JPH09100371A - Bis(2,4-di-tert-butyl-5-methylphenyl) phosphate metal salt compound and its use - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a compd. which increases the crystallization rate of a polymer material after thermal molding and markedly improves the processibility, strengths, and clarity of the material by selecting a specific metal salt compd. SOLUTION: This compd, is represented by the formula [wherein Z is a metal atom M<1> having a valency of (m); or Z is a group represented by the formula; M<2> (OH)n (wherein M<2> is a metal atom of the group IIa, III or IV; and (n) is 1-3) and (m) is 1-3 provided m+n is an integer equal to the valency of M<2> ; or Z is a group represented by the formula: M<3> =0 (wherein M<3> is a metal atom of the group IV) and (m) is 2]. Pref. this compd. is one wherein M<1> is a metal atom of the group Ia or IIa and (m) is the valency of M<1> ; or one wherein M<2> is a metal atom of the group III or IV, (m) is 2, and (n) is an integer lower than the valency of M<2> by 2; or one wherein M<3> is a metal atom of the group IV and (m) is 2.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a novel bis (2,4-ditertiarybutyl-5-methylphenyl) phosphate metal which is useful as a processability, strength and transparency improver for crystalline polymer materials. The present invention relates to salt compounds and uses thereof.

[0002]

2. Description of the Related Art Crystalline polymer materials such as polyethylene, polypropylene, polybutene-1,1,2-polybutadiene, polyethylene terephthalate, polybutylene terephthalate, and polyamide have a slow crystallization rate after heat molding, and therefore have a molding cycle. The time was long and the productivity was poor. In addition, these crystalline polymer materials are not transparent because they shrink due to crystallization after heat molding and large crystals are generated, and the strength is insufficient, and the crystalline part and the amorphous part have different refractive indexes. There was a disadvantage that it was inferior in sex.

In order to solve these drawbacks, it has been proposed to add various crystal nucleating agents or crystallization accelerators, and conventionally, bis (p-tertiary butyl benzoic acid) hydroxyaluminum and adipic acid have been proposed. Carboxylic acid metal salts such as sodium and polyhydric alcohol derivatives such as dibenzylidene sorbitol and bis (methylbenzylidene) sorbitol have been used. However, these compounds are not sufficiently satisfactory in practical use, and many of them accelerate deterioration of the polymer material or reduce mechanical strength, which are not practically satisfactory. Japanese Patent Publication No. 63-8980 and Japanese Patent Application Laid-Open No. 2-73837 describe bis (4-tertiary butylphenyl) phosphate sodium salt, but the transparency and mechanical strength of the polymer material are to some extent. Is improved, but its effect is still insufficient.

[0004]

Therefore, it is an object of the present invention to provide a novel compound useful for improving the processability, strength and transparency of crystalline polymer materials among organic materials, and its use. And

[0005]

The inventors of the present invention have conducted extensive studies in order to overcome the above-mentioned drawbacks of the conventional crystal nucleating agents, and as a result, a new bis (2,4-ditertiary butyl) has been obtained. -5
Methylphenyl) phosphate metal salt compound was created,
By compounding this with an organic material, especially a crystalline organic polymer material, the crystallization speed of the polymer material after heat molding is increased, the molding cycle time is shortened, good processability is achieved, and further crystallization is achieved. It has been found that a polymer material having greatly improved transparency and mechanical strength can be obtained by promoting it, and the present invention has been completed.

That is, the present invention provides (1): general formula

[0007]

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[In the formula, Z and m are defined as follows.
(I): Z represents the metal atom M ¹ and m represents the valence of M ¹ . (Ii): Z is an expression

[0009]

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(Where M ² is a group IIa, II of the periodic table)
A metal atom of group I or group IV, and n is an integer of 1 to 3. ), M represents 1 to 3. However, the sum of m and n is limited to an integer equal to the valence of the metal atom M ² . Or (iii): Z is an expression

[0011]

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(Wherein M ³ represents a metal atom of Group IV of the periodic table), and m represents 2. ] Bis (2,4-di tert-butyl-5-methylphenyl) phosphate metal salt compound represented by

(2): M ¹ is a group Ia or II of the periodic table
A compound which is a metal atom of group a and m is a valence of M ¹ , M ² is a metal atom of group III or IV of the periodic table, m is 2, and n is 2 from a valence of M. Is a non-integer compound, and M ³ is a metal atom of Group IV of the periodic table, and m is 2 and is bis (2,4-ditertiary butyl-5-). Methylphenyl) phosphate metal salt compound,

(3): A bis (2,4-ditertiarybutyl-5-methylphenyl) phosphate metal salt compound of (1), wherein M ¹ is lithium and m is 1.

(4): M ² is aluminum, m is 2 and n is 1 and the bis (2,4-ditertiary) of (1) is used.
Butyl-5-methylphenyl) phosphate metal salt compound,

(5): A crystal nucleating agent for a crystalline organic polymer material comprising the compound of (1), (2), (3), or (4),

(6): A crystalline polymer material containing the compound of (1), (2), (3), or (4),

(7): Containing one or more of the compound of (1), (2), (3) or (4) and an alkali metal salt or an alkaline earth metal salt of an aliphatic carboxylic acid. A crystalline polymer material composition characterized by the following:

(8): The crystalline polymer material is polyethylene, polypropylene, polybutene-1, poly-3-methylbutene, 1,2-polybutadiene, ethylene-vinyl acetate copolymer, ethylene-vinyl chloride copolymer, ethylene-propylene copolymer. , A polyethylene terephthalate, a polybutylene terephthalate, a polyhexamethylene terephthalate, a polytetrafluoroethylene, a polyacetal, a polyphenylene sulfide, a polyamide, a crystalline organic compound comprising the compound of (1), (2), (3), or (4). Crystal nucleating agent for polymeric materials.

(9): The crystalline polymer material is polyethylene, polypropylene, polybutene-1, poly-3-methylbutene, 1,2-polybutadiene, ethylene-vinyl acetate copolymer, ethylene-vinyl chloride copolymer, ethylene-propylene copolymer. Containing polyethylene terephthalate, polybutylene terephthalate, polyhexamethylene terephthalate, polytetrafluoroethylene, polyacetal, polyphenylene sulfide, polyamide, (1), (2), (3), or (4). Characteristic crystalline polymer material.

(10): The crystalline polymer material is polyethylene, polypropylene, polybutene-1, poly-3-methylbutene, 1,2-polybutadiene, ethylene-vinyl acetate copolymer, ethylene-vinyl chloride copolymer,
Ethylene-propylene copolymer, polyethylene terephthalate, polybutylene terephthalate, polyhexamethylene terephthalate, polytetrafluoroethylene,
One or more of the compound (1), (2), (3), or (4), which is a polyacetal, polyphenylene sulfide, or polyamide, and an alkali metal salt or alkaline earth metal salt of an aliphatic carboxylic acid; A crystalline polymer material composition comprising:

[0022]

BEST MODE FOR CARRYING OUT THE INVENTION A compound of the present invention, wherein M ¹ ,
Metal atoms represented by M ² and M ³ are lithium, sodium, potassium, beryllium, magnesium, calcium, strontium, barium, boron, aluminum, gallium, titanium, zirconium, silicon, germanium, tin, lead, antimony, bismuth, Examples include chromium, molybdenum, manganese, iron, cobalt, nickel, palladium, copper, silver, zinc, cadmium, and the like, and particularly Group Ia metals such as lithium, sodium, and potassium, and Group IIa metals such as magnesium, calcium, strontium, and barium. , And I such as boron and aluminum
Group II metals, group IV metals such as zirconium are desirable, and among them, group Ia metals such as lithium, sodium and potassium, group IIa metals such as magnesium, calcium, strontium and barium, and boron, aluminum and gallium. Group III metals are preferable, and among these, lithium and aluminum are particularly preferable.

Accordingly, examples of the compound of the present invention include:
The following compounds may be mentioned.

[0024]

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[0025]

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[0026]

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[0027]

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[0028]

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[0029]

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[0030]

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[0031]

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[0032]

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[0033]

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[0034]

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[0035]

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[0036]

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[0037]

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[0038]

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[0039]

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[0040]

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Among the compounds of the present invention, the compound in which Z is M ¹ can be produced, for example, by the following method.

2,4-Ditertiary butyl-5-methylphenol and phosphorus oxychloride are combined with dimethylformamide, triethylamine, tributylamine, morpholine, dimethylaniline, pyridine, quinoline, collidine, 2-aminopyridine, 3-aminopyridine. , 4-aminopyridine, 1,8-bis (dimethylamino) naphthalene, 1,
In the presence of an amine such as 8-diazabicyclo [5.4.0] undec-7-ene, benzene, toluene, xylene, petroleum ether, hexane, heptane, cyclohexane, acetone, ethyl acetate, diethyl ether, dibutyl ether, di- n-propyl ether, diisopropyl ether, dioxane, tetrahydrofuran, dichloromethane, chloroform, carbon tetrachloride, dichloroethane, 1,2-dichlorotoluene, 1,3-dichlorotoluene, 1,4-dichlorotoluene, 1,2-dichlorobenzene, In a solvent such as 1,3-dichlorobenzene or 1,4-dichlorobenzene, or without solvent, under cooling, or at a temperature from room temperature to the boiling point of the solvent used when the solvent is used, or from room temperature when the solvent is not used Obtained by reacting at temperatures up to 200 ° C Bis (2,4-di-tert-butyl-5-methylphenyl) a phosphorochloridate, hexane, heptane, octane, benzene, toluene, xylene, mesitylene, cyclohexane, petroleum ether,
Dichloromethane, chloroform, carbon tetrachloride, dichloroethane, trichloroethane, tetrachloroethane, chlorobenzene, 1,2-dichlorobenzene, 1,3-dichlorobenzene, 1,4-dichlorobenzene, methanol, ethanol, 1-propanol, isopropyl alcohol, butanol. , Pentanol, cyclohexanol, 1,2-ethanediol, 1,3-propanediol, 1,4-butanediol, diethyl ether, di-
n-propyl ether, diisopropyl ether, dibutyl ether, 1,4-dioxane, tetrahydrofuran, 1,2-dimethoxyethane, 1,2-diethoxyethane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, diethylene glycol, diethylene glycol monomethyl ether , Diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol, acetone, methyl ethyl ketone, methyl isobutyl ketone, ethyl acetate, propyl acetate, butyl acetate, acetonitrile, dimethylformamide, dimethylacetamide, 1,3-dimethyl-2-imidazolidinone , Dimethyl sulfoxide, sulfolane, water Lithium hydroxide, sodium hydroxide, potassium hydroxide, beryllium hydroxide, magnesium hydroxide, calcium hydroxide, in a solvent of, or in a mixed solvent thereof, or without solvent at a temperature from cooling to 200 ° C. Strontium hydroxide, barium hydroxide, boron hydroxide, aluminum hydroxide, gallium hydroxide, titanium hydroxide, zirconium hydroxide, silicon hydroxide,
Germanium hydroxide, tin hydroxide, lead hydroxide, antimony hydroxide, bismuth hydroxide, chromium hydroxide, molybdenum hydroxide, manganese hydroxide, iron hydroxide, cobalt hydroxide, nickel hydroxide, palladium hydroxide, hydroxide The hydrolysis reaction is carried out in the presence of a metal hydroxide of copper, silver hydroxide, zinc hydroxide or cadmium hydroxide. After the reaction, the product is obtained by filtration and drying. If necessary, the obtained target compound can be purified by a usual means such as a recrystallization method or an extraction method.

Of the compounds of the present invention, Z is

[0044]

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(Where M ² is IIa group, II
A metal atom of group I or group IV, and n is an integer of 1 to 3. ), M represents 1 to 3. However, the sum of m and n is limited to an integer equal to the valence of the metal atom M ² . ) Is produced, for example, by the following method.

A compound in which Z is M ¹ which can be synthesized by the above-described synthetic method is added to aluminum chloride,
It is a polyvalent metal halide such as zirconium chloride.

[0047]

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(M ² is a metal atom of group IIa, III or IV of the periodic table, X is a halogen atom, and n is M.
The valence of ) Is reacted and a hydrolysis reaction is performed.
After the reaction, the product is obtained by filtration and drying. If necessary, the obtained target compound can be purified by a usual means such as a recrystallization method or an extraction method.

Further, it is an organic phosphate ester.

[0050]

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And a polyvalent metal alcoholate such as aluminum ethoxide

[0052]

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(M ² is a metal atom of group IIa, III or IV of the periodic table, R is an alkyl group, and n is a valence of M), and a hydrolysis reaction is carried out. After the reaction, the product is obtained by filtration and drying.

The obtained target compound can be purified, if necessary, by a conventional means such as a recrystallization method or an extraction method.

Of the compounds of the present invention, Z is

[0056]

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The compound which is, for example, a compound in which Z is M ¹ is an oxypolyvalent metal halide such as zirconium oxychloride.

[0058]

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(M ³ is a metal atom of Group IV of the periodic table,
X represents a halogen atom. ) Is reacted and a hydrolysis reaction is performed. After the reaction, the product is obtained by filtration and drying. If necessary, the obtained target compound can be purified by a usual means such as a recrystallization method or an extraction method.

In the present invention, examples of the crystalline polymer material having improved transparency include homopolymers and copolymers of α-olefin, specifically polyethylene.
Polypropylene, polybutene-1, poly-3-methylbutene, 1,2-polybutadiene, and ethylene-vinyl acetate copolymer, ethylene-vinyl chloride copolymer,
Examples thereof include ethylene-propylene copolymers. In addition, thermoplastic linear polyesters such as polyethylene terephthalate, polybutylene terephthalate and polyhexamethylene terephthalate, polytetrafluoroethylene, polyacetal, polyphenylene sulfide, and linear polyamides such as polycaprolactam and polyhexamethylene adipamide are also included. .

In the crystalline polymer material composition of the present invention, a metal salt compound of bis (2,4-ditertiarybutyl-5-methylphenyl) phosphate is added to the crystalline polymer material as a crystal nucleating agent. The amount of addition is 0.005 to 5 parts by weight, preferably 0.1 to 2.5 parts by weight, based on 100 parts by weight of the crystalline polymer material. The addition method is not particularly limited, and a method of uniformly mixing with the powder or pellets of the crystalline polymer material can be applied.

The crystalline polymer material of the present invention can be further improved in oxidative stability by adding a phenolic antioxidant. Examples of phenolic antioxidants that can be used include 2,6-ditertiary butyl-4-methylphenol, 4-hydroxymethyl-2,6-ditertiary butylphenol, and 2,6-ditertiary butylphenol. 4-
Ethylphenol, butylated hydroxyanisole, n
-Octadecyl 3- (4-hydroxy-3,5-ditertiary butylphenyl) propionate, distearyl
(4-Hydroxy-3-methyl-5-tertiary butyl) benzyl malonate, propyl gallate, octyl gallate, dodecyl gallate, tocopherol, 2,2'-methylenebis (4-methyl-6-tertiary) Butylphenol), 2,2'-methylenebis (4-ethyl-6-tertiary
Butylphenol), 4,4'-methylenebis (2,2
6-ditertiary butylphenol), 4,4′-butylidene bis (6-tertiary butyl-3-methylphenol),
4,4′-thiobis (6-tertiary butyl-3-methylphenol), styrenated phenol, N, N-hexamethylenebis (3,5-ditertiary butyl-4-hydroxyhydrocinnamide), Bis (3,5-ditertiary butyl-
4-hydroxybenzylphosphonic acid ethyl ester) calcium, 1,1,3-tris (2-methyl-4-hydroxy-5-tertiarybutylphenyl) butane, 1,3,3
5-trimethyl-2,4,6-tris (3,5-di-third
Butyl-4-hydroxybenzyl) benzene, tetrakis [3- (3,5-ditertiarybutyl-4-hydroxyphenyl) propionyloxymethyl] methane, 1,6
-Hexanediol-bis [3- (3,5-ditertiary butyl-4-hydroxyphenyl) propionate],
2,2'-methylenebis (4-methyl-6-cyclohexylphenol), 2,2'-methylenebis [6- (1
-Methylcyclohexyl) -4-methylphenol],
1,3,5-tris (4-tertiary butyl-3-hydroxy-2,6-dimethylbenzyl) isocyanuric acid, 1,
3,5-Tris (3,5-ditertiary butyl-4-hydroxybenzyl) isocyanuric acid, triethylene glycol-bis [3- (3-tertiary butyl-4-hydroxy-)
5-Methylphenyl) propionate], 2,2′-oxamide bis [ethyl 3- (3,5-ditertiarybutyl-4-hydroxyphenyl) propionate], 6-
(4-Hydroxy-3,5-ditertiary butylanilino)
-2,4-dioctylthio-1,3,5-triazine,
Bis [2-tertiary butyl-4-methyl-6- (2-hydroxy-3-tertiary butyl-5-methylbenzyl) phenyl] terephthalate, 3,9-bis [2- [3- (3
-Tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy] -1,1-dimethylethyl]
-2,4,8,10-Tetraoxaspiro [5.5] undecane or 3,9-bis [2- [3- (3,5-ditertiarybutyl-4-hydroxyphenyl) propionyloxy]- 1,1-dimethylethyl] -2,4,8,1
Examples thereof include, but are not limited to, 0-tetraoxaspiro [5.5] undecane.

Furthermore, the oxidation stability can be improved by adding a sulfur-based antioxidant. Sulfur-based antioxidants that can be used are thioalkanoic acid esters, such as dilauryl ester of thiodipropionic acid, dimyristyl ester, distearyl ester, didocosyl ester and the like, glycerin, trimethylolethane, trimethylolpropane. , Pentaerythritol, and esters with polyhydric alcohols such as trishydroxyethyl isocyanurate.

Further, in order to further improve the weather resistance of the composition of the present invention, an ultraviolet absorber, a light stabilizer and the like can be used in combination. Examples of usable ultraviolet absorbers and light stabilizers are phenyl salicylate, p-tertiary butylphenyl salicylate, p-octylphenyl salicylate, 2,4-dihydroxybenzophenone and 2-hydroxy-4-acetoxy. Ethoxybenzophenone, 2-
Hydroxy-4-methoxybenzophenone, 2,2'-
Dihydroxy-4,4'-dimethoxybenzophenone,
2-hydroxy-4-n-octyloxybenzophenone, 2-hydroxy-4-isooctyloxybenzophenone, 2-hydroxy-4-dodecyloxybenzophenone, 2-hydroxy-4-octadecyloxybenzophenone, 2,2'-dihydroxy- 4,4'-Dimethoxy-5,5'-disulfobenzophenone disodium, 2-hydroxy-4- (2-hydroxy-3-methacryloxy) propoxybenzophenone, 2- (2
-Hydroxy-5-methylphenyl) benzotriazole, 2- (2-hydroxy-3,5-ditertiary butylphenyl) benzotriazole, 2- (2-hydroxy-
3-tertiary butyl-5-methylphenyl) -5-chlorobenzotriazole, 2- (2-hydroxy-3,5-
Ditertiary butylphenyl) -5-chlorobenzotriazole, 2- [2-hydroxy-5- (1,1,3,3-
Tetramethylbutyl) phenyl] benzotriazole,
n-Hexadecyl-3,5-ditertiary butyl-4-hydroxybenzoate, 2,4-ditertiary butylphenyl-3,5-ditertiary butyl-4-hydroxybenzoate, ethyl-2-cyano -3,3-diphenyl acrylate, {2,2'-thiobis [4- (1,1,3,3-
Tetramethylbutyl) phenolate]}-n-butylamine nickel, {2,2′-thiobis [4- (1,
1,3,3-Tetramethylbutyl) phenolate]} nickel, bis (3,5-di-tert-butyl-4-hydroxybenzylphosphonate ethyl) nickel, bis (2,2
2,6,6-Tetramethyl-4-piperidyl) sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) -2- (3,5-ditertiary butyl-4 -Hydroxybenzyl) -2-n-butylmalonate, bis (1-acryloyl-2,2,6,6-tetramethyl-
4-Piperidyl) bis (3,5-ditertiary butyl-4)
-Hydroxybenzyl) malonate, tetrakis (2,
2,6,6-tetramethyl-4-piperidyl) -1,
2,3,4-butane tetracarboxylate, poly {[6- (1,1,3,3-tetramethylbutyl) imino-s-triazine-2,4-diyl] [(2,2,
6,6-Tetramethyl-4-piperidyl) imino] hexamethylene [(2,2,6,6-tetramethyl-4-piperidyl) imino]}, poly {(6-morpholino-s-
Triazine-2,4-diyl) [(2,2,6,6-tetramethyl-4-piperidyl) imino] hexamethylene [(2,2,6,6-tetramethyl-4-piperidyl)
Imino]}, 1-hydroxyethyl-2,2,6,6-
Tetramethyl-4-piperidinol / succinic acid condensate,
Cyanuric chloride / tertiary octylamine / 1,6-bis (2,2,6,6-tetramethyl-4-piperidylamino) hexane condensate, salicylic acid type, benzophenone type, benzotriazole type, cyano Acrylate type, nickel compound type, or 2,2,6,6
-Tetramethylpiperidine compounds and the like can be mentioned.

Further, by adding a phosphorus antioxidant to the composition of the present invention, discoloration prevention, heat resistance and weather resistance of the composition can be improved. Examples of phosphorus-based antioxidants that can be used include tris (2,4-ditertiary butylphenyl) phosphite, tetrakis (2,4-ditertiary butylphenyl) -4,4′-biphenylenediphosphonite, Tetrakis (2,4-ditertiarybutyl-5-methylphenyl) -4,4'-biphenylenediphosphonite, bis (2,4-ditertiarybutylphenyl) pentaerythritol diphosphite, bis (2 , 6-ditertiary butyl-4-methylphenyl) pentaerythritol diphosphite, 2,2′-methylenebis (4,6-ditertiary butylphenyl) -2-ethylhexyl phosphite and the like.

When these phenol-based antioxidants, sulfur-based antioxidants, ultraviolet absorbers and light stabilizers, and phosphorus-based antioxidants are used alone or in combination, they are used for crystalline polymer materials. 0.01 to 1 in total
The amount is 0 parts by weight, preferably 0.01 to 5 parts by weight.

The compound of the present invention can be used in combination with other crystal nucleating agents, clarifying agents and the like, if necessary. Crystal nucleating agent,
As a clarifying agent, bis (p-tertiary butyl benzoic acid) hydroxyaluminum, bis (4-tertiary butyl phenyl) phosphate sodium salt, 2,2'-methylene bis (4,6-di tert-butyl phenyl) ) Phosphate sodium salt, dibenzylidene sorbitol, bis (p-
Examples thereof include methylbenzylidene) sorbitol, bis (p-ethylbenzylidene) sorbitol, bis (p-chlorobenzylidene) sorbitol and the like.

Furthermore, by adding an alkali metal salt or an alkaline earth metal salt of an aliphatic carboxylic acid to the composition of the present invention, the transparency and impact strength of the composition can be improved. Examples of the alkali metal include lithium, sodium, potassium and rubidium, and examples of the alkaline earth metal include beryllium, magnesium, calcium, strontium and barium.

Examples of the carboxylic acid of this aliphatic carboxylic acid metal salt include acetic acid, propionic acid, acrylic acid,
Examples include octylic acid, isooctylic acid, nonanoic acid, decanoic acid, lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, ricinoleic acid, 12-hydroxystearic acid, behenic acid, montanic acid, mericinic acid, erucic acid, etc. To be

When these alkali metal salts or alkaline earth metal salts of aliphatic carboxylic acids are used, they can be used in combination at a ratio of 1:10 to 10: 1 with respect to the compound of the present invention. For example, compound 1 of the present invention
On the other hand, a composition in which lithium stearate is added in a ratio of 1 is preferable.

The compound of the present invention may further contain hydrotalcites, metal soaps, heavy metal deactivators, organotin stabilizers, plasticizers, epoxy compounds, pigments, fillers, foaming agents, antistatic agents, if necessary. It can also be used in combination with flame retardants, lubricants, processing aids and the like.

[0072]

[Examples] The synthetic examples of the bis (2,4-ditertiarybutyl-5-methylphenyl) phosphate metal salt compound of the present invention are shown below. However, the present invention is not limited by these.

Synthesis Example 1 Bis (2,4-ditertiary butyl-5-methylphenyl)
Synthesis of phosphorochloridate 2,4 -ditertiary butyl-5-methylphenol 50
g and 54 g of pyridine were charged, and 17.5 g of phosphorus oxychloride was added dropwise at 10 ° C. After dropping, the mixture was reacted at 75 ° C. for 10 hours. After the reaction, the reaction mixture was cooled, toluene was added thereto, the pyridine hydrochloride was filtered off, the filtrate was concentrated, and hexane was added for crystallization. The crystals were filtered off and recrystallized from heptane to give the title compound as white crystals. Melting point:
128-129 ° C.

Synthesis Example 2 Bis (2,4-ditertiary butyl-5-methylphenyl)
Synthesis of sodium phosphate bis (2,4-ditertiary butyl-5-methylphenyl)
Phosphorochloridate 8g, 20% sodium hydroxide 1
5 g, 1,3-dimethyl-2-imidazolidinone 30 g
Was charged and reacted at 60 ° C. for 5 hours. After the reaction,
Water was added and the precipitated crystals were separated by filtration, washed with water and dried to obtain the title compound as white crystals. Melting point: 360
° C (decomposition). Proton nuclear magnetic resonance spectrum ( ¹ H-N
The results of MR), infrared absorption spectrum (IR), and elemental analysis are shown in Table 1.

[0075]

[Table 1]

Synthesis Example 3 Bis (2,4-ditertiary butyl-5-methylphenyl)
Synthesis of Phosphate Potassium Salt The title compound was obtained in the same manner as in Synthesis Example 2 using 15 g of 28% potassium hydroxide instead of 20% sodium hydroxide. Melting point: 326 ° C (decomposition). The results of proton nuclear magnetic resonance spectrum ( ¹ H-NMR), infrared absorption spectrum (IR), and elemental analysis are shown in Table 2.

[0077]

[Table 2]

Synthesis Example 4 Bis (2,4-ditertiary butyl-5-methylphenyl)
Synthesis of phosphate lithium salt Using 30 g of 6% lithium hydroxide instead of 20% sodium hydroxide, the title compound was obtained in the same manner as in Synthesis Example 2. Melting point 320 ° C (decomposition). Proton nuclear magnetic resonance spectrum ( ¹ H-NMR), infrared absorption spectrum (I
R) and the results of elemental analysis are shown in Table 3.

[0079]

[Table 3]

Synthesis Example 5 Hydroxylated-bis {(2,4-ditertiary butyl-5-methyl
Synthesis of (phenyl) phosphate} aluminum salt

[0081]

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6 g of sodium bis (2,4-ditertiarybutyl-5-methylphenyl) phosphate sodium salt was dissolved in 60 ml of methanol, and a solution prepared by dissolving 1.38 g of aluminum trichloride hexahydrate in 30 ml of water was added thereto. It was added dropwise at 35 ° C. After dropping, the mixture was reacted under reflux of methanol for 3 hours, cooled to room temperature, and neutralized with 10% sodium hydroxide. The product was filtered, washed with water, and then dried to obtain 5.4 g of the title compound as a white powder. Melting point: 250 ° C or higher. Table 4 shows the results of infrared absorption spectrum (IR) and elemental analysis.
It was shown to.

[0083]

[Table 4]

Next, the use of the bis (2,4-ditertiarybutyl-5-methylphenyl) phosphate metal salt compound of the present invention will be specifically described.

Test Example 1 The following formulation was uniformly mixed with a Turbula mixer for 10 minutes, and pellets were prepared using an extruder under the following conditions. The prepared pellets had a thickness of 1 m using an injection molding machine.
m test sheet was created.

Unadded polypropylene 100 parts by weight Tetrakis {3- (3,5-0.1 parts by weight ditertiary butyl-4-hydroxyphenyl) propionyl oxymethyl} methane ・ Calcium stearate 0.05 parts by weight 0.3 parts by weight of the phosphate compound of Synthesis Example 2

[0087]

For this sample (Example 1), Haze
The Value (cloudiness value) and Izod (Izod) impact strength were determined. Further, instead of the phosphate compound of Synthesis Example 2, the following compound of Comparative Example 1 was added, the compound of Comparative Example 2 was added, and the phosphate compound of Synthesis Example 2 was not added. Were similarly tested. Table 5 shows the results.

[0089]

[Table 5]

Comparative Example 1 : Bis (p-tertiary butyl benzoic acid) hydroxyaluminum Comparative Example 2 : 2,2'-methylenebis (4,6-di3rd)
-Butylphenyl) phosphate sodium salt

Test Example 2 A test sheet having a thickness of 1 mm was prepared using the following formulation in the same manner as in Test Example 1.

Unadded polypropylene 100 parts by weight n-octadecyl-3- (4 0.1 parts by weight-hydroxy-3,5-ditertiary butylphenyl) propionate Dilaurylthiodipropione 0.2 Parts by weight-phosphate compound of Synthesis Example 2 0.3 parts by weight

For this sample (Example 2), Haze
The Value (cloudiness value) and Izod (Izod) impact strength were determined. Further, the same test was carried out for the one to which the compound of Comparative Example 3 shown below was added instead of the phosphate compound of Synthesis Example 2 and the one to which the phosphate compound of Synthesis Example 2 was not added. Table 6 shows the results.

[0094]

[Table 6]

Comparative Example 3 : Bis (4-tert-butylphenyl) phosphate sodium salt

Test Example 3 A test sheet having a thickness of 1 mm was prepared using the following formulation in the same manner as in Test Example 1.

Unadded polypropylene 100 parts by weight n-octadecyl-3- (4 0.1 parts by weight -hydroxy-3,5-ditertiary butylphenyl) propionate Distearyl thiodipropio 0.2 parts by weight Parts Nate-phosphate compound of Synthesis Example 3 0.3 parts by weight

For this sample (Example 3), Haze
The Value (cloudiness value) and Izod (Izod) impact strength were determined. Further, the same test was carried out for the one to which the compound of Comparative Example 4 shown below was added instead of the phosphate compound of Synthesis Example 3 and the one to which the phosphate compound of Synthesis Example 3 was not added. The results are shown in Table 7.

[0099]

[Table 7]

Comparative Example 4 : Bis (4-tertiarybutylphenyl) phosphate sodium salt

Test Example 4 A test sheet having a thickness of 1 mm was prepared using the following formulation in the same manner as in Test Example 1.

Unadded low-density polyethylene 100 parts by weight 4,4'-thiobis (3-me 0.1 parts by weight chill-6-tertiary butylphenol) 0.35 parts by weight of the phosphate compound of Synthesis Example 4

For this sample (Example 4), Haze
The Value (cloudiness value) and Izod (Izod) impact strength were determined. In addition, instead of the phosphate compound of Synthesis Example 4, the compound of Comparative Example 5 shown below and the one to which the phosphate compound of Synthesis Example 4 was not added were similarly tested. The results are shown in Table 8.

[0104]

[Table 8]

Comparative Example 5 : Sodium salt of 2,2'-methylenebis (4,6-ditertiarybutylphenyl) phosphate

Test Example 5 The following formulation was uniformly mixed with a Turbula mixer for 10 minutes, and pellets were produced using an extruder under the following conditions. The produced pellets had a thickness of 1 m using an injection molding machine.
m test sheet (Haze Value (cloudiness value)
(For measurement) and a test sheet having a thickness of 6.4 mm (for notched Izod impact test) were prepared.

Unadded polypropylene 100 parts by weight Tetrakis [3- (3,5-0.1 parts by weight ditertiary butyl-4-hydroxyphenyl) propionyloxymethyl] methane Dilaurylthiodipropione 0.1. 2 parts by weight-phosphate compound of Synthesis Example 5 0.3 parts by weight

For this sample (Example 5), Haze
Value (cloudiness value) was determined. Further, this sample (Example 5) was subjected to a notched Izod impact test to determine the Izod impact strength. Further, the same test was carried out for the one to which the phosphate compound of Synthesis Example 5 was not added. Table 9 shows the results.

[0109]

[Table 9]

[0110] Test Example 6 The following formulation was used in the same manner as in Test Example 5 to obtain a thickness of 1 mm and 6.4.
A mm test sheet was prepared.

Unadded polypropylene 100 parts by weight Tetrakis [3- (3,5-0.1 parts by weight ditertiary butyl-4-hydroxyphenyl) propionyl oxymethyl] methane Dilaurylthiodipropione 2 parts by weight Lithium stearate 0.15 parts by weight Synthetic example 5 phosphate compound 0.15 parts by weight

Haze for this sample (Example 6)
Value (cloudiness value) was determined. Further, the same test was performed with the compound of Comparative Example 6 shown below added in place of the phosphate compound of Synthesis Example 5. The results are shown in Table 10.

[0113]

[Table 10]

Comparative Example 6 : Bis (4-tertiarybutylphenyl) phosphate aluminum salt

[0115]

The bis (2,4-ditertiary butyl-5-methylphenyl) phosphate metal salt compound of the present invention and the hydroxide of the compound are the crystallization rate of the polymer material after heat molding. It has the characteristics of accelerating the processability and remarkably improving the processability, strength and transparency of the crystalline polymer material. By adding this compound to an organic material, an extremely useful organic crystalline polymer material can be obtained. .

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Kazuo Nakagawa 1480 Kita-Gomizuka, Kusu-cho, Mie-gun, Mie Yoshitomi Pharmaceutical Co., Ltd.Kusu factory (72) Inventor Akito Join Osaka Osaka 2-6-9 Hirano-cho, Chuo-ku, Yokohama-shi Yoshitomi Pharmaceutical Co., Ltd.

Claims (10)

[Claims] 1. A compound of the general formula [In the formula, Z and m are defined as follows. (I): Z represents the metal atom M ¹ and m represents the valence of M ¹ . (Ii): Z
Is the formula (Where M ² is group IIa, group III or I of the periodic table)
A metal atom of V group and n is an integer of 1 to 3. ), M represents 1 to 3. However, the sum of m and n is limited to an integer equal to the valence of the metal atom M ² . Or (iii): Z is of the formula: (Wherein M ³ represents a metal atom of Group IV of the periodic table), and m represents 2. ] The bis (2, 4- ditertiary butyl-5-methylphenyl) phosphate metal salt compound represented by these. Wherein M ¹ is a metal atom of the periodic table group Ia or group IIa, compound m is a valence of M ^1, M ²
Is a metal atom of group III or group IV of the periodic table, and m
Is 2 and n is an integer obtained by subtracting 2 from the valence of M, and M ³ is a metal atom of Group IV of the Periodic Table, and m is 2. Bis (2,4-ditertiary butyl-5-methylphenyl) phosphate metal salt compound. 3. M ¹ is lithium and m is 1,
The bis (2,4-ditertiary butyl-5-methylphenyl) phosphate metal salt compound according to claim 1. 4. The bis (2,4-ditertiary) according to claim 1, wherein M ² is aluminum, m is 2 and n is 1.
Tert-Butyl-5-methylphenyl) phosphate metal salt compound. 5. A crystal nucleating agent for a crystalline organic polymer material, which comprises the compound according to claim 1, 2, 3 or 4. 6. A crystalline polymer material comprising the compound according to claim 1, 2, 3 or 4. 7. A high crystallinity comprising the compound according to claim 1, 2, 3 or 4 and one or more alkali metal salts or alkaline earth metal salts of aliphatic carboxylic acids. Molecular material composition. 8. The crystalline polymer material is polyethylene, polypropylene, polybutene-1, poly-3-methylbutene, 1,2-polybutadiene, ethylene-vinyl acetate copolymer, ethylene-vinyl chloride copolymer, ethylene-propylene copolymer, polyethylene. A crystal nucleating agent for a crystalline organic polymer material comprising the compound according to claim 1, which is terephthalate, polybutylene terephthalate, polyhexamethylene terephthalate, polytetrafluoroethylene, polyacetal, polyphenylene sulfide, or polyamide. 9. The crystalline polymer material is polyethylene, polypropylene, polybutene-1, poly-3-methylbutene, 1,2-polybutadiene, ethylene-vinyl acetate copolymer, ethylene-vinyl chloride copolymer, ethylene-propylene copolymer, polyethylene. A crystalline polymer material comprising the compound according to claim 1, which is terephthalate, polybutylene terephthalate, polyhexamethylene terephthalate, polytetrafluoroethylene, polyacetal, polyphenylene sulfide, or polyamide. . 10. The crystalline polymer material is polyethylene,
Polypropylene, polybutene-1, poly-3-methylbutene, 1,2-polybutadiene, ethylene-vinyl acetate copolymer, ethylene-vinyl chloride copolymer, ethylene-propylene copolymer, polyethylene terephthalate, polybutylene terephthalate, polyhexamethylene terephthalate, polytetrafluoro It contains ethylene, polyacetal, polyphenylene sulfide, polyamide, and the compound according to claim 1, 2, 3 or 4, and one or more kinds of an alkali metal salt or an alkaline earth metal salt of an aliphatic carboxylic acid. A characteristic crystalline polymer material composition.