JPH05140466A - Crystalline synthetic resin composition - Google Patents

Abstract

PURPOSE:To obtain the subject composition improved in transparency and mechanical strength by mixing a crystalline synthetic resin with a specified organic alkali metal compound and a specified metal salt of a cyclic organophosphate each in a specified amount. CONSTITUTION:100 pts.wt. crystalline synthetic resin (e.g. crystalline ethylene/ propylene random copolymer) is mixed with 0.01-5 pts.wt. of at least one of an alkali metal carboxylate (e.g. sodium stearate), an alkali metal beta-diketonate and an alkali metal salt a beta-ketoacetic ester, and 0.01-5 pts.wt. of at least one metal salt of a cyclic organophosphoric ester of formula I (wherein R1 is H or 1-4C alkyl; R2 and R3 are each H or 1-12C alkyl; M is a group II or III metal atom; (a) is the valence of M (e.g. a compound of formula II) to give the objective composition. The obtained composition is suitably used for the manufacture of various moldings, fibers, sheets, etc.

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, more specifically, a synthetic resin containing an alkali metal compound and a cyclic organophosphate polyvalent metal salt.
The present invention relates to a crystalline synthetic resin composition having improved transparency and mechanical properties.

[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 slow crystallization rate after heat-melt molding. Therefore, the molding cycle property is low, and there is a defect that shrinkage occurs due to progress of crystallization after heat molding. Further, these crystalline synthetic resins have drawbacks such as insufficient strength and poor transparency because large crystals are formed.

All of these drawbacks are derived from the crystallinity of the synthetic resin, and it is known that they can be eliminated if the crystallization temperature of the synthetic resin can be raised and fine crystals can be rapidly produced. There is.

It is known to add a crystal nucleating agent or a crystallization accelerator for the purpose of solving the above-mentioned drawbacks, and conventionally, aluminum 4-tert-butylbenzoate, sodium adipate, etc. Carboxylic acid metal salt, sodium bis (4-tert-butylphenyl) phosphate, sodium-2,2′-methylenebis (4,6-di-tert-butylphenyl) phosphate and other acidic phosphoric acid ester metal salts, dibenzylidene sorbitol, Screw (4
A polyhydric alcohol derivative such as -methylbenzylidene) sorbitol has been used.

Among these compounds, JP-A-58-1
The metal salts of cyclic phosphoric acid esters of alkylidene bisphenols described in JP-A No. 736, JP-A-59-184252 and the like have a great effect and are widely used.

Attempts have been made to improve the effect by using these compounds in combination with other metal compounds. For example, JP-A-63-6985.
No. 3, in order to prevent a decrease in rigidity when an aromatic alkali metal phosphate-based nucleating agent and an alkaline earth metal carboxylate such as calcium stearate are used in combination,
A method using hydrotalcite or an alkali metal carboxylate instead of the alkaline earth metal carboxylate has been proposed, and JP-A-1-129050 and JP-A-1-129051 disclose a cyclic organophosphate metal. A method in which a salt and a metal salt of Group 2 of the periodic table of an aliphatic carboxylic acid are used in combination is proposed, and in JP-A-3-79649 and JP-A-3-81368, an acidic organic phosphate compound and an aliphatic carboxylic acid are disclosed. A method in which a metal salt is used in combination is proposed, and in JP-A-3-43437, when a cyclic organic phosphate metal salt is used, in order to prevent a decrease in pH in hot water immersion after irradiation with radiation. In addition, it is proposed to use a hydroxide of an alkali metal, an alkaline earth metal or an aluminum group metal together.

However, the improvement effect of these combinations is still unsatisfactory in practical use, and further improvement has been demanded particularly from the viewpoint of improving the transparency of the crystalline synthetic resin.

[0008]

Means for Solving the Problems The inventors of the present invention have made various studies in view of the present situation, and as a result, have found that a crystalline synthetic resin is
By adding an alkali metal carboxylate, an alkali metal β-diketonate or an alkali metal β-keto acetic acid ester salt, and a cyclic organic phosphoric acid ester metal salt, the transparency of the resin is significantly improved and the mechanical strength is improved. The present invention has been achieved by finding that it also increases.

That is, the present invention is based on 100 parts by weight of the crystalline synthetic resin, and at least one selected from the group consisting of (a) an alkali metal carboxylate, an alkali metal β-diketonate and an alkali metal β-keto acetic acid ester salt. 0.01
To 5 parts by weight and (b) 0.01 to 5 parts by weight of at least one metal salt of a cyclic organic phosphoric acid ester represented by the general formula (I) of the following chemical formula 2 (same as chemical formula 1). The present invention provides a crystalline synthetic resin composition.

[0010]

[Chemical 2] (In the formula, R ₁ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R ₂ and R ₃ each represent a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, and M represents a periodic table element. Represents a group II or group III metal atom, and a represents the valence of the metal represented by M.)

The crystalline synthetic resin composition of the present invention will be described in detail below.

The alkali metal carboxylate, which is the component (a) of the crystalline synthetic resin composition of the present invention, and the alkali metal β-
Examples of the alkali metal constituting the diketonate or the alkali metal β-ketoacetic acid ester salt 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, stearic acid. , Oleic acid, ricinoleic acid, 12-hydroxystearic acid, behenic acid, montanic acid, melissic acid, β-dodecylmercaptoacetic acid, β-dodecylmercaptopropionic acid, β-N-laurylaminopropionic acid, β-N-methyl- Aliphatic monocarboxylic acids such as N-lauroylaminopropionic acid; malonic acid, succinic acid,
Adipic acid, maleic acid, azelaic acid, sebacic acid,
Aliphatic polycarboxylic acids such as dodecanedioic acid, citric acid, butanetricarboxylic acid, butanetetracarboxylic acid; naphthenic acid, cyclopentanecarboxylic acid, 1-methylcyclopentanecarboxylic acid, 2-methylcyclopentanecarboxylic acid, cyclopentenecarboxylic acid , Cyclohexanecarboxylic acid, 1-methylcyclohexanecarboxylic acid, 4-methylcyclohexanecarboxylic acid, 3,5-dimethylcyclohexanecarboxylic acid, 4-butylcyclohexanecarboxylic acid, 4-octylcyclohexanecarboxylic acid, cyclohexenecarboxylic acid, 4-cyclohexene- 1,2-
Alicyclic mono- or polycarboxylic acids such as dicarboxylic acids;
Benzoic acid, toluic acid, xylyl acid, ethylbenzoic acid,
Examples thereof include aromatic mono- or polycarboxylic acids such as 4-tert-butylbenzoic acid, salicylic acid, phthalic acid, trimellitic acid, and pyromellitic acid.

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

Examples of the β-ketoacetic acid ester constituting the alkali metal β-ketoacetic acid ester salt include, for example, ethyl acetoacetate, octyl acetoacetate, lauryl acetoacetate, stearyl acetoacetate, ethyl benzoylacetate, lauryl benzoylacetate. Etc.

The alkali metal carboxylate, the alkali metal β-diketonate or the alkali metal β-ketoacetic acid ester salt as the component (a) is the alkali metal and carboxylic acid, the β-diketone compound or the β-ketoacetic acid ester, respectively. It is a salt of and can be produced by a conventionally known method. Further, among the respective compounds of the component (a), an aliphatic monocarboxylic acid salt of an alkali metal, particularly an aliphatic carboxylic acid salt of lithium is preferable, and an aliphatic monocarboxylic acid salt having 8 to 20 carbon atoms is particularly preferable. preferable.

The amount of the alkali metal carboxylate, the alkali metal β-diketonate or the alkali metal β-ketoacetic ester salt as the component (a) added is 0.01 to 5 relative to 100 parts by weight of the crystalline synthetic resin. Parts by weight, particularly preferably 0.05 to 3 parts by weight.

Further, the crystalline synthetic resin composition of the present invention
In the cyclic organophosphate metal salt represented by the above general formula (I) which is the component (b), the alkyl group having 1 to 4 carbon atoms represented by R ₁ is methyl, ethyl, propyl, isopropyl, Butyl, sec-butyl, isobutyl, etc., and has 1 to 1 carbon atoms represented by R ₂ or R _3.
Examples of the alkyl group of 2 include methyl, ethyl, propyl,
Isopropyl, butyl, secondary butyl, tertiary butyl, amyl, tertiary amyl, hexyl, heptyl, octyl, isooctyl, tertiary octyl, 2-ethylhexyl, nonyl, isononyl, decyl, isodecyl, undecyl, dodecyl, tertiary dodecyl, etc. Can be given.

The metal atom of Group II or Group III of the periodic table represented by M includes calcium, magnesium, strontium, barium, zinc and aluminum.

Therefore, the cyclic organic phosphoric acid ester metal salt represented by the general formula (I) is, for example,
~ The compounds shown in Chemical formula 8 (Compound No. 1 to No. 6) can be mentioned.

[0021]

[Chemical 3]

[0022]

[Chemical 4]

[0023]

[Chemical 5]

[0024]

[Chemical 6]

[0025]

[Chemical 7]

[0026]

[Chemical 8]

The above-mentioned cyclic organic phosphoric acid ester metal salt is a known compound, and a known method, for example, after reacting phosphorus oxychloride with 2,2'-alkylidene bisphenol, a polyvalent metal [the above-mentioned general formula In (I), a metal represented by M] is reacted with an oxide or hydroxide, or
It can be easily produced by reacting with an alkali metal salt and then reacting it with a halide of the above polyvalent metal.

The particle size of the cyclic organophosphate ester metal salt is not particularly limited, and for example, those having an average particle size of 0.01 to 50 μm can be used, but uniform dispersion is possible. In order to achieve this, it is preferable to grind the particles into fine particles having an average particle size of 10 microns or less, particularly 3 microns or less before use.

The amount of the cyclic organophosphate metal salt added is 0.01 with respect to 100 parts by weight of the crystalline synthetic resin.
To 5 parts by weight, preferably 0.03 to 3 parts by weight.

The ratio of the alkali metal salt compound of the component (a) to the cyclic organophosphate polyvalent metal salt of the component (b) is not particularly limited. The effect of the present invention is remarkable when the addition amount of the metal salt compound is equal to or more than the addition amount of the cyclic organophosphate polyvalent metal salt of the component (b).

The additive components such as the component (a) and the component (b) used in the present invention are surface-treated with various dispersants such as higher fatty acids in order to improve their dispersibility. What you have done is fine.

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

In particular, the 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. It is useful when you do. The present invention can be applied regardless of the intrinsic viscosity, isotactic pentad fraction, density, molecular weight distribution, melt flow rate, rigidity, etc. of these polypropylene resins. 37148, 63-37152, 63-90552, 63-210152.
No. 63-213547 and No. 63-243.
No. 150, No. 63-243152, No. 63-
No. 260943, No. 63-260944, No. 63-264650, No. 1-178541, No. 2-49047, No. 2-102242, No. 2-251548, No. 2-. 279746
It can also be suitably used for polypropylene-based resins such as those described in JP-A No. 3-1957571 and the like.

In the crystalline synthetic resin composition of the present invention,
The method of adding each component is not particularly limited, a commonly used method, for example, a method of dry blending a crystalline synthetic resin powder or pellets with an additive powder, a masterbatch containing each component in a high concentration It is possible to use a method in which it is prepared and added to a crystalline synthetic resin. Further, the crystalline synthetic resin composition of the present invention is used as various molded products, fibers, biaxially stretched films, sheets, etc. by known processing methods such as extrusion molding, injection molding, vacuum molding, blow molding, and cross-linking foam molding. Can be used.

The crystalline synthetic resin composition of the present invention also comprises
Applications that undergo various post-treatments, for example, applications that undergo sterilization by radiation such as medical applications or food packaging applications, or to improve surface properties such as paintability, after molding,
It can also be used for applications such as low temperature plasma treatment.

In the crystalline synthetic resin composition of the present invention, if necessary, a phenolic antioxidant, an organic phosphorus antioxidant such as organic phosphite or phosphonite,
A light stabilizer such as a thioether-based antioxidant, an ultraviolet absorber or a hindered amine compound can be added to further improve the oxidative stability and the light stability thereof.
By using a phenol-based antioxidant and / or an organic phosphorus-based antioxidant in combination, it is possible to prevent coloration during heating and deterioration of mechanical properties.

Examples of the above-mentioned phenolic antioxidants include 2,6-di-tert-butyl-p-cresol and 2,6-
Diphenyl-4-octadecyloxyphenol, stearyl (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, distearyl (3,5-di-tert-butyl-4-hydroxybenzyl) phosphonate, thiodiethylenebis [ (3,5-Ditert-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'-butylidene bis (6-tert-butyl-m-cresol), 2,2'-ethylidene bis (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, 1,3,3 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) bropionyloxyethyl] 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-butylphenyl) propionate], triethylene glycol bis [β- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate] and the like.

The amount of the phenolic antioxidant added is preferably 0.00 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 above-mentioned organic phosphorus antioxidant which can be used in the present invention include trisnonylphenyl phosphite, tris (mono and dinonylphenyl) phosphite, tris (2,4-ditertiary butylphenyl) phosphite. Fight, di (tridecyl) pentaerythritol diphosphite, distearyl pentaerythritol diphosphite, bis (2,4-ditert-butylphenyl) pentaerythritol diphosphite, bis (2,6-ditert-butyl-4) -Methylphenyl) pentaerythritol diphosphite, bis (2,4,6-tri-tert-butylphenyl) pentaerythritol diphosphite, tetra (tridecyl) isopropylidene diphenol diphosphite, tetra (tridecyl) -4,4 '-N-butylidene bis (2-tertiary butyl Lu-5-methylphenol) diphosphite, hexa (tridecyl) -1,1,3-tris (3-tert-butyl-4-hydroxy-5-methylphenyl) butanetriphosphite, 2,2'-methylenebis (4,4) 6-di-tert-butylphenyl) octylphosphite, 2,2'-methylenebis (4,6-di-tert-butylphenyl) octadecylphosphite, 2,2'-methylenebis (4,6-di-tert-butylphenyl) Examples thereof include fluorophosphite, tetrakis (2,4-ditert-butylphenyl) biphenylene diphosphonite, and 9,10-dihydro-9-oxa-10phosphaphenanthrene-10-oxide.

The amount of the above organic phosphorus antioxidant added is preferably 0.001 with respect 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 thioether antioxidant include dialkylthiodipropionates such as dilauryl, dimyristyl, myristyl stearyl, and distearyl esters of thiodipropionic acid, and pentaerythritol tetra (β-dodecyl mercaptopropionate). And β-alkylmercaptopropionic acid esters of polyols.

As the above-mentioned ultraviolet absorber, for example,
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-
(2-hydroxy-5-tert-octylphenyl) benzotriazole, 2- (2-hydroxy-3,5-di-tert-butylphenyl) -5-chlorobenzotriazole, 2
-(2-Hydroxy-3-tert-butyl-5-methylphenyl) -5-chlorobenzotriazole, 2- (2-hydroxy-3,5-dicumylphenyl) benzotriazole, 2,2'-methylenebis (4 -Third Octyl-6
-Benzotriazolyl) phenol, 2- (2-hydroxyphenyl) benzotriazoles such as polyethylene glycol ester of 2- (2-hydroxy-3-tert-butyl-5-carboxyphenyl) benzotriazole; phenyl salicylate, resorcinol Benzoates such as monobenzoate, 2,4-di-tert-butylphenyl-3,5-di-tert-butyl-4-hydroxybenzoate and hexadecyl-3,5-di-tert-butyl-4-hydroxybenzoate; 2-ethyl Substituted oxanilides such as -2'-ethoxyoxanilide and 2-ethoxy-4'-dodecyloxanilide; ethyl-α-cyano-
Examples include cyanoacrylates such as β, β-diphenyl acrylate and methyl-2-cyano-3-methyl-3- (p-methoxyphenyl) acrylate.

Examples of the light stabilizer such as the hindered amine compound include 2,2,6,6-tetramethyl-4-piperidyl stearate, 1,2,2,6,6- and the like.
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, tetrakis (2,2
2,6,6-Tetramethyl-4-piperidyl) butane tetracarboxylate, tetrates (1,2,2,6)
6-pentamethyl-4-piperidyl) butanetetracarboxylate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) di (tridecyl) -1,2,
3,4-butane tetracarboxylate, bis (1,
2,2,6,6-pentamethyl-4-piperidyl) -2
-Butyl-2- (3,5-di-tert-butyl-4-hydroxybenzyl) malonate, 1- (2-hydroxyethyl) -2,2,6,6-tetramethyl-4-piperidinol / diethyl succinate Condensate, 1,6-bis (2,
2,6,6-Tetraethyl-4-piperidylamino) hexane / dibromoethane polycondensate, 1,6-bis (2,2
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)
Examples thereof include hindered amine compounds such as -s-triazin-6-ylamino] undecane.

In addition, in the crystalline synthetic resin composition of the present invention, if necessary, a nonionic, cationic or anionic antistatic agent, aluminum-p-tertiary butyl benzoate, dibenzylidene sorbitol, bis ( 4-
Other nucleating agents, such as methylbenzylidene) sorbitol,
Hydrotalcites, aliphatic carboxylic acid salts of alkaline earth metals, pigments, dyes, fillers, foaming agents, flame retardants, lubricants, processing aids and the like can be added.

[0045]

EXAMPLES The crystalline synthetic resin composition of the present invention will be described in more detail below with reference to examples. However, the invention is in no way limited by these examples.

Example 1 The following compounding composition was mixed with a mixer for 5 minutes, and the temperature was 230 ° C. and the rotation speed was 20 rp.
Pellets were made using an extruder under m 2 conditions. 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 according to the method of ASTM D-1003-61. Further, the haze value (haze value) was similarly measured for the test piece after being immersed in hot water of 80 ° C. for 36 hours. The results are shown in Table 1 below. The comparative compounds shown in Table 1 below are the compounds shown in Chemical Formula 9 below.

<Compound> 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-butylphene) 0.1 Nylpropionate] methane Tris (2,4-ditertiarybutylphenyl) phosphite 0.1 Sample compound (see Table 1) 0.2 Lithium laurate 0.1

[0048]

[Chemical 9]

[0049]

[Table 1]

Example 2 The following composition of <Compound> was mixed in a mixer for 5 minutes, and then the temperature was 230 ° C. and the rotation speed was 20 rp.
Pellets were made using an extruder under m 2 conditions. 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,
Izod impact strength at 20 ° C (kg · cm / cm ² , Table 2
Some of them are simply referred to as "impact strength"). The results are shown in Table 2 below.

<Compound> Parts by Weight Crystalline Ethylene-Propylene Random Copolymer 100 (Ethylene Content: 2.5% by Weight, MFR: 7.0 g / 10 min) 2,6-Ditertiarybutyl-4- Methylphenol 0.2 Stearyl-β- (3,5-di-tert-butyl-4-0.1 hydroxyphenyl) propionate Hydrotalcite (Kyowa Kagaku: DHT-4A) 0.05 Cyclic organic phosphate ester metal salt [Compound No. 1 (Chemical Formula 3)] 0.3 Sample compound (see Table 2) (see Table 2)

[0053]

[Table 2] * 1: [However, the comparative compound (Chemical Formula 9) was used in place of Compound No. 1] * 2: (However, Compound No. 1 was not added)

Example 3 The following compounding composition was mixed with a mixer for 5 minutes, and then the temperature was 240 ° C. and the rotation speed was 20 rp.
Pellets were prepared using an extruder under m 2 conditions, and 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. Using this test piece, the same operation as in Example 1 was performed to measure the haze (haze value).
Was measured.

Similarly, a test piece having a thickness of 3.5 mm was prepared, and the test piece was irradiated with 5 megarads of γ-rays using cobalt 60 as a radiation source. Based on JIS K-7110, the test piece which was heated at 100 ° C. for 10 days after γ-ray irradiation and heated for 10 days after this γ-ray irradiation was measured according to JIS K-7110.
The Izod impact strength at 3 ° C was measured. The results are shown in Table 3 below.

<Composition> Parts by Weight Propylene Homopolymer (MFR: 6 g / 10 min) 100 Bis (2,6-di-tert-butyl-4-methylphenyl) 0.05 Pentaerythritol Diphosphite 1,6,11 -Tris [2,4-bis (N-butyl-N-0.1 (2,2,6,6-tetramethyl-4-piperidyl) amino) -s-triazin-6-ylamino] undecane Sample compound ( (See Table 3) 0.3 Lithium stearate 0.2

[0057]

[Table 3]

Example 4 To 100 parts by weight of polyethylene terephthalate having an intrinsic viscosity of 0.66, 0.2 parts by weight of sodium stearate and 0.2 parts by weight of a sample compound (see Table 4) were mixed, and Pellets were made using a screw extruder. Put this pellet in the differential calorimeter,
The temperature was raised at 10 ° C./min, and the crystallization temperature at the time of temperature rise was measured.

After melting at 280 ° C. for 10 minutes, 5
The crystallization temperature when the temperature was lowered at ° C / min was measured, and the ratio of the height H of the endothermic peak when the temperature was lowered to the width W at H / 2 was H /
I asked for W.

The lower the crystallization temperature at the time of temperature rise, the higher the degree of crystallinity obtained when molding with a low temperature mold, and
It is shown that the higher the H / W is, the higher the crystallization temperature is, and the higher the crystallization rate is. The results are shown in Table 4 below.

[0061]

[Table 4]

From the results shown in Tables 1 to 4, the following can be seen. That is, when an alkali metal compound or a cyclic organic phosphoric acid ester metal salt is used alone, the mechanical strength and crystallization rate of the crystalline synthetic resin are improved to some extent, but the effect is practically satisfactory. It is not possible, and the effect of improving transparency is insufficient. In addition, when the alkaline earth metal carboxylate or alkali metal hydroxide and the cyclic organic phosphate ester metal salt are used together, or when the alkali metal carboxylate and the alkali metal salt of cyclic organic phosphate ester are used together. The improvement effect is insufficient.

On the other hand, when the alkali metal carboxylate, the alkali metal β-diketonate or the alkali metal β-keto acetic acid ester salt according to the present invention and the cyclic organic phosphate polyvalent metal salt are used in combination, the crystalline property is obtained. Not only the mechanical strength of the synthetic resin is further improved, but also the transparency, which has been insufficient in the past, is greatly improved, and it is clear that the effect of the present invention is extremely specific.

[0064]

EFFECT OF THE INVENTION The crystalline synthetic resin composition of the present invention has greatly improved transparency and physical properties such as mechanical strength.

Claims (1)

[Claims] 1. To 100 parts by weight of a crystalline synthetic resin, 0.01 to at least one selected from the group consisting of (a) an alkali metal carboxylate, an alkali metal β-diketonate and an alkali metal β-ketoacetic acid ester salt. 5 parts by weight and (b) 0.01 to 5 parts by weight of at least one kind of the cyclic organic phosphoric acid ester metal salt represented by the general formula (I) of the following chemical formula 1 is blended, and a crystalline synthetic resin composition .. [Chemical 1] (In the formula, R ₁ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R ₂ and R ₃ each represent a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, and M represents a periodic table element. Represents a group II or group III metal atom, and a represents the valence of the metal represented by M.)