JP3197354B2 - Crystalline synthetic resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a crystalline synthetic resin composition, and more particularly, to a mixture of a specific cyclic organic phosphate compound and an alkali metal compound, which has improved transparency and mechanical properties. And a crystalline synthetic resin composition.

[0002]

2. Description of the Related Art Crystalline synthetic resins such as polyethylene, polypropylene, polybutene-1, polyethylene terephthalate, polybutylene terephthalate, polyphenylene sulfide, and polyamide have a low crystallization rate after heat-melt molding. Therefore, the molding cycleability is low, and shrinkage occurs due to the progress of crystallization after heat molding. In addition, these crystalline synthetic resins have disadvantages of insufficient strength and poor transparency because large crystals are generated.

[0003] All of these disadvantages are derived from the crystallinity of the synthetic resin, and are known to be eliminated if the crystallization temperature of the synthetic resin can be increased and fine crystals can be rapidly formed. I have.

It is known to add a nucleating agent or a crystallization accelerator for this purpose.
A metal salt of a carboxylic acid such as aluminum tertiary butyl benzoate, sodium adipate, sodium bis (4-
Tert-butylphenyl) phosphate, sodium-2,
2'-methylenebis (4,6-di-tert-butylphenyl)
Acidic phosphate metal salts such as phosphates, and polyhydric alcohol derivatives such as dibenzylidene sorbitol and bis (4-methylbenzylidene) sorbitol have been used.

[0005] Among these compounds, JP-A-58-1
The metal salts of cyclic phosphoric acid esters of alkylidene bisphenols described in JP-A-736-736 and JP-A-59-184252 have large effects and are widely used.

Attempts have also been made to improve the effect by using these compounds in combination with other metal compounds.
No. 3 discloses an alkaline earth metal carboxylate in order to prevent a decrease in rigidity when an aromatic alkali metal phosphate nucleating agent and an alkaline earth metal carboxylate such as calcium stearate are used in combination. A method using a hydrotalcite or an alkali metal carboxylate in place of the above has been proposed.
Japanese Patent Application Laid-Open No. 129051 proposes a method of using a metal salt of a cyclic organic phosphate and a metal salt of a Group 2 metal of the periodic table of an aliphatic carboxylic acid in combination. When an ester metal salt is used, it is proposed to use a hydroxide of an alkali metal, an alkaline earth metal or an aluminum group metal in combination in order to prevent a decrease in pH in hot water immersion after irradiation. .

[0007] However, the improvement effect of these combinations is not yet practically satisfactory, and further improvement has been demanded especially from the viewpoint of improving the transparency of the crystalline synthetic resin.

Further, JP-A-3-79649 and JP-A-3-81368 propose a method in which an acidic organic phosphoric acid ester compound and a metal salt of an aliphatic carboxylic acid are used in combination. When an organic phosphate compound is used, not only is the effect insufficient, but there is a disadvantage that the crystalline synthetic resin is undesirably colored, which is not practically satisfactory.

[0009]

Means for Solving the Problems In view of the present situation, the present inventors have made various studies and found that a specific cyclic organic phosphate compound having an acid anhydride structure in a crystalline synthetic resin and an alkali metal compound. It has been found that the addition of the compound greatly improves the transparency and also increases the mechanical strength, and has reached the present invention.

That is, the present invention relates to (a) a cyclic organic phosphate represented by the following general formula (I) represented by the following general formula (I): An object of the present invention is to provide a crystalline synthetic resin composition comprising 0.01 to 5 parts by weight of at least one kind of a compound and 0.01 to 5 parts by weight of at least one kind of an alkali metal compound.

[0011]

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Hereinafter, the crystalline synthetic resin composition of the present invention will be described in detail.

In the crystalline synthetic resin composition of the present invention, in the cyclic organic phosphate ester compound represented by the general formula (I) of the component (A), the alkyl group having 1 to 4 carbon atoms represented by R ₁ Is methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, isobutyl and the like. Examples of the alkyl group having 1 to 12 carbon atoms represented by R ₂ and R ₃ include methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, tert-butyl, amyl, tert-amyl, hexyl, heptyl, octyl, Isooctyl,
Tertiary octyl, 2-ethylhexyl, nonyl, isononyl, decyl, isodecyl, undecyl, dodecyl, tertiary dodecyl and the like. Examples of the cycloalkyl group represented by R ₂ and R ₃ include cyclopentyl, cyclohexyl, cycloheptyl and the like. The aryl group represented by R ₂ and R ₃ includes phenyl, tolyl, xylyl, ethylphenyl, biphenyl, naphthyl and the like. The aralkyl groups represented by R ₂ and R ₃ include benzyl, phenylethyl, α-methylbenzyl, cumyl and the like.

Accordingly, the compound represented by the general formula (I) used in the crystalline synthetic resin composition of the present invention includes, for example, compounds represented by the following formulas (3) to (6): Compound No. 1 to Compound No. 4).

[0015]

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[0016]

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[0017]

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[0018]

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The cyclic organic phosphate compound of the above-mentioned component (A) is obtained, for example, by reacting an alkylidene bisphenol with phosphorus trichloride and hydrolyzing the cyclic organic phosphate ester compound. The compound can be produced by a dehydrochlorination reaction with the resulting acidic cyclic organic phosphate compound.

Next, specific production examples of the cyclic organophosphate compound used in the present invention will be shown, but the present invention is not limited by the following production examples.

Production Example 1 (Production of Compound No. 1) 2,05'-methylenebis (4,6-di-tert-butylphenyl) phosphoric acid chloride 5.05 g (0.01 mol) and 2,2'-methylenebis 4.85 g (0.01 mol) of (4,6-di-tert-butylphenyl) acid phosphate
Was dissolved in 100 ml of toluene by heating.
5 g (0.015 mol) of triethylamine was added dropwise. After completion of the dropwise addition, the mixture was stirred at 100 ° C. for 1 hour, cooled to room temperature, and the precipitated triethylamine hydrochloride was removed by filtration. The filtrate was desolvated, and the obtained white powder was washed with methanol to obtain a white powder product having a melting point of 254 ° C.

The obtained product had one peak as a result of analysis by liquid chromatography. Further, as a result of infrared spectroscopic analysis, the product had a sharp absorption based on P-O-P at 940 cm ^-1 and was found to be the target product. It was confirmed.

The cyclic organic phosphate compound of the component (A) is not particularly limited in its particle size, and for example, those having an average particle size of 0.01 to 50 microns can be used.

The amount of the cyclic organic phosphoric acid ester compound (a) to be added is 0.01 to 5 parts by weight, preferably 0.03 to 3 parts by weight, based on 100 parts by weight of the crystalline synthetic resin. .

Examples of the alkali metal compound (b) of the crystalline synthetic resin composition of the present invention include alkali metal oxides, alkali metal hydroxides, alkali metal carbonates, alkali metal silicates, and alkali metal aluminates. And alkali metal organic acid salts such as alkali metal carboxylate, alkali metal β-diketonate, alkali metal β-ketoacetate, alkali metal phenolate and the like. In the above, examples of the alkali metal include lithium, sodium, and potassium.

Examples of the carboxylic acid constituting the alkali metal carboxylate include acetic acid, propionic acid, acrylic acid, octylic acid, isooctylic acid, nonanoic acid, decanoic acid, lauric acid, myristic acid, palmitic acid, and the like. Stearic acid, oleic acid, ricinoleic acid, 12-
Fats such as hydroxystearic acid, behenic acid, montanic acid, melicic acid, β-dodecylmercaptoacetic acid, β-dodecylmercaptopropionic acid, β-N-laurylaminopropionic acid, β-N-methyl-N-lauroylaminopropionic acid Aromatic monocarboxylic acids; malonic acid, succinic acid, adipic acid, maleic acid, azelaic acid, sebacic acid, dodecanediic acid, citric acid, butanetricarboxylic acid,
Aliphatic polycarboxylic acids such as butanetetracarboxylic acid;
Naphthenic acid, cyclopentanecarboxylic acid, 1-methylcyclopentanecarboxylic acid, 2-methylcyclopentanecarboxylic acid, cyclopentenecarboxylic acid, cyclohexanecarboxylic acid, 1-methylcyclohexanecarboxylic acid,
-Methylcyclohexanecarboxylic acid, 3,5-dimethylcyclohexanecarboxylic acid, 4-butylcyclohexanecarboxylic acid, 4-octylcyclohexanecarboxylic acid,
Cyclohexene carboxylic acid, 4-cyclohexene-1,
Alicyclic mono- or polycarboxylic acids such as 2-dicarboxylic acid; benzoic acid, toluic acid, xylylic acid, ethylbenzoic acid, 4-tert-butylbenzoic acid, salicylic acid, phthalic acid,
Examples thereof include aromatic mono- or polycarboxylic acids such as trimellitic acid and pyromellitic acid.

Examples of the β-diketone constituting the alkali metal β-diketonate include acetylacetone, pivaloylacetone, palmitoylacetone, benzoylacetone, pivaloylbenzoylacetone, dibenzoylmethane and the like.

Examples of the β-ketoacetate constituting the alkali metal β-ketoacetate include, for example,
Examples include ethyl acetoacetate, octyl acetoacetate, lauryl acetoacetate, stearyl acetoacetate, ethyl benzoyl acetate, and lauryl benzoyl acetate.

The above-mentioned alkali metal carboxylate, alkali metal β-diketonate, alkali metal β-ketoacetate and alkali metal phenolate are the above-mentioned alkali metal and carboxylic acid, β-diketone compound, β-ketoacetate, phenol And can be produced by a conventionally known method.

As the component (b), among these alkali metal compounds, an alkali metal organic acid salt, particularly an alkali metal carboxylate, is preferable, and an aliphatic monocarboxylate having 8 to 20 carbon atoms is particularly preferable. Is preferred.

The amount of the alkali metal compound (b) to be added is 0.0 to 100 parts by weight of the crystalline synthetic resin.
It is preferably 1 to 5 parts by weight, particularly preferably 0.05 to 3 parts by weight.

The ratio of the cyclic organic phosphate compound of the component (A) to the alkali metal compound of the component (B) is not particularly limited, but the addition of the alkali metal compound of the component (B) is particularly important. The effect of the present invention is remarkable when the amount is about 1.5 to 4 times the mol of the cyclic organic phosphate compound of the component (A).

As the crystalline synthetic resin in the present invention,
For example, α-olefin polymers such as low density polyethylene, linear low density polyethylene, high density polyethylene, polypropylene, polybutene-1, poly-3-methylbutene, ethylene / propylene block or random copolymer; polyethylene terephthalate, poly Examples include thermoplastic linear polyesters such as butylene terephthalate and polyhexamethylene terephthalate; and linear polyamides such as polyphenylene sulfide and polycaprolactone and polyhexamethylene adipamide.

In particular, the present invention applies to polypropylene-based resins such as crystalline α-olefin polymers, especially polypropylene, ethylene / propylene copolymers and mixtures of these propylene polymers with other α-olefin polymers. Useful if you do. Further, the present invention can be applied irrespective of the intrinsic viscosity, isotactic pentad fraction, density, molecular weight distribution, melt flow rate, rigidity and the like of these polypropylene resins. JP-A-37148, JP-A-63-37152, JP-A-63-90552, and JP-A-63-210152
JP-A-63-213547 and JP-A-63-243
Nos. 150, 63-243152, 63-
260943, 63-260944, 63-264650, JP-A-1-178541, 2-49047, 2-102242, 2-251548, 2- 279746
And JP-A-3-195751 can also be suitably used.

In the present invention, the method of adding each component is not particularly limited, and a commonly used method, for example, a method of dry-blending a crystalline synthetic resin powder or a pellet with an additive powder, a method of adding each component individually Or a method of preparing a masterbatch containing both at a high concentration and adding this to a crystalline synthetic resin.

The crystalline synthetic resin composition of the present invention can be prepared, for example, by a known method such as extrusion molding, injection molding, vacuum molding, blow molding, foam molding and cross-linking foam molding.
It can be used as various large-sized molded products, fibers, uniaxially or biaxially stretched films, sheets and the like. In addition, the crystalline synthetic resin composition of the present invention may be used for various post-treatments, for example, medical use such as a syringe or food sterilization use such as sterilization by radiation or surface such as paintability. It can also be used for applications such as low-temperature plasma treatment after molding to improve the characteristics.

The crystalline synthetic resin composition of the present invention may further comprise, if necessary, a phenolic antioxidant, an organic phosphorus antioxidant such as organic phosphite or phosphonite,
By adding a light stabilizer such as a thioether-based antioxidant, an ultraviolet absorber or a hindered amine compound, the oxidation stability and the light stability can be further improved.
By using a phenolic antioxidant and / or an organic phosphorus antioxidant in combination, it is possible to prevent coloring during heating and a decrease in mechanical properties.

Examples of the phenolic antioxidants include 2,6-di-tert-butyl-p-cresol and 2,6-di-tert-butyl-p-cresol.
Diphenyl-4-octadecyloxyphenol, stearyl (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, distearyl (3,5-di-tert-butyl-4-hydroxybenzyl) phosphonate, thiodiethylenebis [ (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 4,4'-thiobis (6-tert-butyl-m-cresol), 2-octylthio-4,6-di (3,5- Di-tert-butyl-4-hydroxyphenoxy) -s-triazine, 2,2′-methylenebis (4-methyl-6-tert-butylphenol), bis [3,3-bis (4-hydroxy-3-tert-butyl) Phenyl) butyric acid] glycol ester, 4,
4′-butylidenebis (6-tert-butyl-m-cresol), 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 (3,5-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-di-tert-butyl-4-hydroxyphenyl) ) Propionate] methane, 2-tert-butyl-4-methyl-6- (2-acryloyloxy-3-tert-butyl-5-methylbenzyl)
Phenol, 3,9-bis [1,1-dimethyl-2-hydroxyethyl) -2,4,8,10-tetraoxaspiro [5,5] undecane-bis [β- (3-tert-butyl-4 -Hydroxy-5-methylphenyl) propionate] and triethylene glycol bis [β- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate].

The phenolic antioxidant is preferably added in an amount of 0.005 parts by weight based on 100 parts by weight of the crystalline synthetic resin.
It is 1 to 5 parts by weight, more preferably 0.01 to 3 parts by weight.

Examples of the organophosphorus antioxidants include trisnonylphenyl phosphite, tris (mono and dinonylphenyl) phosphite, tris (2,
4-di-tert-butylphenyl) phosphite, di (tridecyl) pentaerythritol diphosphite, distearylpentaerythritol diphosphite, bis (2
4-di-tert-butylphenyl) pentaerythritol diphosphite, bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, bis (2,4,6-tri-tert-butylphenyl) Pentaerythritol diphosphite, tetra (tridecyl) isopropylidenediphenol diphosphite, tetra (tridecyl) -4,4′-n-butylidenebis (2-tert-butyl-5-methylphenol) diphosphite, hexa (tridecyl)- 1,1,3-tris (3-tert-butyl-4-hydroxy-5-methylphenyl) butanetriphosphite, 2,2′-methylenebis (4,6-di-tert-butylphenyl) octylphosphite, 2, 2'-methylenebis (4,6-di-tert-butylphenyl) octadecylphosphite, 2 2'-methylene bis (4,6
Di-tert-butylphenyl) fluorophosphite, tetrakis (2,4-di-tert-butylphenyl) biphenylenediphosphonite, 9,10-dihydro-9-oxa-10
And phosphaphenanthrene-10-oxide.

The amount of the organic phosphorus antioxidant added is preferably 0.001 to 100 parts by weight of the crystalline synthetic resin.
To 5 parts by weight, more preferably 0.01 to 3 parts by weight.

Examples of the above thioether antioxidants include dialkylthiodipropionates such as dilauryl, dimyristyl, myristylstearyl and distearyl esters of thiodipropionic acid, and pentaerythritol tetra (β-dodecylmercaptopropionate). And β-alkyl mercaptopropionate esters of polyols.

Examples of the ultraviolet absorber include:
2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-
2-hydroxybenzophenones such as octoxybenzophenone and 5,5'-methylenebis (2-hydroxy-4-methoxybenzophenone); 2- (2-hydroxy-5-methylphenyl) benzotriazole,
(2-hydroxy-5-tert-octylphenyl) benzotriazole, 2- (2-hydroxy-3,5-ditert-butylphenyl) -5-chlorobenzotriazole,
-(2-hydroxy-3-tert-butyl-5-methylphenyl) -5-chlorobenzotriazole, 2- (2-hydroxy-3,5-dicumylphenyl) benzotriazole, 2,2'-methylenebis (4 -Third octyl-6
-Benzotriazolyl) phenol, 2- (2-hydroxy-3-tert-butyl-5- (2-octoxycarbonyl) ethyl) benzotriazole, 2- (2-hydroxy-3-tert-butyl-5- 2- (2-hydroxyphenyl) benzotriazoles such as polyethylene glycol ester of (carboxy) ethylphenyl) benzotriazole; phenyl salicylate, resorcinol monobenzoate, 2,4-di-tert-butylphenyl-3,
Benzoates such as 5-di-tert-butyl-4-hydroxybenzoate and hexadecyl-3,5-di-tert-butyl-4-hydroxybenzoate; 2-ethyl-2'-ethoxyoxanilide, 2-ethoxy-4 ' Substituted oxanilides such as dodecyl oxanilide; ethyl-α-cyano-β, β-diphenylacrylate, methyl-2-
And cyanoacrylates such as cyano-3-methyl-3- (p-methoxyphenyl) acrylate.

As the light stabilizer such as the above hindered amine compound, 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, tetrakis (2,2,6,6-tetramethyl-4-piperidyl) -1,2,3,4-butanetetracarboxylate, tetrates (1,2,2) , 6,
6-pentamethyl-4-piperidyl) -1,2,3,4
-Butanetetracarboxylate, bis (1,2,2,
6,6-pentamethyl-4-piperidyl) di (tridecyl) -1,2,3,4-butanetetracarboxylate, 3,9-bis (1,1-dimethyl-2- (tris (2,2, 6,6-tetramethyl-4-piperidyloxycarbonyl) butylcarboxy) ethyl) -2,4
8,10-tetraoxaspiro [5.5] undecane,
3,9-bis (1,1-dimethyl-2- (tris (1,
2,2,6,6-pentamethyl-4-piperidyloxycarbonyl) butylcarboxy) ethyl) -2,4
8,10-tetraoxaspiro [5.5] undecane,
1- (2-hydroxyethyl) -2,2,6,6-tetramethyl-4-piperidinol / diethyl succinate polycondensate, 1,6-bis (2,2,6,6-tetraethyl-
4-piperidylamino) hexane / dibromoethane polycondensate, 1,6-bis (2,2,6,6-tetramethyl-
4-piperidylamino) hexane / 2,4-dichloro-
6-morpholino-s-triazine polycondensate, 1,6-bis (2,2,6,6-tetramethyl-4-piperidylamino) hexane / 2,4-dichloro-6-tert-octylamino-s- Triazine polycondensate, 1,5,8,12-
Tetrakis [2,4-bis (N-butyl-N- (2,
2,6,6-tetramethyl-4-piperidyl) amino)
-S-triazin-6-yl] -1,5,8,12-tetraazadodecane, 1,5,8,12-tetrakis [2,4-bis (N-butyl-N- (1,2,2 , 6,
6-pentamethyl-4-piperidyl) amino) -s-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-triazine-6
Hindered amine compounds such as [ylamino] undecane.

In addition, the crystalline synthetic resin composition of the present invention may contain, if necessary, a nonionic, cationic or anionic antistatic agent, aluminum-p-tert-butylbenzoate, dibenzylidenesorbitol, bis ( 4-
Other nucleating agents such as methylbenzylidene) sorbitol,
Hydrotalcites, alkaline earth metal aliphatic carboxylate salts, pigments, dyes, fillers, foaming agents, flame retardants, lubricants, processing aids, and the like can be added.

[0046]

The present invention will be described in more detail with reference to the following examples. However, the invention is not limited in any way by these examples.

Example 1 The following <combination> compound was mixed for 5 minutes with a mixer,
Pellets were prepared using an extruder at a temperature of 250 ° C. and a rotation speed of 20 rpm. The pellets were molded by an injection molding machine at 250 ° C. and a mold temperature of 60 ° C. to prepare a test piece having a thickness of 1 mm.

The test pieces thus prepared were measured for yellowness using a Hunter colorimeter.
The haze (haze value) was measured according to the method of No. 61. The haze of the test piece after immersion in hot water at 80 ° C. for 36 hours was measured in the same manner. The results are shown in Table 1 below.
Shown in The comparative compounds in the following table are compounds shown in the following [Chemical formula 7].

<Combination> parts by weight ethylene / propylene random copolymer 100 (ethylene content: 3% by weight, MFR: 5.0 g / 10 min) tetrakis [methylene-3- (3,5-di-tert-butylphenyl) Nylpropionate] methane 0.1 Tris (2,4-di-tert-butylphenyl) phosphite 0.1 Sample compound (see [Table 1]) 0.1 Lithium laurate 0.1

[0050]

[Table 1]

[0051]

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Example 2 The following <combination> compound was mixed with a mixer for 5 minutes.
Pellets were prepared using an extruder at a temperature of 230 ° C. and a rotation speed of 20 rpm. The pellets were molded by an injection molding machine at 250 ° C. and a mold temperature of 60 ° C. to prepare a test piece having a thickness of 1 mm. The haze value (haze value) of this test piece was measured in the same manner as in Example 1.

Further, based on ASTM D-256,
The Izod impact strength at 20 ° C. (kg · cm / cm ² ) was measured. The results are shown in Table 2 below.

<Combination> parts by weight crystalline ethylene-propylene random copolymer 100 (ethylene content: 2.5% by weight, MFR: 7.0 g / 10 minutes) 2,6-di-tert-butyl-4- Methylphenol 0.2 Stearyl-β- (3,5-ditert-butyl-4-hydroxyphenyl) propionate 0.1 Hydrotalcite (DHT-4A, manufactured by Kyowa Chemical Co.) 0.05 Cyclic organic phosphate compound ( Compound No. 1 of [Chemical Formula 3] 0.2 Sample compound (see [Table 2]) (See [Table 2])

[0055]

[Table 2]

Example 3 The following mixture was mixed for 5 minutes with a mixer.
Pellets are formed using an extruder under the conditions of a temperature of 240 ° C. and a rotation speed of 20 rpm, and the pellets are formed at 250 ° C. and a mold temperature of 60 ° C. by an injection molding machine using the pellets.
mm test pieces were prepared. Using this test piece, the haze value (haze value) was measured in the same manner as in Example 1.

Similarly, a 3.5 mm-thick test piece was prepared, and this test piece was irradiated with 5 megarads of γ-rays using cobalt 60 as a radiation source. After the irradiation, the sample was heated at 100 ° C. for 10 days.
Izod impact strength at 23 ° C. was measured based on IS K-7110. The results are shown in Table 3 below.

<Combination> Parts by weight Propylene homopolymer (MFR: 6 g / 10 min) 100 bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite 0.05 1,6,11 -Tris [2,4-bis (N-butyl-N- (2,2,6,6-tetramethyl-4-piperidyl) amino) -s-triazin-6-ylamino] undecane 0.1 sample compound ( (See [Table 3]) 0.2 Lithium stearate 0.15

[0059]

[Table 3]

Example 4 Polyethylene terephthalate 100 having an intrinsic viscosity of 0.66
After mixing 0.2 parts by weight of sodium stearate and 0.15 parts by weight of the sample compound with respect to parts by weight, pellets were prepared using a twin-screw extruder. The pellets were put in a differential calorimeter and heated at a rate of 10 ° C./min, and the crystallization temperature during the heating was measured.

After melting at 280 ° C. for 10 minutes,
The crystallization temperature when the temperature was decreased at a rate of ° C./min was measured, and the ratio H / of the height H of the endothermic peak at the time of the temperature decrease to the width W at H / 2 was measured.
W was determined.

As the crystallization temperature at the time of raising the temperature is lower, a molded product having a higher degree of crystallinity can be obtained when molded with a low-temperature mold.
The higher the crystallization temperature at the time of temperature decrease and the larger the H / W, the higher the crystallization speed. The results are shown in Table 4 below.

[0063]

[Table 4]

When the cyclic organic phosphate compound of the component (a) or the alkali metal compound of the component (b) of the present invention is used alone, the transparency, mechanical strength and crystallization of the crystalline synthetic resin are reduced. It is apparent that the speed and the like are hardly improved, and that when these are used alone, no effect as a nucleating agent is exhibited. When an alkali metal compound and an acidic cyclic organic phosphoric acid ester compound (comparative compound) are used in combination, a certain effect is exhibited, but not only is practically insufficient, but also the obtained molded article is colored. There are drawbacks to give.

On the other hand, when the cyclic organic phosphate compound of the component (A) and the alkali metal compound of the component (B) of the present invention are used in combination, the transparency, mechanical strength, crystallization rate, etc. The effect of not only remarkably improving the coloration but also improving the coloration of the molded article is shown, and it is clear that the effect of the present invention is extremely specific.

[0066]

Industrial Applicability The crystalline synthetic resin composition of the present invention has remarkably improved transparency, mechanical strength, crystallization rate and the like, and has excellent coloring properties.

──────────────────────────────────────────────────続 き Continuation of front page (72) Inventor Takashi Takeuchi 5-2-113 Shirahata, Urawa-shi, Saitama Asahi Denka Kogyo Co., Ltd. (56) References JP-A-3-81368 (JP, A) Hei 4-28741 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C08L 1/00-101/16 C08K 3/00-13/08 CA (STN)

Claims (2)

(57) [Claims] (1) 100 parts by weight of a crystalline synthetic resin,
At least one kind of the cyclic organic phosphate compound represented by the following general formula (I) represented by the general formula (I): 0.01 to 5 parts by weight and at least one kind of the alkali metal compound (ii) 0.0
A crystalline synthetic resin composition comprising 1 to 5 parts by weight. Embedded image 2. The crystalline synthetic resin composition according to claim 1, wherein the alkali metal compound is an alkali metal carboxylate.