JP3313836B2 - 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 crystalline synthetic resin obtained by blending an alkali metal compound and a basic organic aluminum salt of a cyclic organic phosphate, with transparency and mechanical properties. And other improved crystalline synthetic resin compositions.

[0002]

2. Description of the Related Art Crystalline synthetic resins such as polyethylene, polypropylene, polybutene-1, polyethylene terephthalate, polybutylene terephthalate, polyphenylene sulfide, polyamide, and polystyrene have crystallization rates after heat-melt molding. , 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. Was.

[0004] For this purpose, it is known to add a nucleating agent or a crystallization accelerator. Conventionally, aluminum tertiary butyl benzoate has been used as the nucleating agent or the crystallization accelerator. Metal salts of carboxylic acids such as sodium and sodium adipate; and acid phosphate metals such as sodium bis (4-tert-butylphenyl) phosphate and sodium-2,2'-methylenebis (4,6-di-tert-butylphenyl) phosphate Polyhydric alcohol derivatives such as salts, dibenzylidene sorbitol and bis (4-methylbenzylidene) sorbitol have been used. Among these compounds, Japanese Patent Application Laid-Open Nos.
The metal salt of a cyclic phosphoric acid ester of alkylidene bisphenols described in JP-A-9-184252 and the like has a large effect and is widely used, but has a problem in other transparency and the like.

Attempts have also been made to improve the effect by using these compounds in combination with other metal compounds.
The publication discloses an alkaline earth metal carboxylate in order to prevent a decrease in rigidity when an alkali earth metal carboxylate such as calcium stearate is used in combination with an aromatic phosphate alkali metal nucleating agent. A method using a hydrotalcite or an alkali metal carboxylate instead has been proposed, and is disclosed in JP-A-1-129050 and JP-A-1-129050.
Japanese Patent No. 129051 proposes a method in which a cyclic organic phosphate metal salt and a metal salt of a Group 2 metal of the aliphatic carboxylic acid are used in combination, and JP-A-3-79649 and JP-A-3-81368 disclose a method. A method in which an acidic organic phosphoric acid ester compound and a metal salt of an aliphatic carboxylic acid are used in combination has been proposed. Japanese Unexamined Patent Publication (Kokai) No. 3-43437 discloses that when a metal salt of a cyclic organic phosphoric acid ester is used, heat after irradiation is irradiated. It has been 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 during immersion in water.

[0006] However, the improvement effect of these combinations is not yet practically satisfactory, and further improvement has been demanded particularly from the viewpoint of improving the transparency of the crystalline synthetic resin.

Further, Japanese Patent Application Laid-Open No. 1-104638, Japanese Patent Application Laid-Open No. 1-104639, and Japanese Patent Application Laid-Open No.
No. 7 proposes to use a basic aluminum salt of an aromatic phosphoric diester in order to improve the processability and heat resistance of a high-rigidity propylene-based resin,
When such a compound is used, the effect of improving the transparency is scarcely recognized, and it has been considered that such a basic aluminum salt compound is poor in the effect of improving the transparency of the crystalline synthetic resin.

Accordingly, an object of the present invention is to provide a crystalline synthetic resin composition having improved transparency, mechanical properties, and the like.

[0009]

As a result of various studies, the present inventors have found that a specific amount of an alkali metal carboxylate, an alkali metal β-diketonate or an alkali metal β-ketoacetate is added to a crystalline synthetic resin. It has been found that the above object can be achieved by adding a specific amount of a basic aluminum salt of a cyclic organic phosphate.

[0010] The present invention has been made based on the above-mentioned findings, and 100% by weight of the crystalline synthetic resin contains at least (a) an alkali metal carboxylate, an alkali metal β-diketonate or an alkali metal β-ketoacetate. 0.01 to 5 parts by weight of one kind and (b) at least one kind of a basic organic aluminum salt of a cyclic organic phosphate ester represented by the following general formula (I) of the following [Chemical formula 2] (same as the above [Chemical formula 1]). 0
The present invention provides a crystalline synthetic resin composition containing 1 to 5 parts by weight.

[0011]

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Hereinafter, the crystalline synthetic resin composition of the present invention will be described in detail. Examples of the alkali metal constituting the alkali metal carboxylate, the alkali metal β-diketonate or the alkali metal β-ketoacetate used as the component (a) in the present invention 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 stearic acid. Oleic acid, ricinoleic acid, 12-hydroxystearic acid, behenic acid, montanic acid, melicic acid, β-dodecylmercaptoacetic acid, β-dodecylmercaptopropionic acid, β-N-laurylaminopropionic acid, β-N-methyl- Aliphatic monocarboxylic acids such as N-lauroylaminopropionic acid; aliphatics such as malonic acid, succinic acid, adipic acid, maleic acid, azelaic acid, sebacic acid, dodecanediic acid, citric acid, butanetricarboxylic acid, butanetetracarboxylic acid Polyvalent carboxylic acid; naphthenic acid, cyclopentane Bonic acid, 1-methylcyclopentanecarboxylic acid, 2-methylcyclopentanecarboxylic acid, cyclopentenecarboxylic acid, cyclohexanecarboxylic acid, 1-methylcyclohexanecarboxylic acid, 4-methylcyclohexanecarboxylic acid, 3,5-dimethylcyclohexanecarboxylic acid, Alicyclic mono- or polycarboxylic acids such as 4-butylcyclohexanecarboxylic acid, 4-octylcyclohexanecarboxylic acid, cyclohexenecarboxylic acid, 4-cyclohexene-1,2-dicarboxylic acid; benzoic acid, toluic acid, xylic acid, ethylbenzoic acid And aromatic mono- or polycarboxylic acids such as acid, 4-tert-butylbenzoic acid, salicylic acid, phthalic acid, trimellitic acid, and pyromellitic acid.

The β-diketone constituting the alkali metal β-diketonate includes, for example, acetylacetone, pivaloylacetone, palmitoylacetone, and the like.
Benzoylacetone, pivaloylbenzoylacetone,
Dibenzoylmethane and the like.

The β-ketoacetate constituting the alkali metal β-ketoacetate is, for example, ethyl acetoacetate, octyl acetoacetate, lauryl acetoacetate, stearyl acetoacetate, ethyl benzoylacetate, lauryl benzoylacetate. And the like.

The alkali metal carboxylate, the alkali metal β-diketonate or the alkali metal β-ketoacetate used as the component (a) in the present invention is composed of the above alkali metal and the above carboxylic acid, β-diketone compound or β-diketone compound. It is a salt with ketoacetic ester and can be produced by a conventionally well-known method. Among the alkali metal carboxylate, alkali metal β-diketonate or alkali metal β-ketoacetate of component (a), an alkali metal aliphatic monocarboxylate is preferable, and the alkali metal aliphatic monocarboxylate is preferable. Lithium is particularly preferred as the alkali metal constituting the carboxylate, and aliphatic monocarboxylate constituting the aliphatic monocarboxylate of the alkali metal is particularly preferably an aliphatic monocarboxylic acid having 8 to 20 carbon atoms. Monocarboxylates are preferred.

The alkali metal carboxylate, alkali metal β-diketonate or alkali metal β of the above component (a)
The amount of ketoacetic acid ester salt added is
It is 0.01 to 5 parts by weight, preferably 0.05 to 3 parts by weight, based on 0 parts by weight.

In the basic aluminum salt compound of the cyclic organic phosphate ester represented by the general formula (I) of the above-mentioned [Chemical Formula 2] of the component (b) used in the present invention, the compound having 1 to 1 carbon atoms represented by R ₁ Examples of the alkyl group of 4 include methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, and isobutyl. 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, tert-octyl, 2-ethylhexyl, nonyl, isononyl, decyl, isodecyl, undecyl, dodecyl, And tridodecyl.

Accordingly, the compounds represented by the above general formula (I) used in the present invention include, for example, compounds No. 1 to No. 3 shown in the following [Chemical Formula 3] to [Chemical Formula 5]. .

[0020]

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[0021]

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[0022]

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The basic aluminum salt of the cyclic organic phosphoric acid ester as the component (b) is, for example, a reaction between an alkali metal salt of an acidic cyclic organic phosphoric acid ester and an aluminum halide or (aqueous) aluminum oxide halide. It can be easily produced by a method of hydrolysis as required, or a method of reacting an acidic cyclic organic phosphate with aluminum alkoxide and then hydrolyzing as necessary.

In the crystalline synthetic resin composition of the present invention, the cyclic organic phosphate ester basic aluminum salt of the component (b) is further added to the following general formula (II):
Can be used in combination. The compound represented by the general formula (II) is obtained by the same method as that of the compound of the general formula (I) of the above [Chemical Formula 2], and as a mixture with the compound of the general formula (I). It can also be obtained.

[0025]

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As a specific example of the cyclic organic phosphate basic aluminum salt represented by the general formula (II) of the above [Chemical Formula 6], a compound No. 1 'of the following [Chemical Formula 7] can be preferably mentioned. .

[0027]

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The shape of the component (b) is not particularly limited. For example, when the component (b) is used in the form of particles, an average particle size of 0.01 to 50 microns can be used. In order to achieve this, it is preferable to use the fine particles having an average particle diameter of 10 μm or less, particularly 3 μm or less.

The amount of the component (b) is 0.01 to 5 parts by weight based on 100 parts by weight of the crystalline synthetic resin.
Preferably it is 0.03 to 3 parts by weight.

The ratio of the alkali metal salt compound of the above component (a) to the basic organic aluminum salt of the cyclic organic phosphate of the above component (b) is not particularly limited.
The effect of the present invention is remarkable when the addition amount of the alkali metal salt compound as the component (a) is equal to or more than the addition amount of the basic organic aluminum salt of the cyclic organic phosphate as the component (b).

The crystalline synthetic resin used in the present invention includes, for example, low-density polyethylene, linear low-density polyethylene, high-density polyethylene, polypropylene, polybutene-1, poly-3-methylbutene, ethylene / propylene block or random. Α-olefin polymers such as copolymers; thermoplastic linear polyesters such as polyethylene terephthalate, polybutylene terephthalate and polyhexamethylene terephthalate; linear polyamides such as polyphenylene sulfide and polycaprolactone; polyhexamethylene adipamide; polystyrene; Poly (alkylalkylene), poly (halogenated styrene), poly (alkoxystyrene), poly (vinyl benzoate), and polystyrene polymers such as copolymers thereof can be used. Is on the occasion can be used alone or in mixture.

Among the above-mentioned crystalline synthetic resins, crystalline α-olefin polymers, especially polypropylene, such as polypropylene, ethylene / propylene copolymers and mixtures of these propylene polymers with other α-olefin polymers, etc. A system resin is preferably used. In the present invention,
The intrinsic viscosity of the polypropylene resin, isotactic pentad fraction, density, molecular weight distribution, melt flow rate, rigidity and the like are not particularly limited, for example,
JP-A-63-37148, JP-A-63-3715
No. 2, JP-A-63-90552, JP-A-63-90552
JP-A-210152, JP-A-63-213547, JP-A-63-243150, JP-A-63-2
43152, JP-A-63-260943,
JP-A-63-260944, JP-A-63-264
650, JP-A-1-178541, JP-A-2-49047, JP-A-2-102242, JP-A-2-251548, JP-A-2-279
No. 746, JP-A-3-195751, and the like can also be suitably used.

In the present invention, the method of blending the component (a) and the component (b) with the crystalline synthetic resin composition is not particularly limited, and a generally used method, for example, a method of mixing a crystalline synthetic resin powder or a pellet with: A method of dry blending each component powder, a method of preparing a master batch containing each component at a high concentration, and adding this to a crystalline synthetic resin can be used. In addition, the crystalline synthetic resin composition of the present invention can be formed into various molded products, fibers, biaxially stretched films, sheets, and the like by well-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 is used for various post-treatments, for example, sterilization by radiation such as medical use or food packaging, or surface properties such as paintability. It can be used for applications in which low-temperature plasma treatment or the like is performed after molding to improve the quality.

Further, the crystalline synthetic resin composition of the present invention comprises
If necessary, a phenolic antioxidant, an organic phosphorus-based antioxidant such as organic phosphite or phosphonite, a thioether-based antioxidant, a UV absorber or a light stabilizer such as a hindered amine compound may be added to increase the crystallinity. Oxidation stability and light stability of the synthetic resin composition can be further improved. In particular, by using a phenolic antioxidant and / or an organic phosphorus antioxidant in combination, coloring during heat processing and mechanical It is possible to prevent a decrease in physical 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-butylphenyl) propionate] and triethylene glycol bis [β- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate].

The amount of the phenolic antioxidant to be added is 0.001 to 5 parts by weight, preferably 0.01 to 3 parts by weight, based on 100 parts by weight of the crystalline synthetic resin.

Examples of the above-mentioned organic phosphorus antioxidants include trisnonylphenyl phosphite, tris (mono and dinonylphenyl) phosphite, and 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) penta Erythritol diphosphite, tetra (tridecyl) isopropylidene diphenol diphosphite, tetra (tridecyl) -4,4′-n-butylidenebis (2-tert-butyl-5-methylphenol) diphosphite, hexa (tridecyl) -1 1,1,3-tris (3-tert-butyl-4-hydroxy-5-methylphenyl) butanetriphosphite, 2,2′-methylenebis (4,6-di-tert-butylphenyl) octyl phosphite, 2,2 '-Methylenebis (4,6-di-tert-butylphenyl) octadecylphosphite, 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 to be added is 0.001 to 5 parts by weight, preferably 0.01 to 3 parts by weight, based on 100 parts by weight of the crystalline synthetic resin.

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

Examples of the ultraviolet absorber include, for example, 2,
4-dihydroxybenzophenone, 2-hydroxy-4
-Methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 5,5'-methylenebis (2-
2-hydroxybenzophenones such as hydroxy-4-methoxybenzophenone); 2- (2-hydroxy-5)
-Methylphenyl) benzotriazole, 2- (2-hydroxy-5-tert-octylphenyl) benzotriazole, 2- (2-hydroxy-3,5-ditert-butylphenyl) -5-chlorobenzotriazole, 2- (2-
Hydroxy-3-tert-butyl-5-methylphenyl)-
5-chlorobenzotriazole, 2- (2-hydroxy-3,5-dicumylphenyl) benzotriazole,
2,2′-methylenebis (4-tert-octyl-6-benzotriazolyl) phenol, 2- (2-hydroxy-
2- (3-tert-butyl-5-carboxyphenyl) benzotriazole such as polyethylene glycol ester
(2-hydroxyphenyl) benzotriazoles; phenyl salicylate, resorcinol monobenzoate, 2,4-di-tert-butylphenyl-3,5-di-tert-butyl-4-hydroxybenzoate, hexadecyl-
Benzoates such as 3,5-ditert-butyl-4-hydroxybenzoate; substituted oxanilides such as 2-ethyl-2'-ethoxyoxanilide and 2-ethoxy-4'-dodecyloxanilide; ethyl-α -Cyano-β, β-
Examples include cyanoacrylates such as diphenyl acrylate and methyl-2-cyano-3-methyl-3- (p-methoxyphenyl) acrylate.

Examples of the hindered amine compound include 2,2,6,6-tetramethyl-4-piperidyl stearate and 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, tetrakis (2,2,6,6-tetramethyl-4-piperidyl) butanetetracarboxylate, tetrates (1,2,2,2) 6,6-pentamethyl-4-piperidyl) butanetetracarboxylate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) di (tridecyl) -1,2,3,4-butanetetracarboxylate Rate, 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 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, 1,5,8,1
2-tetrakis [2,4-bis (N-butyl-N-
(2,2,6,6-tetramethyl-4-piperidyl) amino) -s-triazin-6-yl] -1,5,8,1
2-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-tetra Methyl-
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-ylamino] undecane and the like.

The crystalline synthetic resin composition of the present invention may further 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, aliphatic carboxylate salts of alkaline earth metals, pigments, dyes, fillers, foaming agents, flame retardants, lubricants, processing aids, etc. be able to.

[0044]

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

First, specific production examples of the above-mentioned cyclic organic phosphate basic aluminum salt 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 No. 1 compound shown in Chemical Formula 3 above) Sodium salt of 2,2′-methylenebis (4,6-di-tert-butylphenyl) phosphate 10.2 g (0.02 g)
Mol) 30.5% aluminum chloride aqueous solution 87.4 g
(0.2 mol) and 60 g of methanol were charged, the temperature was raised to 70 ° C. with stirring, and the mixture was stirred and reacted at 70 ° C. for 2 hours. Next, 60 g of distilled water was added, and the mixture was cooled to 20 ° C. to obtain a slurry. The solid was separated from the slurry by filtration, the solid was dissolved in 60 g of toluene, the impurities were separated by filtration, washed with water and dried to obtain 11.0 g of a white powder having a melting point of 300 ° C. or higher.

The analysis results of the product were as follows, and it was confirmed that the product was the target product. Aluminum content: 4.88% (calculated value: 4.95)
%) Phosphorus content: 5.75% (calculated value: 5.68)
%) Sodium content: 100 ppm or less Infrared spectroscopy (cm ^-1 ) 3400 (ν _OH ), 1470 (ν _{P = O} ), 1230, 1100 and 940
(Ν _PO )

Next, the basic organic aluminum salt of a cyclic organic phosphate represented by the above formula [I] used in the present invention and the formula [II] represented by the above formula [6] are used. Specific production examples in which a cyclic organic phosphate basic aluminum salt is obtained as a mixture are shown below, but the present invention is not limited by the following production examples.

Production Example 2 (Preparation of a 1: 1 mixture of No. 1 compound shown in the above [Chemical Formula 3] -No. 1 'compound shown in the above [Chemical Formula 7] 2,2'-methylenebis (4,6-di- Tertiary butylphenyl) phosphate sodium salt 30.5 g (0.06
Mol), 76.2 g of methanol and 76.2 g of distilled water, and the temperature was raised to 70 ° C. with stirring. Then, 20.6 g of an aqueous solution of polyaluminum chloride ^{* was} added dropwise over 1 hour, followed by 2 hours at 70 ° C. The reaction was carried out with stirring. Further, 60 g of distilled water was added, and the mixture was cooled to 20 ° C. to obtain a slurry. The solid was separated from this slurry by filtration, the solid was dissolved in 60 g of toluene, the impurities were separated by filtration, washed with water and dried to obtain 31.8 g of a white powder having a melting point of 300 ° C. or higher. *: Composition formula [Al ₂ (OH) _n Cl _6-n ) _m (n = 3.08), concentration 10.2% as Al ₂ O ₃

The analysis results of the product were as follows. Aluminum content: 3.94% (calculated value: 3.86)
%) Phosphorus content: 6.22% (calculated value: 6.25)
%) Sodium content: 100 ppm or less Infrared spectroscopy (cm ^-1 ) 3400 (ν _OH ), 1470 (ν _{P = O} ), 1230, 1100 and 940
(Ν _PO ) No. 1 compound / No. 1 ′ compound = 1.05 /
At 0.94, almost the desired compound was obtained.

Example 1 A crystalline synthetic resin composition obtained by mixing the following components was mixed in a mixer for 5 minutes, and then the temperature was 230 ° C. and the number of revolutions was 2
Pellets were prepared using an extruder at 0 rpm.
Using these pellets, by injection molding machine, 250 ℃,
Molding was performed at a mold temperature of 60 ° C. to prepare a test piece having a thickness of 1 mm. This test piece (original) was transferred to ASTM D-1003.
The haze (haze value) was measured according to the method of -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.

<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-butyl) -4 0.1 hydroxyphenyl) propionate] methane tris (2,4-di-tert-butylphenyl) phosphite 0.1 sample compound [Table 1] 0.05 lithium laurate 0.1

[0053]

[Table 1]

* 1: Compound represented by the following formula

[0055]

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Example 2 A crystalline synthetic resin composition obtained by mixing the following components was mixed in a mixer for 5 minutes, and then the temperature was changed to 230 ° C. and the number of rotations was set to 2
Pellets were prepared using an extruder at 0 rpm.
Using these pellets, by injection molding machine, 250 ℃,
Molding was performed at 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 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-di-tert-butyl-4-0.1 hydroxyphenyl) propionate hydrotalcite (Kyowa Chemical: DHT-4A) 0.05 Metal salt of cyclic organic phosphate ester 1 0.1 Sample compounds [Table 2] [Table 2]

[0059]

[Table 2]

Example 3 A crystalline synthetic resin composition obtained by mixing the following components was mixed in a mixer for 5 minutes, and then heated at a temperature of 240 ° C. and a rotation speed of 2
Pellets were prepared using an extruder under the condition of 0 rpm, and the pellets were molded at 250 ° C. and a mold temperature of 60 ° C. by an injection molding machine to prepare test pieces having a thickness of 1 mm.
Using this test piece, the haze value (haze value) was measured in the same manner as in Example 1.

A test piece having a thickness of 3.5 mm was prepared in the same manner as described above, and the test piece was irradiated with 5 megarads of γ-rays using cobalt 60 as a radiation source. 10 at 100 ° C after irradiation
JIS K-7 for each of the test pieces before heating (original) and the test pieces after heating for 10 days
The Izod impact strength at 23 ° C. was measured based on No. 110. 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) 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 [ Table 3] 0.1 Lithium stearate 0.15

[0063]

[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 0.1 parts by weight of the sample compound of the following [Table 4] 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 the above pellets were melted at 280 ° C. for 10 minutes, the crystallization temperature when the temperature was lowered at 5 ° C./min was measured. The ratio H / W to the width W was determined. The results are shown in Table 4 below.

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.

[0067]

[Table 4]

From the above results, when the alkali metal carboxylate or the aluminum salt of the cyclic organic phosphate was used alone, the mechanical strength and the crystallization speed of the crystalline synthetic resin composition were improved to some extent. However, the effect was not satisfactory in practical use, and in particular, the effect of improving transparency was insufficient. In addition, when the alkaline earth metal carboxylate or alkali metal hydroxide and the cyclic organic phosphate basic aluminum salt are used in combination, or when the alkali metal carboxylate and the cyclic organic phosphate aluminum salt are used in combination. The improvement effect was insufficient.

On the other hand, the crystalline synthetic resin composition of the present invention in which an alkali metal compound and a cyclic organic phosphate basic aluminum salt are used in combination not only has further improved mechanical strength, but also has been insufficient conventionally. The resulting transparency has also been greatly improved, and it is clear that the effect of the present invention is extremely specific.

[0070]

The crystalline synthetic resin composition of the present invention is excellent in transparency, mechanical properties and the like.

──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-5-156078 (JP, A) JP-A-5-140466 (JP, A) JP-A-2-202939 (JP, A) JP-A-1- 201350 (JP, A) JP-A-64-90238 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C08L 1/00-101/16 C08K 3/00-13/08

Claims (1)

(57) [Claims] (1) 100 parts by weight of a crystalline synthetic resin, (a)
0.01 to 5 parts by weight of at least one kind of alkali metal carboxylate, alkali metal β-diketonate or alkali metal β-ketoacetate and (b) a cyclic compound represented by the following general formula (I): A crystalline synthetic resin composition comprising 0.01 to 5 parts by weight of at least one kind of an organic phosphate basic aluminum salt. Embedded image