JP2022011537A - Foam molded article and method for producing foam molded article - Google Patents

Abstract

To provide a foam molded article excellent in impact resistance and a method for producing a foam molded article.SOLUTION: The foam molded article is obtained by foam molding a resin composition containing a polyolefin resin and a nucleating agent for polyolefin resins which contains a compound represented by the following general formula (1). (In the general formula (1), M represents an alkali metal, an alkaline earth metal, hydroxyaluminum or dihydroxyaluminum; a represents 1 or 2; x represents 1 or 2; ax=2 is satisfied; and Z represents a group having a cyclohexane ring or a benzene ring.)SELECTED DRAWING: None

Description

The present invention relates to an effervescent molded product and a method for producing an effervescent molded product.

Effervescent molded products obtained by foam molding of polyolefin resins are lightweight and have excellent heat resistance, and are therefore used in a wide range of applications such as automobile parts, home appliance housings, building materials, and food containers.

As a foam molded product made of a polyolefin resin, Patent Document 1 proposes a foam sheet obtained by extrusion foam molding of a polypropylene resin.

Japanese Unexamined Patent Publication No. 2000-280334

Depending on the application of the foam molded product, a molded product having excellent impact resistance may be required. However, the foam molded product described in Patent Document 1 has room for further improvement in impact resistance.

Therefore, an object of the present invention is to provide an effervescent molded product having excellent impact resistance and a method for producing the effervescent molded product.

As a result of diligent studies to solve the above problems, the present inventors have found that a specific compound containing an aspartic acid structure exhibits an excellent β-crystal forming action on a polyolefin-based resin. Then, the present inventors have found that the foam-molded product obtained by foam-molding a polyolefin-based resin containing the compound can solve the above-mentioned problems, and have completed the present invention.

（上記一般式（１）中、Ｍはアルカリ金属、アルカリ土類金属、ヒドロキシアルミニウムまたはジヒドロキシアルミニウムを表し、ａは１または２を表し、ｘは１または２を表し、ａｘ＝２を満たす。Ｚは下記一般式（２）または（３）で表される構造を有する基を表す。）

（上記一般式（２）および（３）中、Ｙは直接結合または炭素原子数１～４のアルキレン基を表し、Ｒ^１～Ｒ^１０はそれぞれ独立に、水素原子、ハロゲン原子または炭素原子数１～６のアルキル基を表し、＊はカルボニル炭素と結合する位置を表す。）で表される化合物を含む発泡成形品である。 That is, the present invention is a foam-molded product obtained by foam-molding a resin composition containing a polyolefin-based resin and a nucleating agent for a polyolefin-based resin, and the nucleating agent for a polyolefin-based resin has the following general formula ( 1),

(In the above general formula (1), M represents an alkali metal, an alkaline earth metal, hydroxyaluminum or dihydroxyaluminum, a represents 1 or 2, x represents 1 or 2, and ax = 2 is satisfied. Represents a group having a structure represented by the following general formula (2) or (3).)

(In the above general formulas (2) and (3), Y represents a direct bond or an alkylene group having 1 to 4 carbon atoms, and R ¹ to R ¹⁰ independently represent a hydrogen atom, a halogen atom or 1 carbon atom. It represents an alkyl group of up to 6 and * represents a position to be bonded to a carbonyl carbon.) It is a foamed molded product containing a compound represented by).

In the foamed molded product of the present invention, the content of the nucleating agent for the polyolefin resin is preferably 0.001 to 10 parts by mass with respect to 100 parts by mass of the polyolefin resin.

Further, in the foam molded product of the present invention, it is preferable that the polyolefin-based resin is a polypropylene-based resin.

Further, the foam molded product of the present invention is preferably an automobile part or a home appliance housing.

（上記一般式（１）中、Ｍはアルカリ金属、アルカリ土類金属、ヒドロキシアルミニウムまたはジヒドロキシアルミニウムを表し、ａは１または２を表し、ｘは１または２を表し、ａｘ＝２を満たす。Ｚは下記一般式（２）または（３）で表される構造を有する基を表す。）

（上記一般式（２）および（３）中、Ｙは直接結合または炭素原子数１～４のアルキレン基を表し、Ｒ^１～Ｒ^１０はそれぞれ独立に、水素原子、ハロゲン原子または炭素原子数１～６のアルキル基を表し、＊はカルボニル炭素と結合する位置を表す。）で表される化合物を含む発泡成形品の製造方法である。 Further, the present invention is a method for producing a foam-molded product, which comprises a molding step of foam-molding a resin composition, wherein the resin composition contains a polyolefin-based resin and a nucleating agent for a polyolefin-based resin. The nucleating agent for polyolefin resin is the following general formula (1),

(In the above general formula (1), M represents an alkali metal, an alkaline earth metal, hydroxyaluminum or dihydroxyaluminum, a represents 1 or 2, x represents 1 or 2, and ax = 2 is satisfied. Represents a group having a structure represented by the following general formula (2) or (3).)

(In the above general formulas (2) and (3), Y represents a direct bond or an alkylene group having 1 to 4 carbon atoms, and R ¹ to R ¹⁰ independently represent a hydrogen atom, a halogen atom or 1 carbon atom. It represents an alkyl group of up to 6 and * represents a position to be bonded to a carbonyl carbon.) It is a method for producing a foamed molded product containing a compound represented by).

According to the present invention, it is possible to provide an effervescent molded product having excellent impact resistance and a method for producing the effervescent molded product.

Hereinafter, embodiments of the present invention will be described in detail.
First, the foam molded product according to this embodiment will be described.

<Effervescent molded product>
The foam-molded product according to the present embodiment is a foam-molded product obtained by foam-molding a resin composition containing a polyolefin-based resin and a nucleating agent for a polyolefin-based resin. The nucleating agent for a polyolefin resin contains a compound represented by the following general formula (1).

ここで、上記一般式（１）中、Ｍはアルカリ金属、アルカリ土類金属、ヒドロキシアルミニウムまたはジヒドロキシアルミニウムを表し、ａは１または２を表し、ｘは１または２を表し、ａｘ＝２を満たす。また、Ｚは下記一般式（２）または（３）で表される構造を有する基を表す。

ここで、上記一般式（２）および（３）中、Ｙは直接結合または炭素原子数１～４のアルキレン基を表し、Ｒ^１～Ｒ^１０はそれぞれ独立に、水素原子、ハロゲン原子または炭素原子数１～６のアルキル基を表し、＊はカルボニル炭素と結合する位置を表す。

Here, in the above general formula (1), M represents an alkali metal, an alkaline earth metal, hydroxyaluminum or dihydroxyaluminum, a represents 1 or 2, x represents 1 or 2, and ax = 2 is satisfied. .. Further, Z represents a group having a structure represented by the following general formula (2) or (3).

Here, in the above general formulas (2) and (3), Y represents a direct bond or an alkylene group having 1 to 4 carbon atoms, and R ¹ to R ¹⁰ independently represent a hydrogen atom, a halogen atom or a carbon atom, respectively. It represents an alkyl group of numbers 1 to 6, and * represents a position to be bonded to a carbonyl carbon.

The foam molded product according to this embodiment has excellent impact resistance.

Examples of the polyolefin resin include polyethylene resins such as low density polyethylene, linear low density polyethylene, high density polyethylene, crosslinked polyethylene, and ultrahigh molecular weight polyethylene, homopolypropylene, random copolymer polypropylene, block copolymer polypropylene, and impact copolymer polypropylene. , High-impact copolymer polypropylene, polypropylene-based resins such as maleic anhydride-modified polypropylene, polybutene-1, cycloolefin polymer, poly-3-methyl-1-butene, poly-3-methyl-1-pentene, poly-4-methyl Examples thereof include α-olefin polymers such as -1-pentene, ethylene-methylmethacrylate copolymers, and α-olefin copolymers such as polyethylene-vinyl acetate copolymers. One of these polyolefin resins may be used alone, or two or more thereof may be used in combination. Further, the polyolefin-based resin may be alloyed. Among these, polypropylene-based resin is particularly preferable as the polyolefin-based resin. Molecular weight, degree of polymerization, density, softening point, ratio of insoluble matter in solvent, degree of stereoregularity, presence or absence of catalyst residue, type and compounding ratio of raw material monomer, catalyst used for polymerization The type (for example, a Cheegler catalyst, a metallocene catalyst, etc.) and the like are not particularly limited and may be appropriately selected.

As described above, the nucleating agent for a polyolefin resin contains the compound represented by the above general formula (1).

Examples of the alkali metal represented by M in the general formula (1) include lithium, sodium and potassium. Examples of the alkaline earth metal represented by M include magnesium, calcium, barium and the like. As M, sodium, calcium and hydroxyaluminum are preferable, and sodium is particularly preferable. Further, in the general formula (1), it is particularly preferable that a is 2 and x is 1.

Examples of the alkylene group having 1 to 4 carbon atoms represented by Y in the general formulas (2) and (3) include a methylene group, an ethylene group, a propylene group, a butylene group and an isobutylene group. As Y in the general formulas (2) and (3), a direct bond is preferable, and a methylene group is preferable in the above.

Examples of the halogen atom represented by R ¹ to R ¹⁰ in the general formulas (2) and (3) include fluorine, chlorine, bromine, iodine and the like. Of these, chlorine is particularly preferred.

Examples of the alkyl group having 1 to 6 carbon atoms represented by R ¹ to R ¹⁰ in the general formulas (2) and (3) include a linear or branched alkyl group or a cycloalkyl group. Can be mentioned. Specific examples of the alkyl group having 1 to 6 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, a cyclopropyl group, an n-butyl group, a sec-butyl group and a tert-butyl group. Examples thereof include an isobutyl group, a cyclobutyl group, an n-amyl group, a tert-amyl group, a cyclopentyl group, an n-hexyl group and a cyclohexyl group.

As R ¹ to R ¹⁰ in the general formulas (2) and (3), a hydrogen atom or a halogen atom is preferable, and a hydrogen atom is particularly preferable.

It is preferable that Z in the general formula (1) is a group represented by the general formula (3).

Specific examples of the compound represented by the general formula (1) include the following. However, the nucleating agent for polyolefin-based resin is not limited to these.

The compound represented by the general formula (1) is prepared by reacting, for example, aspartic acid with a carboxylic acid chloride such as a benzoic acid chloride or a cyclohexanecarboxylic acid chloride, and then adding the reaction product obtained to the sodium hydroxide. It can be produced by a method of reacting with a metal hydroxide such as.

If necessary, the nucleating agent for a polyolefin-based resin further contains a compound other than the compound represented by the general formula (1) and having a property of promoting crystallization of the polyolefin-based resin. You may. Examples of such compounds include sodium 2,2'-methylenebis (4,6-di-tert-butylphenyl) phosphate and lithium 2,2'-methylenebis (4,6-di-tert-butylphenyl) phosphate. , Dihydroxyaluminum 2,2'-methylenebis (4,6-di-tert-butylphenyl) phosphate, hydroxyaluminum bis [2,2'-methylenebis (4,6-di-tert-butylphenyl) phosphate] and other aromatics Group phosphate metal salt, sodium benzoate, 4-tert-butyl benzoate aluminum salt, sodium adipate, 2-sodium bicyclo [2.2.1] heptane-2,3-dicarboxylate, calcium cyclohexane-1, Carboxylic acid metal salts such as 2-dicarboxylate, dibenzylene sorbitol, bis (methylbenzylene) sorbitol, bis (3,4-dimethylbenzylene) sorbitol, bis (p-ethylbenzylene) sorbitol, bis (dimethylbenzylene) sorbitol, 1,2,3-Trideoxy-4,6: 5,7-o-bis (4-propylbenzylene) Nonitol and other polyol derivatives, N, N', N "-tris [2-methylcyclohexyl] -1,2 , 3-Propanetricarboxamide, N, N', N "-tricyclohexyl-1,3,5-benzenetricarboxamide, N, N'-dicyclohexylnaphthalenedicarboxamide, 1,3,5-tri (dimethylisopropoil) Examples thereof include amide compounds such as amino) benzene.

The content of the nucleating agent for a polyolefin resin contained in the resin composition is preferably 0.001 to 10 parts by mass with respect to 100 parts by mass of the polyolefin resin. The content of the nucleating agent for the polyolefin resin is more preferably 0.005 part by mass or more, further preferably 0.01 part by mass or more, and 0.02 mass by mass with respect to 100 parts by mass of the polyolefin resin. It is even more preferable that the amount is more than one part. The content of the nucleating agent for the polyolefin resin is more preferably 5 parts by mass or less, more preferably 3 parts by mass or less, and 1 part by mass or less with respect to 100 parts by mass of the polyolefin resin. It is even more preferable, and it is particularly preferable that the amount is 0.5 parts by mass or less.

If necessary, the resin composition may include a phenol-based antioxidant, a phosphorus-based antioxidant, a sulfur-based antioxidant, other antioxidants, a hindered amine compound, an ultraviolet absorber, a fatty acid metal salt, a flame retardant, and the like. Additives such as flame retardant aids, lubricants, fillers, hydrotalcites, antioxidants, optical brighteners, pigments and dyes may be included.

Examples of the phenolic antioxidant include 2,6-di-tert-butyl-4-ethylphenol, 2-tert-butyl-4,6-dimethylphenol, styrated phenol, and 2,2'-methylenebis (4). -Ethyl-6-tert-butylphenol), 2,2'-thiobis- (6-tert-butyl-4-methylphenol), 2,2'-thiodiethylenebis [3- (3,5-di-tert-) Butyl-4-hydroxyphenyl) propionate], 2-methyl-4,6-bis (octylsulfanylmethyl) phenol, 2,2'-isobutylidenebis (4,6-dimethylphenol), isooctyl-3- (3) , 5-Di-tert-butyl-4-hydroxyphenyl) propionate, N, N'-hexane-1,6-diylbis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionamide] , 2,2'-Oxamide-bis [ethyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 2-ethylhexyl-3- (3', 5'-di-tert- Butyl-4'-hydroxyphenyl) propionate, 2,2'-ethylenebis (4,6-di-tert-butylphenol), 3,5-di-tert-butyl-4-hydroxybenzenepropanoic acid and C13-15 alkyl , 2,5-Di-tert-amylhydroquinone, a polymer of hinderedphenol (ADEKA POLYMER ADDITIVES EUROPES SAS trade name "AO.OH.98"), 2,2'-methylenebis [6- (1) -Methylcyclohexyl) -p-cresol], 2-tert-butyl-6- (3-tert-butyl-2-hydroxy 5-methylbenzyl) -4-methylphenylacrylate, 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] calci Um salt, reaction product of 5,7-bis (1,1-dimethylethyl) -3-hydroxy-2 (3H) -benzofuranone and o-xylene, 2,6-di-tert-butyl-4-( 4,6-bis (octylthio) -1,3,5-triazine-2-ylamino) phenol, DL-a-tocophenol (vitamin E), 2,6-bis (α-methylbenzyl) -4-methylphenol , Bis [3,3-bis- (4'-hydroxy-3'-tert-butyl-phenyl) butanoic acid] glycol ester, 2,6-di-tert-butyl-p-cresol, 2,6-diphenyl- 4-Octadecyloxyphenol, stearyl (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, distearyl (3,5-di-tert-butyl-4-hydroxybenzyl) phosphonate, tridecyl-3, 5-tert-Butyl-4-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) -Hydro Xyphenyl) propionyloxyethyl] isocyanurate, tetrakis [methylene-3- (3', 5'-tert-butyl-4'-hydroxyphenyl) propionate] methane, 2-tert-butyl-4-methyl-6- (2) -Acryloyloxy-3-tert-butyl-5-methylbenzyl) phenol, 3,9-bis [2- (3-tert-butyl-4-hydroxy-5-methylhydrocinnamoyleoxy) -1,1-dimethyl) Ethyl] -2,4,8,10-tetraoxaspiro [5.5] undecane, triethylene glycolbis [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, 3- (3,5) such as 3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid amide, lauryl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid amide, etc. -Dialkyl-4-hydroxyphenyl) propionic acid derivative and the like can be mentioned.

Examples of the phosphorus antioxidant include triphenylphosphite, diisooctylphosphite, heptaxis (dipropylene glycol) triphosphite, triisodecylphosphite, diphenylisooctylphosphite, diisooctylphenylphosphite, and diphenyl. Tridecylphosphite, triisooctylphosphite, trilaurylphosphite, diphenylphosphite, tris (dipropylene glycol) phosphite, dioleylhydrogenphosphite, trilauryltrithiophosphite, bis (tridecyl) phosphite, tris (Isodecyl) phosphite, tris (tridecyl) phosphite, diphenyldecylphosphite, dinonylphenylbis (nonylphenyl) phosphite, poly (dipropylene glycol) phenylphosphite, tetraphenyldipropylene glycol diphosphite, trisnonyl Phenyl Phenyl Phenyl Phenyl, Tris (2,4-di-tert-butylphenyl) Phenyl Phenyl, Tris (2,4-Di-tert-Butyl-5-Methylphenyl) Phenyl Phenyl, Tris [2-tert-Butyl-4- (3-tert-Butyl-4-hydroxy-5-Methylphenylthio) -5-Methylphenyl] Phenylphosphite, tri (decyl) phosphite, octyldiphenylphosphite, di (decyl) monophenylphosphite, distearylpenta Mixture of erythritol and calcium stearate salt, alkyl (C10) bisphenol A phosphite, tetraphenyl-tetra (tridecyl) pentaerythritol tetraphosphite, bis (2,4-di-tert-butyl-6-methylphenyl) ethylphos Fight, Tetra (Tridecyl) Isopropyridendiphenol Diphosphite, Tetra (Tridecyl) -4,4'-n-Buchilidenebis (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-Phenylphoenylthrene-10-oxide, (1-methyl-1-propenyl-3-iriden) Tris (1,1-dimethylethyl) -5-methyl-4,1-phenylene) Hexa Tridecylphosphite, 2,2'-methylenebis (4,6-di-tert-butylphenyl) -2-ethylhexylphosphite, 2,2'-methylenebis (4,6-di-tert-butylphenyl) -octadecyl Phosphite, 2,2'-etylidenebis (4,6-di-tert-butylphenyl) fluorophosphite, 4,4'-butylidenebis (3-methyl-6-tert-butylphenylditridecyl) phosphite, tris (2-[(2,4,8,10-tetrakiss-tert-butyldibenzo [d, f] [1,3,2] dioxaphosfepine-6-yl) oxy] ethyl) amine, 3,9 -Bis (4-nonylphenoxy) -2,4,8,10-tetraoxa-3,9-diphosphespiro [5,5] undecane, 2,4,6-tri-tert-butylphenyl-2-butyl -2-Ethyl-1,3-propanediol phosphite, poly 4,4'-isopropyridene diphenol C12-15 alcohol phosphite, bis (diisodecyl) pentaerythritol diphosphite, bis (tridecyl) pentaerythritol diphosphite , Bis (octadecyl) pentaerythritol diphosphite, bis (nonylphenyl) pentaerythritol diphosfite, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis (2,4,6-tri) -Tert-Butylphenyl) pentaerythritol diphosphite, bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, bis (2,4-dicumylphenyl) pentaerythritol diphosphite And so on.

Examples of the sulfur-based antioxidant include tetrakis [methylene-3- (laurylthio) propionate] methane and bis (methyl-4- [3-n-alkyl (C12 / C14) thiopropionyloxy] 5-tert-butylphenyl. ) Sulfuride, ditridecyl-3,3'-thiodipropionate, dilauryl-3,3'-thiodipropionate, dimyristyl-3,3'-thiodipropionate, distearyl-3,3'-thiodipropio Nate, lauryl / stearylthiodipropionate, 4,4'-thiobis (6-tert-butyl-m-cresol), 2,2'-thiobis (6-tert-butyl-p-cresol), distearyl-di Sulfuride is mentioned.

Other antioxidants include N-benzyl-α-phenylnitrone, N-ethyl-α-methylnitrone, N-octyl-α-heptylnitrone, N-lauryl-α-undecylnitrone, N-tetradecyl-α. -Tridecylnitron, N-Hexadecyl-α-Pentadecylnitron, N-octyl-α-Heptadecylnitron, N-Hexadecyl-α-Heptadecylnitrone, N-Octadecyl-α-Pentadecylnitron, N-Heptadecyl-α -Nitron compounds such as heptadecylnitron, N-octadecyl-α-heptadecylnitron, 3-arylbenzofuran-2 (3H) -one, 3- (alkoxyphenyl) benzofuran-2-one, 3- (acyloxyphenyl) benzofuran -2 (3H) -on, 5,7-di-tert-butyl-3- (3,4-dimethylphenyl) -benzofuran-2 (3H) -on, 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) -on, 6 -(2- (4- (5,7-di-tert-2-oxo-2,3-dihydrobenzofuran-3-yl) phenoxy) ethoxy) -6-oxohexyl-6-((6-hydroxyhexanoyl) phenoxy) ethoxy) -6-oxohexyl-6-((6-hydroxyhexanoyl) ) Oxy) hexanoate, 5-di-tert-butyl-3-(4-((15-hydroxy-3,6,9,13-tetraoxapentadecyl) oxy) phenyl) benzofuran-2 (3H) on, etc. Examples thereof include benzofuran compounds.

Examples of the hindered amine compound include 2,2,6,6-tetramethyl-4-piperidyl stearate, 1,2,2,6,6-pentamethyl-4-piperidyl stearate, 2,2,6,6-. Tetramethyl-4-piperidylbenzoate, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, tetrakis (2,2,6,6-tetramethyl-4-piperidyl) -1,2,3 , 4-Butan Tetracarboxylate, Tetrakiss (1,2,2,6,6-Pentamethyl-4-piperidyl) -1,2,3,4-Butane Tetracarboxylate, Bis (2,2,6,6- Tetramethyl-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-piperidyl) Amino) 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-triazine-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-triazine-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-triazine-6-ylamino] undecane, 1,6 , 11-Tris [2,4-bis (N-butyl-N- (1,2,2,6,6-pentamethyl-4-piperidyl) amino-s-triazine-6-ylamino] undecane, 3,9- Bis [1,1-dimethyl-2- {Tris (2,2) , 6,6-Tetramethyl-4-piperidyloxycarbonyl) Butylcarbonyloxy} Ethyl] -2,4,8,10-Tetraoxaspiro [5.5] Undecane, 3,9-Bis [1,1-dimethyl] -2- {Tris (1,2,2,6,6-pentamethyl-4-piperidyloxycarbonyl) butylcarbonyloxy} ethyl] -2,4,8,10-tetraoxaspiro [5.5] undecane, bis (1-Undecyloxy-2,2,6,6-Tetramethylpiperidine-4-yl) Carbonate, 2,2,6,6-Tetramethyl-4-piperidylhexadecanoate, 2,2,6 6-Tetramethyl-4-piperidyl octadecanoate and the like can be mentioned.

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-acryloyloxy) Ethyl) -5-Methylphenyl] benzotriazole, 2- [2-hydroxy-3- (2-methacryloyloxyethyl) -5-tert-butylphenyl] benzotriazole, 2- [2-hydroxy-3- (2-) Methacyoyloxyethyl) -5-tert-octylphenyl] benzotriazole, 2- [2-hydroxy-3- (2-methacryloyloxyethyl) -5-tert-butylphenyl] -5-chlorobenzotriazole, 2- [2 -Hydroxy-5- (2-methacryloyloxyethyl) phenyl] benzotriazole, 2- [2-hydroxy-3-tert-butyl-5- (2-methacryloyloxyethyl) phenyl] benzotriazole, 2- [2-hydroxy -3-tert-Amil-5- (2-methacryloyloxyethyl) phenyl] benzotriazole, 2- [2-hydroxy-3-tert-butyl-5- (3-methacryloyloxypropyl) phenyl] -5-chlorobenzo Triazole, 2- [2-hydroxy-4- (2-methacryloyloxymethyl) phenyl] benzotriazole, 2- [2-hydroxy-4- (3-methacryloyloxy-2-hydroxypropyl) phenyl] benzotriazole, 2- [2-Hydroxy-4- (3-methacryloyloxypropyl) phenyl] 2- (2-hydroxyphenyl) benzotriazoles such as benzotriazole; Phenylsalicylate, 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) Phenylates 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 Substituent oxanilides such as'-ethoxy oxanilide, 2-ethoxy-4'-dodecyl oxanilide; ethyl-α-cyano-β, β-diphenyl acrylate, methyl-2-cyano-3-methyl-3- ( Cyanoacrylates such as p-methoxyphenyl) acrylate; 2- (4,6-diphenyl-1,3,5-triazine-2-yl) -5-hexyloxyphenol, 2- (2-hydroxy-4-oct) Xiphenyl) -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, trioctyl-2,2', 2 "-((1,3,5-triazine-2,4) 6-Triyl) Tris (3-hydroshikibenzene-4-,1-diyl) tripropionate), 2- (4,6-diphenyl-1,3,5-triazine-2-yl) -5-[2 -(2-Ethylhexanoyloxy) ethoxy] phenol, 2,4,6-tris (2-hydroxy-4-hexyloxy-3-methylphenyl) -1,3,5-triazine, 1,12-bis [ Triazines such as 2- [4- (4,6-diphenyl-1,3,5-triazine-2-yl) -3-hydroxyphenoxy] ethyl] dodecandioate; various metal salts or metal chelates, in particular. Examples thereof include salts of nickel and chromium, chelates and the like.

Examples of the fatty acid metal salt include metal salts of fatty acids having 12 to 30 carbon atoms including linear or branched fatty acid residues. Examples of the metal ion constituting the fatty acid metal salt include sodium ion, potassium ion, lithium ion, dihydroxyaluminum ion, calcium ion, zinc ion, barium ion, magnesium ion, hydroxyaluminum ion and the like. Sodium ion, potassium ion, lithium ion and calcium ion are preferable. Fatty acids constituting the fatty acid metal salt include lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, linoleic acid, linolenic acid, arachidic acid, arachidonic acid, behenic acid, lignoseric acid, serotinic acid, montanic acid, and melicin. Acids and the like can be mentioned, and among these, myristic acid and stearic acid are preferable. The fatty acid constituting the fatty acid metal salt may be one in which one or more of the hydrogen atoms of the fatty acid residue are substituted with hydroxyl groups. Examples of such fatty acids include 12-hydroxystearic acid and 12-hydroxyoleic acid.

Examples of the flame retardant include triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, cresyldiphenyl phosphate, cresyl-2,6-dixylenyl phosphate, resorcinolbis (diphenyl phosphate), (1-methylethylidene). -4,1-Phenyltetraphenyldiphosphate, 1,3-Phenyltetrakis (2,6-dimethylphenyl) phosphate, trade names "Adekastab FP-500", "Adekastab FP-600", "Adekastab" manufactured by ADEKA Co., Ltd. FP-800 ”aromatic phosphate ester, divinyl phenylphosphonate, diallyl phenylphosphonate, phosphonic acid ester such as phenylphosphonic acid (1-butenyl), phenyl diphenylphosphinate, methyl diphenylphosphinate, 9,10-dihydro Phenyl acid esters such as -9-oxa-10-phosphaphenanthrene-10-oxide derivative, phosphazene compounds such as bis (2-allylphenoxy) phosphazene, dicredylphosphazene, melamine phosphate, melamine pyrophosphate, melamine polyphosphate, Melum polyphosphate, ammonium polyphosphate, piperazine phosphate, piperazine pyrophosphate, piperazine polyphosphate, phosphorus-containing vinylbenzyl compound and phosphorus-based flame retardants such as red phosphorus, metal hydroxides such as magnesium hydroxide and aluminum hydroxide, and bromine. Bisphenol A type epoxy resin, brominated phenol novolac type epoxy resin, hexabromobenzene, pentabromotoluene, ethylenebis (pentabromophenyl), ethylenebistetrabromophthalimide, 1,2-dibromo-4- (1,2-) Dibromoethyl) cyclohexane, tetrabromocyclooctane, hexabromocyclododecane, bis (tribromophenoxy) ethane, brominated polyphenylene ether, brominated polystyrene and 2,4,6-tris (tribromophenoxy) -1,3,5 -Examples include triazine, tribromophenylmaleimide, tribromophenyl acrylate, tribromophenyl methacrylate, tetrabromobisphenol A-type dimethacrylate, pentabromobenzyl acrylate, and bromine-based flame retardants such as brominated styrene. These flame retardants are preferably used in combination with a drip inhibitor such as fluororesin and a flame retardant aid such as polyhydric alcohol and hydrotalcite.

Examples of the lubricant include saturated fatty acid amides such as stearic acid amide and behenic acid amide, unsaturated fatty acid amides such as oleic acid amide and erucic acid amide, ethylene bisstearic acid amide, butyl stearate, glycerol monostearate, and sorbitan mono. Examples thereof include palmitate, sorbitan monostearate, stearic acid, stearyl alcohol, mannitol, and hardened castor oil.

Examples of the filler include talc, mica, calcium carbonate, calcium oxide, calcium hydroxide, magnesium carbonate, magnesium hydroxide, magnesium oxide, magnesium sulfate, aluminum hydroxide, barium sulfate, glass powder, glass fiber, clay, and dolomite. , Silica, Alumina, Potassium Titanium Whisker, Wallastenite, Fibrous Magnesium Oxysulfate and the like, and the particle size (fiber diameter, fiber length and aspect ratio in the fibrous form) can be appropriately selected and used. .. Among these fillers, talc is particularly preferably used because it has an excellent effect of imparting rigidity and is easily available. Further, as the filler, a surface-treated filler can be used if necessary.

The hydrotalcites may be any complex salt compound containing magnesium, aluminum, a hydroxyl group, a carbonate group and arbitrary water of crystallization, and may be a natural product or a synthetic product. Further, the crystal structure, particle shape and particle size of hydrotalcites are not particularly limited. Further, the hydrotalcites may be those in which at least a part of magnesium or aluminum is replaced with another metal such as an alkali metal or zinc, and at least a part of a hydroxyl group or a carbonic acid group is a other anionic group. It may be replaced. Furthermore, the hydrotalcites may be those obtained by dehydrating crystalline water, and the surface thereof may be a higher fatty acid such as stearic acid, a higher fatty acid metal salt such as an alkali metal oleic acid salt, or an alkali metal salt dodecylbenzenesulfonic acid. It may be coated with an organic sulfonic acid metal salt such as, higher fatty acid amide, higher fatty acid ester, wax or the like.

Examples of the antistatic agent include a low molecular weight antistatic agent using a nonionic, anionic, cationic or amphoteric surfactant, and a high molecular weight antistatic agent using a polymer compound. Examples of the nonionic surfactant include polyethylene glycol type nonionic surfactants such as higher alcohol ethylene oxide adduct, fatty acid ethylene oxide adduct, higher alkylamine ethylene oxide adduct, and polyolefin glycol ethylene oxide adduct; polyethylene oxide and fatty acid ester of glycerin. , Pentaerythlit fatty acid ester, sorbit or sorbitan fatty acid ester, polyhydric alcohol alkyl ether, polyhydric alcohol type nonionic surfactant such as alkanolamine aliphatic amide and the like. Examples of the anionic surfactant include carboxylates such as alkali metal salts of higher fatty acids; sulfate esters such as higher alcohol sulfates and higher alkyl ether sulfates, alkylbenzene sulfonates and alkyl sulfonates. Sulfates such as paraffin sulfonates; phosphate ester salts such as higher alcohol phosphates and the like can be mentioned. Examples of the cationic surfactant include quaternary ammonium salts such as alkyltrimethylammonium salts. Examples of the amphoteric tenside include amino acid type amphoteric tenside agents such as higher alkylaminopropionate, and betaine type amphoteric tenside agents such as higher alkyldimethylbetaine and higher alkyldihydroxyethylbetaine. Among these, anionic surfactants are preferable, and sulfonates such as alkylbenzene sulfonates, alkyl sulfonates, and paraffin sulfonates are particularly preferable.

Examples of the polymer-type antistatic agent include ionomers and block polymers having polyethylene glycol as a hydrophilic portion. Examples of the ionomer include the ionomer described in JP-A-2010-132927. Examples of the polymer having polyethylene glycol as a hydrophilic portion include the polyether ester amide described in JP-A-7-10989, the polymer composed of polyolefin and polyethylene glycol described in US Pat. No. 6,552,131, and JP-A-2016-023254. Examples thereof include a polymer composed of polyester and polyethylene glycol described in the publication.

The fluorescent whitening agent is a compound that absorbs ultraviolet rays of sunlight or artificial light, converts them into visible light of purple to blue and radiates them, thereby promoting the whiteness and bluish tint of the molded product. Examples of the fluorescent whitening agent include benzoxazole compounds C.I. I. Fluorescent Fluorescenter 184; Coumarin-based compound C.I. I. Fluorescent Fluorescent 52; diaminostilbene dissulphonic acid-based compound C.I. I. Fluorescent Fluorescenter 24, 85, 71 and the like can be mentioned.

The pigment is not particularly limited, and a commercially available pigment may be used. Specific examples of the pigment include, for example, Pigment Red 1, 2, 3, 9, 10, 17, 22, 23, 31, 38, 41, 48, 49, 88, 90, 97, 112, 119, 122, 123. , 144, 149, 166, 168, 169, 170, 171, 177, 179, 180, 184, 185, 192, 200, 202, 209, 215, 216, 217, 220, 223, 224, 226, 227, 228 , 240, 254; Pigment Orange 13, 31, 34, 36, 38, 43, 46, 48, 49, 51, 52, 55, 59, 60, 61, 62, 64, 65, 71; Pigment Yellow 1, 3 , 12, 13, 14, 16, 17, 20, 24, 55, 60, 73, 81, 83, 86, 93, 95, 97, 98, 100, 109, 110, 113, 114, 117, 120, 125. , 126, 127, 129, 137, 138, 139, 147, 148, 150, 151, 152, 153, 154, 166, 168, 175, 180, 185; Pigment Green 7, 10, 36; Pigment Blue 15, 15 1, 15: 2, 15: 3, 15: 4, 15: 5, 15: 6, 22, 24, 29, 56, 60, 61, 62, 64; Pigment Violet 1, 15, 19, 23, 27 , 29, 30, 32, 37, 40, 50 and the like.

Dyes include azo dyes, anthraquinone dyes, indigoid dyes, triarylmethane dyes, xanthene dyes, alizarin dyes, acridin dyes, stillben dyes, thiazole dyes, naphthol dyes, quinoline dyes, nitro dyes, indamine dyes, oxadin dyes, and phthalocyanine dyes. , Cyanine dyes and the like.

The foaming ratio of the foamed molded product according to the present embodiment may be appropriately adjusted according to the intended use of the foamed molded product, and may be, for example, 1.3 to 8 times. From the viewpoint of achieving both the light weight and the mechanical properties of the foam-molded product, the foaming ratio of the foam-molded product is preferably 1.5 to 5 times, more preferably 2 to 4 times. Further, the density of the foam-molded product may be appropriately adjusted according to the intended use of the foam-molded product, and may be, for example, 0.1 to 0.7 g / cm ³ . From the viewpoint of achieving both the light weight and the mechanical properties of the foam-molded product, the density of the foam-molded product is preferably 0.18 to 0.6 g / cm ³ , preferably 0.22 to 0.45 g / cm ³ . It is more preferable to have. Here, the "density of the foam molded product" indicates the apparent density measured by the method specified in JIS K 7222.

Specific examples of the foam molded product include automobile parts such as bumpers, side mudguards and fenders, housing appliances, building materials such as pipes, food containers, pipes, cushioning materials and the like. Among these, when the foam-molded product is an automobile part or a home appliance housing, the feature of the foam-molded product according to the present embodiment, which is excellent in impact resistance, can be particularly effectively utilized.

Next, a method for manufacturing the foam molded product according to the present embodiment will be described.

<Manufacturing method of foam molded products>
The method for producing an effervescent molded product according to the present embodiment includes a molding step of foam molding the resin composition. Here, the resin composition contains a polyolefin-based resin and a nucleating agent for a polyolefin-based resin. The nucleating agent for a polyolefin resin contains a compound represented by the above general formula (1).

According to the method for producing an effervescent molded product according to the present embodiment, it is possible to produce an effervescent molded product having excellent impact resistance.

(Preparation process)
First, the above-mentioned resin composition is prepared. The method for preparing the resin composition is not particularly limited, and for example, the powder or pellet of the polyolefin-based resin is dry-blended with the above-mentioned nucleating agent for the polyolefin-based resin and, if necessary, other additives. The above-mentioned method for melt-kneading a mixture obtained by dry-blending the above-mentioned nucleating agent for polyolefin resin and other additives as necessary, the above-mentioned nucleating agent for polyolefin resin and other additions if necessary. A method of processing the agent into a pellet shape and adding it to the polyolefin resin, a master batch containing the above-mentioned nucleating agent for polyolefin resin and other additives as needed in a high concentration in the polyolefin resin was prepared. Examples thereof include a method of adding a master batch to a polyolefin resin. Further, the above-mentioned nucleating agent for polyolefin resin and other additives may be added to the polyolefin resin at the same time, or may be added separately. Here, the values of the melt flow rate, melt tension, etc. of the resin composition are not particularly limited, and are adjusted to be appropriate values according to the type of molding machine in foam molding, the shape of the mold, and the like. do it.

(Molding process)
Next, the resin composition prepared as described above is foam-molded. The foam molding method is not particularly limited, and may be, for example, an injection foam molding method, an extrusion foam molding method, a foam blow molding method, or the like. Examples of the foaming agent used in foam molding include propane, butane, pentane, hexane, cyclobutane, cyclopentane, monochlorologic fluoromethane, trichlorofluoromethane, dichlorodifluoromethane, dichlorotetrafluoroethane, chloromethane, chloroethane and dichloromethane. Physical foaming agents such as azodicarboxylic amides, dinitrosopentamethylenetetramine, azobisisobutyronitrile, p, p'-oxybisbenzenesulfonylhydrazide, citric acid, chemical foaming agents such as sodium hydrogencarbonate, in supercritical states. Examples include carbon dioxide, supercritical fluids such as nitrogen in a supercritical state, and air. When a physical foaming agent or air is used as the foaming agent, the gas pressure inside the mold may be adjusted to be, for example, 0.3 to 2 MPa, preferably 0.3 to 1 MPa. When a chemical foaming agent is used as the foaming agent, the amount of the chemical foaming agent added may be, for example, 0.05 to 0.5 parts by mass with respect to 100 parts by mass of the resin composition. Further, when a chemical foaming agent is used as the foaming agent, the temperature at which the chemical foaming agent is decomposed may be, for example, 50 to 250 ° C, preferably 100 to 220 ° C. The molding temperature in foam molding is not particularly limited, and may be, for example, 150 to 270 ° C. From the viewpoint of obtaining a foam molded product having further excellent impact resistance, the molding temperature is preferably 160 to 240 ° C.

As described above, a foam molded product can be obtained.

Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited by the following examples and the like.

(Examples 1-1 to 1-20, Comparative Example 1-1)
<Preparation of resin composition pellets>
First, a phenolic antioxidant (tetrakis [methylene-3- (3', 5'-tert-butyl-4') is added to 100 parts by mass of homopolypoly (MFR = 8 g / 10 min at 230 ° C. and a load of 2.16 kg). -Hydroxyphenyl) propionate] methane) in an amount of 0.05 parts by mass, a phosphorus-based antioxidant (tris (2,4-di-tert-butylphenyl) phosphite) in an amount of 0.1 part by mass, and a calcium stearate salt in an amount of 0. 05 parts by mass and 0.1 parts by mass of the nucleating agent for a polyolefin resin shown in Table 1 were blended and mixed uniformly to obtain a resin mixture. Subsequently, the resin mixture obtained as described above is put into a single-screw extruder (Laboplast Mill Micro manufactured by Toyo Seiki Seisakusho Co., Ltd.), melt-kneaded at a melting temperature of 230 ° C., and then granulated to resin. Pellets of the composition were obtained. Then, the obtained pellets were dried at 80 ° C. for 8 hours, and then the β crystal ratio of the resin composition was evaluated under the following conditions. The pellets of Comparative Example 1-1 were prepared in the same procedure as the pellets of Example 1-1 except that the nucleating agent for a polyolefin resin was not blended. Further, in Table 1, the "three-dimensional structure" of the nucleating agent for the polyolefin resin represents the three-dimensional structure of the aspartic acid residue, and Z represents the group shown below.

<Evaluation method of β crystal ratio>
The presence or absence of β crystals in the resin composition pellet is determined by performing thermal analysis on the resin composition pellets prepared as described above using a differential scanning calorimetry device (Diamond, manufactured by PerkinElmer). , When the determination of the presence or absence of β crystals was “Yes”, the β crystal ratio was calculated.

Specifically, the resin composition pellets are introduced into the apparatus, the temperature is raised from room temperature to 230 ° C. at a rate of 50 ° C./min under a nitrogen atmosphere, and after holding for 20 minutes, the temperature is raised to 50 ° C. at a rate of 10 ° C./min. After cooling and holding for another 5 minutes, when the temperature was raised to 230 ° C at a rate of 10 ° C / min, an endothermic peak with a peak top near 150 ° C and a peak top near 165 ° C in the second heating process. When an endothermic peak with a peak was observed, it was determined to have β crystal “presence”, and when only an endothermic peak having a peak top near 165 ° C. was observed, it was determined to be β crystal “absent”. When it is determined that there is β crystal, the area of the endothermic peak having a peak top near 150 ° C is the β crystal area, the area of the endothermic peak having the peak top near 165 ° C is the α crystal area, and the β crystal ratio is as follows. Calculated according to the formula.
β crystal ratio = [β crystal area / (α crystal area + β crystal area)] × 100 (%)
The results are shown in Table 1.

(Examples 2-1 to 2-9, Comparative Example 2-1)
<Preparation of resin composition pellets>
70 parts by mass of impact copolymer polypropylene (Prime Polymer, Prime Polypro J707G), 10 parts by mass of ethylene-octene copolymer elastomer (Dow Chemical, Engage 8842), talc (water content 0.1% by mass, laser diffraction) A resin mixture was prepared by blending 20 parts by mass of a particle size D ₅₀ = 14.0 μm according to the method and a bulk specific gravity 0.32 g / mL according to the measurement method described in JIS K5101. 0.05 parts by mass of a phenol-based antioxidant (tetrakis [methylene-3- (3', 5'-tert-butyl-4'-hydroxyphenyl) propionate] methane) with respect to 100 parts by mass of this resin mixture. 0.1 part by mass of phosphorus-based antioxidant (tris (2,4-di-tert-butylphenyl) phosphite), 0.05 part by mass of calcium stearate salt, nuclear agent for polyolefin resin shown in Table 2. Is blended in the addition amounts shown in Table 2, blended with a locking mixer (manufactured by Aichi Electric Co., Ltd.) for 30 minutes, and then charged into a twin-screw extruder (manufactured by Japan Steel Works, TEX-25αIII) at a melting temperature of 230 ° C. After melt-kneading with, granulation was performed to obtain pellets of the resin composition. Then, the obtained pellets were dried at 80 ° C. for 8 hours, and then the β crystal ratio of the resin composition was evaluated under the following conditions. The pellet of Comparative Example 2-1 was prepared in the same procedure as the pellet of Example 2-1 except that the nucleating agent for a polyolefin resin was not blended. Further, in Table 2, the "three-dimensional structure" of the nucleating agent for the polyolefin resin represents the three-dimensional structure of the aspartic acid residue, and Z represents the above-mentioned group.

<Evaluation method of β crystal ratio>
The presence or absence of β crystals in the resin composition pellet was determined by the same method as in Example 1-1 except that the heating rate in the second heating step was changed from 10 ° C / min to 30 ° C / min. , When the determination of the presence or absence of β crystals was “Yes”, the β crystal ratio was calculated. The results are shown in Table 2.

(Examples 3-1 to 3-9, Comparative Example 3-1)
<Preparation of resin composition pellets>
60 parts by mass of impact copolymer polypropylene (Prime Polymer, Prime Polypro J707G), 20 parts by mass of ethylene-octene copolymer elastomer (Dow Chemical, Engage 8842), talc (water content 0.1% by mass, laser diffraction) A resin mixture was prepared by blending 20 parts by mass of a particle size D ₅₀ = 14.0 μm according to the method and a bulk specific gravity 0.32 g / mL according to the measurement method described in JIS K5101. 0.05 parts by mass of a phenol-based antioxidant (tetrakis [methylene-3- (3', 5'-tert-butyl-4'-hydroxyphenyl) propionate] methane) with respect to 100 parts by mass of this resin mixture. 0.1 part by mass of phosphorus-based antioxidant (tris (2,4-di-tert-butylphenyl) phosphite), 0.05 part by mass of calcium stearate salt, nuclear agent for polyolefin resin shown in Table 3. Is blended in the addition amounts shown in Table 3, blended for 30 minutes with a locking mixer (manufactured by Aichi Electric Co., Ltd.), charged into a twin-screw extruder (TEX-25αIII manufactured by Japan Steel Works, Ltd.), and at a melting temperature of 230 ° C. After melt-kneading, granulation was performed to obtain pellets of the resin composition. Then, the obtained pellets were dried at 80 ° C. for 8 hours, and then the β crystal ratio of the resin composition was evaluated under the following conditions. The pellet of Comparative Example 3-1 was prepared in the same procedure as the pellet of Example 3-1 except that the nucleating agent for a polyolefin resin was not blended. Further, in Table 3, the "three-dimensional structure" of the nucleating agent for the polyolefin resin represents the three-dimensional structure of the aspartic acid residue, and Z represents the above-mentioned group.

<Evaluation method of β crystal ratio>
The presence or absence of β crystals in the resin composition pellet was determined by the same method as in Example 2-1. When the determination of the presence or absence of β crystals was “Yes”, the β crystal ratio was calculated. The results are shown in Table 3.

(Example 4-1 and Comparative Example 4-1)
<Preparation of resin composition pellets>
Impact Polyolefin Polypropylene (PrimePolypro J707G, manufactured by Prime Polymer) is a phenolic antioxidant (tetrakis [methylene-3- (3', 5'-tert-butyl-4'-hydroxyphenyl) propionate) with respect to 100 parts by mass. ] Methane) by 0.05 parts by mass, phosphorus-based antioxidant (tris (2,4-di-tert-butylphenyl) phosphite) by 0.1 parts by mass, calcium stearate salt by 0.05 parts by mass, table. The nucleating agent for polyolefin resin described in 4 is blended in the amount shown in Table 4, blended with a locking mixer (manufactured by Aichi Electric Co., Ltd.) for 30 minutes, and then a twin-screw extruder (manufactured by Japan Steel Works, TEX-25αIII). ), Melted and kneaded at a melting temperature of 230 ° C., and then granulated to obtain pellets of the resin composition. Then, the obtained pellets were dried at 80 ° C. for 8 hours, and then the β crystal ratio of the resin composition was evaluated under the following conditions. The pellet of Comparative Example 4-1 was prepared in the same procedure as the pellet of Example 4-1 except that the nucleating agent for a polyolefin resin was not blended. Further, in Table 4, the "three-dimensional structure" of the nucleating agent for the polyolefin resin represents the three-dimensional structure of the aspartic acid residue, and Z represents the above-mentioned group.

<Evaluation method of β crystal ratio>
The presence or absence of β crystals in the resin composition pellet was determined by the same method as in Example 2-1. When the determination of the presence or absence of β crystals was “Yes”, the β crystal ratio was calculated. The results are shown in Table 4.

From the results shown in Tables 1 to 4, β of the polyolefin resin was found in the resin composition pellets of Examples 1-1 to 1-20, 2-1 to 2-9, 3-1 to 3-9 and 4-1. It was confirmed that crystals were formed. On the other hand, in the resin compositions of Comparative Examples 1-1, 21, 3-1 and 4-1, the formation of β crystals of the polyolefin-based resin was not confirmed. The resin composition in which β-crystals of the polyolefin-based resin are produced has excellent impact resistance as compared with the resin composition in which β-crystals are not generated. Therefore, by foam molding the resin compositions of Examples 1-1 to 1-20, 2-1 to 2-9, 3-1 to 3-9 and 4-1, foam molding having excellent impact resistance is performed. You can get the goods.

From the above, it was confirmed that according to the present invention, a foam molded product having excellent impact resistance can be obtained.

Claims (5)

Polyolefin resin and
Nucleating agent for polyolefin resin and
A foam-molded product obtained by foam-molding a resin composition containing
The nucleating agent for polyolefin resin is the following general formula (1),

(In the above general formula (1), M represents an alkali metal, an alkaline earth metal, hydroxyaluminum or dihydroxyaluminum, a represents 1 or 2, x represents 1 or 2, and ax = 2 is satisfied. Represents a group having a structure represented by the following general formula (2) or (3).)

(In the above general formulas (2) and (3), Y represents a direct bond or an alkylene group having 1 to 4 carbon atoms, and R ¹ to R ¹⁰ independently represent a hydrogen atom, a halogen atom or 1 carbon atom. Represents an alkyl group of ~ 6, and * represents a position to be bonded to a carbonyl carbon.)
Effervescent molded product containing the compound represented by. The foamed molded product according to claim 1, wherein the content of the nucleating agent for the polyolefin resin is 0.001 to 10 parts by mass with respect to 100 parts by mass of the polyolefin resin. The foam-molded product according to claim 1 or 2, wherein the polyolefin-based resin is a polypropylene-based resin. The foam molded product according to any one of claims 1 to 3, which is an automobile part or a home appliance housing. A method for producing a foam-molded product, which comprises a molding process for foam-molding a resin composition.
The resin composition contains a polyolefin-based resin and a nucleating agent for a polyolefin-based resin.
The nucleating agent for polyolefin resin is the following general formula (1),

(In the above general formula (1), M represents an alkali metal, an alkaline earth metal, hydroxyaluminum or dihydroxyaluminum, a represents 1 or 2, x represents 1 or 2, and ax = 2 is satisfied. Represents a group having a structure represented by the following general formula (2) or (3).)

(In the above general formulas (2) and (3), Y represents a direct bond or an alkylene group having 1 to 4 carbon atoms, and R ¹ to R ¹⁰ independently represent a hydrogen atom, a halogen atom or 1 carbon atom. Represents an alkyl group of ~ 6, and * represents a position to be bonded to a carbonyl carbon.)
A method for producing an effervescent molded product containing a compound represented by.