JP4338132B2 - Crystal nucleating agent composition and crystalline polymer composition containing the same - Google Patents

Description

  The present invention relates to a crystal nucleating agent composition used in addition to a crystalline polymer compound and a crystalline polymer composition containing the crystal nucleating agent composition, and more specifically, a crystal nucleating agent having a specific composition. The present invention relates to a composition and a crystalline polymer composition comprising the crystal nucleating agent composition.

  Polycrystalline polymers such as polyethylene, polypropylene and polybutene-1, polyester polymers such as polyethylene terephthalate, and crystalline polymers such as polyamide polymers have a slow crystallization rate after heat molding, so molding during processing In addition, there are problems such as a long cycle, and in addition, the molded product may be deformed by crystallization that proceeds even after molding. In addition, these crystalline polymer compound materials have the disadvantage of poor mechanical strength and transparency because large spherulites are formed.

These drawbacks are derived from the crystallinity of the crystalline polymer compound, and it is known that these defects can be solved by rapidly generating fine crystals. Currently, in order to rapidly produce fine crystals, methods such as increasing the crystallization temperature, adding a crystal nucleating agent, a crystallization accelerator, and the like are used.

  As the above crystal nucleating agent or crystallization accelerator, a metal salt of a cyclic phosphate represented by 2,2'-methylenebis (4,6-ditert-butylphenyl) phosphate is used. Patent Documents 1 and 2 report that good use effects can be obtained by using these cyclic phosphate metal salts and aliphatic organic acid metal salts in combination.

  However, the conventional crystal nucleating agent composition has a problem in that the compatibility and / or dispersibility with the crystalline polymer is not sufficient, so that it does not exhibit a sufficient use effect for imparting transparency.

Japanese Published Patent No. Hei 5-43746 Japanese Published Patent No. 2002-338820

  Accordingly, an object of the present invention is to provide a crystal nucleating agent composition that exhibits a sufficient transparency imparting effect and a crystalline polymer composition comprising the crystal nucleating agent composition.

  As a result of repeated studies, the present inventors have found that a specific composition composed of a lithium salt of a cyclic phosphate ester, an aliphatic organic acid metal salt, and an organic acid amide compound can solve the above problem. The present invention has been reached.

The present invention includes 100 parts by mass of a crystal nucleating agent compound represented by the following general formula (I), 5 to 50 parts by mass of an aliphatic organic acid metal salt represented by the following general formula (II), and 5 to 5 of an organic acid amide compound. A crystal nucleating agent composition comprising 50 parts by mass, wherein the mixture of the crystal nucleating agent, the aliphatic organic acid metal salt and the amide compound is mixed into a mortar, ball mill, vibration ball mill, roller mill, rod mill, tube mill, Conical mill, high swing ball mill, pin type mill, hammer mill, knife hammer mill, attrition mill, jet mill, counter jet mill, spiral jet mill, jet mizer, micronizer, nanomizer, macjack mill, micro atomizer, micron mill, Group consisting of rotary cutter, impact grinding type mill, compression shearing type mill It was pulverized by al mill selected, average particle size is to provide a nucleating agent composition is 5μm or less.
(In the formula, R ¹ and R ² represent an alkyl group having 1 to 4 carbon atoms, R ³ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R ⁴ represents an alkyl group having 10 to 30 carbon atoms. A group introduced from an aliphatic organic acid, M represents an alkali metal atom, an alkaline earth metal atom or a zinc atom, and n represents 1 or 2)

  INDUSTRIAL APPLICABILITY The present invention can provide a crystal nucleating agent composition exhibiting a sufficient addition effect with respect to transparency and a crystalline polymer composition containing the crystal nucleating agent composition.

Hereinafter, embodiments of the present invention will be described in detail.
The crystal nucleating agent composition of the present invention comprises a crystal nucleating agent compound represented by the above general formula (I), an aliphatic organic acid metal salt represented by the above general formula (II) and an organic acid amide compound. The composition ratio of the composition component is 5 to 50 parts by mass, preferably 10 to 30 parts by mass of the aliphatic organic acid metal salt with respect to 100 parts by mass of the crystal nucleating agent compound represented by the general formula (I). The organic acid amide compound is 5 to 50 parts by mass, preferably 10 to 30 parts by mass.

In the above general formula (I) according to the present invention, examples of the alkyl group having 1 to 4 carbon atoms represented by R ¹ and R ² include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tertiary Examples of the alkyl group having 1 to 4 carbon atoms represented by R ³ include butyl, and a group exemplified as R ² is preferable, and a methyl group is particularly preferable. R ³ is most preferably a hydrogen atom.

  Specific examples of the crystal nucleating agent compound represented by the general formula (I) include the following compound Nos. 1-No. 6 is mentioned.

  Among the above crystal nucleating agent compounds, Compound No. 2 is preferable because it can impart the best transparency to the crystalline polymer composition.

In the aliphatic organic acid metal salt represented by the general formula (II) according to the present invention, the R ⁴ group is a group derived from an aliphatic organic acid having 10 to 30 carbon atoms. Capric acid, neodecanoic acid, undecanoic acid, lauric acid, tridecanoic acid, myristic acid, pentadecanoic acid, palmitic acid, margaric acid, stearic acid, nonadecanoic acid, arachidic acid, behenic acid, lignoceric acid, ceratin Acid, montanic acid, melissic acid, succinic acid, lindelic acid, tuzuic acid, palmitoleic acid, petrothelic acid, oleic acid, elaidic acid, vaccenic acid, linoleic acid, linoleic acid, γ-linolenic acid, linolenic acid, ricinoleic acid , 12-hydroxystearic acid, naphthenic acid, abietic acid and the like. Of these, stearic acid and 12-hydroxystearic acid are preferable because of low cost and remarkable use effects. Examples of the alkali metal represented by M include lithium, sodium, and potassium, and examples of the alkaline earth metal include magnesium, calcium, strontium, and barium. Among these, lithium, magnesium, and calcium are preferable because they are low in cost and have a remarkable use effect, and lithium is more preferable.

  Examples of the organic acid amide compound according to the present invention include monofatty acid amides such as lauric acid amide, stearic acid amide, oleic acid amide, erucic acid amide, ricinoleic acid amide, and 12-hydroxystearic acid amide; N, N′-ethylene Bislauric acid amide, N, N′-methylenebisstearic acid amide, N, N′-ethylene bisstearic acid amide, N, N′-ethylene bisoleic acid amide, N, N′-ethylene bisbehenic acid amide, N , N′-ethylenebis-12-hydroxystearic acid amide, N, N′-butylene bisstearic acid amide, N, N′-hexamethylene bisstearic acid amide, N, N′-hexamethylene bisoleic acid amide, N N, N′-bisfatty acid amides such as N, N′-xylylenebisstearic acid amide; Alkylolamides such as monomethylolamide, palm oil fatty acid monoethanolamide, diethanolamide stearate; N-oleyl stearamide, N-oleyl oleate, N-stearyl stearate, N-stearyl olein N-substituted fatty acid amides such as acid amide, N-oleyl palmitic acid amide, N-stearyl erucic acid amide; N, N′-dioleyl adipic acid amide, N, N′-distearyl adipic acid amide, N, N N, N'-substituted dicarboxylic acids such as' -dioleoyl sebacic acid amide, N, N'-distearyl sebacic acid amide, N, N'-distearyl terephthalic acid amide, N, N'-distearyl isophthalic acid amide Amides are mentioned. You may use these by 1 type or a 2 or more types of mixture. Of these, N, N′-bisfatty acid amides are preferred because of their low cost and remarkable use effects.

  The crystal nucleating agent composition of the present invention may be obtained by a method of simply mixing each of the above components, and an aliphatic organic acid metal salt and a metal salt on the particle surface of the crystal nucleating agent compound by a topochemical action or mechanochemical action. In order to attach the organic acid amide compound, mortar, ball mill, vibrating ball mill, roller mill, rod mill, tube mill, conical mill, high swing ball mill, pin type mill, hammer mill, knife hammer Mill, Attrition Mill, Jet Mill, Counter Jet Mill, Spiral Jet Mill, Jet Mizer, Micronizer, Nanomizer, Macjack Mill, Micro Atomizer, Micron Mill, Rotary Cutter, Impact Grinding Mill, Compression Shear Mill, etc. Even if it is subjected to pulverizing treatment There. The aliphatic organic acid metal salt and / or organic acid amide compound may be melted without heat, or melted, crystallized, impregnated, spray coated, mixer, colloid mill, premier colloid mill. , A method of attaching a liquid dissolved and / or dispersed in water or an organic solvent to the particle surface of the crystal nucleating agent compound using a Charlotte colloid mill or the like, an aliphatic organic acid metal salt and / or an organic acid amide An evaporation method in which the compound is vaporized and attached or deposited on the surface of the crystal nucleating agent compound may be used.

  Said manufacturing method may be performed individually or in combination of 2 or more types. Moreover, the grinding | pulverization process which provided the shear force is preferably used since the transparency provision effect which is the addition effect of the crystal nucleating agent composition of this invention is strengthened at low cost.

  Specific examples of the pulverizing apparatus for performing the pulverizing treatment with the above-described shearing force include “Attritor” and “Fine Mill” manufactured by Mitsui Mining Co., Ltd., “Planet Ball Mill” and “Codget” manufactured by Seishin Enterprise Co., Ltd. "System α-mkIII", Hosokawa Micron's "Supermicron Mill", "Inomizer", "Counter Jet Mill", "Mechano-Fusion", Hadano Sangyo's "Coloplex", "Ixeed Mill", HEIKO “TI-500ET; HEIKO SAMPLE MILL” and the like.

  The crystal nucleating agent composition of the present invention is not particularly limited by the particle state such as particle diameter and particle size distribution, and may be used in the particle state obtained by the above production method. The crystal nucleating agent component is known to improve dispersibility in a crystalline polymer if the particle size is fine, and the average particle size is preferably 5 μm or less, more preferably 1 μm or less. When the above-described pulverization treatment with a shearing force, which is a preferred embodiment of the present invention, is performed, sufficiently finely divided particles can be obtained.

  The crystalline polymer composition of the present invention has improved transparency and / or strength, etc., comprising the crystalline nucleating agent composition in a crystalline polymer, and the crystalline polymer composition May contain other additive components as necessary.

  Examples of the crystalline polymer include low density polyethylene, linear low density polyethylene, high density polyethylene, isotactic polypropylene, syndiotactic polypropylene, hemiisotactic polypropylene, polybutene-1, and poly-3-methyl. Polyolefins such as α-olefin polymers such as -1-butene, poly-3-methyl-1-pentene, poly-4-methyl-1-pentene, and α-olefin copolymers such as ethylene / propylene block or random copolymer Polymers; thermoplastic linear polyester polymers such as polyethylene terephthalate, polybutylene terephthalate, polyhexamethylene terephthalate; polysulfide polymers such as polyphenylene sulfide; polylactic acid polymers such as polycaprolactone; polyhexamethyl Examples thereof include linear polyamide polymers such as len adipamide; crystalline polystyrene polymers such as syndiotactic polystyrene.

  Among the above-described crystalline polymers, polyolefin-based polymers that are prominent in the use effect of the crystal nucleating agent composition of the present invention are suitable, and polypropylene, ethylene / propylene block or random copolymer, α other than ethylene -Polypropylene resins such as olefin / propylene block or random copolymers and mixtures of these propylene polymers with other α-olefin polymers are particularly suitable.

  In the crystalline polymer composition of the present invention, the content of the crystal nucleating agent composition is not particularly limited. When the amount used is less than 0.005 parts by mass with respect to 100 parts by mass of the crystalline polymer in terms of the mass of the crystal nucleating agent compound, a sufficient addition effect may not be exhibited. 0.005-10 parts by mass is preferable, since 0.015 parts by mass is preferable because it may not only increase the cost without improving the effect, but may affect the physical properties of the resulting polymer product. Is more preferable.

  In addition, other additive components used as needed include hindered amine light stabilizers (HALS), ultraviolet absorbers, phenolic, sulfur and phosphorus antioxidants, and alkali metal salts of organic acids. Well-known and commonly used additives such as can be used.

  Examples of the HALS include compounds represented by the following general formula (III), cyanuric chloride condensation type, high molecular weight type and the like.

(In the formula, m represents an integer of 1 to 6, A represents a hydrogen atom, an m-valent hydrocarbon group having 1 to 18 carbon atoms, an m-valent acyl group, or an m-valent carbamoyl group, and B represents , An oxygen atom, -NH-, or -NRe- having an alkyl group Re having 1 to 8 carbon atoms, Y represents a hydrogen atom, an oxy radical (.O), an alkoxy group having 1 to 18 carbon atoms, or 1 carbon atom. -8 represents an alkyl group or hydroxyl group, and Z represents methine or the following group (IV) having an alkyl group Rf having 1 to 8 carbon atoms.)

  In the general formula (III), examples of the m-valent hydrocarbon group having 1 to 18 carbon atoms represented by A include methane, ethane, propane, butane, second butane, third butane, isobutane, pentane, isopentane, Tertiary pentane, hexane, cyclohexane, heptane, isoheptane, tertiary heptane, n-octane, isooctane, tertiary octane, 2-ethylhexane, nonane, isononane, decane, dodecane, tridecane, tetradecane, pentadecane, hexadecane, heptadecane, octadecane Groups derived from (alkyl group, alkanedi to hexayl group).

The m-valent acyl group in A is derived from a (nm) alkyl ester of carboxylic acid, m-valent carboxylic acid and n-valent carboxylic acid in which m carboxyl groups remain (these are referred to as acyl derivative compounds). It is the group to be done.
Examples of the acyl derivative compound include acetic acid, benzoic acid, 4-trifluoromethylbenzoic acid, salicylic acid, acrylic acid, methacrylic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, and azelain. Acid, sebacic acid, dodecanedioic acid, 2-methylsuccinic acid, 2-methyladipic acid, 3-methyladipic acid, 3-methylpentanedioic acid, 2-methyloctanedioic acid, 3,8-dimethyldecanedioic acid, 3 , 7-dimethyldecanedioic acid, hydrogenated dimer acid, dimer acid, phthalic acid, terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, cyclohexanedicarboxylic acid, trimellitic acid, trimesic acid, propane-1,2,3-tricarboxylic acid, Propane-1,2,3-tricarboxylic acid mono- or dialkyl ester, pentane-1, , 5-tricarboxylic acid, pentane-1,3,5-tricarboxylic acid mono or dialkyl ester, butane-1,2,3,4-tetracarboxylic acid, butane-1,2,3,4-tetracarboxylic acid mono or Trialkyl ester, pentane-1,2,3,4,5-pentacarboxylic acid, pentane-1,2,3,4,5-pentacarboxylic acid mono- or tetraalkyl ester, hexane-1,2,3,4 , 5,6-hexacarboxylic acid, hexane-1,2,3,4,5,6-hexacarboxylic acid mono- or pentaalkyl ester.

The m-valent carbamoyl group in A is a monoalkylcarbamoyl group or dialkylcarbamoyl group derived from an isocyanate compound.
Examples of the isocyanate compound from which the monoalkylcarbamoyl group is derived include tolylene diisocyanate, diphenylmethane-4,4′-diisocyanate, p-phenylene diisocyanate, xylylene diisocyanate, 1,5-naphthylene diisocyanate, 3,3′-dimethyldiphenyl- 4,4′-diisocyanate, dianisidine diisocyanate, tetramethylxylylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane-4,4′-diisocyanate, trans-1,4-cyclohexyl diisocyanate, norbornene diisocyanate, 1,6-hexamethylene diisocyanate, 2,2,4 (2,4,4) -trimethylhexamethylene diisocyanate, lysine diisocyanate, triphenylmethane Examples include triisocyanate, 1-methylbenzole-2,4,6-triisocyanate, and dimethyltriphenylmethane tetraisocyanate. Examples of the dialkylcarbamoyl group include a diethylcarbamoyl group, a dibutylcarbamoyl group, a dihexylcarbamoyl group, a dioctylcarbamoyl group, and the like.

  These groups represented by A may be substituted with a halogen atom, a hydroxyl group, an alkyl group, an alkoxy group, a nitro group, a cyano group or the like.

  Examples of the alkyl group having 1 to 8 carbon atoms represented by Re substituted for N in B in the formula (III) include methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, sec-butyl, isobutyl, amyl, Examples include isoamyl, tertiary amyl, hexyl, cyclohexyl, heptyl, isoheptyl, tertiary heptyl, 1-ethylpentyl, n-octyl, isooctyl, tertiary octyl and 2-ethylhexyl.

Y in formula (III) represents a hydrogen atom, an oxy radical (.O), an alkoxy group having 1 to 18 carbon atoms, an alkyl group having 1 to 8 carbon atoms, or a hydroxyl group.
Examples of the alkoxy group having 1 to 18 carbon atoms include methoxy, ethoxy, propoxy, isopropoxy, butoxy, sec-butyloxy, tert-butyloxy, isobutyloxy, amyloxy, isoamyloxy, hexyloxy, heptyloxy, octyloxy, 2- Examples include ethylhexyloxy, nonyloxy, isononyloxy, decyloxy, dodecyloxy, tridecyloxy, tetradecyloxy, pentadecyloxy, hexadecyloxy, heptadecyloxy, octadecyloxy, and the alkyl group having 1 to 8 carbon atoms. The same group as Re is mentioned, As a C1-C8 alkyl group represented by Rf in Z of Formula (VI), the group similar to Re is mentioned.

  As further specific examples of HALS represented by the above general formula (III), for example, 2,2,6,6-tetramethyl-4-piperidyl stearate, 1,2,2,6,6-pentamethyl -4-piperidyl stearate, 2,2,6,6-tetramethyl-4-piperidylbenzoate, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1,2,2, 6,6-pentamethyl-4-piperidyl) sebacate, bis (1-octoxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate, 1,2,2,6,6-pentamethyl-4-piperidyl Methacrylate, 2,2,6,6-tetramethyl-piperidyl methacrylate, tetrakis (2,2,6,6-tetramethyl-4-piperidyl) -1,2,3,4-butante Lacarboxylate, tetrakis (1,2,2,6,6-pentamethyl-4-piperidyl) -1,2,3,4-butanetetracarboxylate, bis (2,2,6,6-tetramethyl-4 -Piperidyl) .bis (tridecyl) -1,2,3,4-butanetetracarboxylate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) .bis (tridecyl) -1,2, 3,4-butanetetracarboxylate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) -2-butyl-2- (3,5-ditert-butyl-4-hydroxybenzyl) Malonate, 3,9-bis [1,1-dimethyl-2- [tris (2,2,6,6-tetramethyl-4-piperidyloxycarbonyloxy) 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-piperidyloxycarbonyloxy) butyl Carbonyloxy] ethyl] -2,4,8,10-tetraoxaspiro [5.5] undecane and the like.

  As cyanuric chloride condensed HALS, 1,6-bis (2,2,6,6-tetramethyl-4-piperidylamino) hexane / 2,4-dichloro-6-morpholino-s-triazine polycondensate, 1 , 6-Bis (2,2,6,6-tetramethyl-4-piperidylamino) hexane / 2,4-dichloro-6-tert-octylamino-s-triazine polycondensate, 1,5,8,12 Tetrakis [2,4-bis (N-butyl-N- (2,2,6,6-tetramethyl-4-piperidyl) amino) -s-triazin-6-yl] -1,5,8,12 -Tetraazadodecane, 1,5,8,12-tetrakis [2,4-bis (N-butyl-N- (1,2,2,6,6-pentamethyl-4-piperidyl) amino) -s-triazine -6-yl] -1,5,8,12-tetraa Zadodecane, 1,6,11-tris [2,4-bis (N-butyl-N- (2,2,6,6-tetramethyl-4-piperidyl) amino) -s-triazin-6-ylamino] undecane 1,6,11-tris [2,4-bis (N-butyl-N- (1,2,2,6,6-pentamethyl-4-piperidyl) amino) -s-triazin-6-ylamino] undecane Etc.

  The high molecular weight type includes 1- (2-hydroxyethyl) -2,2,6,6-tetramethyl-4-piperidinol / diethyl succinate polycondensate, 1,6-bis (2,2,6 , 6-tetramethyl-4-piperidylamino) hexane / dibromoethane polycondensate and the like.

  Examples of the ultraviolet absorber include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, and 5,5′-methylenebis (2-hydroxy-4-methoxybenzophenone). 2-hydroxybenzophenones such as 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-tertiary o Acetyl-6-benzotriazolylphenol), 2- (2-hydroxy-3-tert-butyl-5-carboxyphenyl) benzotriazole, 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- Methacryloyloxyethyl) -5-tert-octylphenyl] benzotriazole, 2- [2-hydroxy-3- (2-methacryloyloxyethyl) -5-tert-butylphenyl] -5-chlorobenzotriazole, 2- [2 -Hydroxy-5- (2-methacryloyloxyethyl) phenyl] benzo Riazole, 2- [2-hydroxy-3-tert-butyl-5- (2-methacryloyloxyethyl) phenyl] benzotriazole, 2- [2-hydroxy-3-tert-amyl-5- (2-methacryloyloxyethyl) ) Phenyl] benzotriazole, 2- [2-hydroxy-3-tert-butyl-5- (3-methacryloyloxypropyl) phenyl] -5-chlorobenzotriazole, 2- [2-hydroxy-4- (2-methacryloyl) Oxymethyl) phenyl] benzotriazole, 2- [2-hydroxy-4- (3-methacryloyloxy-2-hydroxypropyl) phenyl] benzotriazole, 2- [2-hydroxy-4- (3-methacryloyloxypropyl) phenyl ] 2- (2-hydroxyphenyl) such as benzotriazole Benzotriazoles; 2- (2-hydroxy-4-methoxyphenyl) -4,6-diphenyl-1,3,5-triazine, 2- (2-hydroxy-4-hexyloxyphenyl) -4,6-diphenyl -1,3,5-triazine, 2- (2-hydroxy-4-octoxyphenyl) -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- [2- Hydroxy-4- (3-C12-13 mixed alkoxy-2-hydroxypropoxy) phenyl] -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- [2-hydroxy- 4- (2-acryloyloxyethoxy) phenyl] -4,6-bis (4-methylphenyl) -1,3,5-triazine, 2- (2,4-dihydroxy-3-allylphenyl)- , 6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2,4,6-tris (2-hydroxy-3-methyl-4-hexyloxyphenyl) -1,3,5- 2- (2-hydroxyphenyl) -4,6-diaryl-1,3,5-triazines such as triazine; phenyl salicylate, resorcinol monobenzoate, 2,4-ditertiarybutylphenyl-3,5-diter Tributyl-4-hydroxybenzoate, octyl (3,5-ditert-butyl-4-hydroxy) benzoate, dodecyl (3,5-ditert-butyl-4-hydroxy) benzoate, tetradecyl (3,5-ditert Tributyl-4-hydroxy) benzoate, hexadecyl (3,5-ditert-butyl-4-hydroxy) benzoate, octadecyl (3,5-ditert-butyl) Benzoates such as ru-4-hydroxy) benzoate and behenyl (3,5-ditert-butyl-4-hydroxy) benzoate; 2-ethyl-2'-ethoxyoxanilide, 2-ethoxy-4'-dodecyloxy Substituted oxanilides such as zanilides; cyanoacrylates such as ethyl-α-cyano-β, β-diphenyl acrylate and methyl-2-cyano-3-methyl-3- (p-methoxyphenyl) acrylate; various metal salts Alternatively, metal chelates, particularly nickel or chromium salts or chelates may be mentioned.

  Examples of phosphorus antioxidants include triphenyl phosphite, tris (2,4-ditert-butylphenyl) phosphite, tris (2,5-ditert-butylphenyl) phosphite, and tris (nonylphenyl). Phosphite, tris (dinonylphenyl) phosphite, tris (mono, dimixed nonylphenyl) phosphite, diphenyl acid phosphite, 2,2′-methylenebis (4,6-ditert-butylphenyl) octyl phosphite, Diphenyldecyl phosphite, diphenyloctyl phosphite, di (nonylphenyl) pentaerythritol diphosphite, phenyl diisodecyl phosphite, tributyl phosphite, tris (2-ethylhexyl) phosphite, tridecyl phosphite, trilauryl phosphite, di Butyl acid phosphite, dilauryl acid phosphite, trilauryl trithiophosphite, bis (neopentyl glycol) 1,4-cyclohexanedimethyl diphosphite, bis (2,4-ditert-butylphenyl) pentaerythritol diphos Phyto, bis (2,5-ditert-butylphenyl) pentaerythritol diphosphite, bis (2,6-ditert-butyl-4-methylphenyl) pentaerythritol diphosphite, bis (2,4-dicumyl) Phenyl) pentaerythritol diphosphite, distearyl pentaerythritol diphosphite, tetra (C12-15 mixed alkyl) -4,4'-isopropylidene diphenyl phosphite, bis [2,2'-methylenebis (4,6-dia) Milphenyl)]-isopropyl Ridendiphenyl phosphite, tetratridecyl 4,4'-butylidenebis (2-tert-butyl-5-methylphenol) diphosphite, hexa (tridecyl) 1,1,3-tris (2-methyl-5-tert- Butyl-4-hydroxyphenyl) butane triphosphite, tetrakis (2,4-ditert-butylphenyl) biphenylene diphosphonite, tris (2-[(2,4,7,9-tetrakis tert-butyldibenzo [d , F] [1,3,2] dioxaphosphin-6-yl) oxy] ethyl) amine, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 2- And butyl-2-ethylpropanediol. 2,4,6-tritert-butylphenol monophosphite.

  Examples of phenolic antioxidants include 2,6-ditert-butyl-p-cresol, 2,6-diphenyl-4-octadecyloxyphenol, stearyl (3,5-ditert-butyl-4-hydroxy). Phenyl) propionate, distearyl (3,5-ditert-butyl-4-hydroxybenzyl) phosphonate, tridecyl 3,5-ditert-butyl-4-hydroxybenzylthioacetate, thiodiethylenebis [(3,5- Ditertiary butyl-4-hydroxyphenyl) propionate], 4,4′-thiobis (6-tertiarybutyl-m-cresol), 2-octylthio-4,6-di (3,5-ditertiarybutyl- 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-ditert-butylphenol), 4,4′-butylidenebis (6-tert-butyl-3- Methylphenol), 2,2′-ethylidenebis (4,6-ditert-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-ditert-butyl-4-hydroxybenzyl) isocyanurate, 1,3,5-tris (3,5 Ditertiarybutyl-4-hydroxybenzyl) -2,4,6-trimethylbenzene, 1,3,5-tris [(3,5-ditertiarybutyl-4-hydroxyphenyl) propionyloxyethyl] isocyanurate, Tetrakis [methylene-3- (3 ′, 5′-ditertiarybutyl-4′-hydroxyphenyl) propionate] methane, 2-tertiarybutyl-4-methyl-6- (2-acryloyloxy-3-tertiary Butyl-5-methylbenzyl) phenol, 3,9-bis [2- (3-tert-butyl-4-hydroxy-5-methylhydrocinnamoyloxy) -1,1-dimethylethyl] -2,4,8 , 10-tetraoxaspiro [5.5] undecane, triethylene glycol bis [β- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate] and the like. Can be mentioned.

  Examples of sulfur-based antioxidants include dialkylthiodipropionates such as dilauryl, dimyristyl, myristylstearyl, and distearyl esters of thiodipropionic acid, and polyols such as pentaerythritol tetra (β-dodecylmercaptopropionate). (beta) -alkyl mercaptopropionic acid ester is mentioned.

  Examples of the alkali metal salt of an organic acid include sodium salts, lithium salts, and potassium salts of organic acids exemplified as those for deriving the aliphatic organic acid metal salts.

  The above-described exemplary additives may be used alone or in combination of two or more. The amount of each additive used is less than 0.001 part by mass with respect to 100 parts by mass of the crystalline polymer, and the effect is obtained. In some cases, the addition effect cannot be improved and the cost is increased if the amount exceeds 10 parts by mass, so 0.001 to 10 parts by mass is preferable.

  If necessary, the crystalline polymer composition of the present invention may further include an antistatic agent comprising a cationic surfactant, an anionic surfactant, a nonionic surfactant, an amphoteric surfactant, and the like; Compounds, phosphoric acid ester compounds, phosphoric acid amide compounds, melamine compounds, melamine salt compounds of polyphosphoric acid, fluororesins or metal oxides, flame retardants such as melamine polyphosphate; hydrocarbons, fatty acids, aliphatic alcohols -Based, aliphatic ester-based, aliphatic amide-based or metal soap-based lubricants; various heavy metal deactivators; hydrotalcites; organic carboxylic acids; coloring agents such as dyes and pigments; processing aids such as polyolefin powder; Silica, fine particle silica, silica, diatomaceous earth, clay, kaolin, diatomaceous earth, silica gel, calcium silicate, sericite, kaolinite Silicate inorganic additives such as flint, feldspar powder, meteorite, attapulgite, talc, mica, minesotite, pyrophyllite and silica; fillers such as glass fiber and calcium carbonate; sorbitol transparent such as bis (dibenzylidene) sorbitol An agent or the like can be used.

  In addition, as a method for adding these additives used as necessary, a method of adding the crystal nucleating agent composition of the present invention separately, a method of mixing with the crystal nucleating agent composition of the present invention in advance, A method of adding to a functional polymer, the crystal nucleating agent composition of the present invention, and a granulating aid such as a binder, wax, solvent, silica, etc. used as necessary, previously mixed and granulated in a desired ratio. The method used as a one pack composite additive is mentioned.

  Applications of the crystalline polymer composition of the present invention include automotive resin parts such as bumpers, dashboards, and instrument panels; resin parts for household appliances such as refrigerators, washing machines, and vacuum cleaners; tableware, buckets, bathing articles, etc. Household goods; Resin parts for connection such as connectors; Miscellaneous goods such as toys; Storage containers such as tanks and bottles; Medical molded products such as medical packs, syringes, catheters, and medical tubes; Wall materials, floor materials, windows Building materials such as frames and wallpaper; wire covering materials; agricultural materials such as houses and tunnels; molded products including films and sheets such as food packaging materials such as wraps and trays; and fibers.

[Example]
Hereinafter, the present invention will be described in more detail with reference to production examples, examples and comparative examples. However, the present invention is not limited by the following examples.
[Production Example 1]
Using a roller mill pulverizer (manufactured by HEIKO SEISAKUSHYO; SAMPLE MILL), the crystal nucleating agent composition shown in Table 1 was co-ground for 1 hour at a system temperature of 30 ° C. . 1-No. 6 was obtained.

[Production comparison example]
The crystal nucleating agent compositions having the blending ratios shown in Table 2 were mixed and pulverized by the same method as in Production Example 1 to compare sample Nos. 1-No. 3 was obtained.

[Example 1]
Random copolymer of ethylene / propylene = 3/97 with a melt index of 10 g / 10 min at 230 ° C. and 2.16 kg (polymerization catalyst: Ziegler-Natta catalyst, number average molecular weight: 9.5 × 104, mass average molecular weight: 5 .8 × 105) 100 parts by mass, phenolic antioxidant: tetrakis [methylene-3- (3 ′, 5′-ditert-butyl-4′-hydroxyphenyl) propionate] 0.1 part by mass of methane, phosphorus series Antioxidant: Tris (2,4-di-tert-butylphenyl) phosphite 0.1 part by mass, calcium stearate 0.1 part by mass and the crystal nucleating agent composition shown in Table 1 at 1100 rpm for 5 minutes using a Henschel mixer The mixture was mixed and extruded under the conditions of 250 ° C. and 25 rpm to produce pellets. A haze value (JIS K7105) was evaluated for a test piece having a thickness of 1 mm obtained by injection molding at 230 ° C. The results are shown in Table 3.

[Comparative example]
The system using no crystal nucleating agent composition (Comparative Example 1) and the system in which the crystal nucleating agent composition was changed to a comparative composition (Comparative Examples 2 to 4) were tested by the same method as in Example 1 above. A piece was made and evaluated. The results are shown in Table 4.

[Production Example 2]
The crystal nucleating agent composition No. obtained in Production Example 1 above. 1 and no. 4 using a jet mill pulverizer (Cojet system α-mkIII manufactured by Seishin Enterprise Co., Ltd.), 1 pass pulverization under the conditions of P NOZZLE PRESSURE: 0.75 MPa, G NOZZLE PRESSURE: 0.60 MPa, feeder: 60 g / hour. The crystal nucleating agent composition No. 1 ′ and No. 4 'was obtained.

[Example 2]
Using the crystal nucleating agent composition described in Table 5, a test piece was prepared and evaluated in the same manner as in Example 1 above. The results are shown in Table 5.

Claims (1)

From 100 parts by mass of the crystal nucleating agent compound represented by the following general formula (I), 5 to 50 parts by mass of the aliphatic organic acid metal salt represented by the following general formula (II) and 5 to 50 parts by mass of the organic acid amide compound A composition comprising the crystal nucleating agent, the aliphatic organic acid metal salt, and the amide compound, a mortar, a ball mill, a vibrating ball mill, a roller mill, a rod mill, a tube mill, a conical mill, and a high swing. Ball mill, pin type mill, hammer mill, knife hammer mill, attrition mill, jet mill, counter jet mill, spiral jet mill, jet mizer, micronizer, nanomizer, macjack mill, micro atomizer, micron mill, rotary cutter, impact Selected from the group consisting of pulverizing mills and compression shearing mills Ri Na was pulverized by a pulverizer, average particle diameter of 5μm or less nucleating agent composition.
(In the formula, R ¹ and R ² represent an alkyl group having 1 to 4 carbon atoms, R ³ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R ⁴ represents an alkyl group having 10 to 30 carbon atoms. A group introduced from an aliphatic organic acid, M represents an alkali metal atom, an alkaline earth metal atom or a zinc atom, and n represents 1 or 2)