WO2018150755A1 - Novel compound, nucleating agent, resin composition, and molded article - Google Patents

Abstract

[Problem] To provide a novel and high-performance nucleating agent for polyolefin resins. [Solution] A compound represented by general formula (1); a nucleating agent comprising the compound; a polyolefin resin composition containing the nucleating agent; and a molded article formed from the polyolefin resin composition. (In formula (1), the ring A and the ring B independently represent an aryl group or a cycloalkyl group; and M represents an alkali metal atom.)

Description

Novel compound, nucleating agent, resin composition, and molded article

The present invention relates to a novel metal salt of a dicarboxylic acid hydrazide compound useful as a nucleating agent for polyolefin resins. Furthermore, the present invention relates to a nucleating agent containing the novel compound, a polyolefin-based resin composition containing the nucleating agent, and a molded article comprising the composition.
About.

Polyolefin-based resins such as polyethylene, polypropylene, and polybutene-1 have advantages such as molding processability, heat resistance, electrical properties, mechanical properties, and low specific gravity, and film molding, sheet molding, blow molding, Widely used in various fields as a material for injection molding. However, polyolefin resins have problems such as a slow crystallization rate after heat molding and a long molding cycle during processing. In addition, the molded product may be deformed by crystallization that proceeds after molding. In order to solve the problem derived from the crystallinity of such a polyolefin resin, an additive having an effect of rapidly generating fine crystals of the polyolefin resin is called a nucleating agent (or crystallization accelerator). It is blended with polyolefin. It is also known that such a nucleating agent simultaneously improves the transparency of the polyolefin resin.

Effective compounds as nucleating agents for polyolefin resins include sodium adipate, potassium adipate, aluminum adipate, sodium sebacate, potassium sebacate, aluminum sebacate, sodium benzoate, potassium benzoate, lithium benzoate, benzoate Aluminum oxide, aluminum di-para-t-butylbenzoate, titanium di-para-t-butylbenzoate, chromium di-para-t-butylbenzoate, aluminum hydroxy-di-t-butylbenzoate, β-naphtho Metal salt types such as sodium acid, sodium cyclohexanecarboxylate, sodium cyclopentanecarboxylate, sodium bis (4-tert-butylphenyl) phosphate, sodium 2,2′-methylenebis (4,6-di-ter Phosphate metal salt types such as -butylphenyl) phosphate and lithium-2,2'-methylenebis (4,6-di-tert-butylphenyl) phosphate, dibenzylidene sorbitol, bis (methylbenzylidene) sorbitol and bis (dimethyl) Representative examples include sorbitol types such as benzylidene) sorbitol, stearic acid amide, ethylenebislauric acid amide, palmitic acid amide, hydroxystearic acid amide, erucic acid amide, trimesic acid tris (t-butylamide) and other carboxylic acid amide types, and rosin type. Is.

Although these various nucleating agents are known, they satisfy all requirements such as effective concentration, dispersibility in polyolefin resin, influence on color tone and moldability of polyolefin resin, price, and handleability. There are few nucleating agents, and each nucleating agent has advantages and disadvantages. For this reason, the development of new nucleating agents continues. For example, an organic carboxylic acid metal salt type nucleating agent is advantageous over a sorbitol type nucleating agent at a single price, but may be inferior to other nucleating agents in terms of dispersibility in a polymer and crystallization promoting effect. As an improvement example of the organic carboxylic acid metal salt type nucleating agent, for example, Patent Document 1 discloses di-sodium bicyclo [2.2.1] heptane-2,3-dicarboxylate, calcium bicyclo [2.2. 1] It is described that a bicyclic compound such as heptane-2,3-dicarboxylate exhibits a crystallization promoting effect superior to a conventionally used nucleating agent such as calcium stearate. Patent Document 2 discloses that a composition comprising a combination of cis-2 sodium hexahydrophthalate and an acid supplement is more effective in promoting crystallization than a combination of a conventional nucleating agent such as sodium benzoate and an acid supplement. Is described.

On the other hand, Patent Document 3 by the present applicant describes that a hydrazide compound having a cyclohexyl group or a phenyl group functions as a nucleating agent for polyolefin resin. Further, in Patent Document 4, a crystal nucleating agent selected from the group consisting of metal salts of aromatic organophosphates, dibenzylidene sorbitol derivatives, carboxylic acid metal salts, rosin acid partial metal salts, and talc is water-soluble ionic. It is described that a composition supported on an inorganic powder containing a copolymer exhibits a nucleating agent effect while maintaining the mechanical properties of a polyolefin-based resin.

JP-T-2004-531613 JP-T-2004-524417 Patent Registration No. 5465457 Japanese Patent Laid-Open No. 2003-12868

However, there is still room for improvement in the above-mentioned nucleating agents, and a demand for new nucleating agents remains. Therefore, the present inventor has eagerly sought for a compound effective as a nucleating agent.

The second object of the present invention is to provide a polyolefin resin composition having a high added value as a molding material in which a more excellent nucleating agent is blended.

As a result of intensive studies in order to solve the above-mentioned problems, the inventors of the present invention blend a metal salt of a specific dicarboxylic acid hydrazide compound, which is a novel compound that is not disclosed in the above-mentioned patent documents, with a polyolefin resin. As a result, it was found that a polyolefin-based resin composition with improved crystallinity was obtained, and the present invention was completed. That is, the present invention is as follows.
(Invention 1) A compound represented by the following formula (1).

(In Formula (1), Ring A and Ring B represent an aryl group having 6 to 20 carbon atoms or a cycloalkyl group having 3 to 20 carbon atoms, M represents an alkali metal atom, and an aryl group or cycloalkyl group) The group may be substituted with a hydroxyl group, a halogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms and an alkenyl group having 2 to 10 carbon atoms. (The alkyl group therein may be interrupted by a carbonyl group or an oxygen atom, and may have an unsaturated bond.)
(Invention 2) The compound according to (Invention 1) represented by the following formula (2).

(In the formula (2), M represents an alkali metal atom, and R ¹ to R ⁹ each independently represents a hydrogen atom, a hydroxyl group, a halogen atom, an alkyl group having 1 to 10 carbon atoms, or 1 to 10 represents an alkoxy group, an alkenyl group having 2 to 10 carbon atoms, and the alkyl group or the alkyl group in the alkoxy group may be interrupted by a carbonyl group or an oxygen atom, and has an unsaturated bond. May be good.)
(Invention 3) A nucleating agent containing the compound represented by the formula (1) or (2).

(Invention 4) A polyolefin resin and the nucleating agent according to (3), wherein the total amount of one or more compounds represented by the above formula (1) or the above formula (2) is 100 mass of the above polyolefin resin. A polyolefin-based resin composition in the range of 0.0001 to 10 parts by mass with respect to parts.

(Invention 5) A molded article comprising the polyolefin resin composition according to (Invention 4).

ADVANTAGE OF THE INVENTION According to this invention, the novel compound which can provide the resin composition which has the outstanding nucleating agent effect and has little anisotropy of shrinkage | contraction rate, a nucleating agent composition using this, and polyolefin resin composition Articles and molded articles thereof can be provided.

[Nuclear compound]
Hereinafter, embodiments of the present invention will be described in detail. The compound of the present invention is a novel compound and useful as a nucleating agent for thermoplastic resins including polyolefin resins. In the present specification, such a compound of the present invention is referred to as a “nucleating agent compound”. This nucleating agent compound is a metal salt of a dicarboxylic acid hydrazide compound represented by the following general formula (1).

In formula (1), ring A and ring B represent an aryl group having 6 to 20 carbon atoms or a cycloalkyl group having 3 to 20 carbon atoms, M represents an alkali metal atom, an aryl group or a cycloalkyl group May be substituted with a hydroxyl group, a halogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms and an alkenyl group having 2 to 10 carbon atoms. The alkyl group may be interrupted by a carbonyl group or an oxygen atom, and may have an unsaturated bond.

Examples of the aryl group having 6 to 20 carbon atoms of the ring A and the ring B in the formula (1) include phenyl, naphthyl, biphenyl, anthracenyl and the like, and the hydrogen atom of the aryl group is a hydroxyl group, a halogen atom, a carbon atom. It may be substituted with an alkyl group having 1 to 10 atoms, an alkoxy group having 1 to 10 carbon atoms, and an alkenyl group having 2 to 10 carbon atoms.

Examples of the cycloalkyl group having 3 to 20 carbon atoms of the ring A and the ring B in the formula (1) include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and the like. The hydrogen atom of the cycloalkyl group is a hydroxyl group, a halogen atom, It may be substituted with an atom, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, and an alkenyl group having 2 to 10 carbon atoms.

Examples of the alkyl group having 1 to 10 carbon atoms include linear or branched alkyl groups and cycloalkyl groups having 3 to 10 carbon atoms. Specifically, for example, methyl, ethyl, propyl, isopropyl, cyclopropyl, butyl, sec-butyl, tert-butyl, isobutyl, cyclobutyl, amyl, tert-amyl, cyclopentyl, hexyl, cyclohexyl, heptyl, cycloheptyl, octyl , Cyclooctyl, isooctyl, tert-octyl, 2-ethylhexyl, nonyl, isononyl, decyl and the like.

Examples of the alkoxy group having 1 to 10 carbon atoms include linear or branched alkoxy groups and cycloalkoxy groups having 5 to 10 carbon atoms. Specific examples include methoxy, ethoxy, n-propoxy, n-butoxy, n-hexyloxy, 1-methylethoxy, 2-methylpropoxy, 1-methylbutoxy, 4-methylpentyloxy, cyclohexyloxy and the like. It is done.

Examples of the alkenyl group having 2 to 10 carbon atoms include vinyl, allyl, propenyl, decenyl and the like.

The nucleating agent compound of the present invention is preferably a compound represented by the following formula (2).

In the formula (2), M represents an alkali metal atom, and R ¹ to R ⁹ each independently represents a hydrogen atom, a hydroxyl group, a halogen atom, an alkyl group having 1 to 10 carbon atoms, or 1 to 10 carbon atoms. Represents an alkenyl group having 2 to 10 carbon atoms, and the alkyl group or the alkyl group in the alkoxy group may be interrupted by a carbonyl group or an oxygen atom, or may have an unsaturated bond Good.

Typical examples of such a nucleating agent compound of the present invention are compounds represented by the following formulas (3-1) to (3-16).

[Method for producing nucleating agent compound]
As shown in the following reaction formula, the nucleating agent compound of the present invention is obtained as a water-insoluble alkali metal salt by saponifying the precursor (4) corresponding to the compound represented by the formula (1) in an alkaline aqueous solution. it can.

(The definitions of A, B, and M in the above formula are the same as those in formula (1). In the formula, R ″ represents an alkyl group having 1 to 10 carbon atoms.)

The precursor (4) can be synthesized according to the following reaction formula. That is, it can be easily synthesized by reacting hydrazine or a derivative thereof with a carboxyl group-containing compound or an acid halide.

Wherein R _a is an aryl group having 6 to 20 carbon atoms or a cycloalkyl group having 3 to 20 carbon atoms corresponding to ring A in formula (1), and R _b is a ring B in formula (1). Corresponding aryl group having 6 to 20 carbon atoms or cycloalkyl group having 3 to 20 carbon atoms, R ′ is a hydrocarbon group, R ″ is an alkyl group having 1 to 10 carbon atoms, and X is a halogen atom. .)

[Nuclear agent]
The nucleating agent compound of the present invention is useful as a nucleating agent for polyolefin resins. The nucleating agent of the present invention may be composed of the nucleating agent compound of the present invention, or may contain other additives in addition to the nucleating agent compound of the present invention. Although there is no restriction | limiting in particular in content of the nucleating agent compound in the nucleating agent of this invention, Preferably it is 10 mass% or more with respect to the nucleating agent whole quantity, More preferably, it is 80 mass% or more. The other additive combined with the nucleating agent compound is not limited as long as it is an additive that can be blended with the polyolefin resin. For example, one or more additives including known nucleating agents described later are used. Can do.

[Polyolefin resin composition]
The polyolefin resin composition of the present invention is a composition comprising a polyolefin resin and the nucleating agent of the present invention. The nucleating agent compound of the present invention is 0.0001 to 10 parts by mass with respect to 100 parts by mass of the polyolefin resin. Preferably, the nucleating agent of the present invention is blended with a polyolefin-based resin so as to have a concentration of 0.005 to 5 parts by mass, more preferably 0.01 to 0.5 parts by mass. If the concentration of the nucleating agent compound is less than 0.0001 parts by mass with respect to 100 parts by mass of the polyolefin resin, the effect of addition is insufficient, and if it is more than 10 parts by mass, the effect of the nucleating agent compound of the present invention as a nucleating agent May not be obtained.

Examples of the polyolefin resin used in the polyolefin 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, hemiisotactic polypropylene, cycloolefin polymer, stereoblock polypropylene, poly-3-methyl-1-butene, poly-3-methyl-1-pentene, poly-4-methyl-1-pentene, etc. α-olefin polymer, ethylene / propylene block or random copolymer, impact copolymer polypropylene, ethylene-methyl methacrylate copolymer, ethylene-methyl acrylate copolymer, ethylene-ethyl acrylate copolymer Body, 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 present invention, these two or more types may be blended and used, a block copolymer may be formed and used as a block polymer type, or the resin may be alloyed. Further, chlorinated products of these polyolefin resins may be used.

The polyolefin resin elastomer is a polyolefin such as polypropylene or polyethylene as a hard segment, an elastomer such as ethylene-propylene rubber as a soft segment, and an elastomer obtained by blending these, or an elastomer obtained by dynamic crosslinking. Is mentioned. Examples of the hard segment include at least one selected from polypropylene homopolymer, polypropylene block copolymer, polypropylene random copolymer, 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. Two or more of these may be blended and used.

The polyolefin resin production method includes Ziegler catalyst, Ziegler-Natta catalyst, metallocene catalyst and other various polymerization catalysts as cocatalyst, catalyst carrier, chain transfer agent, gas phase polymerization, solution polymerization, emulsion polymerization, In various polymerization methods such as bulk polymerization, resins with physical properties suitable for packaging materials such as temperature, pressure, concentration, flow rate and various polymerization conditions such as removal of catalyst residues can be obtained, and physical properties suitable for molding processing of packaging materials. It is produced by appropriately selecting a resin that can be obtained. Number average molecular weight, weight average molecular weight, molecular weight distribution, melt flow rate, melting point, melting peak temperature, isotactic, syndiotactic and other stereoregularity of polypolyolefin resin, presence or absence of branching, specific gravity, 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, etc. can be appropriately selected according to the desired characteristics. it can.

In the polyolefin-based resin composition of the present invention, any known resin additive (for example, a phenol-based antioxidant, a phosphorus-based antioxidant, a thioether-based antioxidant, and the like, as long as the effects of the present invention are not significantly impaired) Antioxidants, hindered amine compounds, UV absorbers, other nucleating agents, flame retardants, flame retardant aids, lubricants, fillers, hydrotalcites, fatty acid metal salts, antistatic agents, pigments, dyes, etc.) You may let them.

Examples of the phenolic antioxidant include 2,6-di-tert-butyl-4-methylphenol, 2,6-di-tert-butyl-4-ethylphenol, and 2-tert-butyl-4,6-dimethyl. Phenol, styrenated phenol, 2,2'-methylenebis (4-ethyl-6-tert-butylphenol), 2,2'-thiobis- (6-tert-butyl-4-methylphenol), 2,2'-thio Diethylenebis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 2-methyl-4,6-bis (octylsulfanylmethyl) phenol, 2,2′-isobutylidenebis ( 4,6-dimethylphenol), isooctyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, N, N′-hexane-1,6-diylbis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionamide, 2,2′-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-hydroxy-benzenepropanoic acid and esters of C13-15 alkyl, 2,5-di-tert-amylhydroquinone, hindered Polymer of phenol (trade name AO.OH.98 manufactured by Adeka Palmalol), 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-hydroxyphenyl) ) Propionate, bis [monoethyl (3,5-di-tert-butyl-4-hydroxybenzyl) phosphonate] calcium salt, 5,7-bis (1,1-dimethyl) Ruethyl) -3-hydroxy-2 (3H) -benzofuranone and o-xylene reaction product, 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, Decyl-3,5-tert-butyl-4-hydroxybenzylthioacetate, thiodiethylenebis [(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-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] iso Anurate, tetrakis [methylene-3- (3 ′, 5′-tert-butyl-4′-hydroxyphenyl) propionate] methane, 2-tert-butyl-4-methyl-6- (2-acryloyloxy-3-tert -Butyl-5-methylbenzyl) phenol, 3,9-bis [2- (3-tert-butyl-4-hydroxy-5-methylhydrocinnamoyloxy) -1,1-dimethylethyl] -2,4 8,10-tetraoxaspiro [5.5] undecane, 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- (3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid amide, lauryl-3- (3,5-di-tert-butyl-4-hydroxy And 3- (3,5-dialkyl-4-hydroxyphenyl) propionic acid derivatives such as phenyl) propionic acid amide.
In the present invention, tetrakis [methylene-3- (3 ′, 5′-tert-butyl-4′-hydroxyphenyl) propionate] methane is preferable because it is inexpensive and has an excellent stabilizing effect on the polypolyolefin resin.

When the phenolic antioxidant is blended, the blending amount is preferably 0.001 to 5 parts by weight and more preferably 0.01 to 1.0 part by weight with respect to 100 parts by weight of the polyolefin resin.

Phosphorous antioxidants include, for example, triphenyl phosphite, diisooctyl phosphite, heptakis (dipropylene glycol) triphosphite, triisodecyl phosphite, diphenylisooctyl phosphite, diisooctylphenyl phosphite, diphenyltri Decyl 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, diphenyldecylphosphite, dinonylphenylbis (no Ruphenyl) phosphite, poly (dipropylene glycol) phenyl phosphite, tetraphenyldipropylene glycol 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] phos Phyto, tri (decyl) phosphite, octyl diphenyl phosphite, di (decyl) monophenyl phosphite, distearyl pentaerythritol diphosphite, a mixture of distearyl pentaerythritol and calcium stearate, alkyl (C10) Sphenol 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) isopropylidenediphenol diphos Sulphite, 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) 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) hexatridecyl phosphite, 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] dioxaphosphine-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 C12-1 Alcohol phosphite, and the like.
The blending amount of the phosphorus antioxidant is preferably 0.001 to 20 parts by mass, more preferably 0.01 to 5 parts by mass with respect to 100 parts by mass of the polyolefin resin.

Examples of the thioether-based antioxidant include 3,3′-thiodipropionic acid, alkyl (C12-14) thiopropionic acid, di (lauryl) -3,3′-thiodipropionate, and di (tridecyl) -3. , 3'-thiodipropionate, di (myristyl) -3,3'-thiodipropionate, di (stearyl) -3,3'-thiodipropionate, di (octadecyl) -3,3'-thio Dipropionate, lauryl stearyl thiodipropionate, tetrakis [methylene-3- (dodecylthio) propionate] methane, thiobis (2-tert-butyl-5-methyl-4,1-phenylene) bis (3- (dodecylthio) propionate ), 2,2′-thiodiethylenebis (3-aminobutenoate), 4,6-bis (octylthiomethyl) -o-creso 2,2′-thiodiethylenebis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 2,2′-thiobis (4-methyl-6-tert-butylphenol), 2,2′-thiobis (6-tert-butyl-p-cresol), 2-ethylhexyl- (3,5-di-tert-butyl-4-hydroxybenzyl) thioacetate, 4,4′-thiobis (6- tert-butyl-3-methylphenol), 4,4′-thiobis (4-methyl-6-tert-butylphenol), 4,4 ′-[thiobis (methylene)] bis (2-tert-butyl-6-methyl) -1-hydroxybenzyl), bis (4,6-di-tert-butylphenol-2-yl) sulfide, tridecyl-3,5-di-tert-butyl- 4-hydroxybenzylthioacetate, 1,4-bis (octylthiomethyl) -6-methylphenol, 2,4-bis (dodecylthiomethyl) -6-methylphenol, distearyl-disulfide, bis (methyl-4 -[3-n-alkyl (C12 / C14) thiopropionyloxy] 5-tert-butylphenyl) sulfide and the like.
When the thioether-based antioxidant is blended, the blending amount is preferably 0.001 to 20 parts by weight, and more preferably 0.01 to 5 parts by weight with respect to 100 parts by weight of the polyolefin-based resin.

Other antioxidants include, for example, N-benzyl-α-phenylnitrone, N-ethyl-α-methylnitrone, N-octyl-α-heptylnitrone, N-lauryl-α-undecylnitrone, N-tetradecyl- α-tridecylnitrone, N-hexadecyl-α-pentadecylnitrone, N-octyl-α-heptadecylnitrone, N-hexadecyl-α-heptadecylnitrone, N-octadecyl-α-pentadecylnitrone, N-heptadecyl- Nitron compounds such as α-heptadecylnitrone and N-octadecyl-α-heptadecylnitrone, 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 And benzofuran compounds such as-((15-hydroxy-3,6,9,13-tetraoxapentadecyl) oxy) phenyl) benzofuran-2 (3H) one.
When the other antioxidant is blended, the blending amount is preferably 0.001 to 20 parts by weight, and more preferably 0.01 to 5 parts by weight with respect to 100 parts by weight of the polyolefin resin.

Examples of hindered amine compounds include 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- 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, 6,11-tris [2,4-bis (N-butyl-N- (2,2,6,6-tetramethyl-4-piperidyl) amino) -s-triazin-6-yl] aminoundecane, 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} decanedionate, bis {4- (2,2,6,6-tetramethyl-1-undecyloxy) piperidyl) carbonate, TINUVIN NOR 371 manufactured by Ciba Specialty Chemicals.

In the case of blending the hindered amine compound, the blending amount is preferably 0.001 to 5 parts by mass, more preferably 0.005 to 0.5 parts by mass with respect to 100 parts by mass of the polyolefin resin.

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 tert-butyl-5-carboxyphenyl) benzotriazole polyethylene glycol ester, 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-te t-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 and 2- [2-hydroxy-4- (3-methacryloyloxypropyl) phenyl] benzotriazole Phenyl) benzotriazoles; Nilsalicylate, 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 '-Ethoxyoxanilide, 2-ethoxy-4'-dodecylo Substituted oxanilides such as zanilide; cyanoacrylates such as ethyl-α-cyano-β, β-diphenyl acrylate, methyl-2-cyano-3-methyl-3- (p-methoxyphenyl) acrylate; various metal salts; Alternatively, metal chelates, particularly nickel, chromium salts, chelates, and the like can be given.

The blending amount in the case of blending the ultraviolet absorber is preferably 0.001 to 5 parts by mass, more preferably 0.005 to 0.5 parts by mass with respect to 100 parts by mass of the polyolefin resin.

Other nucleating agents different from the nucleating agent of the present invention 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-butylaluminum benzoate aluminum salt, adipine Carboxylic acid metal salts such as sodium and disodium bicyclo [2.2.1] 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'-dicyclohexylnaphthalenedicarboxamide, Examples thereof include amide compounds such as 1,3,5-tri (dimethylisopropoylamino) benzene.
In the case of blending other nucleating agent, the total amount with the nucleating agent of the present invention is preferably 0.05 to 10 parts by mass with respect to 100 parts by mass of the polyolefin resin, and 0.01 to 0.001. 5 parts by mass is more preferable.

Examples of the flame retardant 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, trade name ADEKA STAB (registered trademark) FP-500 manufactured by ADEKA Corporation, trade name ADEKA STAB (trade name) manufactured by ADEKA Corporation (Trademark) FP-600, ADEKA Corporation trade name ADK STAB (registered trademark) FP-800, etc., aromatic phosphate ester, phenylphosphonate divinyl, phenylphosphonate diallyl, phenylphosphonic acid (1-buteni ) Phosphonic acid esters such as phenyl diphenylphosphinate, methyl diphenylphosphinate, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide derivatives, etc., bis (2-allylphenoxy) Phosphazene compounds such as phosphazene and dicresyl phosphazene, melamine phosphate, melamine pyrophosphate, melamine polyphosphate, melam polyphosphate, ammonium polyphosphate, piperazine phosphate, piperazine pyrophosphate, piperazine polyphosphate, phosphorus-containing vinylbenzyl compounds and red phosphorus Phosphorus flame retardant such as magnesium hydroxide, metal hydroxide such as magnesium hydroxide, brominated bisphenol A type epoxy resin, brominated phenol novolac type epoxy resin, hexabromobenzene, pen Bromotoluene, 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, tribromophenylmaleimide, tribromophenyl acrylate, tribromophenyl methacrylate, tetrabromo Examples thereof include bisphenol A-type dimethacrylate, pentabromobenzyl acrylate, and brominated flame retardants such as brominated styrene. These flame retardants are preferably used in combination with anti-drip agents such as fluororesins and flame retardant aids such as polyols and hydrotalcites.
The blending amount when the flame retardant is blended is preferably 1 to 50 parts by weight and more preferably 10 to 30 parts by weight with respect to 100 parts by weight of the polyolefin resin.

The lubricant is added for the purpose of imparting lubricity to the surface of the molded body and enhancing the damage prevention effect. Examples of the lubricant include hydrocarbon lubricants such as low molecular wax, paraffin wax, polyethylene wax, chlorinated hydrocarbon, and fluorocarbon; natural wax lubricants such as carnauba wax and candeli wax; lauric acid, stearic acid, and behenic acid Fatty acid lubricants such as higher fatty acids such as oxyfatty acids such as hydroxystearic acid; aliphatic amide compounds such as stearylamide, laurylamide, oleylamide, or alkylenebisfats such as methylenebisstearylamide, ethylenebisstearylamide Aliphatic amide-based lubricants such as aliphatic amide compounds; fatty acid monohydric alcohol ester compounds such as stearyl stearate, butyl stearate, distearyl phthalate; glycerin tristearate, sorbitan tristearate Fatty acid polyhydric alcohol ester compounds such as rate, pentaerythritol tetrastearate, dipentaerythritol hexastearate, polyglycerin polyricinoleate, hydrogenated castor oil; monovalent fatty acids such as adipic acid / stearic acid ester of dipentaerythritol and many Fatty alcohol ester lubricants such as complex ester compounds of basic organic acids and polyhydric alcohols; Aliphatic alcohol lubricants such as stearyl alcohol, lauryl alcohol and palmityl alcohol; Metal soaps; Montane such as partially saponified montanate esters Examples include acid-based lubricants; acrylic-based lubricants; and silicone oils. These may be used alone or in combination of two or more.
The blending amount when the lubricant is blended is preferably 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 polyolefin resin.

Fillers include, for example, talc, mica, calcium carbonate, calcium oxide, calcium hydroxide, magnesium carbonate, magnesium hydroxide, magnesium oxide, magnesium sulfate, aluminum hydroxide, barium sulfate, glass powder, glass fiber, clay, dolomite, Mica, silica, alumina, potassium titanate whisker, wollastonite, fibrous magnesium oxysulfate and the like can be mentioned, and the particle diameter (in the fibrous form, fiber diameter, fiber length and aspect ratio) can be appropriately selected and used. it can. Moreover, what was surface-treated as needed can be used for a filler.
When blending the filler, the blending amount is preferably 0.01 to 80 parts by weight, more preferably 1 to 50 parts by weight with respect to 100 parts by weight of the polyolefin resin. Hydrotalcite is a natural product or a synthetic product. It is a complex salt compound consisting of magnesium, aluminum, hydroxyl group, carbonate group and any water of crystallization known as, which is obtained by substituting a part of magnesium or aluminum with other metals such as alkali metal or zinc, or other hydroxyl group or carbonate group And those substituted with an anionic group. Such hydrosites are typically alkali metal-substituted hydrotalcites represented by the following formula (5) or Al—Li hydrotalcites represented by the following formula (6): It is kind.

(In formula (5), X1 and X2 represent numbers satisfying the conditions: 0 ≦ X2 / X1 <10, 2 ≦ X1 + X2 ≦ 20, and p represents 0 or a positive number.)

In formula (6), A ^q− represents a q-valent anion, and p represents 0 or a positive number. Further, 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, higher fatty acid amide, higher fatty acid ester or wax.

Hydrotalcites may be natural products or synthetic products. As synthesis methods, 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 Publication No. Hei 5- The publicly known method described in 179052 gazette etc. is mentioned. Hydrotalcites can be used without being limited by their crystal structure, crystal particles, and the like. When the hydrotalcite is blended, the blending amount is preferably 0.001 to 5 parts by mass, more preferably 0.05 to 3 parts by mass with respect to 100 parts by mass of the polyolefin resin.

Fatty acid metal salts include, for example, capric acid, 2-ethylhexanoic acid, undecylic acid, lauric acid, tridecylic acid, myristic acid, pentadecylic acid, palmitic acid, margaric acid, stearic acid, nonadecylic acid, arachidic acid, heicosyl acid Saturated fatty acids such as behenic acid, tricosylic acid, lignoceric acid, serotic acid, montanic acid, melicic acid, 4-decenoic acid, 4-dodecenoic acid, palmitoleic acid, α-linolenic acid, linoleic acid, γ-linolenic acid, stearidone Examples thereof include linear unsaturated fatty acids such as acid, petroceric acid, oleic acid, elaidic acid, vaccenic acid, eicosapentaenoic acid, docosapentaenoic acid, docosahexaenoic acid, and aromatic fatty acids such as trimesic acid. Acid, stearic acid, 12-hydroxystearic acid Saturated fatty acids such as are preferred.

Examples of the metal salts of fatty acids include alkali metals, magnesium, calcium, strontium, barium, titanium, manganese, iron, zinc, silicon, zirconium, yttrium, barium, or hafnium. Particularly, sodium, lithium, potassium, etc. The alkali metal is preferred.

When the fatty acid metal salt is blended, the blending amount is preferably 0.001 to 5 parts by weight and more preferably 0.03 to 3.0 parts by weight with respect to 100 parts by weight of the polyolefin resin.

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. Antistatic agents may be used alone, or two or more types of antistatic agents may be used in combination.

The blending amount when blending the antistatic agent is preferably 0.01 to 20 parts by mass, more preferably 3 to 10 parts by mass with respect to 100 parts by mass of the polyolefin resin.

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, 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, 56, 60, 61, 62, 64; Pigment violet 1, 19, 23, 27, 29, 30, 32, 37, 40, 50 and the like.

Dyes include, for example, 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 Examples thereof include dyes and dyes such as cyanine dyes, and a plurality of these may be used in combination.

In the resin composition of the present invention, the method of blending the metal salt of the dicarboxylic acid hydrazide compound with the polyolefin resin is not particularly limited, and can be performed by a conventionally known method. For example, polypolyolefin-based resin powder or pellets and an additive may be mixed by dry blending, and a part of the additive may be preblended and then dry blended with the remaining components. After dry blending, for example, mixing may be performed using a mill roll, a Banbury mixer, a super mixer, or the like, and kneading may be performed using a single screw or twin screw extruder. This mixing and kneading is usually performed at a temperature of about 120 to 220 ° C. A method of adding an additive at the polymerization stage of a polyolefin-based resin, after mixing in a desired ratio together with a granulating aid such as a binder, wax, solvent, silica, etc., and then granulating to make a one-pack composite additive, A method of adding a one-pack composite additive to a polyolefin resin, a method of preparing a masterbatch containing the additive at a high concentration, and adding the masterbatch to the polyolefin resin can be used.

The resin composition of the present invention can be obtained by uniformly mixing and kneading the above components. Although the method is not particularly limited, for example, dry blending is performed with a mixer such as a Henschel mixer or a tumbler, and the processing temperature is 100 ° C. using an extruder, a Banbury mixer, a roll, a Brabender plastograph, a kneader, or the like. Manufactured by kneading at ~ 260 ° C. Among these, it is preferable that the mixer is manufactured using a Henschel mixer, and the processing machine is manufactured using an extruder, particularly a twin screw extruder.

The molded article of the present invention is molded using the resin composition of the present invention. Molding can be performed using a known molding method. For example, a molded product 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 molded article 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, miscellaneous goods such as toys, and tanks. Examples of such products include molded products such as storage and storage containers, films, and fibers.

Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited by the following examples.

[Synthesis of Nucleator Compound (3-1)]
1.1 mol of methyl 4-chloroformylbenzoate and 4 mol of triethylamine are reacted in dichloroethane per mole of benzoylhydrazide to give methyl-4- (2-benzohydrazine-1-carbonyl) benzoate as a precursor It was synthesized as (4-3-1). This precursor (4-3-1) was saponified in an alkaline solution in which sodium hydroxide was dissolved in a water / ethanol mixed solvent to obtain a nucleating agent compound represented by formula (3-1): sodium 4- ( 2-Benzoylhydrazine-1-carbonyl) benzoate was obtained. This synthetic route is shown below.

[Synthesis of Nucleator Compound (3-2)]
The sodium hydroxide used for saponification of the precursor (4-3-1) was changed to lithium hydroxide, and a nucleating agent compound represented by the following formula (3-2): lithium-4- (2-benzoyl) Hydrazine-1-carbonyl) benzoate was obtained.

[Synthesis of Nucleator Compound (3-3)]
1.1 mole of methyl 4-chloroformylbenzoate per 4 moles of 4-chlorobenzohydrazide, 4 moles of triethylamine are reacted in dichloroethane to give methyl-4- (2-benzohydrazine-1-carbonyl) Benzoate was synthesized as the following precursor (4-3-3). This precursor (4-3-3) was saponified in an alkaline solution in which sodium hydroxide was dissolved in a water / ethanol mixed solvent. The saponified product was separated and washed as a precipitate to obtain a nucleating agent compound represented by the following formula (3-3): sodium 4- (2- (4-chlorobenzoyl) hydrazine-1-carbonyl) benzoate.

[Synthesis of Nuclear Agent Compound (3-4)]
The sodium hydroxide used for the saponification of the precursor (4-3-3) was changed to lithium hydroxide, and a nucleating agent compound represented by the following formula (3-4): lithium-4- (2- ( 4-Chlorobenzoyl) hydrazine-1-carbonyl) benzoate was obtained.

[Production of polyolefin resin composition]
Phenolic antioxidant: tetrakis [methylene-3- (3 ′, 5′-ditert-butyl-4′-hydroxyphenyl) propionate per 100 parts by mass of homopolypropylene (melt flow rate: 7.7 g / 10 min) ] 0.05 part by weight of methane, phosphorus antioxidant: 0.1 part by weight of tris (2,4-di-tert-butylphenyl) phosphite, metal soap: 0.05 part by weight of calcium stearate, and Table 1 A nucleating agent compound (3-1), (3-2), (3-3), (3-4) in the amount shown in FIG. 6 was added and mixed, and a twin screw extruder manufactured by Ikegai Co., Ltd. (with PCM30, 60 mesh) Was granulated at an extrusion temperature of 230 ° C. to obtain pellets. Thus, the polyolefin resin compositions (Examples 1 to 7) of the present invention were obtained. On the other hand, a pellet of a composition for comparison (Comparative Example 1) was obtained under the same conditions except that the nucleating agent compound was changed to sodium benzoate.

[Evaluation of polyolefin resin composition]
(1) Crystallization temperature The obtained pellet was finely broken, 5 mg was weighed and filled into an aluminum pan, and the crystallization temperature was measured with a differential scanning calorimeter (apparatus: Diamond manufactured by Perkin Elmer). The temperature was raised to 230 ° C. at a rate of 50 ° C./min, held for 5 minutes, and then cooled to 50 ° C. at 10 ° C./min, and the temperature of the measured exothermic peak (° C.) was obtained as the crystallization temperature. . After leaving it in a thermostat at 23 ° C. and 50% humidity for 48 hours, the flexural modulus (MPa) was measured with a bending tester (manufactured by Shimadzu Corporation; AG-IS) in accordance with ISO178. The results are shown in Table 1.

(2) Flexural modulus After the pellets of Examples 1 to 7 and Comparative Example 1 were dried at 60 ° C. for 5 hours, using an injection molding machine (EC-220 manufactured by Toshiba Machine Co., Ltd.), an injection temperature of 230 ° C. and a mold Bending test pieces of 80 mm × 10 mm × 4 mm were produced by injection molding at a temperature of 40 ° C. This test piece was allowed to stand for 48 hours in a thermostat at 23 ° C. and 50% humidity. Thereafter, the flexural modulus (MPa) of the test piece was measured in accordance with ISO178 using a bending tester (AG-IS manufactured by Shimadzu Corporation). After leaving still for 48 hours or more in a thermostat at 23 ° C. and 50% humidity, the flexural modulus (MPa) was measured with a bending tester (manufactured by Shimadzu Corporation; AG-IS) in accordance with ISO178. The results are shown in Table 1.

(3) Deflection temperature under load (HDT)
Immediately after molding the test piece produced in (2), it was allowed to stand for 48 hours in a thermostat at 23 ° C. and 50% humidity. Thereafter, the deflection temperature (° C.) of flatwise load was measured according to ISO75 (load 1.8 MPa). The results are shown in Table 1.

(4) Izod impact strength After the pellets of Examples 1 to 7 and Comparative Example 1 were dried at 60 ° C. for 5 hours, using an injection molding machine (EC-220 manufactured by Toshiba Machine Co., Ltd.), an injection temperature of 230 ° C. and a mold Injection molding was carried out at a temperature of 40 ° C. to produce a 60 mm × 60 mm × 1 mm flat test piece. This test piece was allowed to stand for 48 hours in a thermostat at 23 ° C. and 50% humidity. Thereafter, the Izod impact strength (J / m) of the test piece was measured according to ISO180. The results are shown in Table 1.

(5) The test piece manufactured by shrinkage ratio anisotropy (4) was immediately placed in a thermostat at 23 ° C. and 50% humidity for 48 hours after molding. The ratio (L _MD / L _TD ) of the MD direction (resin flow direction) dimension (L _MD ) (mm) and the TD direction (width direction) dimension (L _TD ) (mm) of the test specimen after standing is a polyolefin resin. It was calculated as an index (shrinkage ratio anisotropy) of a dimensional change of a molded article made of the composition. The closer the shrinkage ratio anisotropy is to 1, the higher the dimensional stability of the molded product shape. The results are shown in Table 1.

In Examples 1 to 8, a significant increase in the crystallization temperature is seen compared to Comparative Example 1 in which no nucleating agent was added. Sodium benzoate used in Comparative Example 2 is a conventional nucleating agent, and its crystallization temperature raising effect is poor compared to Examples 1-8. Therefore, the nucleating agent compounds (3-1), (3-2), (3-3), and (3-4) have a remarkable effect of improving the crystallization temperature with respect to polyolefin resins, particularly polypropylene resins, That is, it can be seen that it has a remarkable nuclear growth effect.

Furthermore, since the flexural modulus, HDT, and Izod impact strength of Examples 1 to 8 show values equal to or higher than those of Comparative Examples 1 and 2, the nucleating agent compound of the present invention impairs the mechanical properties of the polyolefin resin. It can be seen that it exhibits the function as a nucleating agent while improving the mechanical properties of the polyolefin resin. In addition, it can be seen from the results in Table 1 that there is no problem in the dimensional stability of the molded product obtained from the polyolefin resin composition by blending the nucleating agent of the present invention.

The compounds of the present invention contribute to the production of molding materials containing polyolefin resins as excellent nucleating agents for polyolefin resins. The polyolefin-based resin composition containing the compound of the present invention as a nucleating agent is particularly suitable for automotive materials, housing materials, mechanical / mechanical parts, and the like.

Claims (5)

1. A compound represented by the following formula (1).
   

   

   
   (In Formula (1), Ring A and Ring B represent an aryl group having 6 to 20 carbon atoms or a cycloalkyl group having 3 to 20 carbon atoms, M represents an alkali metal atom, and an aryl group or cycloalkyl group) The group may be substituted with a hydroxyl group, a halogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms and an alkenyl group having 2 to 10 carbon atoms. (The alkyl group therein may be interrupted by a carbonyl group or an oxygen atom, and may have an unsaturated bond.)
2. The compound of Claim 1 represented by the following formula | equation (2).
   

   

   
   (In the formula (2), M represents an alkali metal atom, and R ¹ to R ⁹ each independently represents a hydrogen atom, a hydroxyl group, a halogen atom, an alkyl group having 1 to 10 carbon atoms, or 1 to 10 represents an alkoxy group, an alkenyl group having 2 to 10 carbon atoms, and the alkyl group or the alkyl group in the alkoxy group may be interrupted by a carbonyl group or an oxygen atom, and has an unsaturated bond. May be.)
3. A nucleating agent containing one or more compounds represented by the above formula (1) or the above formula (2).
4. Including a polyolefin-based resin and the nucleating agent according to claim 3,
   A polyolefin resin composition in which the total amount of one or more compounds represented by the above formula (1) or the above formula (2) is in the range of 0.0001 to 10 parts by mass with respect to 100 parts by mass of the polyolefin resin. object.
5. A molded article comprising the polyolefin resin composition according to claim 4.