JP3445672B2 - Crystalline synthetic resin composition - Google Patents

Description

Description: 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 comprising an alkali metal compound and a basic aluminum salt of a cyclic organic phosphate. The present invention relates to a crystalline synthetic resin composition having improved transparency, mechanical properties, and the like, which are added. 2. Description of the Related Art Crystalline synthetic resins such as polyethylene, polypropylene, polybutene-1, polyethylene terephthalate, polybutylene terephthalate, polyphenylene sulfide, polyamide, and syndiotactic polystyrene are produced by heat-melt molding. Has low drawbacks due to the low crystallization rate and shrinkage due to the progress of crystallization after heat molding.
In addition, these crystalline synthetic resins have disadvantages of insufficient strength due to generation of large crystals and poor transparency. [0003] All of these drawbacks are derived from the crystallinity of the synthetic resin, and it is known that if the crystallization temperature of the synthetic resin can be increased and fine crystals can be rapidly formed, it can be solved. It is known to add a nucleating agent or a crystallization accelerator for this purpose.
Metal salts of carboxylic acids such as aluminum tert-butylbenzoate, 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. JP-A-6-65270 proposes an improvement in the performance as a nucleating agent by a substituent of an alkylidene bisphenol, and a metal normal salt of bis (3-methyl-4,6-di-tert-butylphenyl) phosphate is proposed. Is used. 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 Patent Application Laid-Open No. 3-43437 discloses that when a metal salt of a cyclic organic phosphoric acid ester is used, hot water 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 to prevent a decrease in pH during immersion. [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, Japanese Patent Application Laid-Open Nos. 1-104638, 1-104639 and 1-104647 disclose aromatic phosphate diesters for improving the processability and heat resistance of high-rigidity propylene-based resins. It has been proposed to use a basic aluminum salt, but when such a compound was used, the effect of improving transparency was hardly recognized. It has been considered that such a basic aluminum salt is not effective in improving the transparency of the crystalline synthetic resin. It has been proposed in Japanese Patent Application Laid-Open No. 5-156078 to improve the transparency of a crystalline synthetic resin by using an alkali metal carboxylate in combination with this basic aluminum salt. However, such compositions have not yet been satisfactory in terms of improving transparency. Means for Solving the Problems The present inventors have made various studies in view of the present situation, and as a result, have found that an alkali metal carboxylate and a basic aluminum salt of a cyclic organic phosphate are added to a crystalline synthetic resin. It has been found that the addition greatly improves the transparency and also increases the mechanical strength, and has reached the present invention. [0010] That is, the present invention relates to a crystalline synthetic resin 100
(A) 0.01 to 5 parts by weight of at least one kind of alkali metal carboxylate, and (b) at least one kind of basic aluminum salt of cyclic organic phosphate represented by the following general formula (I) based on parts by weight. The present invention provides a crystalline synthetic resin composition to which 0.01 to 5 parts by weight is added. Less than,
The crystalline synthetic resin composition of the present invention will be described in detail. [0011] The alkali metal constituting the alkali metal carboxylate (a) used in the present invention includes lithium, sodium, potassium and the like. The carboxylic acids constituting the alkali metal carboxylate include, for example, 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, melicic acid, β-dodecylmercaptoacetic acid, β-dodecylmercaptopropionic acid, β-N-laurylaminopropionic acid, β-N- Aliphatic monocarboxylic acids such as methyl-N-lauroylaminopropionic acid; malonic acid, succinic acid,
Adipic acid, maleic acid, azelaic acid, sebacic acid,
Aliphatic polycarboxylic acids such as dodecanediacid, 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, xylic 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. The alkali metal carboxylate (a) used in the present invention is a salt of the above alkali metal and carboxylic acid, and can be produced by a conventionally known method.
Among the alkali metal carboxylate salts of component (a), an aliphatic monocarboxylate salt of an alkali metal, in particular, an aliphatic monocarboxylate salt of lithium is preferable, and particularly, an aliphatic monocarboxylate salt having 8 to 20 carbon atoms. Carboxylates are preferred. The alkali metal carboxylate is added in an amount of 0.01 to 5 parts by weight per 100 parts by weight of the crystalline synthetic resin.
Parts by weight, and particularly preferably 0.05 to 3 parts by weight. Further, the component (b) of the present invention has the general formula (I)
In the cyclic organic phosphate basic aluminum salt represented by R ₁ and R ₂ , the number of carbon atoms is 1 to 1
Examples of the alkyl group 2 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, tertiary dodecyl, etc. And particularly preferably an alkyl group having 1 to 5 carbon atoms. Further, as the cycloalkyl group, cyclopentyl, cyclohexyl, α-
Methylcyclohexyl and the like. As the compound represented by the general formula (I) used in the present invention, the following compounds can be exemplified. Embedded image Embedded image Embedded image The basic aluminum salt of the cyclic organic phosphate of component (b) is, for example, a reaction of an alkali metal salt of an acidic cyclic organic phosphate with an aluminum halide or an aluminum oxide halide. It can be easily produced by a method of hydrolyzing as appropriate, a method of reacting an acidic cyclic organic phosphate with aluminum alkoxide, and then hydrolyzing as necessary. The basic organic aluminum salt of a cyclic organic phosphate is not particularly limited in its particle size. For example, those having an average particle size of 0.01 to 50 μm 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 basic organic aluminum salt of the cyclic organic phosphate is added in an amount of 0.01 to 5 parts by weight, preferably 0.03 parts by weight, per 100 parts by weight of the crystalline synthetic resin.
３3 parts by weight. The ratio of the alkali metal carboxylate (a) to the cyclic organic phosphate basic aluminum salt (b) is not particularly limited.
The effect of the present invention is remarkable when the added amount of the alkali metal carboxylate as the component is equal to or more than the added amount of the cyclic organic phosphate basic aluminum salt 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, and syndiotactic Tic polystyrene and the like. In particular, the present invention is applied to a polypropylene-based resin such as a crystalline α-olefin polymer, especially polypropylene, an ethylene / propylene copolymer, and a mixture of these propylene polymers with other α-olefin polymers. Useful for In addition, the present invention provides a stereoregularity such as isotactic or syndiotactic of these polypropylene resins, isotactic pentad fraction, intrinsic viscosity, density, molecular weight distribution,
It can be applied irrespective of the melt flow rate, rigidity and the like.
-37152, 63-90552, 6
JP-A-3-210152, JP-A-63-213547, JP-A-63-243150, JP-A-63-24315
No. 2, 63-260943, 63-26
JP-A-0944, JP-A-63-264650, JP-A-1-178541, JP-A-2-49047, JP-A-2-102242, JP-A-2-251548,
It can also be suitably used for polypropylene resins as described in JP-A-2-279746 and JP-A-3-195751. In the present invention, the method of adding each component is not particularly limited, and generally used methods, for example,
A method of dry-blending the crystalline synthetic resin powder or pellets with the additive powder, a method of preparing a master batch containing each component at a high concentration, and adding this to the crystalline synthetic resin can be used. Further, the crystalline synthetic resin composition of the present invention, extrusion molding, injection molding, vacuum molding,
It can be used as various molded products, fibers, biaxially stretched films, sheets and the like by well-known processing methods such as blow molding and cross-linked foam molding. The composition of the present invention may be used for various post-treatments, for example, for sterilization by radiation such as medical use or food packaging, or for improving surface properties such as paintability. In addition, it can also be used for applications in which low-temperature plasma treatment or the like is performed after molding. Further, the crystalline synthetic resin composition of the present invention includes:
If necessary, a phenolic antioxidant, an organic phosphorus antioxidant such as organic phosphite or phosphonite, a thioether antioxidant, a UV absorber or a light stabilizer such as a hindered amine compound are added, and the oxidation stability and light The stability can be further improved. In particular, by using a phenolic antioxidant and / or an organic phosphorus antioxidant in combination, it is possible to prevent coloring and mechanical properties from being reduced during heating. The phenolic antioxidants usable in the present invention include, for example, 2,6-di-tert-butyl-p-cresol, 2,6-diphenyl-4-octadecyloxyphenol, stearyl-β- (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-butylphenyl) butylic 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-ditert-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 addition amount of these phenolic antioxidants is usually 0.00
It is 1 to 5 parts by weight, preferably 0.01 to 3 parts by weight. Examples of the organophosphorus antioxidant that can be used in the present invention include trisnonylphenyl phosphite, tris (mono and dinonylphenyl) phosphite, tris (2,4-ditertbutylphenyl) phosphite,
Di (tridecyl) pentaerythritol diphosphite, distearylpentaerythritol diphosphite, bis (2,4-ditertbutylphenyl) pentaerythritol diphosphite, bis (2,6-ditertbutyl-4-methyl) Phenyl) pentaerythritol diphosphite, bis (2,4,6-tritert-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'-methylenebis (4,6-ditertbutylbutyl) Nyl) octyl phosphite, 2,2′-methylenebis (4,6-di-tert-butylphenyl) octadecyl phosphite, 2,2′-methylenebis (4,6-di-tert-butylphenyl) fluorophosphite, tetrakis ( 2,4-ditert-butylphenyl) biphenylenediphosphonite, 9,10-dihydro-9-oxa-10phosphaphenanthrene-10-oxide and the like. The addition amount of these organic phosphorus-containing compounds is usually 0.001 to 5 per 100 parts by weight of the crystalline synthetic resin.
Parts by weight, preferably 0.01 to 3 parts by weight. Examples of thioether antioxidants include thiodipropionic acid dilauryl, dimyristyl,
And dialkylthiodipropionates such as myristylstearyl and distearyl esters, and β-alkylmercaptopropionates of polyols such as pentaerythritol tetra (β-dodecylmercaptopropionate). As the ultraviolet absorber, for example, 2,4
-Dihydroxybenzophenone, 2-hydroxy-4-
2-hydroxybenzophenones such as methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, and 5,5′-methylenebis (2-hydroxy-4-methoxybenzophenone); 2- (2-hydroxy-5
-Methylphenyl) benzotriazole, 2- (2-hydroxy-5-tert-octylphenyl) benzotriazole, 2- (2-hydroxy-3,5-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-di-tert-butyl-4-hydroxybenzoate; substituted oxanilides such as 2-ethyl-2'-ethoxyoxanilide and 2-ethoxy-4'-dodecyloxanilide; ethyl-α -Cyano-β,
β-diphenyl acrylate, methyl-2-cyano-3
And cyanoacrylates such as -methyl-3- (p-methoxyphenyl) acrylate. Light stabilizers such as hindered amine compounds include, 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, tetrakis (2,2,
6,6-tetramethyl-4-piperidyl) butanetetracarboxylate, tetrakis (1,2,2,6,6-
Pentamethyl-4-piperidyl) butanetetracarboxylate, bis (1,2,2,6,6-pentamethyl-
4-piperidyl) di (tridecyl) -1,2,3,4
-Butanetetracarboxylate, bis (1,2,2,
6,6-pentamethyl-4-piperidyl) -2-butyl-2- (3,5-ditert-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- Trioctylamino-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-triazine-6
-Ylamino] undecane, 1,6,11-tris [2,4-bis (N-butyl-N- (1,2,2,6,
Hindered amine compounds such as 6-pentamethyl-4-piperidyl) amino) -s-triazin-6-ylamino] undecane. In addition, if necessary, other nucleating agents such as aluminum-p-tert-butylbenzoate, dibenzylidene sorbitol, bis (4-methylbenzylidene) sorbitol may be added to the crystalline synthetic resin composition of the present invention. , Antistatic agents such as partial esters of polyhydric alcohols and diethanol stearylamine, hydrotalcites, aliphatic carboxylate salts of alkaline earth metals, alkyl alcohols such as lauryl alcohol and stearyl alcohol, pigments, dyes and fillers , A foaming agent, a flame retardant, a lubricant, a processing aid, and the like. Hereinafter, the present invention will be described in more detail by way of examples. However, the invention is not limited to these examples. Reference Example: Synthesis Example of Compound No. 1
2'-methylenebis (3-methyl-4,6-di-tert-butylphenyl) phosphate sodium salt 10.72 g
(0.02 mol) was dissolved in methanol and 2.41 g (0.04 mol) of aluminum trichloride hexahydrate was stirred at 40 ° C.
(1 mol) was added dropwise as a 50 ml aqueous solution over 30 minutes. After completion of the dropwise addition, the mixture was stirred for 4 hours under reflux of methanol and cooled to room temperature.
H was set to 6. The product was filtered to obtain 9.84 g (yield 92%) of white powder having a melting point of 300 ° C. or higher. Compound No.
2 and 3 were similarly synthesized. (Example 1) Each component was mixed at a ratio shown in Table 1 by a mixer for 5 minutes, and then the temperature was 230 ° C and the number of rotations was 20.
Pellets were produced using an extruder under the condition of rpm.
The pellets were molded by an injection molding machine at 250 ° C. and a mold temperature of 60 ° C. to produce a test piece having a thickness of 1 mm.
The haze value (haze value) of this test piece was measured in accordance with the method of ASTM D-1003-61. Table 2 shows the results.
Shown in [Table 1] [Table 2] Example 2 Each component was mixed at a ratio shown in Table 3 by a mixer for 5 minutes, and then the temperature was 230 ° C. and the number of revolutions was 20.
Pellets were produced using an extruder under the condition of rpm.
The pellets were molded at 250 ° C. and a mold temperature of 60 ° C. by an injection molding machine 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. The results are shown in Table-4. [Table 3] [Table 4] Example 3 Each component was mixed at a ratio shown in Table 5 with a mixer for 5 minutes, and then heated to a temperature of 240 ° C. and a rotation speed of 20.
Pellets were produced using an extruder under the condition of rpm, and the pellets were molded using an injection molding machine at 250 ° C. and a mold temperature of 60 ° C. to produce a test piece 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. The results are shown in Table-6. [Table 5] [Table 6] When the alkali metal carboxylate and the cyclic organic phosphate basic aluminum salt are used in combination,
By using 2,2′-alkylidenebis (3-methyl-4,6-alkyl-substituted phenyl) phosphate and a basic salt of aluminum, 2,2′-alkylidenebis (4,6-alkyl-substituted phenyl) phosphate can be used. A crystalline synthetic resin composition having more excellent transparency than using a basic salt of aluminum can be obtained.

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Claims (1)

(57) [Claim 1] With respect to 100 parts by weight of the crystalline synthetic resin,
(A) at least one alkali metal carboxylate;
A crystalline synthetic resin composition to which 0.01 to 5 parts by weight of (b) at least one kind of a cyclic organic phosphate basic aluminum salt represented by the following general formula (I) is added. Embedded image