JP2019044063A - Crystallization retarder, polyolefin resin composition containing the same, and molding thereof - Google Patents

Abstract

To provide: a crystallization retarder capable of inhibiting crystallization of a polyolefin resin without deteriorating physical properties thereof; a polyolefin resin composition containing the same; and a molding thereof.SOLUTION: The crystallization retarder comprises a compound represented by the general formula (1) in the figure, where Mrepresents Mg, Ba, Sr or Co. The polyolefin resin composition contains a polyolefin resin and the crystallization retarder added thereto, and preferably contains 0.01 to 10 pts.mass of the compound represented by the general formula (1) based on 100 pts.mass of the polyolefin resin.SELECTED DRAWING: None

Description

  The present invention relates to a crystallization retarder, a polyolefin resin composition containing the same, and a molded article thereof, and more specifically, a crystallization retarder capable of suppressing crystallization without impairing the physical properties of the polyolefin resin, The present invention relates to a polyolefin resin composition containing the same (hereinafter, also simply referred to as "resin composition") and a molded article thereof.

  Polyolefin resins have high transparency and are excellent in physical properties such as rigidity, moldability, solvent resistance, impact strength and the like, and are inexpensive and therefore are used in a wide range of applications. The addition of a nucleating agent promotes the crystallization action of the polyolefin resin, and can improve the physical properties of a molded article obtained by molding the polyolefin resin composition.

  On the other hand, in the case of producing a laminate having a fiber material, a film material, or a wood / fiber material as a base, it is necessary to suppress the crystallization of the polyolefin resin. As a method of suppressing the crystallization of the polyolefin resin, impurities such as a polymerization catalyst, by-products in olefin polymerization, thermal decomposition products, etc. are removed to form a uniform resin, or low molecular compounds such as oligomers are blended and non-polymerized. It is known that the crystallinity of the polyolefin resin is reduced by increasing the crystal part.

  For example, as a crystallization retarder of a polyolefin resin, Patent Document 1 proposes a silicone oil, and Patent Document 2 proposes an amorphous olefin resin and a low crystalline olefin resin. In addition, Non-Patent Document 1 discloses that zinc hettate is effective in delaying the crystallization of isotactic polypropylene.

JP-A-9-176407 WO 2016/104789

“The Crystallization Behavior of Isotactic Polypropylene Induced by a Novel Antinucleating Agent and Its Inhibition Mechanism of Nucleation” Industrial & Engineering Chemistry Research (2015), 54 (31), 7650-7657

  However, when a silicone oil, an amorphous olefin resin, or a low crystalline olefin resin is blended, there arises a problem that the physical properties of the base resin are impaired. In addition, the crystallization delay effect by zinc hettate is insufficient, and further improvement has been desired.

  Therefore, an object of the present invention is to provide a crystallization retarder capable of suppressing the crystallization of the polyolefin resin without impairing the physical properties, a polyolefin resin composition containing the same, and a molded article thereof. .

  MEANS TO SOLVE THE PROBLEM As a result of repeating earnestly examining in order to solve the said subject, the present inventors discover that the compound which has a predetermined | prescribed structure can suppress crystallization, without impairing the physical property of polyolefin resin, and this We came to complete the invention.

（式（１）中、Ｍ^１は、Ｍｇ、Ｂａ、Ｓｒ、またはＣｏを表す。）で表される化合物からなることを特徴とするものである。 That is, the crystallization retarder of the present invention has the following general formula (1),

(Wherein, in the formula (1), M ¹ represents Mg, Ba, Sr, or Co).

  The polyolefin resin composition of the present invention is characterized by containing the crystallization retarder of the present invention with respect to the polyolefin resin.

  In the polyolefin resin composition of this invention, it is preferable to contain 0.01-10 mass parts of said crystallization retarders with respect to 100 mass parts of polyolefin resin.

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

  ADVANTAGE OF THE INVENTION According to this invention, the crystallization retarder which can suppress the crystallization, and the polyolefin resin composition containing this, and its molded article can be provided, without impairing the physical property of polyolefin resin.

で表される化合物からなる。ここで、式中のＭ^１は、マグネシウム（Ｍｇ）、バリウム（Ｂａ）、ストロンチウム（Ｓｒ）、またはコバルト（Ｃｏ）を表す。また、「結晶化遅延剤」とはポリオレフィン系樹脂に配合することにより、ポリオレフィン系樹脂の結晶化温度を低下させる物質をいう。上記一般式（１）で表される化合物の具体例として、下記の化合物が挙げられる。 Hereinafter, embodiments of the present invention will be described in detail. The crystallization retarder of the present invention has the following general formula (1),

It consists of a compound represented by these. Here, M ¹ in the formula represents magnesium (Mg), barium (Ba), strontium (Sr), or cobalt (Co). The term "crystallization retardation agent" refers to a substance that lowers the crystallization temperature of a polyolefin resin by blending it with the polyolefin resin. The following compounds may be mentioned as specific examples of the compound represented by the above general formula (1).

  The polyolefin resin composition of the present invention contains a crystallization retarder represented by the general formula (1) with respect to the polyolefin resin. 0.01-10 mass parts is preferable with respect to 100 mass parts of polyolefin resin, and, as for the compounding quantity of the crystallization retarder represented by General formula (1), 0.05-5 mass parts is more preferable, and 0 Further preferred is from 1 to 1.0 parts by mass. If the amount is less than 0.01 parts by mass, the effects of the present invention may not be obtained. If the amount is more than 10 parts by mass, bleed out from the molded article may occur. Moreover, when there are many crystallization retarders, this will become a non-uniform | heterogenous nucleus and crystallization of polyolefin resin may be accelerated | stimulated.

  Examples of polyolefin resins used in the resin composition of the present invention include low density polyethylene (LDPE), linear low density polyethylene (L-LDPE), high density polyethylene (HDPE), isotactic polypropylene, syndiotactic polypropylene Such as tic polypropylene, hemiisotactic polypropylene, cycloolefin polymer, stereoblock polypropylene, poly-3-methyl-1-butene, poly-3-methyl-1-pentene and 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- Chill acrylate copolymer, ethylene - vinyl acetate copolymer, ethylene - alpha-olefin copolymer such as polyvinyl alcohol resin (EVOH). These may be an elastomer. In the resin composition of the present invention, these two or more kinds may be blended and used, a block copolymer may be formed and used as a block polymer type, and the resin may be alloyed. . Moreover, chlorinated compounds of these polyolefin resins may be used.

  Elastomers obtained by blending polyolefins such as polypropylene and polyethylene as hard segments and rubbers such as ethylene-propylene rubber as soft segments as elastomers of polyolefin resins, or elastomers obtained by dynamic crosslinking Can be mentioned.

  Examples of the hard segment include 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), vinyl acetate homopolymer and the like. You may blend and use these 2 or more types.

  The method of producing the polyolefin resin includes Ziegler catalyst, Ziegler-Natta catalyst, metallocene catalyst and other various polymerization catalysts as cocatalyst, catalyst carrier, chain transfer agent, and also gas phase polymerization, solution polymerization, emulsion polymerization, bulk In various polymerization methods such as polymerization, resins having physical properties suitable for packaging materials such as temperature, pressure, concentration, flow rate, removal of catalyst residues and the like, and physical properties suitable for molding processing of packaging materials Is appropriately selected and manufactured. Number average molecular weight, weight average molecular weight, molecular weight distribution, melt flow rate, melting point, melting peak temperature, stereoregularity such as isotactic, syndiotactic, etc., presence or absence of branching, specific gravity, to various solvents of polyolefin resin The ratio of dissolved components, Haze, gloss, impact strength, flexural modulus, Olsen stiffness, other characteristics, and whether each characteristic value satisfies a specific equation can be appropriately selected according to the desired characteristics. .

  In the resin composition of the present invention, any known resin additive (for example, a phenolic antioxidant, a phosphorus antioxidant, a thioether antioxidant, a UV absorber) as long as the effects of the present invention are not significantly impaired Hindered amine compounds, flame retardants, flame retardant aids, lubricants, fillers, hydrotalcites, antistatic agents, pigments, optical brighteners, dyes, etc.) may be contained.

  As a phenolic antioxidant, 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'-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, 3, 5-di-tert-butyl-4-hydroxy-benzenepropanoic acid and ester of C13-15 alkyl, 2,5-di-tert-amyl hydroquinone, polymer of hindered phenol (trade name "AO, manufactured by Adeka Palmarol Co., Ltd.) .OH. 98 "), 2,2'-methylenebis [6- (1-methylcyclohexyl) -p-cresol], 2- ert-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, 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-hydroxyl Product of the reaction of 2- (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-ter -Butyl-4-hydroxybenzylthioacetate, thiodiethylene bis [(3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 4,4'-thiobis (6-tert-butyl-m-cresol) , 2-octylthio-4,6-di (3,5-di-tert-butyl-4-hydroxyphenoxy) -s-triazine, 2,2'-methylenebis (4-methyl-6-tert-butylphenol), bis [3,3-bis (4-hydroxy-3-tert-butylphenyl) butyric acid] glycol ester, 4,4'-butylidenebis (2,6-di-tert-butylphenol), 4,4'-butylidenebis ( 6-tert-butyl-3-methylphenol), 2,2'-ethylidene bis (4,6-di-ter t-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, tetet Kiss [methylene-3- (3 ′, 5′-di-tert-butyl-4′-hydroxyphenyl) propionate] methane, 2-tert-butyl-4-methyl-6- (2-acryloyloxy-3-tert -Butyl-5-methylbenzyl) phenol, 3,9-bis [2- (3-tert-butyl-4-hydroxy-5-methylhydrocinnamoyloxy) -1,1-dimethylethyl] -2,4, 8,10-Tetraoxaspiro [5.5] undecane, 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-hydroxyl) Ciphenyl) propionic acid amide, myristyl 3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid amide, lauryl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) And 3- (3,5-dialkyl-4-hydroxyphenyl) propionic acid derivatives such as propionic acid amide. One of these may be used alone, or two or more may be used in combination. 0.001-5 mass parts are preferable with respect to 100 mass parts of polyolefin resin, and, as for the compounding quantity in the case of mix | blending a phenolic antioxidant, More preferably, it is 0.03-3 mass parts.

  Examples of phosphorus-based antioxidants include triphenyl phosphite, diisooctyl phosphite, heptakis (dipropylene glycol) triphosphite, triisodecyl phosphite, diphenyl isooctyl phosphite, diisooctyl phenyl phosphite, diphenyl Tridecyl phosphite, triisooctyl phosphite, trilauryl phosphite, diphenyl phosphite, tris (dipropylene glycol) phosphite, diisodecyl pentaerythritol diphosphite, dioleyl hydrogen phosphite, trilauryl trithiophosphite, bis (Tridecyl) phosphite, tris (isodecyl) phosphite, tris (tridecyl) phosphite, diphenyl decyl phosphite, dinonylphenylbi (Nonylphenyl) phosphite, poly (dipropylene glycol) phenyl phosphite, tetraphenyldipropyl glycol diphosphite, tris nonylphenyl 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, distearyl pentaerythritol diphosphite, mixture of distearyl pentaerythritol and calcium stearate, alkyl (C1 ) Bisphenol A phosphite, di (tridecyl) pentaerythritol diphosphite, di (nonylphenyl) pentaerythritol diphosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis (2, 6-Di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, bis (2,4,6-tri-tert-butylphenyl) pentaerythritol diphosphite, bis (2,4-dicumylphenyl) Pentaerythritol diphosphite, tetraphenyl-tetra (tridecyl) pentaerythritol tetraphosphite, bis (2,4-di-tert-butyl-6-methylphenyl) ethyl phosphite, tetra (tridecyl) isopropylidene diphenol Diphosphite, tetra (tridecyl) -4,4′-n-butylidenebis (2-tert-butyl-5-methylphenol) diphosphite, hexa (tridecyl) -1,1,3-tris (2-methyl-4-hydroxy- 5-tert-Butylphenyl) butanetriphosphite, 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-dimethylethyl) -5-methyl-4,1-phenylene) hexatridecyl phosphite, 2,2′-methylenebis (4,6 -Di-tert-butylphenyl) -2-ethylhexyl phosphite, 2,2'-methylene (4,6-di-tert-butylphenyl) -octadecyl phosphite, 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] dioxaphosphe) Pin-6-yl) oxy] ethyl) amine, 3,9-bis (4-nonylphenoxy) -2,4,8,10-tetraoxa-3,9-diphosphes spiro [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, and the like. One of these may be used alone, or two or more may be used in combination. 0.001-10 mass parts are preferable with respect to 100 mass parts of polyolefin resin, and, as for the compounding quantity in the case of mix | blending phosphorus antioxidant, More preferably, it is 0.01-0.5 mass part.

  Examples of thioether-based antioxidants include tetrakis [methylene-3- (laurylthio) propionate] methane, bis (methyl-4- [3-n-alkyl (C12 / C14) thiopropionyloxy) 5-tert-butylphenyl ) Sulfide, ditridecyl-3,3'-thiodipropionate, dilauryl-3,3'-thiodipropionate, dimyristyl-3,3'-thiodipropionate, distearyl-3,3'-thiodipropioate , Lauryl / stearylthiodipropionate, 4,4'-thiobis (6-tert-butyl-m-cresol), 2,2'-thiobis (6-tert-butyl-p-cresol), distearyl-di Sulfide is mentioned. One of these may be used alone, or two or more may be used in combination. 0.001-10 mass parts are preferable with respect to 100 mass parts of polyolefin resin, and, as for the compounding quantity in the case of mix | blending a thioether type antioxidant, More preferably, it is 0.01-0.5 mass part.

  UV absorbers include, for example, 2-hydroxybenzophenones such as 2,4-dihydroxybenzophenone, 5,5'-methylenebis (2-hydroxy-4-methoxybenzophenone), etc .; 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) Polyethylene glycol ester of 3-tert-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- ert-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-hydroxy) such as 2-hydroxy-4- (3-methacryloyloxy-2-hydroxypropyl) phenyl] benzotriazole, 2- [2-hydroxy-4- (3-methacryloyloxypropyl) phenyl] benzotriazole Phenyl) benzotriazoles; 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-4) Benzoates such as -hydroxy) benzoate, octadecyl (3,5-di-tert-butyl-4-hydroxy) benzoate, behenyl (3,5-di-tert-butyl-4-hydroxy) benzoate etc; 2-ethyl-2 '-Ethoxyoxanilide, 2-ethoxy-4'-dodesi Substituted oxanilides such as oxanilide; Cyanoacrylates such as ethyl-α-cyano-β, β-diphenyl acrylate, methyl-2-cyano-3-methyl-3- (p-methoxyphenyl) acrylate; various metal salts, Or metal chelates, particularly salts of nickel, chromium, or chelates. One of these may be used alone, or two or more may be used in combination. 0.001-10 mass parts are preferable with respect to 100 mass parts of polyolefin resin, and, as for the compounding quantity in the case of mix | blending a ultraviolet absorber, More preferably, it is 0.01-0.5 mass part.

  As the hindered amine compounds, for example, 2,2,6,6-tetramethyl-4-piperidyl stearate, 1,2,2,6,6-pentamethyl-4-piperidyl stearate, 2,2,6,6- Tetramethyl-4-piperidyl benzoate, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, tetrakis (2,2,6,6-tetramethyl-4-piperidyl) -1,2,3 2,4-butanetetracarboxylate, tetrakis (1,2,2,6,6-pentamethyl-4-piperidyl) -1,2,3,4-butanetetracarboxylate, bis (2,2,6,6- Tetramethyl-4-piperidyl) .di (tridecyl) -1,2,3,4-butanetetracarboxylate, bis (1,2,2,6,6-pentamethyl-4-piperi) B) -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 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 2,6,6-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-) Examples include tetramethyl) piperidyl} decantionate, bis {4- (2,2,6,6-tetramethyl-1-undecyloxy) piperidyl) carbonate and the like. One of these may be used alone, or two or more may be used in combination. 0.001-10 mass parts are preferable with respect to 100 mass parts of polyolefin resin, and, as for the compounding quantity in the case of mix | blending a hindered amine compound, More preferably, it is 0.01-0.5 mass part.

  As a flame retardant, for example, triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, cresyl diphenyl phosphate, cresyl-2, 6-dixylenyl phosphate, resorcinol bis (diphenyl phosphate), (1-methyl ethylidene) -4,1-phenylene tetraphenyl diphosphate, 1,3-phenylene tetrakis (2,6-dimethylphenyl) phosphate, trade name "ADEKA STAB FP-500" manufactured by DEKA, "ADEKA STAB FP-600", "ADEKA STAB Phosphate of FP-800, diphenyl ester of phenylphosphonate, diallyl phenylphosphonate, diallyl phenylphosphonate, phenylphosphonic acid (1-butenyl), phenyl diphenylphosphinate, diphenyl phosphite Phosphinic acid esters such as methyl 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide derivatives, phosphazene compounds such as bis (2-allylphenoxy) phosphazene and dicresyl phosphazene, and melamine phosphate Phosphorus flame retardants such as melamine pyrophosphate, melamine polyphosphate, melamine polyphosphate, ammonium polyphosphate, piperazine phosphate, piperazine pyrophosphate, piperazine polyphosphate, phosphorus-containing vinyl benzyl compound and red phosphorus, magnesium hydroxide, hydroxide Metal hydroxides such as aluminum, brominated bisphenol A epoxy resin, brominated phenol novolak epoxy resin, hexabromobenzene, pentabromotoluene, ethylene bis (pentabromophenyl), ethylene bis tetrabu Mophthalimide, 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 bromine And bromine-based flame retardants such as styrene. One of these may be used alone, or two or more may be used in combination. 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 blending amount in the case of blending the flame retardant is preferably 1 to 100 parts by mass, and more preferably 10 to 70 parts by mass with respect to 100 parts by mass of the polyolefin resin.

  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, Sorbitan monostearate, mannitol, stearic acid, hydrogenated castor oil, stearic acid amide, oleic acid amide, ethylenebisstearic acid amide and the like can be mentioned. One of these may be used alone, or two or more may be used in combination. 0.01-2 mass parts is preferable with respect to 100 mass parts of polyolefin resin, and, as for the compounding quantity in the case of mix | blending a lubricating agent, More preferably, it is 0.03-0.5 mass part.

  As the filler, for example, talc, mica, calcium carbonate, calcium oxide, calcium hydroxide, magnesium hydroxide, magnesium hydroxide, magnesium hydroxide, magnesium oxide, magnesium sulfate, aluminum hydroxide, barium sulfate, glass powder, glass fiber, clay, dolomite Silica, alumina, potassium titanate whiskers, wallastonite, fibrous magnesium oxysulfate, etc., and the particle diameter (fiber diameter, fiber length and aspect ratio in fibrous form) can be appropriately selected and used. . One of these may be used alone, or two or more may be used in combination. Moreover, the filler can use what was surface-treated as needed. The blending amount in the case of blending the filler is preferably 1 to 80 parts by mass, more preferably 3 to 50 parts by mass, still more preferably 5 to 40 parts by mass with respect to 100 parts by mass of the polyolefin resin .

  The hydrotalcites are complex salt compounds consisting of magnesium, aluminum, hydroxyl group, carbonate group and any crystal water known as natural products or synthetic compounds, and some of magnesium or aluminum are alkali metal, zinc and others. What substituted by metal, and what substituted the hydroxyl group and the carbonic acid group by the other anion group is mentioned, For example, the metal of the hydrotalcite represented by following General formula (2) is substituted by the alkali metal Are listed. Further, as the Al—Li-based hydrotalcites, compounds 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 the general formula (2), x1 and x2 each represent a number satisfying the condition represented by the following formula, 0 ≦ x2 / x1 <10, 2 ≦ x1 + x2 ≦ 20, and p is 0 or a positive number. Represent.

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、これら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 the general formula (3), A ^q- represents a q-valent anion, and p represents 0 or a positive number. In addition, the carbonate anion in these hydrotalcites may be partially substituted by another anion.

  The hydrotalcites may be those obtained by dehydrating water of crystallization, and higher fatty acids such as stearic acid, higher fatty acid metal salts such as alkali metal oleate, and organic sulfonic acid metals such as alkali metal dodecylbenzene sulfonate It may be coated with a salt, a higher fatty acid amide, a higher fatty acid ester or a wax.

  The hydrotalcites may be natural products or may be synthetic products. As a method of synthesizing hydrotalcites, JP-B-46-2280, JP-B-50-30039, JP-B-51-29129, JP-B-3-36839, JP-A-61-174270. Examples thereof include known methods described in JP-A-5-179052 and the like. In addition, hydrotalcites can be used without being limited to the crystal structure, crystal particles and the like. One of these may be used alone, or two or more may be used in combination. 0.001-5 mass parts are preferable with respect to 100 mass parts of polyolefin resin, and, as for the compounding quantity in the case of mix | blending hydrotalcites, More preferably, it is 0.01-3 mass parts.

  Examples of antistatic agents include cationic antistatic agents such as fatty acid quaternary ammonium ion salts and polyamine quaternary salts; higher alcohol phosphate ester salts, higher alcohol EO adducts, polyethylene glycol fatty acid esters, alkyl of anionic type Anionic antistatic agents such as sulfonates, higher alcohol sulfuric acid ester salts, higher alcohol ethylene oxide adduct sulfuric acid ester salts, higher alcohol ethylene oxide adduct phosphoric acid ester salts; polyhydric alcohol fatty acid esters, polyglycol phosphoric acid esters, polyoxy acids Nonionic antistatic agents such as ethylene alkyl allyl ether; amphoteric antistatic agents such as amphoteric alkylbetaine such as alkyldimethylaminoacetic acid betaine, and imidazoline type amphoteric activator. 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 antistatic agent is preferably 0.03 to 2 parts by mass, and more preferably 0.1 to 0.8 parts by mass with respect to 100 parts by mass of the polyolefin resin.

  As the pigment, commercially available pigments can also be used. For example, pigment red 1, 2, 3, 9, 10, 17, 22, 23, 31, 31, 38, 41, 48, 49, 88, 90, 97, 112 119, 122, 123, 144, 149, 166, 168, 169, 170, 171, 179, 180, 184, 185, 192, 200, 202, 209, 215, 216, 217, 220, 223, 224 226, 227, 228, 240, 254; pigment oranges 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, 00, 109, 110, 113, 114, 117, 120, 125, 126, 127, 129, 137, 138, 147, 148, 150, 151, 152, 153, 154, 166, 168, 175, 180, 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. One of these may be used alone, or two or more may be used in combination.

  The fluorescent whitening agent is a compound that absorbs the ultraviolet rays of sunlight or artificial light and converts it into visible light of purple to blue to promote the whiteness or bluishness of the molded product by the fluorescent action. As the fluorescent whitening agents, stiloxazole compounds C.I. I. Fluorescent Brightner 184; coumarin compound C.I. I. Fluorescent Brightner 52; diaminostilbenedisulfonic acid compound C.I. I. Fluorescent Brightner 24, 85, 71 etc. are mentioned. The blending amount in the case of using the fluorescent whitening agent is preferably 0.00001 to 0.1 part by mass, and more preferably 0.00005 to 0.05 part by mass with respect to 100 parts by mass of the polyolefin resin.

  As dyes, azo dyes, anthraquinone dyes, indigoid dyes, triarylmethane dyes, xanthene dyes, alizarin dyes, acridine dyes, stilbene dyes, thiazolyl dyes, naphthol dyes, quinoline dyes, nitro dyes, indamine dyes, oxazine dyes, phthalocyanine dyes And cyanine dyes and the like, and these may be used alone or in combination of two or more.

  When shaping | molding the polyolefin resin composition of this invention, it can shape | mold using a well-known shaping | 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.

  The polyolefin resin composition of the present invention may be used for film materials, fiber materials, laminates having a wood / fiber material as a base, for example, polyolefin resin in the molding process of polyolefin resin compositions. Applications include the need to delay crystallization.

  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 1-1 to 1-6, Comparative Examples 1-1 to 1-11]
As a thermoplastic resin, 100 parts by mass of homopolypropylene (melt flow rate 8 g / 10 min; 2.16 kg × 230 ° C. according to ISO standard 1133), a phenolic antioxidant (tetrakis [methylene-3- (3 ′, 5 ′)] -Tert-Butyl-4'-hydroxyphenyl) propionate] methane) 0.05 parts by mass, phosphorus-based antioxidant (tris (2,4-di-tert-butylphenyl) phosphite) 0.1 parts by mass, stear 0.05 parts by mass of calcium phosphate and the compounds described in Table 1 were compounded, and after mixing for 1 minute at 1000 rpm with a Henschel mixer, they were granulated at an extrusion temperature of 230 ° C. using a twin-screw extruder. After the granulated pellets were dried at 60 ° C. for 8 hours, the crystallization temperature, the semicrystallization time and the flexural modulus were evaluated under the conditions described below. Each result is shown in Table 1.

<Crystallization temperature>
A small amount of the obtained pellet was cut out, and the crystallization temperature was measured using a differential scanning calorimeter (manufactured by Diamond Perkin Elmer). In the measurement, the temperature is raised from a room temperature to 230 ° C. at a rate of 50 ° C./min, held for 10 minutes, and cooled to 125 ° C. at a rate of −200 ° C./min. The crystallization temperature was defined as

<Semi-crystallization time>
A small amount of the obtained pellet is cut out, heated to 300 ° C. at a rate of 50 ° C./min with a differential scanning calorimeter (Diamond; Perkin Elmer Co., Ltd.), held for 10 minutes, and specified at a rate of −200 ° C./min. The temperature is cooled to a temperature of 220 ° C. to 230 ° C., and after reaching 125 ° C., the temperature is maintained for 30 minutes, and the time for half the heat of endothermic enthalpy required for crystallization is determined. And

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

HHHD-Mg: magnesium head acid HHHD-Ba: head acid barium HHHD-Sr: head acid strontium HHHD-Co: cobalt head acid Control: head acid compound-free HHHD-Zn: head acid zinc HHHD-Na: head acid sodium HHHD -K: potassium head acid HHHD-Li: lithium head acid HHHD-Cu: head acid copper HHHD-Ni: head acid nickel HHHD-Ca: head acid calcium HHHD-Al (OH): head acid aluminum hydroxide HHHD- Cr (OH): chromic acid monohydroxide

  From Examples 1-1 to 1-6, the crystallization retarder of the present invention can obtain crystallization retardation effect equal to or higher than that of the known zinc acid zincate and physical properties equal to or higher than Control of Comparative Example 1 can be obtained. It could be confirmed that

[Examples 2-1 to 2-3, Comparative examples 2-1 to 2]
Pellets were granulated under the same conditions as Example 1-1 except that the compounds described in Table 1 were changed to the compounds described in Table 2. The granulated pellets were dried at 60 ° C. for 8 hours and then evaluated for shrinkage anisotropy by the following procedure. The results are shown in Table 2.

(Shrinkage anisotropy)
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.) The injection molding was carried out, and the test piece was produced. 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 shrinkage of the test piece, ΔMD (%), ΔTD (%) were determined according to the following equation.

The shrinkage ratio anisotropy was calculated by substituting the obtained ΔMD and ΔTD into the following equation. When the shrinkage rate anisotropy is large, the degree to which the molded product is warped or deformed is increased. In general, the closer the shrinkage anisotropy is to 1, the less these problems are encountered.

  From the comparison of Comparative Example 2-2 and Comparative Example 2-1, the improvement of the shrinkage rate anisotropy by the zinc acid acid compound was slight. On the other hand, it can be confirmed from Examples 2-1 to 2-3 that the crystallization retarder of the present invention has improved shrinkage anisotropy.

  From the above, the crystallization retarder of the present invention can obtain crystallization retardation effect and physical property improvement effect equal to or more than the conventional crystallization retarder, and the shrinkage rate is different compared with the conventional crystallization retarder. It can be seen that the directivity is improved. That is, the crystallization retarder of the present invention exhibits excellent crystallization retardation effect without losing the physical properties inherent to the resin, and the molded article using the crystallization retarder of the present invention has an improved shrinkage rate anisotropy. Was confirmed.

Claims (4)

The following general formula (1),

A crystallization retarder characterized by comprising a compound represented by (in the formula (1), M ¹ represents Mg, Ba, Sr, or Co).   A polyolefin resin composition comprising the crystallization retarder according to claim 1 with respect to the polyolefin resin.   The polyolefin resin composition according to claim 2, wherein the crystallization retarder is contained in an amount of 0.01 to 10 parts by mass with respect to 100 parts by mass of the polyolefin resin. A molded article comprising the polyolefin resin composition according to claim 2 or 3.