TW201838961A - Nucleating agent and resin composition containing same - Google Patents

Abstract

To provide a novel high-performance nucleating agent for a polyolefin-based resin. A nucleating agent for a polyolefin-based resin, which contains a compound represented by formula (1). (In formula (1), R1, R2, R3 and R4 independently represent a hydrogen atom, a hydroxyl group, a halogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms or an alkenyl group having 2 to 10 carbon atoms, wherein the alkyl group or an alkyl group in the alkyl group or the alkoxy group may be disrupted by a carbonyl group or an oxygen atom or may have an unsaturated bond, or two vicinal alkyl groups may together form a 6-membered or shorter hydrocarbon ring; and M1 and M2 independently represent a n-valent metal atom, and n represents 1 or 2, wherein M1 and M2 may be the same as or different from each other when n is 1, and M1 and M2 are the same as each other and M1 and M2 together form a single metal atom when n is 2).

Description

Nucleating agent and resin composition containing nucleating agent

The present invention relates to a nucleating agent which uses a specific carboxylic acid salt having a high phthalic acid skeleton as an active ingredient and a resin composition which is adjusted into a polyolefin-based resin.

The olefin-based resin such as polyethylene, polypropylene, and polybutene-1 has advantages such as moldability, heat resistance, electrical properties, mechanical properties, and low specific gravity, and is formed into a film, a sheet, a blow, and an injection. Raw materials such as molding are widely used in various fields. However, the olefin-based resin has a problem that the crystallization rate after heat molding is slow, and the molding cycle at the time of processing is long. Moreover, the molded article may be deformed by crystallization which is also performed after the molding.

These defects are all derived from the crystallinity of the olefin-based resin, and a nucleating agent or a crystallization accelerator is added to rapidly form fine crystals, thereby solving the above problems. Further, it is known to improve the transparency of an olefin resin or other plastic by adding a nucleating agent.

As such a nucleating agent, an aromatic carboxylate, an organic phosphate, a benzylidene sorbitol compound, a rosin metal salt, talc, and the like have been conventionally used (Patent Documents 1, 2, and 3). Among them, various compounds have been proposed as nucleating agents selected from aromatic carboxylates (Patent Document 4). In particular, it is known that a metal salt of an aromatic carboxylic acid such as an aluminum benzoate or a sodium salt exhibits a nucleating agent effect in a relatively small amount, and has a long history of use as the nucleating agent (Non-Patent Document 1). However, as a polyolefin resin, a metal salt of the above-mentioned conventional benzoic acid which is a main component of an aromatic carboxylate used for a nucleating agent for a polypropylene resin for molding which is required to improve crystallinity. At present, there is a need to further expand the options for nucleating agents for polyolefin resins, particularly polypropylene resins. (Previous Technical Literature) (Patent Literature)

[Patent Document 1] Japanese Patent Laid-Open No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. Bulletin (Non-patent literature)

Non-Patent Document 1: "Heterogeneous Nucleating Agents for Polypropylene Crystallization" JOURNAL OF APPLIED POLYMER SCIENCE VOL. 11 (1967), Page. 673-685

(The problem that the invention wants to solve)

The present inventors have explored novel and high-performance nucleating agents for polyolefin resins, particularly polypropylene resins. (Technical means to solve the problem)

As a result, the present inventors have found that a specific carboxylate having a high phthalic acid skeleton functions as an excellent nucleating agent for a polyolefin resin, particularly a polypropylene resin. That is, the present invention is as follows.

(Invention 1) A nucleating agent for a polyolefin-based resin, which comprises a compound represented by the following formula (1).

[Chemical Formula 1]

(In the formula (1), R ¹ , R ² , R ³ and R ⁴ each independently represent a hydrogen atom, a hydroxyl group, a halogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or carbon. The alkyl group of 2 to 10, the alkyl group of the alkyl group or the alkoxy group may be interrupted by a carbonyl group or an oxygen atom, or may be an alkyl group bonded to two adjacent carbon atoms, which may have an unsaturated bond. It can be integrated to form up to 6 hydrocarbon rings. M ¹ and M ² represent n-valent metal atoms, and n is 1 or 2. When n is 1, M ¹ and M ² may be the same or different. When it is 2, M ¹ is the same as M ² and M ¹ and M ² represent 1 metal atom.)

(Invention 2) The nucleating agent according to Invention 1, wherein the above formula (1) is a formula (1-1) or a formula (1-2).

[Chemical Formula 2]

(In the formula (1-1), M ¹ and M ² represent a lithium atom (Li) or a potassium atom (K), and may be the same as or different from each other, and R ¹ , R ² , R ³ and R ⁴ are each independently A hydrogen atom, a hydroxyl group, a halogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, or an alkyl group in an alkyl group or an alkoxy group may be a carbonyl group. Or the oxygen atom is interrupted, or it may be an unsaturated bond. The two alkyl groups bonded to two adjacent carbon atoms may be integrated to form up to six hydrocarbon rings.

[Chemical Formula 3]

(In the formula (1-2), M ¹ represents any one of Zn, Ca, and Mg, and R ¹ , R ² , R ³ and R ⁴ each independently represent a hydrogen atom, a hydroxyl group, a halogen atom, or a carbon number of 1; An alkyl group of ～10, an alkoxy group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an alkyl group in an alkyl group or an alkoxy group may be interrupted by a carbonyl group or an oxygen atom, or may have an unsaturated bond. The two alkyl groups bonded to two adjacent carbon atoms can be integrated to form up to six hydrocarbon rings.

(Invention 3) The nucleating agent according to Invention 1 or 2, which further comprises a phenol-based antioxidant, a phosphorus-based antioxidant, a thioether-based antioxidant, another antioxidant, a hindered amine compound, an ultraviolet absorber, and a nucleation One or more additives of a solvent, a flame retardant, a flame retardant auxiliary, a lubricant, a filler, a hydrotalcite, a fatty acid metal salt, an antistatic agent, a pigment, and a dye.

(Invention 4) A resin composition containing a polyolefin-based resin and any one of Inventions 1 to 3 of 0.0001 to 10 parts by mass based on 100 parts by mass of the nucleating agent.

(Invention 5) The resin composition according to Invention 4, wherein the polyolefin-based resin comprises a polypropylene-based resin.

(Invention 6) A molded article comprising the resin composition of Invention 5. (cf. the efficacy of prior art)

The nucleating agent of the present invention can greatly increase the crystallization temperature of the polyolefin resin. Therefore, the molding time of the polyolefin-based resin containing the nucleating agent of the present invention is shorter than the present. Further, the nucleating agent of the present invention has an effect of improving the rigidity or impact resistance of the polyolefin resin or suppressing warpage or deformation of the polyolefin resin molded article. The nucleating agent of the present invention has a high utilization value especially for a polypropylene-based resin.

Hereinafter, embodiments of the present invention will be described in detail. [Nucleating Agent Compound] The nucleating agent of the present invention must contain a metal salt containing a compound having a high phthalic acid skeleton represented by the following formula (1) as an active ingredient. In the present specification, such an essential active ingredient is referred to as a "nucleating agent compound".

(In the formula (1), R ¹ , R ² , R ³ and R ⁴ each independently represent a hydrogen atom, a hydroxyl group, a halogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or carbon. The alkyl group of 2 to 10, the alkyl group of the alkyl group or the alkoxy group may be interrupted by a carbonyl group or an oxygen atom, or may be an alkyl group bonded to two adjacent carbon atoms, which may have an unsaturated bond. It can be integrated to form up to 6 hydrocarbon rings. M ¹ and M ² represent n-valent metal atoms, and n is 1 or 2. When n is 1, M ¹ and M ² may be the same or different. When it is 2, M ¹ is the same as M ² and M ¹ and M ² represent 1 metal atom.)

Examples of the alkyl group having 1 to 10 carbon atoms include a linear or branched alkyl group or a polycycloalkyl group having 3 to 10 carbon atoms. Specific examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, a cyclopropyl group, a butyl group, a second butyl group, a third butyl group, an isobutyl group, a cyclobutyl group, a pentyl group, and a third group. Pentyl, cyclopentyl, hexyl, cyclohexyl, heptyl, cycloheptyl, octyl, cyclooctyl, isooctyl, trioctyl, 2-ethylhexyl, decyl, isodecyl, fluorenyl Wait.

Examples of the alkoxy group having 1 to 10 carbon atoms include a linear or branched alkoxy group or a cycloalkyloxy group having 5 to 10 carbon atoms. Specific examples thereof include a methoxy group, an ethoxy group, a n-propoxy group, a n-butoxy group, a n-hexyloxy group, a 1-methylethoxy group, a 2-methylpropoxy group, and a 1-methyl group. An oxy group, a 4-methylpentyloxy group, a cyclohexyloxy group or the like.

Examples of the alkenyl group having 2 to 10 carbon atoms include a vinyl group, an allyl group, a propenyl group, and a nonenyl group.

Two alkyl groups bonded to two adjacent carbon atoms represent two alkyl groups bonded to two adjacent carbon atoms of the benzene ring, and hydrocarbon rings having up to six carbon atoms represent a cyclopropyl group and a ring. Butyl, cycloheptyl, cyclohexyl, benzene ring.

Preferred metal atom systems Li (n = 1), K (n = 1), Zn (n = 2), Ca (n = 2), and Mg (n = 2) constituting M ¹ and M ² described above.

The nucleating agent compound represented by the above formula (1) is preferably a nucleating agent compound represented by the following formula (1-1) or formula (1-2). The nucleating agent compound of the present invention can also be used as long as it is represented by the above formula (1).

[Chemical Formula 4]

(In the formula (1-1), M ¹ and M ² represent Li or K, and may be the same as or different from each other, and R ¹ , R ² , R ³ and R ⁴ each independently represent a hydrogen atom, a hydroxyl group or a halogen atom. An alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, or an alkyl group in an alkyl group or an alkoxy group may be interrupted by a carbonyl group or an oxygen atom, or may be In the case of an unsaturated bond, two alkyl groups bonded to two adjacent carbon atoms may be integrated to form up to six hydrocarbon rings.

The nucleating agent compound represented by the above formula (1-1) can be produced by a method according to a known method for producing a metal carboxylate, and by, for example, a compound having a high phthalic acid skeleton and a metal hydroxide in an aqueous solution. It is produced by the reaction of (M ¹ OH, M ² OH).

The nucleating agent compound represented by the above formula (1-1) is, for example, a compound represented by the following formula (1-1-1) to (1-1-9) (nucleating agent compound (1-1-1)~ Nucleating agent compound (1-1-9)).

[Chemical Formula 5]

[Chemical Formula 6]

[Chemical Formula 7]

[Chemical Formula 8]

[Chemical Formula 9]

[Chemical Formula 10]

[Chemical Formula 11]

[Chemical Formula 12]

[Chemical Formula 13]

The nucleating agent compound represented by the above formula (1) is also preferably a nucleating agent compound represented by the following formula (1-2). The nucleating agent compound of the present invention can also be used as long as it is represented by the above formula (1).

[Chemical Formula 14]

(In the formula (1-2), M ¹ represents any one of Zn, Ca, and Mg, and R ¹ , R ² , R ³ and R ⁴ each independently represent a hydrogen atom, a hydroxyl group, a halogen atom, or a carbon number of 1; An alkyl group of ～10, an alkoxy group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an alkyl group in an alkyl group or an alkoxy group may be interrupted by a carbonyl group or an oxygen atom, or may have an unsaturated bond. The two alkyl groups bonded to two adjacent carbon atoms may be integrated to form up to six hydrocarbon rings.) The nucleating agent compound represented by the above formula (1-2) can be used in accordance with a known carboxylic acid. a method for producing an acid metal salt, and having a high phthalic acid skeleton by, for example, reacting a compound having a high phthalic acid skeleton with a metal hydroxide (M ¹ OH) or based on dissolving in an aqueous alkali solution The neutralization reaction of the metal salt of the compound (M ¹ Cl) is carried out.

When the nucleating agent of the present invention contains the nucleating agent compound represented by the above formula (1-2), it contains a by-product formed when the nucleating agent compound represented by the above formula (1-2) is produced. Such by-products are mainly multimers in which a compound having a high phthalic acid skeleton is bonded to a carboxyl group via a metal atom: Zn, Ca or Mg. The multimer contains a compound containing 2 or 3 molecules of a high phthalic acid skeleton.

The nucleating agent compound represented by the above formula (1-2) is, for example, a compound represented by the following formula (1-2-1) to (1-2-9) (nucleating agent compound (1-2-1)~ Nucleating agent compound (1-2-9)).

[Chemical Formula 15]

[Chemical Formula 16]

[Chemical Formula 17]

[Chemical Formula 18]

[Chemical Formula 19]

[Chemical Formula 20]

[Chemical Formula 21]

[Chemical Formula 22]

[Chemical Formula 23]

[Nucleating Agent] The nucleating agent of the present invention is an additive for blending with a polyolefin-based resin, and includes the above-described nucleating agent compound. The content of the nucleating agent compound in the nucleating agent of the present invention is not particularly limited, but is usually 10% by mass or more, preferably 80% by mass or more. The nucleating agent of the present invention may be an additive for a polyolefin resin composed only of the above nucleating agent compound, or may be an additive for a polyolefin resin composed of a mixture of the above nucleating agent compound and another compound or material.

The component other than the above-mentioned nucleating agent compound contained in the nucleating agent of the present invention does not impair the effect of the above-mentioned nucleating agent, and does not damage the polyolefin resin of the nucleating agent of the present invention to a large extent. Performance is not limited. As such other components, an additive which is usually blended in a polyolefin-based resin, for example, a phenol-based antioxidant, a phosphorus-based antioxidant, a thioether-based antioxidant, another antioxidant, a hindered amine compound, an ultraviolet absorber, or the like, is usually used. One or more of a flame retardant, a flame retardant auxiliary, a lubricant, a filler, a hydrotalcite, a fatty acid metal salt, an antistatic agent, a pigment, and a dye. The content of the other components in the nucleating agent of the present invention is not particularly limited, and as a result of blending the nucleating agent of the present invention with a polyolefin-based resin, components other than the nucleating agent compound component are also based on the polyolefin-based resin. The amount of the resin present in an appropriate amount is preferred.

Examples of the phenolic antioxidant include 2,6-di-tert-butyl-4-methylphenol, 2,6-di-tert-butyl-4-ethylphenol, and 2-tert-butyl group. -4,6-dimethylphenol, styrenated phenol, 2,2'-methylenebis(4-ethyl-6-tert-butylphenol), 2,2'-thiobis-(6 -T-butyl-4-methylphenol), 2,2'-thiodivinyl bis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], 2 -Methyl-4,6-bis(octylsulfonylmethyl)phenol, 2,2'-isobutylene bis(4,6-dimethylphenol), isooctyl-3- (3,5-di-t-butyl-4-hydroxyphenyl)propionate, N,N'-hexane-1,6-diylbis[3-(3,5-di-third) 4-hydroxyphenyl)propanamide, 2,2'-oxalylamine-bis[ethyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate] , 2-ethylhexyl-3-(3',5'-di-t-butyl-4'-hydroxyphenyl)propionate, 2,2'-ethylene double (4,6-di-third Butyl phenol), 3,5-di-t-butyl-4-hydroxy-phenylpropanic acid and C13-15 alkyl ester, 2,5-di-third amyl hydroquinone, hindered phenol Polymer (Adeka Palmarole Corpo Ration.Product name AO.OH.98), 2,2'-methylenebis[6-(1-methylcyclohexyl)p-cresol], 2-t-butyl-6-(3- Tributyl-2-hydroxy-5-methylbenzyl)-4-methylphenyl acrylate, 2-[1-(2-hydroxy-3,5-di-p-pentylphenyl)ethyl ]-4,6-di-third amyl phenyl acrylate, 6-[3-(3-tert-butyl-4-hydroxy-5-methyl)propoxy]-2,4,8, 10-tetra-t-butylbenzo[d,f][1,3,2]-dioxaphosphepin, hexamethylene bis[3-(3,5-di- Third butyl-4-hydroxyphenyl)propionate, bis[monoethyl(3,5-di-t-butyl-4-hydroxybenzyl)phosphate]calcium salt, 5,7-bis ( Reaction product of 1,1-dimethylethyl)-3-hydroxy-2(3H)-benzofuranone (Benzofuranone) with o-xylene, 2,6-di-t-butyl-4-( 4,6-bis(octylthio)-1,3,5-triazin-2-ylamino)phenol, DL-a-tocopherol (vitamin E), 2,6-bis (α- Methylbenzyl)-4-methylphenol, bis[3,3-bis-(4'-hydroxy-3'-t-butyl-phenyl)butanoic acid]diol, 2,6-di -T-butyl-p-cresol, 2,6-diphenyl-4-18 Alkoxyphenol, stearyl (3,5-di-t-butyl-4-hydroxyphenyl)propionate, distearyl (3,5-di-tert-butyl-4-hydroxybenzyl) Phosphate, tridecyl-3,5-tert-butyl-4-hydroxybenzyl thioacetate, thiodiethylene bis[(3,5-di-t-butyl-4-hydroxyl) Phenyl)propionate], 4,4'-thiobis(6-t-butyl-m-cresol), 2-octylthio-4,6-di(3,5-di-t-butyl- 4-hydroxyphenoxy)-trimethylene, 2,2'-methylenebis(4-methyl-6-tert-butylphenol), bis[3,3-bis(4-hydroxy-3- Tributylphenyl)butyrate]diol, 4,4'-butylene bis(2,6-di-tert-butylphenol), 4,4'-butylene bis(6-t-butyl) -3-methylphenol), 2,2'-extended ethyl bis(4,6-di-tert-butylphenol), 1,1,3-tris(2-methyl-4-hydroxy-5- Tert-butylphenyl)butane, bis[2-t-butyl-4-methyl-6-(2-hydroxy-3-t-butyl-5-methylbenzyl)phenyl]p-benzene Dicarboxylate, 1,3,5-tris(2,6-dimethyl-3-hydroxy-4-tributylbenzyl)isocyanurate, 1,3,5-tris (3, 5-di-t-butyl-4-hydroxybenzyl)isocyanurate, 1,3,5- (3,5-di-t-butyl-4-hydroxybenzyl)-2,4,6-trimethylbenzene, 1,3,5-tri[(3,5-di-t-butyl- 4-hydroxyphenyl)propenyloxyethyl]isocyanurate, tetrakis[methylene-3-(3',5'-tert-butyl-4'-hydroxyphenyl)propionate Methane, 2-t-butyl-4-methyl-6-(2-propenylmethoxy-3-tert-butyl-5-methylbenzyl)phenol, 3,9-bis[2- (3-t-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-t-butyl-4-hydroxyphenyl)propanoic acid decylamine, palmityl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propanoic acid decylamine, myristyl- 3-(3,5-di-t-butyl-4-hydroxyphenyl)propanoic acid decylamine, lauryl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionic acid A 3-(3,5-dialkyl-4-hydroxyphenyl)propionic acid derivative such as guanamine.

For the nucleating agent of the present invention, tetrakis[methylene-3-(3',5'-t-butyl-4'-hydroxyphenyl)propionate]methane is inexpensive and stabilizes the olefin resin. It is excellent because it is excellent in effect.

With respect to the content of the phenolic antioxidant in the nucleating agent of the present invention, the nucleating agent of the present invention is blended with the polyolefin resin, and the phenolic resistance is 100 parts by mass based on the polyolefin resin. The oxidizing agent is present in an amount of 0.001 to 5 parts by mass, typically in a concentration of 0.01 to 1.0 part by mass.

Examples of the phosphorus-based antioxidant include triphenyl phosphite, diisooctylphosphite, bismuth dipropylene glycol triphosphite, triisodecyl phosphite, and diphenyl isooctyl phosphite. , diisooctylphenyl phosphite, diphenyltridecyl phosphite, triisooctyl phosphite, trilauryl phosphite, diphenyl phosphite, tris(dipropylene glycol) Phosphate ester, diisodecyl neopentyl alcohol diphosphite, dioleyl hydrogen phosphite, trilauryl trithiophosphite, bis(tridecyl) phosphite, tris(isodecyl) Phosphite, tris(tridecyl)phosphite, diphenylphosphonium phosphite, dinonylphenyl bis(nonylphenyl)phosphite, poly(dipropylene glycol)phenylphosphite Ester, tetraphenyldipropylene glycol diphosphite, tridecylphenylphosphite, tris(2,4-di-t-butylphenyl)phosphite, tris(2,4-di-third Butyl-5-methylphenyl)phosphite, tris[2-t-butyl-4-(3-t-butyl-4-hydroxy-5-methylphenylthio)-5- Phenyl phosphite, tris(癸) Phosphite, octyl diphenyl phosphite, bis(indenyl)monophenylphosphite, distearyl pentaerythritol diphosphite, distearyl pentaerythritol and hard a mixture of calcium sulphate, alkyl (C10) bisphenol A phosphite, di(tridecyl) pentaerythritol diphosphite, bis(nonylphenyl) pentaerythritol diphosphite , bis(2,4-di-t-butylphenyl)neopentitol diphosphite, bis(2,6-di-t-butyl-4-methylphenyl)neopentanol Phosphite, bis(2,4,6-tri-tert-butylphenyl)neopentitol diphosphite, bis(2,4-diisopropylphenylphenyl)nepentaerythritol Phosphate ester, tetraphenyl-tetrakis(tridecyl)neopentanol tetraphosphite, bis(2,4-di-tert-butyl-6-methylphenyl)ethyl phosphite, four (tridecyl)isopropylidenediphenol diphosphite, tetrakis(tridecyl)-4,4'-n-butylidenebis(2-tert-butyl-5-methylphenol) Phosphite, hexadecyltridecyl-1,1,3-tris(2-methyl-4-hydroxy-5-t-butylphenyl)butane triphosphite, tetra (2,4- Second-third Butylphenyl)biphenyl diphosphite, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, (1-methyl-1-propene-3-ylidene) Tris(1,1-dimethylethyl)-5-methyl-4,1-phenylene)hexa-tridecylphosphite, 2,2'-methylenebis(4,6 -di-t-butylphenyl)-2-ethylhexyl phosphite, 2,2'-methylenebis(4,6-di-t-butylphenyl)-octadecylphosphite Ester, 2,2'-extended ethyl bis(4,6-di-t-butylphenyl)fluorophosphite, 4,4'-butylene bis(3-methyl-6-t-butyl Phenyl di-tridecyl phosphite, tris(2-[(2,4,8,10-tetra-t-butyldibenzo[d,f][1,3,2]dioxo Heterophosphono-6-yl)oxy]ethyl)amine, 3,9-bis(4-mercaptophenoxy)-2,4,8,10-tetraoxa-3,9- Diphosphorus [5,5]undecane, 2,4,6-tri-tert-butylphenyl-2-butyl-2-ethyl-1,3-propanediol phosphite, poly 4,4 '-Isopropylene diphenol C12-15 alkanol phosphite.

The preferred content of the phosphorus-based antioxidant in the nucleating agent of the present invention is a result of blending the nucleating agent of the present invention with a polyolefin-based resin, and is based on 100 parts by mass of the polyolefin-based resin. The oxidizing agent is present in an amount of from 0.001 to 20 parts by mass, typically in a concentration of from 0.01 to 5 parts by mass.

Examples of the thioether-based antioxidant include 3,3'-thiodipropionic acid, alkyl (C12-14) thiopropionic acid, and di(lauryl)-3,3'-thiodipropionate. , bis(tridecyl)-3,3'-thiodipropionate, bis(myristyl)-3,3'-thiodipropionate, bis(stearyl)-3,3 '-Thiodipropionate, di(octadecyl)-3,3'-thiodipropionate, laurylstearylthiodipropionate, tetrakis[methylene-3-( Dodecylthio)propionate]methane, thiobis(2-tert-butyl-5-methyl-4,1-phenylene)bis(3-(dodecylthio)propane Acid ester), 2,2'-thiodiethyl bis(3-aminobutenoate), 4,6-bis(octylthiomethyl)o-cresol, 2,2'-thio Diethyl bis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], 2,2'-thiobis(4-methyl-6-tributyl) Phenol), 2,2'-thiobis(6-t-butyl-p-cresol), 2-ethylhexyl-(3,5-di-t-butyl-4-hydroxybenzyl)sulfide Acetate, 4,4'-thiobis(6-tert-butyl-3-methylphenol), 4,4'-thiobis(4-methyl-6-t-butyl) Phenol), 4,4'-[thiobis(methylene)]bis(2-tert-butyl-6-methyl-1-hydroxybenzyl), bis(4,6-di-third) Phenolic-2-yl) sulfide, tridecyl-3,5-di-t-butyl-4-hydroxybenzyl thioacetate, 1,4-bis(octylthiomethyl)- 6-methylphenol, 2,4-bis(dodecylthiomethyl)-6-methylphenol, distearyl-disulfide, bis(methyl-4-[3-n-alkyl) C12/C14) thiopropoxycarbonyl]-5-t-butylphenyl) sulfide or the like.

The preferred content of the thioether-based antioxidant in the nucleating agent of the present invention is a result of blending the nucleating agent of the present invention with a polyolefin-based resin, and is a thioether relative to 100 parts by mass of the polyolefin-based resin. The antioxidant is present in an amount of 0.001 to 20 parts by mass, typically in a concentration of 0.01 to 5 parts by mass.

As the other antioxidant, N-benzyl-α-phenylnitrone, N-ethyl-α-methylnitrone, N-octyl-α-heptyl nitrone, N-lauryl-α- may be mentioned. Undecyl nitrone, N-tetradecyl-α-tridecyl nitrone, N-hexadecyl-α-pentadecyl nitrone, N-octyl-α-heptadecyl Nitronone, N-hexadecyl-α-heptadecyl nitrone, N-octadecyl-α-pentadecyl nitrone, N-heptadecyl-α-heptadecyl nitrone a nitrone compound such as N-octadecyl-α-heptadecyl nitrone, 3-arylbenzofuran-2(3H)-one, 3-(alkoxyphenyl)benzofuran-2 -ketone, 3-(decyloxyphenyl)benzofuran-2(3H)-one, 5,7-di-t-butyl-3-(3,4-dimethylphenyl)-benzo Furan-2(3H)-one, 5,7-di-t-butyl-3-(4-hydroxyphenyl)-benzofuran-2(3H)-one, 5,7-di-third 3-{4-(2-hydroxyethoxy)phenyl}-benzofuran-2(3H)-one, 6-(2-(4-(5,7-di-t-butyl-) 2-oxy-2,3-dihydrobenzofuran-3-yl)phenoxy)ethoxy)-6-oxohexyl-6-((6-hydroxyhexyl)oxy)hexanoic acid Methyl ester, 5-di-tert-butyl-3-( a benzofuran compound such as 4-((15-hydroxy-3,6,9,13-tetraoxapentadecyl)oxy)phenyl)benzofuran-2(3H)one or the like.

With respect to the preferred content of the above-mentioned other antioxidant in the nucleating agent of the present invention, the nucleating agent of the present invention is blended with the polyolefin-based resin, and the other antioxidant is based on 100 parts by mass of the polyolefin-based resin. 0.001 to 20 parts by mass, typically in an amount of 0.01 to 5 parts by mass.

As the hindered amine compound, for example, 2,2,6,6-tetramethyl-4-piperidinyl stearate, 1,2,2,6,6-pentamethyl-4-piperidinyl group can be mentioned. Fatty acid ester, 2,2,6,6-tetramethyl-4-piperidyl benzoate, bis(2,2,6,6-tetramethyl-4-piperidinyl) sebacate , tetrakis(2,2,6,6-tetramethyl-4-piperidinyl)-1,2,3,4-butane tetracarboxylate, tetrakis (1,2,2,6,6-five Methyl-4-piperidinyl)-1,2,3,4-butanetetracarboxylate, bis(2,2,6,6-tetramethyl-4-piperidinyl)-di(13 Alkyl)-1,2,3,4-butane tetracarboxylate, bis(1,2,2,6,6-pentamethyl-4-piperidinyl)-di(tridecyl)- 1,2,3,4-butane tetracarboxylate, bis(1,2,2,4,4-pentamethyl-4-piperidinyl)-2-butyl-2-(3,5- Di-t-butyl-4-hydroxybenzyl)malonate, 1-(2-hydroxyethyl)-2,2,6,6-tetramethyl-4-piperidinol/succinic acid diethyl Ester condensation polymer, 1,6-bis(2,2,6,6-tetramethyl-4-piperidinyl)hexane/2,4-dichloro-6-morpholinyl--triterpene polycondensation 1,6-bis(2,2,6,6-tetramethyl-4-piperidinyl)hexane/2,4-dichloro-6-th-octylamino-s-triazine Polycondensate, 1,5,8,12-tetra[2,4-bis(N-butyl-N-(2,2,6,6-tetramethyl) 4-piperidinyl)amino)-s-tris-6-yl]-1,5,8,12-tetraazadodecane, 1,5,8,12-tetra[2,4- Bis(N-butyl-N-(1,2,2,6,6-pentamethyl-4-piperidyl)amino)--tris--6-yl]-1,5,8,12 - tetraazadecane, 1,6,11-tris[2,4-bis(N-butyl-N-(2,2,6,6-tetramethyl-4-piperidyl)amino) )---tris--6-yl]aminoundecane, 1,6,11-tri[2,4-bis(N-butyl-N-(1,2,2,6,6-penta-) 4--4-piperidyl)amino)-s-tris-6-yl]aminoundecane, bis{4-(1-octyloxy-2,2,6,6-tetramethyl)per Pyridyl}indoledione, bis{4-(2,2,6,6-tetramethyl-1-undecyloxy)piperidinyl}carbonate, TINUVIN NOR 371 by Ciba Specialty Chemicals Corporation, etc. .

The content of the above-mentioned hindered amine compound in the nucleating agent of the present invention is a result of blending the nucleating agent of the present invention with a polyolefin-based resin, and the hindered amine compound is based on 100 parts by mass of the polyolefin-based resin. 0.001 to 5 parts by mass, typically in an amount of 0.005 to 0.5 parts by mass.

Examples of the ultraviolet absorber include 2-hydroxybenzophenone such as 2,4-dihydroxybenzophenone and 5,5'-methylenebis(2-hydroxy-4-methoxybenzophenone). Ketones; 2-(2-hydroxy-5-methylphenyl)benzotriazole, 2-(2-hydroxy-5-th-octylphenyl)benzotriazole, 2-(2-hydroxy- 3,5-di-t-butylphenyl)-5-chlorobenzotriazole, 2-(2-hydroxy-3-t-butyl-5-methylphenyl)-5-chlorobenzotriene Oxazole, 2-(2-hydroxy-3,5-diisopropylphenylphenyl)benzotriazole, 2,2'-methylenebis(4-thyloctyl-6-benzotriazolyl) Phenol), polyethylene glycol ester of 2-(2-hydroxy-3-t-butyl-5-carboxyphenyl)benzotriazole, 2-[2-hydroxy-3-(2-propenyloxy) Ethyl)-5-methylphenyl]benzotriazole, 2-[2-hydroxy-3-(2-methylpropenyloxyethyl)-5-tert-butylphenyl]benzotrien Oxazole, 2-[2-hydroxy-3-(2-methylpropenyloxyethyl)-5-th-octylphenyl]benzotriazole, 2-[2-hydroxy-3-(2- Methacryloxyethyl)-5-tert-butylphenyl]-5-chlorobenzotriazole, 2-[2-hydroxy-5-(2-methylpropenyloxyethyl)benzene Benzotriazole, 2-[2 -hydroxy-3-tert-butyl-5-(2-methylpropenyloxyethyl)phenyl]benzotriazole, 2-[2-hydroxy-3-tripentyl-5-(2 -Methethyloxyethyl)phenyl]benzotriazole, 2-[2-hydroxy-3-t-butyl-5-(3-methylpropenyloxypropyl)phenyl]- 5-chlorobenzotriazole, 2-[2-hydroxy-4-(2-methylpropenyloxymethyl)phenyl]benzotriazole, 2-[2-hydroxy-4-(3-methyl) Acryloxy-2-hydroxypropyl)phenyl]benzotriazole, 2-[2-hydroxy-4-(3-methylpropenyloxypropyl)phenyl]benzotriazole, etc. 2 -(2-hydroxyphenyl)benzotriazoles; phenyl salicylate, resorcinol monobenzoate, 2,4-di-t-butylphenyl-3,5-di- Tributyl-4-hydroxybenzoate, octyl (3,5-di-t-butyl-4-hydroxy)benzoate, dodecyl (3,5-di-t-butyl) 4-hydroxy)benzoate, tetradecyl (3,5-di-t-butyl-4-hydroxy)benzoate, cetyl (3,5-di-t-butyl) -4-hydroxy)benzoate, octadecyl (3,5-di-t-butyl-4-hydroxy)benzoate, behenyl (3,5-di-third) Keto-4-hydroxy)benzene a benzoate such as an acid ester; a substituted oxanilide such as 2-ethyl-2'-ethoxyoxalin; 2-ethoxy-4'-dodecyloxalin; a cyanoacrylate such as ethyl-α-cyano-β,β-diphenylacrylate or methyl-2-cyano-3-methyl-3-(p-methoxyphenyl)acrylate; Examples of the various metal salts or metal chelate compounds include nickel, chromium salts, and chelate compounds.

The preferred content of the above-mentioned ultraviolet absorber in the nucleating agent of the present invention is a result of blending the nucleating agent of the present invention with a polyolefin-based resin, and the ultraviolet absorber is based on 100 parts by mass of the polyolefin-based resin. 0.001 to 5 parts by mass, typically in an amount of 0.005 to 0.5 parts by mass.

Examples of the flame retardant include triphenyl phosphate, tricresyl phosphate, tri-xylylene phosphate, cresyl diphenyl phosphate, cresol-2,6-di-xylylene ester, and resorcinol. Bis(diphenyl phosphate), (1-methylethyl)-4,1-phenylphenyltetraphenyl diphosphate, 1,3-phenylene tetrakis(2,6-dimethylbenzene Aromatic phosphoric acid such as a phosphate ester, a product name of Adekastub (registered trademark) FP-500 manufactured by ADEKA CORPORATION, a brand name Adekastub (registered trademark) FP-600 manufactured by ADEKA CORPORATION, and a brand name Adekastub (registered trademark) FP-800 manufactured by ADEKA CORPORATION. Phosphonates such as esters, divinyl phenylphosphonate, diallyl phenylphosphonate, phenylphosphonic acid (1-butenyl), phenyl diphenylphosphinate, methyl diphenylphosphinate , 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide derivative, hypophosphite, bis(2-allylphenoxy)phosphazene, xylenylphosphine A phosphazene compound such as nitrene, melamine phosphate, melamine pyrophosphate, melamine polyphosphate, melam polyphosphate, ammonium polyphosphate, piperazine phosphate, piperazine pyrophosphate, polyphosphoric acid Phosphate, phosphorus-containing vinyl benzyl compound, phosphorus-based flame retardant such as red phosphorus, metal hydroxide such as magnesium hydroxide or aluminum hydroxide, brominated bisphenol A epoxy resin, brominated phenol novolak ring Oxygen resin, hexabromobenzene, pentabromotoluene, ethyl bis(pentabromophenyl), ethyl bistetrabromophthalimide, 1,2-dibromo-4-(1,2- Dibromoethyl)cyclohexane, tetrabromocyclooctane, hexabromocyclododecane, bis(tribromophenoxy)ethane, brominated polyphenylene ether, brominated polystyrene and 2,4,6 -Tris(tribromophenoxy)-1,3,5-triazine, tribromophenylmaleimide, tribromophenyl acrylate, tribromophenyl methacrylate, tetrabromobisphenol A type II Brominated flame retardants such as methacrylate, pentabromobenzyl acrylate and brominated styrene. These flame retardants are preferably used together with an anti-drip agent such as a fluororesin or a flame retardant auxiliary such as a polyol or a hydrotalcite.

The lubricant is added to impart lubricity to the surface of the molded body and to improve the scratch resistance. Examples of the lubricant include hydrocarbon-based lubricants such as low molecular waxes, paraffin waxes, polyethylene waxes, chlorinated hydrocarbons, and fluorocarbons; natural wax-based lubricants such as carnauba wax and candelilla wax; lauric acid, a higher fatty acid such as stearic acid or behenic acid, or a fatty acid-based lubricant such as a hydroxy fatty acid such as hydroxystearic acid; an aliphatic guanamine compound such as stearylamine, laurylamine or decylamine or a methylene group; An aliphatic amide-based lubricant such as an alkylene diamine amide such as ethylenestearylamine or ethylenebis-stearamide; stearyl stearate, hard Fatty acid monool ester compounds such as butyl citrate and distearyl phthalate; glyceryl tristearate, sorbitan tristearate, pentaerythritol tetrastearate, dipentaerythritol Fatty acid polyol ester compounds such as alcohol hexa-stearate, polyglycerol polyricinoleate, hydrogenated castor oil; mono-fatty acids such as adipic acid/stearate of dipentaerythritol and polybasic fatty acids and polyhydric alcohols a fatty acid alcohol ester-based lubricant such as a complex ester compound; Aliphatic alcohols, lauryl alcohol, palmityl alcohol and other alcohol-based lubricants; metal soaps; montanic acid ester partially saponified montanic acid-based lubricant and the like; acrylic lubricant; polyethylene oxide silicon oil. These may be used alone or in combination of two or more.

The preferred content of the above-mentioned lubricant in the nucleating agent of the present invention is a result of blending the nucleating agent of the present invention with a polyolefin-based resin, and the lubricant is 0.01 to 100 parts by mass based on the polyolefin-based resin. 2 parts by mass, typically in an amount of 0.03 to 0.5 parts by mass.

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 white clouds. Stone, mica, cerium oxide, aluminum oxide, potassium titanate whisker, ash stone, fibrous magnesium oxysulfate, etc., and the particle size (fiber diameter or fiber length and aspect ratio) can be appropriately selected. Further, the filler can be used as a surface treatment person as needed.

With respect to the preferred content of the above-mentioned filler in the nucleating agent of the present invention, the nucleating agent of the present invention is blended with the polyolefin-based resin, and the filler is 0.01 to 0.01 parts by mass based on 100 parts by mass of the polyolefin-based resin. 80 parts by mass, typically in an amount of from 1 to 50 parts by mass.

The hydrotalcite is a complex salt compound composed of magnesium, aluminum, a hydroxyl group, a carbonate group, and any crystal water known as a natural product or a composition, and is not particularly limited. Any one in which one of magnesium or aluminum is substituted with another metal such as an alkali metal or zinc, or a hydroxyl group or a carbonate group is substituted with another anion group, for example, a hydrotalcite to be represented by the following formula (2) is used. An Al-Li-based hydrotalcite represented by the following formula (3), in which a metal is substituted with an alkali metal.

[Chemical Formula 24]

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

[Chemical Formula 25]

(In the formula (3), A ^q- represents a q-valent anion, and p represents 0 or a positive number. Further, the carbonate anion in the hydrotalcite type may be substituted with a part of the other anion.)

The hydrotalcite may be dehydrated from crystal water, or may be a higher fatty acid metal such as stearic acid or a higher fatty acid metal salt such as an alkali metal oleate or an alkali metal salt of dodecylbenzenesulfonate. A coating such as a salt, a higher fatty acid guanamine, a higher fatty acid ester or a wax.

The hydrotalcites may be natural or may be synthetic. Examples of the synthesis method include Japanese Patent Publication No. Sho 46-2280, Japanese Patent Publication No. Sho 50-30039, Japanese Patent Publication No. Sho 51-29129, Japanese Patent Publication No. Hei 3-36839, and Japanese Patent Laid-Open A well-known method described in Japanese Laid-Open Patent Publication No. Hei 5-179052, and the like. Further, the hydrotalcite can be used in a form that is not limited to its crystal structure, crystal particles, or the like.

With respect to the preferred content of the hydrotalcites in the nucleating agent of the present invention, the nucleating agent of the present invention is blended with the polyolefin-based resin, and the hydrotalcite is used as a result of 100 parts by mass of the polyolefin-based resin. 0.001 to 5 parts by mass, typically in an amount of 0.05 to 3 parts by mass.

Examples of the fatty acid metal salt include fatty acid decanoic acid, 2-ethylhexanoic acid, undecanoic acid, lauric acid, tridecanoic acid, myristic acid, pentadecanoic acid, palmitic acid, heptadecanoic acid, stearic acid, and ten. Saturated fatty acids such as nonaic acid, icosonic acid, behenic acid, behenic acid, trisuccinic acid, tetracosanoic acid, octadecanoic acid, octadecanoic acid, and tridecanoic acid; 4-decenoic acid, 4-dodecenoic acid, palmitoleic acid, alpha-linolenic acid, linoleic acid, gamma-linolenic acid, stearic acid, petroselinic acid, oleic acid, a linear unsaturated fatty acid such as elaidic acid, 11-octadecenoic acid, eicosapentaenoic acid, docosapentaenoic acid or docosahexaenoic acid; benzene Aromatic fatty acids such as trimesic acid, especially saturated fatty acids such as myristic acid, stearic acid, and 12-hydroxystearic acid are preferred.

Examples of the metal salt of the fatty acid include an alkali metal, magnesium, calcium, barium, strontium, titanium, manganese, iron, zinc, cerium, zirconium, lanthanum, cerium, or lanthanum, and the like, especially alkali metals such as sodium, lithium, and potassium. good.

With respect to the preferred content of the above-mentioned fatty acid metal salt in the nucleating agent of the present invention, the nucleating agent of the present invention is blended with the polyolefin-based resin, and the fatty acid metal salt is 100 parts by mass based on the polyolefin-based resin. 0.001 to 5 parts by mass, typically in an amount of 0.03 to 3.0 parts by mass.

Examples of the antistatic agent include cationic antistatic agents such as fatty acid quaternary ammonium ion salts and polyamine quaternary salts; higher alcohol phosphate salts, higher alcohol EO adducts, polyethylene glycol fatty acid esters, and anionic types. Anionic antistatic agent such as alkyl sulfonate, higher alcohol sulfate, higher alcohol ethylene oxide adduct sulfate, higher alcohol ethylene oxide adduct phosphate; polyol fatty acid ester, Nonionic antistatic agents such as polyethylene glycol phosphate and polyoxyethylene alkyl allyl ether; amphoteric alkyl betaine such as alkyl dimethylaminoacetate betaine, and imidazoline type amphoteric active agent Antistatic agent. The antistatic agent may be used singly or in combination of two or more kinds of antistatic agents.

With respect to the preferable content of the above-mentioned antistatic agent in the nucleating agent of the present invention, the nucleating agent of the present invention is blended with the polyolefin-based resin, and as a result of the antistatic agent, 100 parts by mass of the polyolefin-based resin is used. 0.01 to 20 parts by mass, typically in an amount of 3 to 10 parts by mass.

Commercially available pigments can be used as the pigment, and for example, pigment red 1, 2, 3, 9, 10, 17, 22, 23, 31, 38, 41, 48, 49, 88, 90, 97, 112, 119, 122 can be cited. , 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, etc.

Examples of the dyes include azo dyes, anthraquinone dyes, indigo dyes, triarylmethane dyes, xanthenes dyes, alizarin dyes, acridine dyes, stilbene dyes, thiazole dyes, naphthol dyes, Quinoline dye, nitro dye, indamine dye, oxazine dye, anthraquinone dye, cyanine dye, etc., may be used in combination.

In the nucleating agent of the present invention, a known compound other than the nucleating agent of the present invention can be blended. Examples of such a nucleating agent include sodium 2,2'-methylenebis(4,6-di-t-butylphenyl)phosphate and 2,2'-methylenebis (4,6-). Di-t-butylphenyl)lithium phosphate, hydroxyaluminum bis[2,2'-methylenebis(4,6-di-t-butylphenyl)phosphate], sodium benzoate, 4-third Metal salts of butyl benzoate, sodium adipate and sodium bicyclo [2.2.1] heptane-2,3-dicarboxylate, bis-benzyl sorbitol, bis (methyl benzyl) Base) sorbitol, bis(3,4-dimethylbenzyl) sorbitol, bis(p-methylbenzyl) sorbitol and bis(dimethylbenzyl) sorbitol, 1 , 2,3-trideoxy-4,6:5,7-di-((4-propylphenyl)methylene) decyl alcohol and other polyol derivatives, N, N', N"-three [2 -Methylcyclohexyl]-1,2,3-propane trimethylamine, N,N',N"-tricyclohexyl-1,3,5-benzenetridecylamine, N,N'-dicyclohexylnaphthalene A decylamine compound such as dimethylamine or 1,3,5-tris(dimethylisopropylamino)benzene.

In the preferred content of the above-mentioned other nucleating agent in the nucleating agent of the present invention, the nucleating agent of the present invention is blended with the polyolefin-based resin, and the other nucleation is based on 100 parts by mass of the polyolefin-based resin. The agent is present in an amount of 0.05 to 10 parts by mass, typically in a concentration of 0.01 to 0.5 parts by mass.

[Resin Composition] The resin composition of the present invention contains a polyolefin resin and a resin composition of the above nucleating agent. The content of the nucleating agent in the resin composition of the present invention is not particularly limited as long as it is an effect of exhibiting the effect of the nucleating agent, and is usually 0.0001 to 10 parts by mass based on 100 parts by mass of the polyolefin resin. It is preferably 0.005 to 5 parts by mass, more preferably 0.01 to 0.5 parts by mass. When the blending amount of the nucleating agent is less than 0.0001 parts by mass, the effect of addition may be insufficient, and if it is more than 10 parts by mass, the nucleating agent may bleed out from the molded article.

The polyolefin-based resin used in the resin composition of the present invention is not particularly limited. For example, low density polyethylene (LDPE), linear low density polyethylene (L-LDPE), high density polyethylene (HDPE), isotactic polypropylene, syndiotactic polypropylene, semi-isotactic polypropylene, and ring can be used. Olefin polymer, stereotactic block polypropylene, poly-3-methyl-1-butene, poly-3-methyl-1-pentene, poly-4-methyl-1-pentene, etc. Olefin polymer, ethylene/propylene block or random copolymer, impact copolymerized polypropylene, ethylene-methyl methacrylate copolymer, ethylene-methyl acrylate copolymer, ethylene-ethyl acrylate copolymer, ethylene-acrylic acid An α-olefin copolymer such as a butyl ester copolymer, an ethylene-vinyl acetate copolymer or an ethylene-vinyl alcohol resin (EVOH) may be an elastomer composed of a polyolefin resin. In the present invention, two or more kinds of these may be used in combination, or a block copolymer may be used to form a block polymer type, and the resin may be alloyed. Further, a chloride of the olefin-based resin may be used.

Examples of the elastomer of the polyolefin resin include a polyolefin such as polypropylene or polyethylene as a hard segment, a rubber such as an ethylene-propylene rubber as a soft segment, and an elastomer obtained by mixing the rubber resin. Or an elastomer obtained by dynamic crosslinking. The hard segment may, for example, be at least one selected from the group consisting of a polypropylene homopolymer, a polypropylene block copolymer, and a polypropylene random copolymer. Examples of the soft segment include an ethylene-propylene copolymer (EPM), an ethylene-propylene-diene copolymer (EPDM), an ethylene-vinyl acetate copolymer (EVA), and a vinyl acetate homopolymer. These two or more types may be mixed and used.

In the method for producing an olefin resin, a carrier or a carrier for a catalyst, a chain transfer agent, and various polymerization methods such as gas phase polymerization, solution polymerization, emulsion polymerization, and overall polymerization are appropriately selected to obtain temperature and pressure. And a resin suitable for the physical properties of the packaging material, such as a concentration, a flow rate, or a removal of a catalyst residue, or a resin which can obtain a physical property suitable for the molding process of the packaging material, to manufacture Ziegler catalyst, Ziegler-Nano Tower catalyst, metallocene catalyst and various other polymerization catalysts. Number average molecular weight, weight average molecular weight, molecular weight distribution, melt flow rate, melting point, melting peak temperature, stereoregularity, syndiotacticity, degree of branching, specific gravity, dissolved component of various solvents of olefin resin The ratio, haze, gloss, impact strength, flexural modulus, Olsen rigidity, other characteristics, and whether or not each characteristic value satisfies a specific formula can be appropriately selected depending on desired characteristics.

The resin composition of the present invention may optionally contain the above-mentioned known resin additives (for example, a phenol-based antioxidant, a phosphorus-based antioxidant, a thioether-based antioxidant, and other antioxidants) within a range that does not significantly impair the effects of the present invention. , hindered amine compound, ultraviolet absorber, flame retardant, flame retardant aid, lubricant, filler, hydrotalcite, fatty acid metal salt, antistatic agent, pigment, dye, etc.), in addition to the nucleating agent of the present invention A well-known nucleating agent. As the above various additives, the same as those used in the nucleating agent of the present invention can be used.

The blending amount is not particularly limited as long as it is a usual amount. When the various additives described above are also supplied from the nucleating agent of the present invention, the above various additives which are finally present in the resin composition of the present invention are adjusted in such a range as to exhibit the functions of the respective additives and exhibit the properties of the polyolefin-based resin. The amount.

The content of the phenolic antioxidant in the resin composition of the present invention is preferably 0.001 to 5 parts by mass, and usually 0.01 to 1.0 part by mass, based on 100 parts by mass of the polyolefin resin. The content of the phosphorus-based antioxidant in the resin composition of the present invention is preferably 0.001 to 20 parts by mass, and usually 0.01 to 5 parts by mass, based on 100 parts by mass of the polyolefin resin. The content of the thioether-based antioxidant in the nucleating agent of the present invention is preferably 0.001 to 20 parts by mass, and usually 0.01 to 5 parts by mass, based on 100 parts by mass of the polyolefin resin. The content of the above-mentioned other antioxidant in the nucleating agent of the present invention is preferably 0.001 to 20 parts by mass, and usually 0.01 to 5 parts by mass, based on 100 parts by mass of the polyolefin resin. The content of the hindered amine compound in the nucleating agent of the present invention is preferably 0.001 to 5 parts by mass, and typically 0.005 to 0.5 parts by mass, based on 100 parts by mass of the polyolefin resin. The content of the ultraviolet absorber in the nucleating agent of the present invention is preferably 0.001 to 5 parts by mass, and typically 0.005 to 0.5 parts by mass, based on 100 parts by mass of the polyolefin resin. The content of the flame retardant in the nucleating agent of the present invention is preferably from 1 to 50 parts by mass, and usually from 10 to 30 parts by mass, per 100 parts by mass of the polyolefin resin. The content of the lubricant in the nucleating agent of the present invention is preferably 0.01 to 2 parts by mass, and usually 0.03 to 0.5 parts by mass, based on 100 parts by mass of the polyolefin resin. The content of the filler in the nucleating agent of the present invention is preferably from 0.01 to 80 parts by mass, and usually from 1 to 50 parts by mass, per 100 parts by mass of the polyolefin resin. The content of the hydrotalcite in the nucleating agent of the present invention is preferably 0.001 to 5 parts by mass, and typically 0.05 to 3 parts by mass, based on 100 parts by mass of the polyolefin resin. The content of the hydrotalcite in the nucleating agent of the present invention is preferably 0.001 to 5 parts by mass, and typically 0.05 to 3 parts by mass, based on 100 parts by mass of the polyolefin resin. The content of the hydrotalcite in the nucleating agent of the present invention is preferably 0.001 to 5 parts by mass, and typically 0.05 to 3 parts by mass, based on 100 parts by mass of the polyolefin resin. The content of the above-mentioned other nucleating agent in the nucleating agent of the present invention is preferably 0.05 to 10 parts by mass, and typically 0.01 to 0.5 parts by mass, based on 100 parts by mass of the polyolefin resin.

In the resin composition of the present invention, the method of blending the nucleating agent of the present invention with an olefin-based resin is not particularly limited, and can be carried out by a conventionally known method. For example, the olefin-based resin powder or granules and the additive may be mixed by a dry mixer, or may be dry-mixed with the remaining components after pre-mixing a part of the above-mentioned resin additive containing the nucleating agent of the present invention. After dry mixing, for example, a roll, a Banbury mixer, a super mixer, or the like may be used for mixing, and kneading may be carried out using a uniaxial or twin screw extruder or the like. This mixing and kneading is usually carried out at a temperature of about 120 to 220 °C. The method of adding an additive to a polymerization stage of an olefin-based resin, mixing with a granulation aid such as a binder, a wax, a solvent, or a cerium oxide, etc., may be carried out in advance at a desired ratio, and then granulated as a one-pack composite additive. A method of adding the one-package composite additive to the olefin-based resin, a method of preparing the master batch containing the additive at a high concentration, and adding the master batch to the olefin-based resin.

The resin composition of the present invention can be obtained by mixing and kneading the above components. The method is not particularly limited, and for example, dry mixing is carried out using a mixer such as a Henschel mixer or a rotating drum, and an extruder, a Banbury mixer, a roll, and a Brabender plastic measuring instrument are used ( A Brabender Plastograph, a kneader, and the like are produced by kneading at a processing temperature of 100 ° C to 260 ° C. Among these, the mixer uses a Henschel mixer, and the processing machine is preferably manufactured using an extruder, especially using a twin-screw extruder.

The molded article of the present invention is formed by using the resin composition of the present invention. The forming can be formed by a known forming method. For example, a molded article can be obtained by an injection molding method, an extrusion molding method, a blow molding method, a vacuum molding method, an inflation molding method, a calender molding method, a coagul molding method, a dip molding method, a foam molding method, or the like.

Examples of the use of the molded article of the present invention include automobile materials such as a bumper, a meter, and an instrument panel, housing applications such as a refrigerator, a washing machine, and a sweeper; household items such as food containers, buckets, and bathing articles; and miscellaneous goods such as toys; A molded article such as a tank or the like, a film for storage, a film, a fiber, or the like. (Example)

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

[Example 1, Example 2, Example 3, Comparative Example 1, Comparative Example 2, Comparative Example 3] (Nucleating Agent Compound) The following compound·Compound 1-1-1 was used as a nucleating agent compound: The lithium salt of the high phthalic acid represented by the formula (1-1-1). Comparative Compound A: a sodium salt of high phthalic acid represented by the following formula (A). Comparative Compound B: a sodium salt of benzoic acid represented by the following formula (B).

[Chemical Formula 26]

(Nucleating Agent) The above nucleating agent compound and the following additives were mixed in the amounts shown in Table 1 to produce the present invention and a comparative nucleating agent. In Comparative Example 1, any of the above nucleating agent compounds was not blended. · Phenolic antioxidant: tetra [methylene-3-(3',5'-di-t-butyl-4'-hydroxyphenyl)propionate] methane-phosphorus antioxidant: three (2, 4-di-t-butylphenyl)phosphite·Fatty acid metal salt: calcium stearate

(Resin composition) The nucleating agent was added and mixed with 100 parts by mass of a homopolypropylene (melt flow rate: 8 g/10 min), and a twin screw extruder (PCM-30: manufactured by Ikegai Corp.) was used at 230. The resin composition of the present invention and the comparative resin composition were obtained by melt-kneading at °C. The results obtained by the following evaluation of the pellets obtained by granulating the respective resin compositions are shown in Table 1.

(crystallization temperature) The obtained pellet was broken into small pieces and weighed 5 mg to be filled in an aluminum pan, and crystallization was measured by a differential scanning calorimeter (device: diamond manufactured by PerkinElmer Co., Ltd.). temperature. The temperature was raised to 230 ° C at a temperature increase rate of 50 ° C / min, and after maintaining for 5 minutes, it was cooled to 50 ° C at 10 ° C / min, and the temperature ( ° C) of the measured exothermic peak was taken as the crystallization temperature.

(Bending Elastic Modulus) The obtained pellets were injection molded at an injection temperature of 230 ° C and a mold temperature of 40 ° C using an injection molding machine (device: EC-220, manufactured by TOSHIBA MACHINE CO., LTD.) to produce 80 mm × 10 mm × 4 mm test piece. The test piece was allowed to stand in a standard state at room temperature of 23 ° C and a humidity of 50% for 48 hours. Then, using a bending tester (manufactured by SHIMADZU CORPORATION; AG-IS), the flexural modulus (MPa) of the test piece was measured in accordance with the conditions of ISO178.

(Flexural strength) The obtained pellets were injection-molded using an injection molding machine (device: EC-220, manufactured by TOSHIBA MACHINE CO., LTD.) at an injection temperature of 230 ° C and a mold temperature of 40 ° C to produce 80 mm × 10 mm. × 4 mm test piece. The test piece was allowed to stand in a standard state at room temperature of 23 ° C and a humidity of 50% for 48 hours. Then, the deflection temperature (HDT, (°C)) of the test piece when it was laid flat was measured in accordance with ISO 75 (load: 1.8 MPa). The higher the HDT, the higher the flexural strength of the test piece.

(Ehrlich Impact Strength) The obtained pellets were injection-molded using an injection molding machine (device: EC-220, manufactured by TOSHIBA MACHINE CO., LTD) at an injection temperature of 230 ° C and a mold temperature of 40 ° C to produce a notch. Test piece. The test piece was allowed to stand in a standard state at room temperature of 23 ° C and a humidity of 50% for 48 hours. Then, the Izod impact strength (J/m) of the test piece was measured in accordance with the conditions of ISO180.

[Table 1]

From the evaluation results shown in Table 1, it was found that in Examples 1, 2, and 3, the crystallization temperature of the polypropylene was remarkably increased by the blending of the nucleating agent of the present invention. Further, in Examples 1, 2, and 3, the bending strength, flexural strength, and impact strength of the polypropylene composition also increased by the blending of the nucleating agent of the present invention. On the other hand, in Comparative Examples 2 and 3 in which other nucleating agents were used, the increase in the crystallization temperature of polypropylene was small, and the obtained polypropylene composition had a bending strength, a flexural strength, and an impact strength ratio. difference. As described above, in the present invention, both the moldability and the mechanical strength of the polyolefin resin can be improved.

[Example 4, Example 5, Comparative Example 4, Comparative Example 5] (Nucleating Agent Compound) The following compounds were used as the nucleating agent compound. Compound 1-2-1: a calcium salt of high phthalic acid represented by the following formula (1-2-1). Compound 1-2-2: a zinc salt of high phthalic acid represented by the following formula (1-2-2). Comparative Compound B: a sodium salt of benzoic acid represented by the following formula (B).

[Chemical Formula 27]

(Synthesis of Nucleating Agent Compound 1-2-1) To a slurry of 3.24 g (0.018 mol) of high phthalic acid and 10 g of water, 2.88 g (0.072 mol) of sodium hydroxide, 30 g of water, and hydr Aqueous sodium solution was stirred at room temperature for 30 minutes. After stirring, an aqueous solution obtained by dissolving a calcium salt (0.036 mol) in 30 g of water was added dropwise, and the mixture was stirred at room temperature for 1 hour. After stirring, the white precipitate was removed by filtration, washed with water, and dried to obtain a nucleating agent compound 1-2-1 represented by the following formula (1-1).

(Synthesis of Nucleating Agent Compound 1-2-2) To a slurry obtained by mixing 3.24 g (0.018 mol) of high phthalic acid and 10 g of water, 2.88 g (0.072 mol) of sodium hydroxide, 30 g of water, and hydroxide were added. Aqueous sodium solution was stirred at room temperature for 30 minutes. After stirring, an aqueous solution obtained by dissolving zinc salt (0.036 mol) in 30 g of water was added dropwise, and the mixture was stirred at room temperature for 1 hour. After stirring, the white precipitate was removed by filtration, washed with water, and dried to obtain a nucleating agent compound 1-2-2 represented by the following formula (1-2).

(Nucleating Agent) The nucleating agent compound and the following additives were mixed in the amounts shown in Table 2 to produce the present invention and a comparative nucleating agent. In Comparative Example 4, any of the above nucleating agent compounds was not blended. · Phenolic antioxidant: tetra [methylene-3-(3',5'-di-t-butyl-4'-hydroxyphenyl)propionate] methane-phosphorus antioxidant: three (2, 4-di-t-butylphenyl)phosphite·Fatty acid metal salt: calcium stearate

(Resin composition) The nucleating agent was added and mixed with 100 parts by mass of a homopolypropylene (melt flow rate: 8 g/10 min), and a twin screw extruder (PCM-30: manufactured by Ikegai Corp.) was used at 230. The resin composition of the present invention and the comparative resin composition were obtained by melt-kneading at °C. Each resin composition was granulated to obtain granules. The pellet was dried at 60 ° C for 5 hours in the following evaluation. The evaluation results are shown in Table 2.

(Shrinkage Anisotropy at the Time of Forming) The degree of warpage or deformation at the time of molding of the above pellets was evaluated. By injection molding machine (device: EC-220 manufactured by TOSHIBA MACHINE CO., LTD), the injection temperature was 230 ° C, the mold temperature was 40 ° C, and the mold shape was 60 mm (machine direction (MD ₀ )) × 60 mm (lateral direction (TD ₀ )). × 2 mm (thickness) The obtained pellet was injection-molded to produce a test piece. The test piece was allowed to stand under a standard condition of room temperature 23 ° C and a humidity of 50% for 48 hours, and its MD size (MD ₄₈ ) (mm) and TD size (TD ₄₈ ) (mm) were measured. The MD shrinkage ratio (?MD) (%) and the TD shrinkage ratio (?TD) (%) of the test piece were determined according to the following formula.

[Expression 1]

[Expression 2]

The deviation between the obtained ΔMD and ΔTD is represented by the shrinkage rate anisotropy (%) obtained by the following formula.

[Expression 3]

The larger the shrinkage anisotropy, the larger the shrinkage anisotropy at the time of molding of the test piece, and the higher the degree of warpage or deformation. In the present invention, the case where the shrinkage anisotropy is 5% or less is evaluated as acceptable, and the case where the shrinkage anisotropy is more than 5% is evaluated as unacceptable.

(crystallization temperature) The obtained pellet was broken into small pieces and weighed 5 mg to be filled in an aluminum pan, and crystallization was measured by a differential scanning calorimeter (device: diamond manufactured by PerkinElmer Co., Ltd.). temperature. The temperature was raised to 230 ° C at a temperature increase rate of 50 ° C / min, and after maintaining for 5 minutes, it was cooled to 50 ° C at 10 ° C / min, and the temperature ( ° C) of the measured exothermic peak was taken as the crystallization temperature.

[Table 2]

From the evaluation results shown in Table 2, in Examples 4 and 5, the crystallization temperature of the polypropylene was greatly increased by the blending of the nucleating agent of the present invention. Further, in Examples 4 and 5, the shrinkage anisotropy at the time of molding of the polypropylene composition was improved by the blending of the nucleating agent of the present invention. On the other hand, in Comparative Example 5 using a conventional nucleating agent, the crystallization temperature of the polypropylene slightly increased, but the shrinkage anisotropy at the time of molding the polypropylene composition was inferior. As described above, the nucleating agent of the present invention exhibits an excellent nucleating agent effect while maintaining the shrinkage anisotropy at the time of molding the polyolefin resin.

Thus, it was confirmed that the polypropylene in which the nucleating agent of the present invention is blended can be injection-molded in a shorter cycle while maintaining or improving mechanical strength or shape stability. (industrial availability)

According to the present invention, the quality and molding efficiency of a molded article using a polyolefin resin can be improved. The polyolefin-based resin composition obtained in the present invention can expand the use of the conventional polyolefin-based resin material.

The nucleating agent of the present invention is used for polyolefins such as injection molded articles requiring strength, food containers requiring improvement in shrinkage anisotropy, thin molded articles such as medical containers, and large molded articles such as bumpers for automobile materials. Useful as an additive to a resin composition. The polyolefin-based resin composition obtained in the present invention can produce a large-sized molded article of higher quality.

no

no

Claims (6)

A nucleating agent for a polyolefin-based resin, which comprises a compound represented by the following formula (1), In the formula (1), R ¹ , R ² , R ³ and R ⁴ each independently represent a hydrogen atom, a hydroxyl group, a halogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms or a carbon number. The alkenyl group of 2 to 10, the alkyl group of the alkyl group or the alkoxy group may be interrupted by a carbonyl group or an oxygen atom, or may have an unsaturated bond, and 2 alkyl groups bonded to two adjacent carbon atoms may be used. Integrating to form up to 6 hydrocarbon rings; M ¹ and M ² represent n-valent metal atoms, n is 1 or 2; when n is 1, M ¹ and M ² may be the same or different; when n is At 2 o'clock, M ¹ is the same as M ² and M ¹ and M ² represent 1 metal atom. The nucleating agent according to claim 1, wherein the above formula (1) is a formula (1-1) or a formula (1-2), In the formula (1-1), M ¹ and M ² represent Li or K, and may be the same as or different from each other, and R ¹ , R ² , R ³ and R ⁴ each independently represent a hydrogen atom, a hydroxyl group, a halogen atom, An alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms or an alkenyl group having 2 to 10 carbon atoms, or an alkyl group in an alkyl group or an alkoxy group may be interrupted by a carbonyl group or an oxygen atom, or may have In the case of an unsaturated bond, two alkyl groups bonded to two adjacent carbon atoms may be integrated to form up to six hydrocarbon rings; In the formula (1-2), M ¹ represents any one of Zn, Ca, and Mg, and R ¹ , R ² , R ³ and R ⁴ each independently represent a hydrogen atom, a hydroxyl group, a halogen atom, and a carbon number of 1 to 1; An alkyl group of 10, an alkoxy group having 1 to 10 carbon atoms or an alkenyl group having 2 to 10 carbon atoms; an alkyl group in an alkyl group or an alkoxy group may be interrupted by a carbonyl group or an oxygen atom, or may have an unsaturated bond. The two alkyl groups bonded to two adjacent carbon atoms may be integrated to form up to six hydrocarbon rings. The nucleating agent according to claim 1 or 2, which further comprises a phenolic antioxidant, a phosphorus antioxidant, a thioether antioxidant, another antioxidant, a hindered amine compound, and ultraviolet absorption. A composition of one or more additives selected from the group consisting of a nucleating agent, a nucleating agent, a flame retardant, a flame retardant auxiliaries, a lubricant, a filler, a hydrotalcite, a fatty acid metal salt, an antistatic agent, a pigment, and a dye. A resin composition comprising: a polyolefin-based resin; and the nucleating agent according to any one of claims 1 to 3, wherein the composition is 100 parts by mass based on 100 parts by mass of the polyolefin-based resin The nucleating agent is 0.0001 to 10 parts by mass. The resin composition according to claim 4, wherein the polyolefin resin comprises a polypropylene resin. A molded article comprising the resin composition described in claim 5 of the patent application.