JP2007224132A - Nucleating agent - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain a nucleating agent having improving effect on crystallization temperature and mechanical strength of crystalline polymer and a crystalline polymer composition comprising the nucleating agent. <P>SOLUTION: The nucleating agent is an alkaline earth metal phenoxide compound of a compound containing three phenolic hydroxy groups in the molecule or a zinc phenoxide compound of a compound containing three phenolic hydroxy groups in the molecule. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a nucleating agent and a crystalline polymer composition containing the nucleating agent, and the crystalline polymer composition is mainly used as a molding material for various resin parts and the like.

  Polycrystalline polymers such as polyethylene, polypropylene and polybutene, polyester polymers such as polyethylene terephthalate, and crystalline polymers such as polyamide polymers have a slow crystallization rate after heat molding, so the molding cycle during processing is low. In addition, there is a problem such as a long time, and the molded product may be deformed due to crystallization that proceeds even after molding. In addition, since these crystalline polymers produce large crystals when heat-molded, they have the disadvantage that the strength of the molded product is insufficient or the transparency is inferior.

  These disadvantages are derived from the crystallinity of the crystalline polymer, 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 nucleating agent, a crystallization accelerator, and the like are used.

  As the above nucleating agent or crystallization accelerator, for example, sodium benzoate, 4-tert-butylbenzoic acid aluminum salt, carboxylic acid metal salt such as sodium adipate, and the like are conventionally known. Furthermore, zinc glycerolate (patent document 1), dibenzylidene sorbitol or a derivative thereof (patent documents 2 to 4), polyhydric alcohol alkaline earth metal salt or a combination of zinc salt and dibenzylidene sorbitol (patent document 6), Compounds such as specific types of unsaturated bicyclic dicarboxylic acids and salts (Patent Document 7) and specific types of saturated bicyclic dicarboxylic acids and salts (Patent Documents 8 and 9) have been reported.

  However, conventional nucleating agents or crystallization accelerators such as carboxylic acids, carboxylic acid derivatives, carboxylic acid metal salts, polyhydric alcohols, polyhydric alcohol derivatives, polyhydric alcohol metal alkoxides are added to the crystalline polymer. However, the improvement of the crystallization temperature and the improvement of the mechanical strength has not been satisfactory yet.

Japanese Patent No. 3182148 Japanese Patent Laid-Open No. 51-22740 JP 56-161444 A JP-A-58-17135 Japanese Patent Laid-Open No. 10-25295 Japanese Patent No. 3336114 JP-T-2004-531613 JP-T-2004-531613 Special table 2004-530006 gazette

  Accordingly, an object of the present invention is to provide a nucleating agent having an excellent effect of improving the crystallization temperature and mechanical strength of a crystalline polymer, and a crystalline polymer composition containing the nucleating agent. is there.

As a result of intensive studies to solve the above-mentioned problems, the present inventors have focused on a metal alkoxide compound of a specific polyhydric phenol and have completed the present invention.
That is, the present invention provides a nucleating agent which is an alkaline earth metal phenoxide compound of a compound having three phenolic hydroxyl groups in the molecule or a zinc phenoxide compound of a compound having three phenolic hydroxyl groups in the molecule. Thus, the above-mentioned purpose has been achieved.

Moreover, this invention achieves the said objective by providing the nucleating agent by which a phenoxide compound is represented with the following general formula (I).

［式中、Ｒ¹、Ｒ²及びＲ³は、各々独立に、水素原子または炭素原子数１〜９のアルキル基を表し、Ｍは、アルカリ土類金属原子または亜鉛原子を表す。］

[Wherein R ¹ , R ² and R ³ each independently represents a hydrogen atom or an alkyl group having 1 to 9 carbon atoms, and M represents an alkaline earth metal atom or a zinc atom. ]

Moreover, this invention achieves the said objective by providing the nucleating agent composition containing the said nucleating agent.
Moreover, this invention achieves the said objective by providing the crystalline polymer composition containing the said nucleating agent or the said nucleating agent composition.
Moreover, this invention achieves the said objective by providing the said crystalline polymer composition whose crystalline polymer is a polyolefin-type polymer.

  ADVANTAGE OF THE INVENTION According to this invention, the nucleating agent excellent in the improvement effect of the crystallization temperature of a crystalline polymer and the mechanical strength improvement, and the crystalline polymer composition containing this nucleating agent can be provided.

Hereinafter, preferred embodiments of the present invention will be described in detail.
The nucleating agent of the present invention is an alkaline earth metal phenoxide compound of a compound having three phenolic hydroxyl groups in the molecule or a zinc phenoxide compound of a compound having three phenolic hydroxyl groups in the molecule.

  Examples of compounds having three phenolic hydroxyl groups in the molecule include pyrogallol, gallic acid, gallic acid esters (methyl gallate, ethyl gallate, propyl gallate, butyl gallate, etc.) and the like. From the viewpoint of improving the crystallization temperature and mechanical strength of the molecule, pyrogallol is preferred.

  Moreover, as a preferable nucleating agent of this invention, the compound represented by the following general formula (I) is mentioned from the point of the improvement of the crystallization temperature of crystalline polymer, and the improvement of mechanical strength.

［式中、Ｒ¹、Ｒ²及びＲ³は、各々独立に、水素原子、炭素原子数１〜９のアルキル基を表し、Ｍは、アルカリ土類金属原子または亜鉛原子を表す。］

[Wherein, R ¹ , R ² and R ³ each independently represents a hydrogen atom or an alkyl group having 1 to 9 carbon atoms, and M represents an alkaline earth metal atom or a zinc atom. ]

In the general formula (I), the alkyl group having 1 to 9 carbon atoms represented by R ¹ , R ² and R ³ includes methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, tert-butyl and isobutyl. , Amyl, tertiary amyl, hexyl, heptyl, octyl, isooctyl, 2-ethylhexyl, tertiary octyl, nonyl, tertiary nonyl and the like.
In the general formula (I), examples of the alkaline earth metal represented by M include magnesium, calcium, strontium, barium and the like.

M is preferably a zinc atom from the viewpoint of improving the crystallization temperature of the crystalline polymer and improving the mechanical strength.
Preferable examples of the compound represented by the general formula (I) from the viewpoint of improving the crystallization temperature of the crystalline polymer and improving the mechanical strength include the following compound No. 1 which is a zinc phenoxide compound of pyrogallol. 1 is mentioned.

The method for producing the compound represented by the general formula (I) is not particularly limited. For example, a phenol compound having three phenolic hydroxyl groups in the molecule such as pyrogallol, an alkaline earth metal compound or zinc What is necessary is just to make it react with a compound and to make a phenoxide compound.
Specifically, the above compound No. Taking 1 as an example, pyrogallol and zinc oxide may be reacted in the presence of an acid catalyst at about 150 ° C. for about 3 hours.

  The nucleating agent of the present invention may be used alone or as a nucleating agent composition containing a nucleating agent or additive other than the nucleating agent. When using as this nucleating agent composition, 1-100 mass% is preferable and, as for content of the nucleating agent of this invention in this nucleating agent composition, 10-100 mass% is more preferable. The content of the nucleating agent composition of the present invention in the crystalline polymer composition of the present invention is preferably 0.005 to 10 for the nucleating agent of the present invention with respect to 100 parts by mass of the crystalline polymer. The amount is such that it is part by mass, more preferably 0.01 to 2.5 parts by mass. Examples of the nucleating agent other than the nucleating agent of the present invention that can be blended in the nucleating agent composition and additives include those other than the nucleating agent of the present invention that can be blended in the crystalline polymer composition described later. Examples include nucleating agents and additives.

The crystalline polymer composition of the present invention in which the nucleating agent of the present invention is contained in a crystalline polymer is excellent in that the crystallization temperature and mechanical strength are improved.
Examples of the crystalline polymer include low density polyethylene, linear low density polyethylene, high density polyethylene, isotactic polypropylene, syndiotactic polypropylene, hemiisotactic polypropylene, stereoblock polypropylene, polybutene-1, Α-olefin polymers such as poly-3-methyl-1-butene, poly-3-methyl-1-pentene, poly-4-methyl-1-pentene, α-olefins such as ethylene / propylene block or random copolymer Polyolefin polymers such as olefin copolymers; Thermoplastic linear polyester polymers such as polyethylene terephthalate, polybutylene terephthalate and polyhexamethylene terephthalate; Polysulfide polymers such as polyphenylene sulfide; Polycaprolactone And polylactic acid polymers such as polyhexamethylene adipamide, and crystalline polystyrene polymers such as syndiotactic polystyrene.

  As the crystalline polymer used in the crystalline polymer composition of the present invention, among these crystalline polymers, polyolefin polymers that exhibit the remarkable effects of using the nucleating agent of the present invention are preferable, Polypropylene resins such as polypropylene, ethylene / propylene block or random copolymer, α-olefin / propylene block or random copolymer other than ethylene, and mixtures of these propylene polymers and other α-olefin polymers Particularly preferred.

  The content of the nucleating agent of the present invention in the crystalline polymer composition of the present invention is not particularly limited, but is 0.005 to 10 parts by mass with respect to 100 parts by mass of the crystalline polymer. Preferably, 0.01-2.5 mass parts is more preferable. When the amount is less than 0.005 parts by mass, the sufficient addition effect may not be exhibited. When the amount exceeds 10 parts by mass, the addition effect is not improved and the cost is increased, and the crystalline polymer composition is increased. This may affect the physical properties of the molded product obtained from the above.

  The crystalline polymer composition of the present invention may contain a nucleating agent or an additive other than the nucleating agent of the present invention, if necessary.

  Examples of the nucleating agent other than the nucleating agent of the present invention include alcoholate metal salts such as zinc glycerolate and zinc propane triolate; lithium benzoate, sodium benzoate, aluminum benzoate, 4-tert-butylbenzoic acid aluminum salt, Carboxylic acid metal salts such as sodium adipate; sodium bis (4-tert-butylphenyl) phosphate, sodium-2,2′-methylenebis (4,6-ditert-butylphenyl) phosphate, aluminum bis [2,2 ′ -Acid phosphate metal salts such as methylene-bis- (4,6-ditert-butylphenyl) phosphate; polyhydric alcohol derivatives such as dibenzylidene sorbitol, bis (methylbenzylidene) sorbitol, bis (dimethylbenzylidene) sorbitol; Disodium bisci B Unsaturated [2.2.1] bicyclic dicarboxylates such as [2.2.1] heptene dicarboxylate; Saturated [2 .2] bicyclic [2.2.1] heptane dicarboxylate and the like. 2.1] Bicyclic dicarboxylate and the like. These nucleating agents other than the nucleating agent of the present invention are preferably used in an amount of 0.05 to 10 parts by mass with respect to 100 parts by mass of the crystalline polymer in the crystalline polymer composition of the present invention. .

Additives used as necessary include hindered amine light stabilizers (HALS), UV absorbers, phosphorus antioxidants, phenolic antioxidants, sulfur antioxidants, aliphatic organic acid metal salts Well-known and commonly used additives such as
Examples of the HALS include compounds represented by the following general formula (II), cyanuric chloride condensed HALS, and high molecular weight HALS.

（式（II）中、ｍは、１〜６の整数を表し、Ａは、水素原子、炭素数１〜１８のｍ価の炭化水素基、ｍ価のアシル基またはｍ価のカルバモイル基を表し、Ｂは、酸素原子、−ＮＨ−又は炭素数１〜８のアルキル基（Ｒｅ）を有する−ＮＲｅ−を表し、Ｙは、水素原子、オキシラジカル（・Ｏ）、炭素数１〜１８のアルコキシ基、炭素数１〜８のアルキル基またはヒドロキシル基を表し、Ｚは、メチン、または炭素数１〜８のアルキル基（Ｒｆ）を有する下記一般式（III）で表される基を表す。）

(In formula (II), m represents an integer of 1 to 6, and 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. , B represents an oxygen atom, —NH—, or —NRe— having an alkyl group (Re) having 1 to 8 carbon atoms, and Y represents a hydrogen atom, an oxy radical (.O), an alkoxy having 1 to 18 carbon atoms. A group, an alkyl group having 1 to 8 carbon atoms or a hydroxyl group, and Z represents a group represented by the following general formula (III) having methine or an alkyl group having 1 to 8 carbon atoms (Rf).

  In the general formula (II), the m-valent C1-C18 hydrocarbon group represented by A includes 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, peptadecane, octadecane And groups derived from hydrocarbon compounds such as alkyl groups (alkanedi or hexayl groups).

  In the general formula (II), the m-valent acyl group represented by A is a group derived from a carboxylic acid, a group derived from an m-valent carboxylic acid, or a carboxyl group derived from an n-valent carboxylic acid. Is a group derived from an alkyl ester containing m remaining (nm) ester groups (the carboxylic acid, m-valent carboxylic acid and the alkyl ester are referred to as acyl derivative compounds).

  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, pyromellitic acid, trimesic acid, propane-1,2,3 -Tricarboxylic acid, propane-1,2,3-tricarboxylic acid mono- or dialkyl ester Pentane-1,3,5-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 to trialkyl ester, pentane-1,2,3,4,5-pentacarboxylic acid, pentane-1,2,3,4,5-pentacarboxylic acid mono to tetraalkyl ester, hexane-1, Examples include 2,3,4,5,6-hexacarboxylic acid, hexane-1,2,3,4,5,6-hexacarboxylic acid mono- or pentaalkyl ester.

In the general formula (II), the m-valent carbamoyl group represented by A is a monoalkylcarbamoyl group or a 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 (2,2,4) -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.
The m-valent hydrocarbon group having 1 to 18 carbon atoms, the m-valent acyl group, and the m-valent carbamoyl group are halogen atoms, hydroxyl groups, alkyl groups, alkoxy groups, nitro groups, cyano groups, and the like. May be substituted.

  In the general formula (II), the alkyl group having 1 to 8 carbon atoms represented by Re, which the group represented by B has, includes methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, tert-butyl. , Isobutyl, amyl, isoamyl, tertiary amyl, hexyl, cyclohexyl, heptyl, isoheptyl, tertiary heptyl, 1-ethylpentyl, n-octyl, isooctyl, tertiary octyl, 2-ethylhexyl and the like.

In the general formula (II), the alkoxy group having 1 to 18 carbon atoms represented by Y is methoxy, ethoxy, propoxy, isopropoxy, butoxy, sec-butyloxy, tert-butyloxy, isobutyloxy, amyloxy, isoamyloxy , Hexyloxy, heptyloxy, octyloxy, 2-ethylhexyloxy, nonyloxy, isononyloxy, decyloxy, dodecyloxy, tridecyloxy, tetradecyloxy, pentadecyloxy, hexadecyloxy, peptadecyloxy, octadecyloxy, etc. Is mentioned. Examples of the alkyl group having 1 to 8 carbon atoms represented by Y include the same groups as those described above for Re.
Examples of the alkyl group having 1 to 8 carbon atoms represented by Rf in the general formula (III) representing Z in the general formula (II) include the same groups as those described above for Re.

  Specific examples of the compound represented by the general formula (II) include, 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-butanetetracarboxy 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 -Tet Raoxaspiro [5.5] undecane, 3,9-bis [1,1-dimethyl-2- [tris (1,2,2,6,6-pentamethyl-4-piperidyloxycarbonyloxy) butylcarbonyloxy] ethyl] -2,4,8,10-tetraoxaspiro [5.5] undecane and the like.

  Examples of the cyanuric chloride condensed HALS that can be used in the crystalline polymer composition of the present invention include 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) C) -s-triazin-6-yl] -1,5,8,12-tetraazadodecane, 1,6,11-tris [2,4-bis (N-butyl-N- (2,2,6) , 6-tetramethyl-4-piperidyl) amino) -s-triazin-6-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 and the like.

  Examples of the high molecular weight HALS that can be used in the crystalline polymer composition of the present invention include 1- (2-hydroxyethyl) -2,2,6,6-tetramethyl-4-piperidinol / diethyl succinate. Examples thereof include condensates and 1,6-bis (2,2,6,6-tetramethyl-4-piperidylamino) hexane / dibromoethane polycondensate.

  Examples of the ultraviolet absorber that can be used in the crystalline polymer composition of the present invention include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 5 2-hydroxybenzophenones such as 2,5'-methylenebis (2-hydroxy-4-methoxybenzophenone); 2- (2-hydroxy-5-methylphenyl) benzotriazole, 2- (2-hydroxy-5-tert-octyl) Phenyl) benzotriazole, 2- (2-hydroxy-3,5-ditert-butylphenyl) -5-chlorobenzotriazole, 2- (2-hydroxy-3-tert-butyl-5-methylphenyl) -5 Chlorobenzotriazole, 2- (2-hydroxy-3,5-dicumylphenyl) Benzotriazole, 2,2′-methylenebis (4-tert-octyl-6-benzotriazolylphenol), polyethylene glycol ester of 2- (2-hydroxy-3-tert-butyl-5-carboxyphenyl) benzotriazole, 2- [2-hydroxy-3- (2-acryloyloxyethyl) -5-methylphenyl] benzotriazole, 2- [2-hydroxy-3- (2-methacryloyloxyethyl) -5-tert-butylphenyl] benzo Triazole, 2- [2-hydroxy-3- (2-methacryloyloxyethyl) -5-tert-octylphenyl] benzotriazole, 2- [2-hydroxy-3- (2-methacryloyloxyethyl) -5-third Butylphenyl] -5-chlorobenzotriazole, 2- [2-hydroxy-5 -(2-methacryloyloxyethyl) phenyl] benzotriazole, 2- [2-hydroxy-3-tert-butyl-5- (2-methacryloyloxyethyl) phenyl] benzotriazole, 2- [2-hydroxy-3-tertiary 3-amyl-5- (2-methacryloyloxyethyl) phenyl] benzotriazole, 2- [2-hydroxy-3-tert-butyl-5- (3-methacryloyloxypropyl) phenyl] -5-chlorobenzotriazole, 2- [2-hydroxy-4- (2-methacryloyloxymethyl) phenyl] benzotriazole, 2- [2-hydroxy-4- (3-methacryloyloxy-2-hydroxypropyl) phenyl] benzotriazole, 2- [2-hydroxy -4- (3-methacryloyloxypropyl) phenyl 2- (2-hydroxyphenyl) benzotriazoles such as benzotriazole; 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-C12-13mixed 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-triazi 2- (2,4-dihydroxy-3-allylphenyl) -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2,4,6-tris (2-hydroxy- 2- (2-hydroxyphenyl) -4,6-diaryl-1,3,5-triazines such as 3-methyl-4-hexyloxyphenyl) -1,3,5-triazine; phenyl salicylate, resorcinol monobenzoate 2,4-ditert-butylphenyl-3,5-ditert-butyl-4-hydroxybenzoate, octyl (3,5-ditert-butyl-4-hydroxy) benzoate, dodecyl (3,5-ditert Tributyl-4-hydroxy) benzoate, tetradecyl (3,5-ditert-butyl-4-hydroxy) benzoate, hexadecyl (3,5-ditert-butyl-4-hydride) Roxy) benzoates, octadecyl (3,5-ditert-butyl-4-hydroxy) benzoate, benzoates such as behenyl (3,5-ditert-butyl-4-hydroxy) benzoate; 2-ethyl-2′-ethoxy Substituted oxanilides such as oxanilide and 2-ethoxy-4′-dodecyloxanilide; ethyl-α-cyano-β, β-diphenylacrylate, methyl-2-cyano-3-methyl-3- (p-methoxy) Cyanoacrylates such as phenyl) acrylate; metal salts or metal chelates of various metals such as nickel and chromium.

  Examples of the phosphorus antioxidant that can be used in the crystalline polymer composition of the present invention include triphenyl phosphite, tris (2,4-ditertiarybutylphenyl) phosphite, and tris (2,5 -Di-tert-butylphenyl) phosphite, tris (nonylphenyl) phosphite, tris (dinonylphenyl) phosphite, tris (mono, dimixed nonylphenyl) phosphite, diphenyl acid phosphite, 2,2'-methylenebis (4,6-ditert-butylphenyl) octyl phosphite, diphenyl decyl phosphite, diphenyl octyl phosphite, di (nonylphenyl) pentaerythritol diphosphite, phenyl diisodecyl phosphite, tributyl phosphite, tris (2-ethylhexyl) ) Phosphi , Tridecyl phosphite, trilauryl phosphite, dibutyl acid phosphite, dilauryl acid phosphite, trilauryl trithiophosphite, bis (neopentyl glycol) 1,4-cyclohexanedimethyl diphosphite, bis (2, 4-ditert-butylphenyl) pentaerythritol diphosphite, bis (2,5-ditert-butylphenyl) pentaerythritol diphosphite, bis (2,6-ditert-butyl-4-methylphenyl) pentaerythritol Diphosphite, bis (2,4-dicumylphenyl) pentaerythritol diphosphite, distearyl pentaerythritol diphosphite, tetra (C12-15 mixed alkyl) -4,4′-isopropylidene diphenyl phosphite, bis [ 2, 2 '-Methylenebis (4,6-diamilphenyl)]-isopropylidene diphenyl 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-butyl-2-ethylpropanediol, 2,4,6-tritert-butylphenol Over mono-phosphite, and the like.

  Examples of the phenolic antioxidant that can be used in the crystalline polymer composition of the present invention include 2,6-ditert-butyl-p-cresol, 2,6-diphenyl-4-octadecyloxyphenol. , Stearyl (3,5-ditert-butyl-4-hydroxyphenyl) propionate, distearyl (3,5-ditert-butyl-4-hydroxybenzyl) phosphonate, tridecyl 3,5-ditert-butyl-4 -Hydroxybenzylthioacetate, thiodiethylenebis [(3,5-ditert-butyl-4-hydroxyphenyl) propionate], 4,4'-thiobis (6-tert-butyl-m-cresol), 2-octylthio- 4,6-di (3,5-ditert-butyl-4-hydroxyphenoxy) -s-triazine, 2,2′-methylenebis (4- Til-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-hydroxy Benzyl) isocyanurate, 1,3,5-tris (3,5-ditert-butyl-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-tert-butyl-5-methylbenzyl) phenol, 3,9-bis [2- (3-tert-butyl-4-hydroxy-5-methylhydro) Cinnamoyloxy) -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.

  Examples of the sulfur-based antioxidant that can be used in the crystalline polymer composition of the present invention include dialkylthiols such as dilauryl ester, dimyristyl ester, myristyl stearyl ester, and distearyl ester of thiodipropionic acid. Examples thereof include β-alkyl mercaptopropionic acid esters of polyols such as dipropionates and pentaerythritol tetra (β-dodecyl mercaptopropionate).

  Examples of the aliphatic organic acid metal salt that can be used in the crystalline polymer composition of the present invention include acetic acid, propionic acid, butyric acid, isobutyric acid, valeric acid, caproic acid, caprylic acid, 2-ethylhexanoic acid, and pelargon. Acid, 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, serotic acid, montanic acid, Melicic acid, succinic acid, lindelic acid, tuzuic acid, palmitoleic acid, petraseric acid, oleic acid, elaidic acid, vaccenic acid, linoleic acid, linoelaidic acid, γ-linolenic acid, linolenic acid, ricinoleic acid, 12-hydroxystearic acid An aliphatic organic acid such as acid, naphthenic acid, and abietic acid; Lithium, sodium, potassium, magnesium, calcium, strontium, barium, zinc, those derived from a metal such as aluminum. Among the aliphatic organic acid metal salts obtained from these aliphatic organic acids and metals, magnesium stearate, calcium stearate, and zinc stearate are 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, phosphate ester compounds, phosphate amide compounds, melamine compounds, melamine salt compounds of polyphosphoric acid, flame retardants such as fluororesins or metal oxides; hydrocarbons, fatty acids, aliphatic alcohols, aliphatics Lubricants such as ester, aliphatic amide, and metal soaps; heavy metal deactivators; hydrotalcite; organic carboxylic acids; colorants such as dye pigments; processing aids such as polyolefin powder; fumed silica, fine particle silica, Silica, diatomaceous earth, clay, kaolin, silica gel, calcium silicate, sericite, kaolinite, flint, feldspar powder, meteorite, attapul It can be used additives such as fillers such as calcium carbonate; Yaito, talc, mica, minnesotaite, silicate-based additives such as pyrophyllite.

  In the crystalline polymer composition of the present invention, the above additives can be used alone or in combination of two or more as required, and the amount of each additive used is 100 parts by mass of the crystalline polymer. On the other hand, 0.001-10 mass parts is preferable. If the amount is less than 0.001 part by mass, the effect may not be obtained. If the amount exceeds 10 parts by weight, the addition effect cannot be improved and the cost increases.

  Further, as a method for adding these additives used as necessary to the crystalline polymer, a method of adding them to the crystalline polymer separately from the nucleating agent of the present invention, A method of adding a mixture or composition to a crystalline polymer by mixing, a method of adding the mixture or composition to a crystalline polymer, and a granulating agent such as a binder, wax, solvent, silica, etc. Examples thereof include a method of previously mixing with an auxiliary agent or the like in a desired ratio, and granulating to make a one-pack composite additive, and adding the one-pack composite additive to the crystalline polymer.

  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 and baths. Household goods such as goods; Resin parts for connection such as connectors; Miscellaneous goods such as toys; Medical molded products such as medical packs, syringes, catheters, and medical tubes; Wall materials, flooring, window frames, wallpaper, etc. Construction materials; 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.

Hereinafter, the present invention will be described in more detail with reference to examples and comparative examples. However, the present invention is not limited by the following examples.
In addition, a manufacture example shows the synthesis example of a nucleating agent, and an Example shows preparation and evaluation of the crystalline polymer composition containing the nucleating agent obtained by the manufacture example. Moreover, a comparative example shows preparation and evaluation of the comparative crystalline polymer composition which does not contain a nucleating agent, and the comparative crystalline polymer composition containing a comparative nucleating agent.

[Production Example 1]
A nucleating agent (Compound No. 1) was synthesized by the following method.

  That is, zinc oxide (5 g), pyrogallol (8.5 g) and catalytic zinc acetate dihydrate (0.5 g) were added to a 200 ml three-necked flask. MSP (40 ml) and diethylene monobutyl ether (3 ml) were added as solvents and reacted at 140 ° C. for 3 hours. After cooling to room temperature, ethanol (20 ml) and water (10 ml) were added. All operations were performed in a nitrogen atmosphere. The product was filtered off and washed with 30 ml of ethanol to give a black solid in 82% yield. The obtained individual had a zinc content of 37 wt%, which almost coincided with the theoretical value (34.5%).

[Example 1, Comparative Examples 1 to 4]
Using the nucleating agent described in Table 1, a crystalline polymer composition having the following composition was prepared to prepare a test piece.
That is, the following blended components precisely added to polypropylene powder (2.5 kg) were added, blended at 1000 rpm for 1 minute with a Henschel mixer, and then granulated at 240 ° C. and 25 rpm using a φ30 mm single screw extruder (60 mesh). The obtained pellets were injection molded at an injection temperature of 230 ° C. and a mold temperature of 50 ° C. to obtain various test pieces. Immediately after injection molding, the test piece was transferred to a constant temperature bath at 23 ° C. and allowed to stand for 7 days, and then subjected to physical property tests (crystallization temperature, flexural modulus). The results are shown in [Table 1].

<Combination>
Polypropylene powder 100 parts by mass tetrakis [methylene-3- (3 ′, 5′-ditert-butyl-4′-
Hydroxyphenyl) propionate ... 0.1 parts by weight Tris (2,4-ditert-butylphenyl) phosphite ... 0.1 parts by weight Calcium stearate ... 0.05 parts by mass nucleating agent (Table 1) ... .... 0.1 parts by mass

<Method for measuring crystallization temperature>
-Measurement sample adjustment method The pellet was made into a film with a press molding machine (230 ° C., 50 t × 30 seconds). A small piece cut out with a φ6 mm punch was inserted into and closely attached to a DSC measurement pan to obtain a DSC measurement sample. Various measurements were performed using Diamond-DSC manufactured by Perkin-Elmer.
-Crystallization temperature measurement It heated up to 230 degreeC at 20 degreeC / min, and hold | maintained for 10 minutes. Then, it cooled to 80 degreeC at 10 degree-C / min, and measured crystallization temperature.

<Bending elastic modulus measurement method>
Stress-strain measurement was performed at 20 mm / min in a room maintained at 23 ° C., and the flexural modulus was obtained from the initial tangential slope. The average of three test results was taken as the measured value (ISO 178 compliant).

  As comparative nucleating agents, the following comparative compounds 1 to 3 were similarly tested. The results are shown in Table 1.

Claims (6)

  A nucleating agent which is an alkaline earth metal phenoxide compound of a compound having three phenolic hydroxyl groups in the molecule or a zinc phenoxide compound of a compound having three phenolic hydroxyl groups in the molecule. A nucleating agent, wherein the phenoxide compound according to claim 1 is represented by the following general formula (I).

[Wherein R ¹ , R ² and R ³ each independently represents a hydrogen atom or an alkyl group having 1 to 9 carbon atoms, and M represents an alkaline earth metal atom or a zinc atom. ]   A nucleating agent composition comprising the nucleating agent according to claim 1 or 2.   A crystalline polymer composition comprising the nucleating agent according to claim 1 or 2, or the nucleating agent composition according to claim 3.   The crystalline polymer composition according to claim 4, wherein the content of the nucleating agent according to claim 1 or 2 is 0.005 to 10 parts by mass with respect to 100 parts by mass of the crystalline polymer.   6. The crystalline polymer composition according to claim 4, wherein the crystalline polymer is a polyolefin polymer.