and then cooled to 50° C. at −10° C./min. In the obtained chart, the peak top temperature of the exothermic peak in the cooling process was defined as the crystallization temperature (°C).
Figure JPOXMLDOC01-appb-T000011
Figure JPOXMLDOC01-appb-T000011
Figure JPOXMLDOC01-appb-I000012
Figure JPOXMLDOC01-appb-I000013
Figure JPOXMLDOC01-appb-I000014
Figure JPOXMLDOC01-appb-I000015
Figure JPOXMLDOC01-appb-I000016
Figure JPOXMLDOC01-appb-I000012
Figure JPOXMLDOC01-appb-I000013
Figure JPOXMLDOC01-appb-I000014
Figure JPOXMLDOC01-appb-I000015
Figure JPOXMLDOC01-appb-I000016
　以上より、本発明の核剤は、ポリオレフィン系樹脂に対して優れた核剤効果を発揮することが確認された。
  From the above, it was confirmed that the nucleating agent of the present invention exerts an excellent nucleating agent effect on the polyolefin resin.

Claims (8)

  1. 　ポリアミドを含むポリオレフィン系樹脂用核剤であって、
    　前記ポリアミドが、ジカルボン酸とジアミンとが脱水縮合した構造を有し、
    　前記ジカルボン酸および前記ジアミンのうち少なくとも一方が環構造を有することを特徴とするポリオレフィン系樹脂用核剤。     A nucleating agent for polyolefin-based resin containing polyamide,
    The polyamide has a structure in which dicarboxylic acid and diamine are dehydrated and condensed,
    At least one of the dicarboxylic acid and the diamine has a ring structure, which is a nucleating agent for a polyolefin resin.
  2. 　前記ジカルボン酸が、芳香族ジカルボン酸である請求項１記載のポリオレフィン系樹脂用核剤。 The nucleating agent for polyolefin resin according to claim 1, wherein the dicarboxylic acid is an aromatic dicarboxylic acid.
  3. 　前記ジアミンが、アルキレンジアミン、下記一般式（１）または（２）、
           
    Figure JPOXMLDOC01-appb-I000001
    で表される脂環式ジアミン（ここで、Ｚ２、Ｚ３、Ｚ４、Ｚ５、Ｚ６は、直接結合、炭素原子数１～１０のアルキレン基を表し、環に結合する水素原子は炭素原子数１～１０のアルキル基で置換されていてもよい。）、並びに、下記一般式（３）または（４）、
           
    Figure JPOXMLDOC01-appb-I000002
    で表される芳香族ジアミン（ここで、Ｚ７、Ｚ８、Ｚ９、Ｚ１０、Ｚ１１は、直接結合、炭素原子数１～１０のアルキレン基を表し、環に結合する水素原子は炭素原子数１～１０のアルキル基で置換されていてもよい。）からなる群から選ばれる少なくとも１種である請求項１または２記載のポリオレフィン系樹脂用核剤。     The diamine is an alkylenediamine, the following general formula (1) or (2),

    Figure JPOXMLDOC01-appb-I000001
    An alicyclic diamine represented by (wherein Z 2 , Z 3 , Z 4 , Z 5 and Z 6 represent a direct bond, an alkylene group having 1 to 10 carbon atoms, and a hydrogen atom bonded to the ring is Optionally substituted with an alkyl group having 1 to 10 carbon atoms), and the following general formula (3) or (4),

    Figure JPOXMLDOC01-appb-I000002
    (Wherein Z 7 , Z 8 , Z 9 , Z 10 and Z 11 represent a direct bond or an alkylene group having 1 to 10 carbon atoms, and the hydrogen atom bonded to the ring is a carbon atom). The nucleating agent for a polyolefin-based resin according to claim 1 or 2, which is at least one selected from the group consisting of (optionally substituted with an alkyl group having 1 to 10 atoms).
  4. 　前記ポリアミドの融点または分解点が２５０℃以上である請求項１～３のうちいずれか一項記載のポリオレフィン系樹脂用核剤。 The nucleating agent for polyolefin resin according to any one of claims 1 to 3, wherein the melting point or decomposition point of the polyamide is 250°C or higher.
  5. 　前記ポリアミドの重量平均分子量が、２０，０００以下である請求項１～４のうちいずれか一項記載のポリオレフィン系樹脂用核剤。 The nucleating agent for polyolefin resin according to any one of claims 1 to 4, wherein the weight average molecular weight of the polyamide is 20,000 or less.
  6. 　請求項１～５のうちいずれか一項記載のポリオレフィン系樹脂用核剤と、フェノール系酸化防止剤、リン系酸化防止剤、硫黄系酸化防止剤、その他の酸化防止剤、ヒンダードアミン化合物、紫外線吸収剤、その他の核剤、難燃剤、難燃助剤、滑剤、充填剤、ハイドロタルサイト類、帯電防止剤、顔料および染料からなる群から選ばれる１種以上と、を含有することを特徴とするポリオレフィン系樹脂用核剤組成物。 A nucleating agent for a polyolefin resin according to any one of claims 1 to 5, a phenolic antioxidant, a phosphorus antioxidant, a sulfur antioxidant, other antioxidants, a hindered amine compound, and ultraviolet absorption. Agent, other nucleating agent, flame retardant, flame retardant aid, lubricant, filler, hydrotalcite, antistatic agent, one or more selected from the group consisting of pigments and dyes, and A nucleating agent composition for a polyolefin resin.
  7. 　ポリオレフィン系樹脂と、請求項１～５のうちいずれか一項記載のポリオレフィン系樹脂用核剤と、を含み、
    　前記ポリオレフィン系樹脂１００質量部に対する前記ポリアミドの含有量が、０．００１～１０質量部であることを特徴とするポリオレフィン系樹脂組成物。     A polyolefin-based resin, and the polyolefin-based resin nucleating agent according to any one of claims 1 to 5,
    Content of the said polyamide with respect to 100 mass parts of said polyolefin resin is 0.001-10 mass parts, The polyolefin resin composition characterized by the above-mentioned.
  8. 　請求項７記載のポリオレフィン系樹脂組成物からなることを特徴とする成形品。 A molded article comprising the polyolefin resin composition according to claim 7.
PCT/JP2019/050920 2018-12-27 2019-12-25 Nucleating agent for polyolefin-based resin, nucleating agent composition for polyolefin-based resin containing same, polyolefin-based resin composition, and molded product thereof WO2020138205A1 (en)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2010024191A1 (en) * 2008-08-28 2010-03-04 株式会社Adeka Polyolefin resin composition
US20130283642A1 (en) * 2011-01-07 2013-10-31 Alois Pieber Boot with an element in shell form
JP2014111761A (en) * 2012-11-12 2014-06-19 Kuraray Co Ltd Polyamide resin composition
WO2014103054A1 (en) * 2012-12-28 2014-07-03 三菱瓦斯化学株式会社 Polyethylene-based structure

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2010024191A1 (en) * 2008-08-28 2010-03-04 株式会社Adeka Polyolefin resin composition
US20130283642A1 (en) * 2011-01-07 2013-10-31 Alois Pieber Boot with an element in shell form
JP2014111761A (en) * 2012-11-12 2014-06-19 Kuraray Co Ltd Polyamide resin composition
WO2014103054A1 (en) * 2012-12-28 2014-07-03 三菱瓦斯化学株式会社 Polyethylene-based structure

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