JP2019127496A - Nucleating agent, olefin resin composition containing the same, and molded article thereof - Google Patents

Abstract

To provide: a nucleating agent which enables production of a molded article having a good hue without necessity of adding pigment; an olefin resin composition containing the same; and a molded article thereof.SOLUTION: Provided is a metal salt of an alicyclic dicarboxylic acid, where a metal of the metal salt is a metal atom or a metal hydroxide. The metal salt of an alicyclic dicarboxylic acid is preferably a compound represented by the following general formula (1), where Min the general formula (1) represents Co, Cu, Ni, Mn, Pb, Nd(OH), Pr(OH), La(OH), Ce(OH), and Cr(OH).SELECTED DRAWING: None

Description

  TECHNICAL FIELD The present invention relates to a nucleating agent, an olefin resin composition containing the same, and a molded article thereof, specifically, a nucleating agent which does not require blending of a pigment and can produce a molded article having good color tone of the molded article. The present invention relates to an olefin resin composition containing the same and a molded article thereof.

  Thermoplastic resin is a building material, an automobile material, a material for household appliances and electronic materials, a fiber material, a material for packaging, a material for agriculture, a housing material for household appliances, life according to various physical properties such as molding processability and low specific gravity. It is widely used in various molded articles such as sundry goods, films, sheets and structural parts.

  The coloring of molded articles of thermoplastic resins is increasingly being unpainted for cost reduction and measures against volatile organic compounds (VOCs). As unpainted resin materials, pigments and brighteners and other colorants are blended with acrylic resins such as ABS resin and AES resin (acrylonitrile / ethylene / styrene resin or acrylonitrile / ethylene / propylene / diene / styrene resin). What has been known. However, acrylic resins have difficulty in impact resistance and chemical resistance, and therefore, applicable applications are limited.

  Therefore, non-coating with an olefin resin such as polyethylene, polypropylene, polybutene-1 and the like, which is excellent in molding processability, heat resistance, mechanical properties, low specific gravity, etc., is desired. However, since the olefin resin has a low crystallization speed after molding, the molding cycle property is low, and a large crystal is generated by the progress of crystallization after heat molding, and there is a drawback that transparency and strength are insufficient. . All of these drawbacks are derived from the crystallinity of the olefin resin, and if the crystallization temperature of the olefin resin can be raised to rapidly form fine crystals, the above problems can be solved. Are known.

  Examples of nucleating agents for olefin resins include sodium benzoate, aluminum salt of 4-tert-butylbenzoic acid, sodium adipate and disodium bicyclo [2.2.1] heptane-2,3-dicarboxylate Carboxylic acid metal salt of sodium bis (4-tert-butylphenyl) phosphate, sodium 2,2′-methylenebis (4,6-di-tert-butylphenyl) phosphate, lithium-2,2′-methylenebis (4 Cyclic organophosphate metal salts such as 6-di-tert-butylphenyl) phosphate, dibenzylidene sorbitol, bis (methyl benzylidene) sorbitol, bis (3,4- dimethyl benzylidene) sorbitol, bis (p-ethyl benzylidene) sorbitol , And bis ( A polyhydric alcohol derivative such as tilbenzylidene) sorbitol, N, N ′, N ″ -tris [2-methylcyclohexyl] -1,2,3-propanetricarboxamide, N, N ′, N ″ -tricyclohexyl-1, Compounds such as 3,5-benzenetricarboxamide, N, N'-dicyclohexyl naphthalene dicarboxamide, and amide compounds such as 1,3,5-tri (2,2-dimethylpropanamido) benzene are known.

  Under such circumstances, Patent Document 1 discloses a polypropylene composition in which a coloring composition containing a pigment, polypropylene, an organic phosphate nucleating agent and a calcium salt of a fatty acid is added to and dispersed in the polypropylene to be colored. Things have been proposed. Further, Patent Document 2 proposes a colored resin composition in which a colorant selected from iron oxide pigments, azo pigments and phthalocyanine pigments and a nucleating agent are mixed, and this is a warp after heat molding. Is shown to be small. Further, Patent Documents 3 and 4 propose using a salt of cyclohexanedicarboxylic acid and a metal cation as a nucleating agent additive for a crystalline thermoplastic polymer.

JP-A-8-081592 Unexamined-Japanese-Patent No. 11-349740 Patent No. 3958215 Patent No. 4046610

  However, since the pigment changes the color tone of the molded product by a small amount, adjustment of the blending amount is severe and stable production of the molded product having the same color tone is difficult. Moreover, when using a pigment and a nucleating agent together, in order to prevent a color nonuniformity, the process to which a pigment is disperse | distributed to a nucleating agent was needed, and there existed a fault which an operation | work becomes complicated.

  Therefore, an object of the present invention is to provide a nucleating agent capable of producing a molded article having good color tone without requiring blending of a pigment, an olefin resin composition containing the same, and a molded article thereof.

  As a result of intensive studies to solve the above-mentioned problems, the present inventors have used an olefin resin composition having various color tones by containing a specific compound with respect to the olefin resin, and the same. The present inventors have found that a molded article can be provided, and have completed the present invention.

  That is, the nucleating agent of the present invention is a metal salt of alicyclic dicarboxylic acid, and the metal of the metal salt is a metal atom or a metal hydroxide.

（一般式（１）中のＭ^１は、Ｃｏ、Ｃｕ、Ｎｉ、Ｍｎ、Ｐｂ、Ｎｄ（ＯＨ）、Ｐｒ（ＯＨ）、Ｌａ（ＯＨ）、Ｃｅ（ＯＨ）、Ｃｒ（ＯＨ）を表す。）で表される化合物であることが好ましい。 In the nucleating agent of the present invention, the metal salt of the alicyclic dicarboxylic acid is represented by the following general formula (1),

(M ¹ in the general formula (1) represents Co, Cu, Ni, Mn, Pb, Nd (OH), Pr (OH), La (OH), Ce (OH), Cr (OH).) It is preferable that it is a compound represented by these.

  The olefin resin composition of the present invention is characterized in that the nucleating agent of the present invention is contained in an amount of 0.001 to 10 parts by mass with respect to 100 parts by mass of the olefin resin.

  The molded article of the present invention is characterized by using the olefin resin composition of the present invention.

  According to the present invention, it is possible to provide a nucleating agent capable of producing a molded article having good color tone without the need for blending of a pigment, an olefin resin composition containing the same, and a molded article thereof.

Hereinafter, embodiments of the present invention will be described in detail.
First, the nucleating agent of the present invention will be described. The nucleating agent of the present invention is a metal salt of alicyclic dicarboxylic acid, and the metal of the metal salt is a metal atom or a metal hydroxide. And the nucleating agent of this invention can improve physical properties with respect to olefin resin, and can manufacture the molded object of a color tone without a color nonuniformity.

  As a metal atom which concerns on the nucleating agent of this invention, a typical metal element, a transition metal element, etc. are mentioned, The metal element contained in periodic table group 1-13 is mentioned. Moreover, as a metal hydroxide which concerns on the nucleating agent of this invention, the hydroxide of said metal atom is mentioned.

で表される化合物が好ましい。ここで、一般式（１）中のＭ^１は、Ｃｏ、Ｃｕ、Ｎｉ、Ｍｎ、Ｐｂ、Ｎｄ（ＯＨ）、Ｐｒ（ＯＨ）、Ｌａ（ＯＨ）、Ｃｅ（ＯＨ）、Ｃｒ（ＯＨ）を表す。 In the nucleating agent of the present invention, as the metal salt of the alicyclic dicarboxylic acid, the following general formula (1),

The compound represented by these is preferable. Here, M ¹ in the general formula (1) represents Co, Cu, Ni, Mn, Pb, Nd (OH), Pr (OH), La (OH), Ce (OH), or Cr (OH). .

  As a method for producing the compound represented by the general formula (1), 1,2-cyclohexanedicarboxylic acid is easily substituted with a halide or an alkali metal and then easily neutralized with a desired metal atom. It can be manufactured.

  Next, the olefin resin composition of the present invention will be described. Examples of the olefin resin used in the olefin resin composition of the present invention include low density polyethylene (LDPE), linear low density polyethylene (L-LDPE), high density polyethylene (HDPE), isotactic polypropylene, and Shinji. Α such as tactic polypropylene, hemiisotactic polypropylene, cycloolefin polymer, stereoblock polypropylene, poly-3-methyl-1-butene, poly-3-methyl-1-pentene, poly-4-methyl-1-pentene -Olefin polymer, ethylene / propylene block or random copolymer, impact copolymer polypropylene, ethylene-methyl methacrylate copolymer, ethylene-methyl acrylate copolymer, ethylene-ethyl acrylate copolymer, ethylene Butyl acrylate copolymer, ethylene - vinyl acetate copolymer, ethylene - alpha-olefin copolymer such as polyvinyl alcohol resin (EVOH). These may be an elastomer. In the olefin resin composition of the present invention, these two or more kinds may be blended and used, or a block copolymer may be formed and used as a block polymer type, and the resin is alloyed. It is also good. In addition, chlorinated products of these olefin resins may be used.

  As an elastomer of an olefin resin, an elastomer obtained by blending these using polyolefin such as polypropylene or polyethylene as a hard segment and rubber such as ethylene-propylene rubber as a soft segment, or an elastomer obtained by dynamic crosslinking Can be mentioned.

  The hard segment includes, for example, at least one selected from polypropylene homopolymers, polypropylene block copolymers, polypropylene random copolymers and the like.

  Examples of the soft segment include ethylene-propylene copolymer (EPM), ethylene-propylene-diene copolymer (EPDM), ethylene-vinyl acetate copolymer (EVA), and vinyl acetate homopolymer. You may blend and use these 2 or more types.

  The olefin resin production method includes Ziegler catalyst, Ziegler-Natta catalyst, metallocene catalyst and other various polymerization catalysts as promoters, catalyst carriers, chain transfer agents, gas phase polymerization, solution polymerization, emulsion polymerization, In various polymerization methods such as bulk polymerization, various polymerization conditions such as temperature, pressure, concentration, flow rate, removal of catalyst residue and the like can be appropriately selected so that a resin having desired physical properties can be obtained. Number average molecular weight of olefin resin, weight average molecular weight, molecular weight distribution, melt flow rate, melting point, melting peak temperature, stereoregularity such as isotactic, syndiotactic, presence or absence of branching, specific gravity, to various solvents The ratio of dissolved components, haze, gloss, impact strength, flexural modulus, olsen stiffness, other characteristics, and whether each characteristic value satisfies a specific formula can be appropriately selected according to the desired characteristics. .

  In the olefin resin composition of the present invention, the nucleating agent of the present invention is in the range of 0.001 to 10 parts by mass with respect to 100 parts by mass of the olefin resin. If the compounding amount is less than 0.001 part by mass, the nucleating agent effect may not be obtained, and if it exceeds 10 parts by mass, dispersion in the olefin resin becomes difficult and the physical properties and appearance of the molded product become It may be adversely affected.

  In the olefin resin composition of the present invention, any known resin additive (for example, a phenol type antioxidant, a phosphorus type antioxidant, a thioether type antioxidant, an ultraviolet ray, etc.) as long as the effects of the present invention are not significantly impaired. Absorbers, hindered amine compounds, nucleating agents, flame retardants, flame retardant aids, lubricants, fillers, hydrotalcites, antistatic agents, pigments, fluorescent whitening agents, dyes, and the like).

  Examples of the phenolic antioxidant include 2,6-di-tert-butyl-4-ethylphenol, 2-tert-butyl-4,6-dimethylphenol, styrenated phenol, 2,2′-methylenebis (4- Ethyl-6-tert-butylphenol), 2,2'-thiobis- (6-tert-butyl-4-methylphenol), 2,2'-thiodiethylenebis [3- (3,5-di-tert-butyl) -4-hydroxyphenyl) propionate], 2-methyl-4,6-bis (octylsulfanylmethyl) phenol, 2,2'-isobutylidenebis (4,6-dimethylphenol), isooctyl-3- (3 5-di-tert-butyl-4-hydroxyphenyl) propionate, N, N'-hexane-1,6-diylbis [3- ( 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 Polymer of tert-butyl-4-hydroxy-benzenepropanoic acid and C13-15 alkyl, 2,5-di-tert-amylhydroquinone, hindered phenol (trade name “AO.OH. 98 "), 2,2'-methylenebis [6- (1-methylcyclohexyl) -p-cresol], 2-ter. -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-butyl benz [D, f] [1,3,2] -dioxaphospobin, hexamethylene bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, bis [monoethyl (3,5) -Di-tert-butyl-4-hydroxybenzyl) phosphonate] calcium salt, 5,7-bis (1,1-dimethylethyl) -3-hydroxy-2 ( The reaction product of 3H) -benzofuranone with o-xylene, 2,6-di-tert-butyl-4- (4,6-bis (octylthio) -1,3,5-triazin-2-ylamino) phenol, DL-a-tocopherol (vitamin E), 2,6-bis (α-methylbenzyl) -4-methylphenol, bis [3,3-bis- (4′-hydroxy-3′-tert-butyl-phenyl) ) 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-bu 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-Bis (4-hydroxy-3-tert-butylphenyl) butyric acid] glycol ester, 4,4'-butylidenebis (2,6-di-tert-butylphenol), 4,4'-butylidenebis (6 -Tert-butyl-3-methylphenol), 2,2'-ethylidenebis (4,6-di-tert-butyl) (Tylphenol), 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-tributyl-4′-hydroxyphenyl) propionate] methane, 2-tert-butyl-4-methyl-6- (2-acryloyloxy-3-tert-butyl- 5-Methylbenzyl) phenol, 3,9-bis [2- (3-tert-butyl-4-hydroxy-5-methylhydrocinnamoyloxy) -1,1-dimethylethyl] -2,4,8,10 -Tetraoxaspiro [5.5] undecane, 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-hydroxypheny Propionic acid amide, myristyl 3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid amide, lauryl 3- (3,5-di-tert-butyl-4-hydroxyphenyl) Examples include 3- (3,5-dialkyl-4-hydroxyphenyl) propionic acid derivatives such as propionic acid amide.

  The compounding quantity in the case of mix | blending a phenolic antioxidant is 0.001-5 mass parts with respect to 100 mass parts of olefin resin, More preferably, it is 0.03-3 mass parts.

  The phosphorus-based antioxidants include, for example, triphenyl phosphite, diisooctyl phosphite, heptakis (dipropylene glycol) triphosphite, triisodecyl phosphite, diphenyl isooctyl phosphite, diisooctyl phenyl phosphite, diphenyl tri 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, diphenyl decyl phosphite, dinonylphenyl bis (nonylphenyl) phosphite, poly (dipropylene group) Cole) phenyl phosphite, tetraphenyl dipropyl glycol diphosphite, trisnonyl phenyl 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, Octyl diphenyl phosphite, di (decyl) monophenyl phosphite, mixture of distearyl pentaerythritol and calcium stearate, alkyl (C10) bisphenol A phosphite, tetraphenyl tetra (tridecyl) penta erythritol tetra phosphite Bis (2,4-di-tert-butyl-6-methylphenyl) ethyl phosphite, tetra (tridecyl) isopropylidenediphenol diphosphite, tetra (tridecyl) -4,4′-n-butylidenebis (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) biphenylenediphosphonite, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, (1-methyl-1-propenyl-3-ylidene) tris (1 1,1-Dimethylethyl) -5-methyl-4,1-phenylene) hexatrideci Sulfite, 2,2'-methylenebis (4,6-di-tert-butylphenyl) -2-ethylhexyl phosphite, 2,2'-methylenebis (4,6-di-tert-butylphenyl) -octadecyl phosphite, 2,2′-ethylidenebis (4,6-di-tert-butylphenyl) fluorophosphite, 4,4′-butylidenebis (3-methyl-6-tert-butylphenylditridecyl) phosphite, tris (2- [(2,4,8,10-tetrakis-tert-butyldibenzo [d, f] [1,3,2] dioxaphosphin-6-yl) oxy] ethyl) amine, 3,9-bis ( 4-nonylphenoxy) -2,4,8,10-tetraoxa-3,9-diphosphisspiro [5,5] undecane, 2,4,6-tri tert-butylphenyl-2-butyl-2-ethyl-1,3-propanediol phosphite, poly 4,4′-isopropylidenediphenol 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-di Mill phenyl) pentaerythritol diphosphite, and the like.

  The compounding quantity in the case of mix | blending a phosphorus antioxidant is 0.001-10 mass parts with respect to 100 mass parts of olefin resin, More preferably, it is 0.01-0.5 mass part.

  Thioether-based antioxidants are, for example, 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 Can be mentioned.

  The compounding quantity in the case of mix | blending a thioether type | system | group antioxidant is 0.001-10 mass parts with respect to 100 mass parts of olefin resin, More preferably, it is 0.01-0.5 mass part.

  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), 2- (2-hydroxy-3-) polyethylene glycol ester of ert-butyl-5-carboxyphenyl) benzotriazole, 2- [2-hydroxy-3- (2-acryloyloxyethyl) -5-methylphenyl] benzotriazole, 2- [2-hydroxy-3- (2-methacryloyloxyethyl) -5-tert-butylphenyl] benzotriazole, 2- [2-hydroxy-3- (2-methacryloyloxyethyl) -5-tert-octylphenyl] benzotriazole, 2- [2- Hydroxy-3- (2-methacryloyloxyethyl) -5-tert-butylphenyl] -5-chlorobenzotriazole, 2- [2-hydroxy-5- (2-methacryloyloxyethyl) phenyl] benzotriazole, 2- [ 2-hydroxy-3-ter -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-chlorobenzotriazole, 2- [2-hydroxy-4- (2-methacryloyloxymethyl) phenyl] benzotriazole, 2- [2 2- (2-hydroxyphenyl) such as 2-hydroxy-4- (3-methacryloyloxy-2-hydroxypropyl) phenyl] benzotriazole, 2- [2-hydroxy-4- (3-methacryloyloxypropyl) phenyl] benzotriazole ) Benzotriazoles; Rusalicylate, 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-4) Benzoates such as -hydroxy) benzoate, octadecyl (3,5-di-tert-butyl-4-hydroxy) benzoate, behenyl (3,5-di-tert-butyl-4-hydroxy) benzoate; 2-ethyl-2 '-Ethoxy oxanilide, 2-ethoxy-4'-dodecyl oxi Substituted oxanilides such as nilide; cyanoacrylates such as ethyl-.alpha.-cyano-.beta.,. Beta.-diphenylacrylate, methyl-2-cyano-3-methyl-3- (p-methoxyphenyl) acrylate; 2- (2-) Hydroxy-4-octoxyphenyl) -4,6-bis (2,4-di-tert-butylphenyl) -s-triazine, 2- (2-hydroxy-4-methoxyphenyl) -4,6-diphenyl- Triaryltriazines such as s-triazine and 2- (2-hydroxy-4-propoxy-5-methylphenyl) -4,6-bis (2,4-di-tert-butylphenyl) -s-triazine; Metal salts or metal chelates, particularly nickel, chromium salts, or chelates.

  The compounding quantity in the case of mix | blending a ultraviolet absorber is 0.001-10 mass parts with respect to 100 mass parts of olefin resin, More preferably, it is 0.01-0.5 mass part.

  The hindered amine compounds are, for example, 2,2,6,6-tetramethyl-4-piperidyl stearate, 1,2,2,6,6-pentamethyl-4-piperidyl stearate, 2,2,6,6-tetra Methyl-4-piperidylbenzoate, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, tetrakis (2,2,6,6-tetramethyl-4-piperidyl) -1,2,3, 4-butanetetracarboxylate, tetrakis (1,2,2,6,6-pentamethyl-4-piperidyl) -1,2,3,4-butanetetracarboxylate, bis (2,2,6,6-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-butanetetracarboxylate, 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-piperidinol / 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-tetra Methyl-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, , 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-tetra Examples thereof include methyl) piperidyl} decantionate, bis {4- (2,2,6,6-tetramethyl-1-undecyloxy) piperidyl) carbonate and the like.

  The compounding quantity in the case of mix | blending a hindered amine compound is 0.001-10 mass parts with respect to 100 mass parts of olefin resin, More preferably, it is 0.01-0.5 mass part.

  Examples of flame retardants include 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, manufactured by ADEKA Co., Ltd., trade name “ADEKA STAB FP-500”, “ADEKA STAB FP-600”, “ADEKA STAB FP- Phosphonates such as aromatic phosphoric acid ester of “800”, divinyl phenylphosphonate, diallyl phenylphosphonate, and phenylphosphonic acid (1-butenyl), phenyl diphenylphosphinate, diphenyl phosphite Phosphazene esters such as methyl acid, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide derivatives, phosphazene compounds such as bis (2-allylphenoxy) phosphazene, dicresyl phosphazene, melamine phosphate, Phosphorus flame retardants such as melamine pyrophosphate, melamine polyphosphate, melam polyphosphate, ammonium polyphosphate, piperazine phosphate, piperazine pyrophosphate, piperazine polyphosphate, phosphorus-containing vinyl benzyl compound and red phosphorus, magnesium hydroxide, aluminum hydroxide Metal hydroxide such as brominated bisphenol A type epoxy resin, brominated phenol novolac type epoxy resin, hexabromobenzene, pentabromotoluene, ethylene bis (pentabromophenyl), ethylene bis tetrabromide Phthalimide, 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, tribromophenylmaleimide, tribromophenyl acrylate, tribromophenyl methacrylate, tetrabromobisphenol A type dimethacrylate, pentabromobenzyl acrylate, and brominated Brominated flame retardants, such as styrene, etc. can be mentioned. These flame retardants are preferably used in combination with anti-drip agents such as fluorocarbon resins and the like, and flame retardant aids such as polyhydric alcohols and hydrotalcites.

  The compounding quantity in the case of mix | blending a flame retardant is 1-100 mass parts with respect to 100 mass parts of olefin resin, More preferably, it is 10-70 mass parts.

  A lubricant is added for the purpose of imparting lubricity to the surface of the molded body to enhance the scratch resistance. As the lubricant, for example, 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, monoglyceride stearate, sorbitan monopalmitate tartrate, Examples include sorbitan monostearate, mannitol, stearic acid, hydrogenated castor oil, stearic acid amide, oleic acid amide, ethylene bis stearic acid amide and the like. One of these may be used alone, or two or more may be used in combination.

  The blending amount in the case of blending the lubricant is 0.01 to 2 parts by mass, more preferably 0.03 to 0.5 parts by mass with respect to 100 parts by mass of the olefin resin.

  Hydrotalcite is a complex salt compound composed of magnesium, aluminum, hydroxyl group, carbonate group and any crystal water known as a natural product or synthetic product, and a part of magnesium or aluminum is replaced with other metals such as alkali metals and zinc. And those in which a hydroxyl group or a carbonic acid group is substituted with another anion group. Specifically, for example, the metal of the hydrotalcite represented by the following general formula (2) is substituted with an alkali metal The thing is mentioned. In addition, as the Al—Li hydrotalcite, a compound represented by the following general formula (3) can also be used.

ここで、一般式（２）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。

Here, in general formula (2), 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.

ここで、一般式（３）中、Ａ^ｑ−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、前記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。

Here, in general formula (3), A ^q− represents a q-valent anion, and p represents 0 or a positive number. The carbonate anion in the hydrotalcite may be partially substituted with another anion.

  Hydrotalcite may be obtained by dehydrating crystallization water, higher fatty acid such as stearic acid, higher fatty acid metal salt such as alkali metal oleate, organic sulfonic acid metal such as alkali metal dodecylbenzenesulfonate. It may be coated with a salt, a higher fatty acid amide, a higher fatty acid ester or a wax.

  Hydrotalcites may be natural products or synthetic products. Examples of these synthesis methods include Japanese Patent Publication No. 46-2280, Japanese Patent Publication No. 50-30039, Japanese Patent Publication No. 51-29129, Japanese Patent Publication No. 3-36839, Japanese Patent Publication No. 61-174270, Japanese Patent Laid-Open No. Hei. The well-known method described in the 5-179052 grade | etc., Is mentioned. Further, the hydrotalcites can be used without being limited to the crystal structure, crystal particles and the like.

  The compounding quantity in the case of mix | blending hydrotalcites is 0.001-5 mass parts with respect to 100 mass parts of olefin resin, More preferably, it is 0.01-3 mass parts.

  Examples of the antistatic agent include cationic antistatic agents such as fatty acid quaternary ammonium ion salts and polyamine quaternary salts; higher alcohol phosphoric acid ester salts, higher alcohol EO adducts, polyethylene glycol fatty acid esters, anionic alkyl sulfones. Anionic antistatic agents such as acid salt, higher alcohol sulfate ester salt, higher alcohol ethylene oxide adduct sulfate ester salt, higher alcohol ethylene oxide adduct phosphate ester salt; polyhydric alcohol fatty acid ester, polyglycol phosphate ester, polyoxyethylene Nonionic antistatic agents such as alkyl allyl ethers; amphoteric antistatic agents such as amphoteric alkylbetaines such as alkyldimethylaminoacetic acid betaine and imidazoline type amphoteric activators. Such antistatic agents may be used alone, or two or more kinds of antistatic agents may be used in combination.

  The compounding quantity in the case of mix | blending an antistatic agent is 0.03-2 mass parts with respect to 100 mass parts of olefin resin, More preferably, it is 0.1-0.8 mass part.

  A commercially available pigment can also be used as the 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, 171, 171, 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, 09, 110, 113, 114, 117, 120, 125, 126, 127, 129, 137, 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, Pigment Violet 1, 15, 19, 23, 27, 29, 30, 32, 37, 40, 50 and the like.

  A fluorescent whitening agent is a compound that promotes the whiteness and bluishness of a molded article by a fluorescent action that absorbs sunlight and artificial ultraviolet rays, and radiates them by converting them into visible light of purple to blue. As a fluorescent whitening agent, a stiloxazole compound C.I. I. Fluorescent Brightner 184; coumarin compound C.I. I. Fluorescent Brightner 52; diaminostilbene disulfonic acid compound C.I. I. Fluorescent Brightner 24, 85, 71 etc. are mentioned.

  The compounding quantity in the case of using a fluorescent brightening agent is 0.00001-0.1 mass part with respect to 100 mass parts of olefin resin, More preferably, it is 0.00005-0.05 mass part.

  As dyes, azo dyes, anthraquinone dyes, indigoid dyes, triarylmethane dyes, xanthene dyes, alizarin dyes, acridine dyes, stilbene dyes, thiazole dyes, naphthol dyes, quinoline dyes, nitro dyes, indamine dyes, oxazine dyes, phthalocyanine dyes And dyes such as cyanine dyes, and the like, and these may be used as a mixture of two or more.

  The molded product of the present invention can be molded from the olefin resin composition of the present invention using a known molding method. For example, a molded article can be obtained using an injection molding method, an extrusion molding method, a blow molding method, a vacuum molding method, an inflation molding method, a calendar molding method, a slush molding method, a dip molding method, a foam molding method or the like.

  Applications of the olefin-based resin composition of the present invention include automobile materials such as bumpers, dashboards and instrument panels, housing applications such as refrigerators, washing machines and vacuum cleaners, household goods such as tableware, buckets and bathing goods, and miscellaneous goods such as toys. Examples include molded products such as storage and storage containers for products, tanks, and molded products such as films and fibers.

  Hereinafter, the present invention will be more specifically described by way of examples, but the present invention is not limited at all by the following examples and the like.

[Examples 1 to 14, Comparative Example 1]
Phenolic antioxidant: tetrakis [methylene-3- (3 ′, 5′-di-tert-butyl-4′-hydroxyphenyl) propionate] methane relative to 100 parts by mass of homopolypropylene (melt flow rate: 8 g / 10 min) 0.05 parts by mass, phosphorus antioxidant: 0.1 parts by mass of tris (2,4-ditert-butylphenyl) phosphite, 0.05 parts by mass of calcium stearate, and the compounds shown in Table 1 After mixing at 1000 rpm × 1 min with a Henschel mixer, granulation was performed at an extrusion temperature of 200 ° C. using a twin-screw extruder. The granulated pellets were dried at 60 ° C. for 8 hours and evaluated as follows.

<Crystallization temperature (Tc)>
The crystallization temperature (Tc) was measured using the said pellet using the differential scanning calorimeter (made by Diamond Perkin-Elmer company). In the chart obtained by heating from room temperature to 230 ° C. at a rate of 50 ° C./min, holding for 10 minutes, and then cooling to 50 ° C. at a rate of −10 ° C./min, the endothermic reaction has the peak top The temperature at which the

<Flexural modulus>
Using the above pellets, using an injection molding machine (EC 100-2A; made by Toshiba Machine Co., Ltd.), injection molding is carried out under the conditions of a mold temperature of 50 ° C and a resin temperature of 200 ° C to create test pieces of dimensions 80mm × 10mm × 4mm. After standing for 48 hours or more with a thermostat at 23 ° C., the flexural modulus (MPa) was measured according to ISO 178 using a bending tester “AG-IS” manufactured by Shimadzu Corporation.

<Load deflection temperature (HDT)>
Using the above pellets, using an injection molding machine (EC 100-2A; made by Toshiba Machine Co., Ltd.), injection molding is carried out under the conditions of a mold temperature of 50 ° C and a resin temperature of 200 ° C to create test pieces of dimensions 80mm × 10mm × 4mm. After standing for at least 48 hours in a thermostat at 23 ° C., HDT (° C.) was measured in accordance with ISO 75 (load 0.45 MPa).

<Y. I. , A ^* value, b ^* value>
Using the above pellets, using an injection molding machine (EC100-2A; made by Toshiba Machine Co., Ltd.), injection molding is performed under the conditions of a mold temperature of 50 ° C and a resin temperature of 230 ° C to create a test piece of dimensions 60mm x 60mm x 2mm The sample was allowed to stand for 48 hours or longer in a thermostat at 23 ° C., and then the spectrophotometer (Color-Eye 7000A: manufactured by X-rite) was used to measure the Y.O. I. , A ^* value, b ^* value were measured.

<Haze>
Using the above pellets, using an injection molding machine (EC100-2A; made by Toshiba Machine Co., Ltd.), injection molding is performed under the conditions of a mold temperature of 50 ° C and a resin temperature of 200 ° C to create test pieces of dimensions 100mm x 100mm x 2mm. After standing for at least 48 hours in a thermostat at 23 ° C., Haze (%) was measured in accordance with ISO 14782 with Haze Guard 2 (manufactured by BYK Additives & Instruments).

<MD / TD>
Resin temperature 200 ° C, mold temperature 50 ° C, mold shape 60 mm (MD direction) x 60 mm (TD direction) x 2 mm (thickness) using the above pellets by an injection molding machine (EC 100-2A; manufactured by Toshiba Machine Co., Ltd.) ) Was injection molded to prepare a test piece. Immediately after injection molding, the test piece was allowed to stand for 48 hours or more with a thermostat at 23 ° C., and then the dimensions in the MD direction (MD1) and the dimensions in the TD direction (TD1) of the test pieces were measured. The MD shrinkage (%) and the TD shrinkage (%) of the test pieces were determined according to the following formulas.
ΔMD (%) = (60−MD1) / 60 × 100
ΔTD (%) = (60−TD1) / 60 × 100
The obtained ΔMD and ΔTD were substituted into the following equation to calculate MD / TD (shrinkage factor anisotropy).

  When the shrinkage rate anisotropy is large, the degree of deformation due to warping in molding increases. In general, the closer the shrinkage anisotropy is to 1, the less these problems are encountered.

<Appearance>
When the test piece used in the Haze test was visually observed and color unevenness was confirmed on the test piece, the color tone of the test piece of Comparative Example 1 could be changed without color unevenness. If it was, it was evaluated as “◯”.

※１：一般式（１）中のＭ^１
※２：結晶化温度

* 1: M ¹ in general formula (1)
※ 2: Crystallization temperature

Compared with the case where the nucleating agent of Comparative Example 1 was not blended, the molded product of the present invention had a nucleating agent effect, and it was confirmed that the molded product was vividly colored without color unevenness. In particular, a molded product containing a compound in which M ¹ in the general formula (1) is Co, Cu, Cr (OH), Pb, Nd (OH), Pr (OH), or La (OH) is anisotropic. A molded article having a low shrinkage ratio was obtained.

Claims (4)

  A metal salt of an alicyclic dicarboxylic acid, wherein the metal of the metal salt is a metal atom or a metal hydroxide. The metal salt of the alicyclic dicarboxylic acid is represented by the following general formula (1),

(M ¹ in general formula (1) represents Co, Cu, Ni, Mn, Pb, Nd (OH), Pr (OH), La (OH), Ce (OH), Cr (OH). The nucleating agent according to claim 1, which is a compound represented by the formula:   An olefin resin composition comprising 0.001 to 10 parts by mass of the nucleating agent according to claim 1 or 2 with respect to 100 parts by mass of the olefin resin. A molded product comprising the olefin resin composition according to claim 3.