JP2003335968A - Nucleating agent composition and crystalline polymer composition containing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a nucleating agent composition exhibiting sufficient added effects, and to provide a crystalline polymer composition containing the nucleating agent. <P>SOLUTION: The crystalline polymer composition is obtained by adding the granular nucleating agent composition obtained by fixing each component of (a) 100 pts.wt. nucleating agent component comprising at least one kind selected from nucleating agent compounds represented by general formulas (I) and (II), (b) 10-2,000 pts.wt. silicic acid-based inorganic additive component, and optionally (c) 0-10,000 pts.wt. other additive components to each other. <P>COPYRIGHT: (C)2004,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a crystal nucleating agent composition and a crystalline polymer composition containing the crystal nucleating agent composition, and more specifically, a crystal composed of a specific cyclic phosphate metal salt. Nucleating agent component, silicic acid-based inorganic additive component, and other additive components optionally used, relating to a particle-shaped crystal nucleating agent composition obtained by fixing each component in the crystal nucleating agent composition particles .

[0002]

2. Description of the Related Art Crystalline polymers typified by polypropylene have problems such as a long molding cycle during processing because the crystallization rate after heat molding is slow. As a result, the molded product may be deformed. Further, these crystalline polymer compound materials have drawbacks in that the strength is insufficient and the transparency is poor because large spherulites are formed.

It is known that these drawbacks are derived from the crystallinity of the crystalline polymer compound and can be eliminated by rapidly forming crystals. Currently, in order to rapidly generate fine spherulites, methods such as increasing the crystallization temperature and adding a crystal nucleating agent, a crystallization accelerator, etc. are used.

As the above-mentioned crystal nucleating agent or crystallization accelerator, for example, sodium benzoate, 4-tert-butylbenzoic acid aluminum salt, carboxylic acid metal salt such as sodium adipate; sodium bis (4-tert-butylphenyl) Phosphate, metal salt of phosphoric acid ester such as sodium-2,2′-methylenebis (4,6-di-tert-butylphenyl) phosphate; Dibenzylidene sorbitol, bis (methylbenzylidene) sorbitol, bis (dimethylbenzylidene) sorbitol, etc. A compound such as a polyhydric alcohol derivative is used.

Further, inorganic additives having a silicon-oxygen bond in the molecular structure of silica, talc, mica, minesotite, etc. (hereinafter sometimes referred to as silicic acid type inorganic additives).
Is known to have the effect of improving the physical properties such as strength of the crystalline polymer. Regarding the combined use of the silicic acid-based inorganic additive and the above crystal nucleating agent, for example, combined use of silica and a metal salt compound of a cyclic phosphoric acid ester is reported in JP-A-4-55472, and mica and cyclic phosphoric acid are reported. The combined use of a metal salt compound of an ester is reported in JP-A-5-156079.

However, the crystal nucleating agent and / or
Or, in silicic acid type inorganic additive alone or in a mere mixed system,
There is a problem that the expected sufficient addition effect is not exhibited with respect to the addition amount.

[0007]

SUMMARY OF THE INVENTION Therefore, an object of the present invention is to provide a crystal nucleating agent composition exhibiting a sufficient addition effect and a crystalline polymer composition containing the crystal nucleating agent composition. It is in.

[0008]

Means for Solving the Problems As a result of extensive studies, the inventors of the present invention fixedly fix each component by pulverizing a specific crystal nucleating agent compound and a silicic acid type inorganic additive in the presence of each component. The inventors arrived at the present invention by finding that the crystal nucleating agent composition obtained as a result can solve the above problems.

A first aspect of the present invention is 100 parts by mass of a crystal nucleating agent component (a) consisting of at least one selected from the group of crystal nucleating agent compounds represented by the following general formulas (I) and (II), silicic acid. Inorganic additive component (b) 10 to 2,000 parts by mass and other additive component (c) 0 optionally used
˜10,000 parts by mass with respect to a particle-shaped crystal nucleating agent composition in which each component is fixed in the particle.

[0010]

[Chemical 2]

(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 M 1 represents an alkali metal atom. Represents
n represents 1 or 2. ) A second aspect of the present invention relates to the crystal nucleating agent composition according to the first aspect of the present invention, which is fixed and atomized by using a pulverizer. The third aspect of the present invention is that the silicic acid-based inorganic additive component (b) is
The crystal nucleating agent composition according to the first or second aspect of the present invention, which is talc and / or mica. A fourth aspect of the present invention is the crystal nucleating agent composition according to any one of the first to third aspects of the present invention, wherein the other additive component (c) contains an aliphatic organic acid metal salt (cm). Regarding The fifth of the present invention is the first to the first of the present invention.
And a crystalline nucleating agent composition (A) and a crystalline polymer (P) according to any one of 4 above. The sixth aspect of the present invention relates to the crystalline polymer composition according to the fifth aspect of the present invention, wherein the crystalline polymer (P) is a polyolefin-based polymer.

[0012]

BEST MODE FOR CARRYING OUT THE INVENTION Embodiments of the present invention will be described in detail below. The crystal nucleating agent composition (A) of the present invention comprises 100 mass% of the crystal nucleating agent component (a) consisting of at least one selected from the group of the crystal nucleating agent compounds represented by the general formulas (I) and (II). Parts, silicic acid-based inorganic additives (b) 10
2,000 parts by mass, and 0 to 10,000 parts by mass of other additive component (c) which is optionally used are fixed in the particles of the crystal nucleating agent composition by pulverization treatment or the like. It is a crystalline nucleating agent composition.

The crystal nucleating agent component (a) according to the present invention is at least one selected from the group of crystal nucleating agent compounds represented by the above general formulas (I) and (II).
The compounds represented by the general formulas (I) and (II) are known compounds used as crystal nucleating agents in crystalline polymers.
In the general formulas (I) and (II), 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,
Secondary butyl and tertiary butyl may be mentioned, and examples of the alkyl group represented by R ³ and having 1 to 4 carbon atoms include those similar to R ^1, and as the alkali metal atom represented by M ^1. Examples include lithium, sodium and potassium.

Specific examples of the compound represented by the above general formula (I) include, for example, compound No. 1 to
No. 6 is mentioned.

[0015]

[Chemical 3]

Specific examples of the compound represented by the above general formula (II) include, for example, compound N shown below.
o. 7-No. 10.

[0017]

[Chemical 4]

The silicic acid-based inorganic additive component (b) according to the present invention is an inorganic additive having a silicon-oxygen bond in its molecular structure, that is, one or a mixture of two or more silicic acid-based inorganic additives. It consists of The silicic acid-based inorganic additive component (b) may be a synthesized compound or a natural mineral. Examples of the silicic acid-based inorganic additive include fumed silica, fine particle silica, silica, diatomaceous earth, clay, kaolin, silica gel, calcium silicate, sericite, kaolinite, flint, feldspar powder, vermiculite, attapulgite, talc, mica. , Minesotite, pyrophyllite, and the like. Among them, those having a layered particle structure and those having a silicon content of 15% by mass or more are preferable. Examples of these preferable inorganic additives include sericite, kaolinite, talc, mica, minnesite and pyrophyllite, and talc and mica are more preferable. The silicic acid-based inorganic additive component (b) has a water content of 1 mass% or less, and an average particle diameter D50 (mass average; particle diameter corresponding to an integrated value of 50% on a mass basis) of 10 μm or less. The thing is more preferable.

In the crystal nucleating agent composition (A) of the present invention,
The composition ratio of the crystal nucleating agent component (a) to the silicic acid-based inorganic additive component (b) is in a range that gives the crystalline polymer good transparency and strength. The composition ratio of the silicic acid-based inorganic additive component (b) is 10 to 2.0 with respect to 100 parts by mass of the crystal nucleating agent component (a).
The amount is 00 parts by mass, preferably 50 to 2,000 parts by mass, more preferably 100 to 1,000 parts by mass.

In the crystal nucleating agent composition (A) of the present invention,
Other additive components (c) used as required include aliphatic organic acid metal salts (cm), hindered amine light stabilizers (sometimes abbreviated as HALS), ultraviolet absorbers, phenols, sulfur. Well-known and commonly used additives such as system-based and phosphorus-based antioxidants can be used.

Examples of the metal salt of aliphatic organic acid (cm) include acetic acid, propionic acid, butyric acid, isobutyric acid, valeric acid, caproic acid, caprylic acid, 2-ethylhexanoic acid, pelargonic 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,
Cerotic acid, montanic acid, melissic acid, tohsuccinic acid, linderic acid, tzunic acid, palmitoleic acid, petroselinic acid, oleic acid, elaidic acid, vaccenic acid, linoleic acid, linoelaidic acid, γ-linolenic acid, linolenic acid,
Examples include fatty acid organic acids such as ricinoleic acid, 12-hydroxystearic acid, naphthenic acid, and abietic acid, and metals such as lithium, sodium, potassium, magnesium, calcium, strontium, barium, zinc, and aluminum.

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

[0023]

[Chemical 5]

(In the formula, m represents an integer of 1 to 6, and A
Is a hydrogen atom, an m-valent hydrocarbon group having 1 to 18 carbon atoms, m
Represents a divalent 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,
Represents an alkyl group having 1 to 8 carbon atoms or a hydroxyl group, Z
Represents methine or the following group (IV) having an alkyl group Rf having 1 to 8 carbon atoms. )

[0025]

[Chemical 6]

In the above general formula (III), the m-valent hydrocarbon group having 1 to 18 carbon atoms represented by A is methane, ethane, propane, butane, secondary butane, tertiary butane, isobutane, pentane. , Isopentane, tertiary pentane, hexane, cyclohexane, heptane, isoheptane, tertiary heptane, n-octane, isooctane, tertiary octane, 2-ethylhexane, nonane, isononane,
Examples thereof include groups derived from decane, dodecane, tridecane, tetradecane, pentadecane, hexadecane, heptadecane and octadecane (alkyl group, alkanedi or hexayl group).

The m-valent acyl group in the above A means a (nm) alkyl ester of a carboxylic acid, an m-valent carboxylic acid, and an n-valent carboxylic acid having m carboxyl groups remaining (these are referred to as acyl derivative compounds. ) Is a group derived from. 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 azelaine. 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-1,3,5-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- 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,
Examples thereof include 5,6-hexacarboxylic acid mono- or pentaalkyl ester.

The m-valent carbamoyl group in A above is
A monoalkylcarbamoyl group or a dialkylcarbamoyl group derived from an isocyanate compound. Examples of the isocyanate compound for deriving a monoalkylcarbamoyl group 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-hexa Methylene diisocyanate, 2,2,4 (2,2,4) -trimethylhexamethylene diisocyanate, lysine diisocyanate, triphenylmethane triisocyanate, 1
-Methylbenzol-2,4,6-triisocyanate, dimethyltriphenylmethanetetraisocyanate and the like can be mentioned. As the dialkylcarbamoyl group,
Examples thereof include a diethylcarbamoyl group, a dibutylcarbamoyl group, a dihexylcarbamoyl group and a dioctylcarbamoyl group. The group 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.

As the alkyl group having 1 to 8 carbon atoms and represented by Re which is substituted for N in B of the formula (III), methyl, ethyl, propyl, isopropyl, butyl, sec-butyl,
Examples thereof include tert-butyl, isobutyl, amyl, isoamyl, tert-amyl, hexyl, cyclohexyl, heptyl, isoheptyl, tert-heptyl, 1-ethylpentyl, n-octyl, isooctyl, tert-octyl and 2-ethylhexyl. Y in the 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, secondary butyloxy, tertiary butyloxy, isobutyloxy,
Amyloxy, isoamyloxy, hexyloxy, heptyloxy, octyloxy, 2-ethylhexyloxy, nonyloxy, isononyloxy, decyloxy, dodecyloxy, tridecyloxy, tetradecyloxy, pentadecyloxy, hexadecyloxy, heptadecyloxy, Octadecyloxy may be mentioned, and examples of the alkyl group having 1 to 8 carbon atoms include the same groups as Re. 1 carbon atom represented by Rf in Z of formula (III)
Examples of the alkyl group of to 8 include the same groups as Re.

HALS represented by the above general formula (III)
Further specific examples of, 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-piperidyl benzoate, 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-butanetetracarboxylate, 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-butane tetracarboxylate, 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-di-tert-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-piperidyl Oxycarbonyloxy) butylcarbonyloxy]
Ethyl] -2,4,8,10-tetraoxaspiro [5.5] undecane and the like can be mentioned.

As the 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-tertiaryoctylamino-s-triazine polycondensate, 1,5,8,12-tetrakis [2,4-bis (N-butyl-N- (2,2
6,6-Tetramethyl-4-piperidyl) amino) -s
-Triazin-6-yl] -1,5,8,12-tetraazadodecane, 1,5,8,12-tetrakis [2,4
-Bis (N-butyl-N- (1,2,2,6,6-pentamethyl-4-piperidyl) amino) -s-triazin-6-yl] -1,5,8,12-tetraazadodecane, 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.

As the high molecular weight type, 1- (2-hydroxyethyl) -2,2,6,6-tetramethyl-4 is used.
-Piperidinol / diethyl succinate polycondensate, 1,6
-Bis (2,2,6,6-tetramethyl-4-piperidylamino) hexane / dibromoethane polycondensate and the like can be mentioned.

Examples of the ultraviolet absorber include 2,4-
2-hydroxybenzophenones such as dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, and 5,5′-methylenebis (2-hydroxy-4-methoxybenzophenone); 2- (2 -Hydroxy-5-methylphenyl) benzotriazole, 2- (2-hydroxy-5-tert-octylphenyl) benzotriazole, 2- (2-hydroxy-3,5-di-tert-butylphenyl) -5-chlorobenzo Triazole, 2- (2-hydroxy-3-tert-butyl-5-methylphenyl) -5
-Chlorobenzotriazole, 2- (2-hydroxy-
3,5-dicumylphenyl) benzotriazole, 2,
2'-methylenebis (4-tertiary octyl-6-benzotriazolylphenol), 2- (2-hydroxy-3-
Polyethylene glycol ester of tert-butyl-5-carboxyphenyl) benzotriazole, 2- [2-hydroxy-3- (2-acryloyloxyethyl) -5
-Methylphenyl] benzotriazole, 2- [2-hydroxy-3- (2-methacryloyloxyethyl)-
5-tert-butylphenyl] benzotriazole, 2-
[2-Hydroxy-3- (2-methacryloyloxyethyl) -5-tert-octylphenyl] benzotriazole, 2- [2-hydroxy-3- (2-methacryloyloxyethyl) -5-tert-butylphenyl]- 5-chlorobenzotriazole, 2- [2-hydroxy-5-
(2-methacryloyloxyethyl) phenyl] benzotriazole, 2- [2-hydroxy-3-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-methacryloyloxymethyl) phenyl] benzotriazole, 2- [2-hydroxy-4- (3-methacryloyloxy-2-hydroxypropyl) phenyl] benzotriazole, 2-
2- (2-, such as [2-hydroxy-4- (3-methacryloyloxypropyl) phenyl] benzotriazole
Hydroxyphenyl) 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) -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2,4,6-tris (2-hydroxy-3-methyl-4-hexyloxy) 2- (2-hydroxyphenyl) -4,6-diaryl-1,3,5-triazines such as phenyl) -1,3,5-triazine; phenyl salicylate, resorcinol monobenzoate, 2,4-ditertiary Butylphenyl-3,5-di-tert-butyl-4-hydroxybenzoate, octyl (3,5-di-tert-butyl-
4-hydroxy) benzoate, dodecyl (3,5-di-tert-butyl-4-hydroxy) benzoate, tetradecyl (3,5-di-tert-butyl-4-hydroxy) benzoate, hexadecyl (3,5-di-tert-butyl) Benzoates such as -4-hydroxy) benzoate, octadecyl (3,5-di-tert-butyl-4-hydroxy) benzoate, behenyl (3,5-di-tert-butyl-4-hydroxy) benzoate; 2-ethyl-2 Substituted oxanilides such as'-ethoxyoxanilide and 2-ethoxy-4'-dodecyloxanilide; ethyl-α-cyano-β,
β-diphenyl acrylate, methyl-2-cyano-3
Cyanoacrylates such as -methyl-3- (p-methoxyphenyl) acrylate; various metal salts or metal chelates, particularly nickel or chromium salts or chelates.

Examples of phosphorus antioxidants include triphenyl phosphite, tris (2,4-ditert-butylphenyl) phosphite, tris (2,5-ditert-butylphenyl) phosphite, tris ( Nonylphenyl) phosphite, tris (dinonylphenyl) phosphite, tris (mono-dimixed nonylphenyl) phosphite, diphenylacid phosphite, 2,2'-methylenebis (4,6-ditertiarybutylphenyl) octyl Phosphite, diphenyldecylphosphite, diphenyloctylphosphite, di (nonylphenyl) pentaerythritol diphosphite, phenyldiisodecylphosphite, tributylphosphite, tris (2-
Ethylhexyl) phosphite, tridecyl phosphite, trilauryl phosphite, dibutyl acid phosphite, dilauryl acid phosphite, trilauryl trithiophosphite, bis (neopentyl glycol) -1,4-cyclohexane dimethyl diphosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis (2,5-di-tert-butylphenyl) pentaerythritol diphosphite, bis (2,6-di-tert-butyl-4-methylphenyl) ) Pentaerythritol diphosphite, bis (2,4-dicumylphenyl) pentaerythritol diphosphite,
Distearyl pentaerythritol diphosphite, tetra (C12-15 mixed alkyl) -4,4'-isopropylidene diphenylphosphite, bis [2,2'-
Methylenebis (4,6-diamylphenyl)]-isopropylidenediphenylphosphite, tetratridecyl-
4,4'-butylidene bis (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-butyl dibenzo [d, f] [1,3,
2] Dioxaphosphepin-6-yl) oxy] ethyl) amine, 9,10-dihydro-9-oxa-10
-Phosphaphenanthrene-10-oxide, 2-butyl-2-ethylpropanediol-2,4,6-tri-tert-butylphenol monophosphite and the like can be mentioned.

As the phenolic antioxidant, for example,
2,6-di-tert-butyl-p-cresol, 2,6-diphenyl-4-octadecyloxyphenol, stearyl (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, distearyl (3,5 -Di-tert-butyl-
4-hydroxybenzyl) phosphonate, tridecyl
3,5-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-methyl-6-tert-butylphenol), bis [3,3-bis (4-hydroxy-3-)
Tert-Butylphenyl) butyric acid] glycol ester, 4,4′-butylidene bis (2,6-di-tert-butylphenol), 4,4′-butylidene bis (6-
Tert-butyl-3-methylphenol), 2,2′-ethylidenebis (4,6-di-tert-butylphenol), 1,
1,3-Tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, bis [2-tert-butyl-4]
-Methyl-6- (2-hydroxy-3-tert-butyl-5
-Methylbenzyl) phenyl] terephthalate, 1,
3,5-tris (2,6-dimethyl-3-hydroxy-
4-tert-butylbenzyl) isocyanurate, 1,3,
5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, 1,3,5-tris (3,3
5-di-tert-butyl-4-hydroxybenzyl) -2,
4,6-trimethylbenzene, 1,3,5-tris
[(3,5-di-tert-butyl-4-hydroxyphenyl)
Propionyloxyethyl] isocyanurate, tetrakis [methylene-3- (3 ', 5'-ditert-butyl-
4'-hydroxyphenyl) propionate] methane,
2-tert-butyl-4-methyl-6- (2-acroyloxy-3-tert-butyl-5-methylbenzyl) phenol, 3,9-bis [2- (3-tert-butyl-4-hydroxy) -5-Methylhydrocinnamoyloxy) -1,1
-Dimethylethyl] -2,4,8,10-tetraoxaspiro [5.5] undecane, triethylene glycol bis [β- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate], etc. Can be mentioned.

Examples of the sulfur-based antioxidants include dialkylthiodipropionates such as dilauryl, dimyristyl, myristyl stearyl, and distearyl esters of thiodipropionic acid and pentaerythritol tetra (β-dodecylmercaptopropionate). .Beta.-alkyl mercaptopropionic acid esters of the above polyols.

As the other additive component (c) used as necessary according to the present invention, in addition to those exemplified above, cationic surfactants, anionic surfactants, nonionic surfactants, Antistatic agents consisting of amphoteric surfactants; halogen compounds, phosphoric acid ester compounds, phosphoric acid amide compounds, melamine compounds, melamine salt compounds of polyphosphoric acid, flame retardants such as fluororesins or metal oxides; carbonization Hydrogen-based, fatty acid-based, aliphatic alcohol-based, aliphatic ester-based, aliphatic amide-based lubricants; heavy metal deactivators; hydrotalcites; organic carboxylic acids; coloring agents such as dyes and pigments; processing aids such as polyolefin powders Agents: Examples include fillers such as glass fiber and calcium carbonate.

In the crystal nucleating agent composition (A) of the present invention,
As other additives to be used, it is preferable to use an aliphatic organic acid metal salt because the aliphatic organic acid metal salt may improve the use effect of the crystal nucleating agent in some cases. Particularly, the aliphatic organic acid metal salt is selected from lauric acid, tridecanoic acid, myristic acid, pentadecanoic acid, palmitic acid, margaric acid, stearic acid, and the metal is lithium,
One selected from magnesium, calcium, and zinc is preferable, and these can be used alone or in combination of two or more.

The other additives (c) exemplified above may be used alone or in combination of two or more, and the amount thereof is 0 to 10 relative to 100 parts by mass of the crystal nucleating agent component (a). , 00
It is 0 part by mass. If the amount used exceeds 10,000 parts by mass, the combined effect of the crystal nucleating agent component (a) and the inorganic additive (b) of the present invention cannot be obtained. The amount of the aliphatic organic acid metal salt (cm) used is preferably 10 to 1,000 parts by mass with respect to 100 parts by mass of the crystal nucleating agent component (a).

One of the methods for producing the crystal nucleating agent composition (A) of the present invention is as follows. The crystal nucleating agent component (a), the inorganic additive component (b) and other additives used as necessary. The agent component (c) is pulverized in the coexistence of the components (a) and (b) and optionally other additive component (c), that is, in the same system (hereinafter referred to as co-milling. It may be done) method. The apparatus used and the manufacturing conditions are not particularly limited. The co-pulverization treatment may be performed only with each component, and if necessary, a medium such as a solvent or wax may be used. Regarding each of the components (a) to (c), even if the whole amount is supplied to the apparatus at the same time or the whole amount is divided and inserted in small amounts, one component is entirely supplied and the other components are divided and inserted in small amounts. However, it is essential that the components (a) to (c) are mixed in a state in which the desired effects can be exhibited. Further, the crystal nucleating agent composition (A) obtained by carrying out the co-milling treatment is one in which the treated components are fixed by physically and / or mechanochemically binding, and as a result, By the co-milling treatment, a particle size larger than the particle size of each raw material component may be obtained.

Examples of the above-mentioned production method include a method in which each component is subjected to co-pulverization treatment for a time period in which a desired particle size is obtained, using a pulverizer. Examples of the pulverizer include a mortar, a ball mill, a roller mill, a rod mill, a tube mill, a conical mill, a vibrating ball mill, a high swing ball mill, a pin type mill, a hammer mill, an attrition mill, a jet mill, a jet mizer, a micronizer, and a nanomizer. Macjack mill, micro atomizer, micron mill, rotary cutter and the like can be mentioned.

As another manufacturing method, a method of fixing each component to a desired strength by using a kneading machine or the like, or, after fixing, finely pulverizing to a desired particle size as needed can be mentioned. To be Further, as another production method, the crystal nucleating agent component (a) is dissolved in an organic solvent and added to the silicic acid-based inorganic additive component (b) and other additive component (c) used as necessary. Or a method of obtaining the same by further fixing treatment or atomization.

The particles of the crystal nucleating agent composition according to the present invention have properties such as particle size, bulk specific gravity, and angle of repose, etc., as long as they are within the range suitable for use as an ordinary polymer additive in workability and operability. It is not limited by the shape and physical properties of the particles. With respect to the average particle size of the particles, D50 (mass average; particle size corresponding to integrated value 50% on mass basis) 0.3 to 100
μm is preferable, 0.3 to 50 μm is more preferable, the bulk specific gravity is preferably 0.25 g / ml or more, and the angle of repose is preferably 45 ° or less.

The crystalline polymer composition of the present invention is obtained by adding the above crystal nucleating agent composition (A) to the crystalline polymer (P) and has improved transparency and / or strength. And
In the crystalline polymer composition, in addition to the crystal nucleating agent composition (A) of the present invention, a crystal nucleating agent other than the crystal nucleating agent component (a) and a crystal nucleating agent composition (A) were used. The inorganic additive component (b), other additive component (c) and the like may be mixed and added as the resin additive component (d).

Examples of the crystalline polymer (P) include low density polyethylene, linear low density polyethylene,
High density polyethylene, isotactic polypropylene, syndiotactic polypropylene, hemi-isotactic polypropylene, polybutene-1, poly-3-methyl-1-butene, poly-3-methyl-1-pentene, poly-4-methyl-1-pentene Polyolefin polymers such as α-olefin polymers such as α-olefin copolymers such as ethylene / propylene block or random copolymer; thermoplastic linear polyesters such as polyethylene terephthalate, polybutylene terephthalate and polyhexamethylene terephthalate Polymers; polyphenylene sulfide; polycaprolactone; linear polyamide polymers such as polyhexamethylene adipamide; crystalline polystyrene polymers such as syndiotactic polystyrene;
Polyacetal; liquid crystal polymer; aliphatic polyester-based biodegradable polymers such as polylactic acid, polyglycolic acid, polyethylene succinate, and copolymers thereof.

Among the above-mentioned crystalline polymers, a polyolefin-based polymer, which has a remarkable effect of using the crystal nucleating agent composition (A) of the present invention, is preferable, and polypropylene, ethylene / propylene block, or random copolymerization is preferable. Coalescence, α-olefin / propylene block or random copolymer other than ethylene, and these propylene-based polymers and other α-
A polypropylene resin such as a mixture with an olefin polymer is particularly suitable.

In the crystalline polymer composition of the present invention, the content of the crystal nucleating agent composition (A) is not particularly limited. The amount of the crystal nucleating agent composition (A) used is 100 parts by mass of the crystalline polymer (P) in terms of the crystal nucleating agent compound (a) represented by the general formula (I) and / or (II). On the other hand, if the amount is less than 0.005 parts by mass, the addition effect may not be sufficiently exhibited, and if the amount exceeds 10 parts by mass, not only the addition effect is not improved but the cost becomes high, but also the obtained polymer product Since it may affect the physical properties, 0.005 to 10 parts by mass is preferable, 0.01 to 2.5
The mass part is more preferable.

As a method of adding the crystalline nucleating agent composition (A) of the present invention to the crystalline polymer (P), the crystalline nucleating agent composition (A) of the present invention can be added to the crystalline polymer (P). ) And the additive component for resin (d) are separately added, the crystal nucleating agent composition (A) and the additive component for resin (d) are mixed in advance, and this is added to the crystalline polymer. A desired ratio of the crystal nucleating agent composition (A) of the present invention and the additive component (d) for resin together with a binder, a wax, a solvent, a granulating aid (e) such as silica and the like, which are used as necessary, in advance. And a method of using as a masterbatch after mixing and granulating in 1.

Applications of the crystalline polymer composition of the present invention include resin parts for automobiles such as bumpers, dashboards and instrument panels; resin parts for home electric appliances such as refrigerators, washing machines and vacuum cleaners; tableware, Household goods such as buckets and bath products; miscellaneous goods such as toys; storage and storage containers such as tanks; pipes and tubes; sheets, films and tapes; fibers, non-woven fabrics and the like.

[0050]

EXAMPLES 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 to the examples below.

The talc and mica used are as follows. Talc: MICRONWHITE # 5000S (Hayashi Kasei product, average particle size (D50) 2.8 μm) Mica: A-21 (Nihon Talc product, average particle size (D50)
8.0 μm)

The average particle size (D50) was determined by using a laser diffraction particle size distribution analyzer (manufactured by Shimadzu Corporation; SALD-2100) using water or 2-propanol as a dispersion solvent, and optionally a surfactant (Asahi Denka Co., Ltd.). Industrial Co., Ltd .; ADEKA COR EC-4500)
Was measured using.

[Manufacturing Example 1] A composition prepared by mixing a crystal nucleating agent component and an inorganic additive component as shown in Table 1 was used for 2 using a roller mill grinder (manufactured by HEIKO SEISAKUSYO; SAMPE MILL, TI-500ET). A time co-milling process was performed. Table 1 shows the average particle sizes measured for the obtained crystal nucleating agent composition.

[0054]

[Table 1]

[Production Example 2] 10 as a crystal nucleating agent component
0 parts by weight of compound No. 2 and 7 as an inorganic additive component
00 parts by mass of talc (# 5000S) was subjected to co-pulverization treatment using the pulverizer shown in Table 2. Table 2 shows the average particle size of the obtained crystal nucleating agent composition.

[0056]

[Table 2]

[Production Example 3] 100 parts by mass of the crystal nucleating agent component shown in Table 3 and 200 parts by mass of talc (# 5000S),
And, as the other additive components, the aliphatic organic acid metal salt compounds shown in Table 3 were subjected to co-milling treatment under the same conditions as in Production Example 1. Table 3 shows the average particle size of the obtained crystal nucleating agent composition. In Production Example 3-4, as the crystal nucleating agent component, Compound No. 2 and compound No. An equal mass mixture of 7 was used.

[0058]

[Table 3]

Example 1 Melt Index (230
C, load 2.16 kg) 8 g / 10 min propylene 10
0 parts by mass, phenolic antioxidant: tetrakis [methylene-3- (3 ', 5'-ditertiary butyl-4'-hydroxyphenyl) propionate] methane 0.1 parts by mass, phosphorus antioxidant: Tris 0.1 parts by mass of (2,4-di-tert-butylphenyl) phosphite, 0.1 part by mass of hydrotalcite (DHT-4A manufactured by Kyowa Chemical Industry Co., Ltd.), and the crystal nucleating agent composition shown in Tables 4 to 6. Were mixed with a Henschel mixer at 1,100 rpm for 5 minutes, and were mixed with an extruder at 250 ° C.,
Pellets were manufactured under the condition of 130 rpm. This was injection-molded at a mold temperature of 50 ° C. and 250 ° C. to prepare a test piece having a thickness of 4 mm, and the flexural modulus (ASTM D-790) was evaluated. The results are shown in Tables 4-5.

[Comparative Example 1] In comparison with Example 1 above, a crystal nucleating agent compound No. having no crystal nucleating agent composition, and having been subjected to pulverization treatment and having an average particle diameter (D50) of 15.6 μm was used. Two
Also, a test piece was prepared and evaluated in the same manner as in Example 1, using a mixture of the compound and the silicic acid-based inorganic additive having the same composition as that of the corresponding Example without simply performing co-milling treatment. .
The results are shown in Tables 4-5.

[0061]

[Table 4]

[0062]

[Table 5]

[Example 2] Melt flow index 1
100 parts by weight of a random copolymer of ethylene / propylene = 3/97 of 0, phenolic antioxidant: tetrakis [methylene-3- (3 ′, 5′-ditertiary butyl-4′-]
Hydroxyphenyl) propionate] methane 0.1 part by mass, phosphorus-based antioxidant: tris (2,4-ditertiarybutylphenyl) phosphite 0.1 part by mass, hydrotalcite (Kyowa Chemical Industry DHT-4A). ) 0.05 parts by mass and the crystal nucleating agent composition shown in Table 6 were mixed with a Henschel mixer at 1100 rpm for 5 minutes, and the mixture was mixed at 250 ° C for 13 minutes.
Pellets were manufactured by extrusion at 0 rpm. This is injection molded at a mold temperature of 50 ° C and 250 ° C to a thickness of 1 m.
A test piece of m and a test piece of 4 mm were prepared. For the 1 mm piece, the haze value (JISK7105) was evaluated and 4 m
The flexural modulus of m pieces was evaluated in the same manner as in Example 1. The results are shown in Tables 6-7.

[Comparative Example 2] In contrast to Example 2 above, a crystal nucleating agent composition was not used, a silicic acid-based inorganic additive was not used, a crystal nucleating agent compound and a crystal nucleating agent compound and a silicic acid-based inorganic addition A test piece was prepared and evaluated in the same manner as in Example 2 by using a mixture of the agent and the corresponding composition having the same composition as that of the corresponding Example without simply performing co-pulverization treatment. The results are shown in Tables 6-7. The crystal nucleating agent compound used here was pulverized, and the average particle diameter (D50) was the compound No. 1
Is 14.1 μm, and the compound No. 2 is 9.8 μm
And compound No. 7 is 11.4 μm.

[0065]

[Table 6]

[0066]

[Table 7]

[0067]

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

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor: Shiki Ban             Asahi, 5-2-13 Shirahata, Saitama City, Saitama Prefecture             Denka Kogyo Co., Ltd. (72) Inventor Naofumi Kawamoto             Asahi, 5-2-13 Shirahata, Saitama City, Saitama Prefecture             Denka Kogyo Co., Ltd. F term (reference) 4J002 BB031 BB051 BB121 BB151                       BB171 BC031 BP021 CB001                       CF031 CF051 CF061 CF071                       CF181 CL011 CL031 CN011                       DJ017 DJ037 DJ047 DJ057                       EG028 EG038 EG048 EW046                       FD040 FD050 FD070 FD206                       FD207

Claims (6)

[Claims] 1. A crystal nucleating agent component (a) comprising 100 parts by mass of at least one selected from the group of crystal nucleating agent compounds represented by the following general formulas (I) and (II), and a silicic acid-based inorganic additive component. (B) 10 to 2,000 parts by mass and 0 to 10,000 parts by mass of other additive component (c) used as necessary, each crystal nucleating agent formed by fixing each component in the particle. Composition. [Chemical 1] (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, M 1 represents an alkali metal atom, and n Represents 1 or 2.) 2. The crystal nucleating agent composition according to claim 1, which is fixed and atomized by using a pulverizer. 3. The crystal nucleating agent composition according to claim 1, wherein the silicic acid-based inorganic additive component (b) is talc and / or mica. 4. The crystal nucleating agent composition according to claim 1, wherein the other additive component (c) contains an aliphatic organic acid metal salt (cm). 5. A crystalline polymer composition comprising the crystal nucleating agent composition (A) according to any one of claims 1 to 4 and a crystalline polymer (P). 6. The crystalline polymer composition according to claim 5, wherein the crystalline polymer (P) is a polyolefin-based polymer.