JPH08134260A - Crystalline synthetic resin composition - Google Patents

Abstract

PURPOSE: To obtain a crystalline synthetic resin compsn. improved in clarity, mechanical characteristics, etc. CONSTITUTION: The compsn. is prepd. by compounding 100 pts.wt. crystalline synthetic resin with 0. 01-5 pts.wt. at least one alkali metal carboxylate and 0.01-5 pts.wt., at least one basic aluminum salt of a cyclic org. phosphoric ester represented by the formula (wherein R1 and R2 are each 1-12C alkyl or cycloalkyl; and R3 is H or methyl).

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 specifically, to a crystalline synthetic resin obtained by adding an alkali metal compound and a basic aluminum salt of a cyclic organic phosphoric acid ester, to the 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 syndiotactic polystyrene can be crystallized after heat-melt molding. Since the speed is slow, the molding cycle property is low, and there is a defect that shrinkage occurs due to progress of crystallization after heat molding.
In addition, these crystalline synthetic resins have drawbacks such as insufficient strength because of the formation of large crystals and poor transparency.

It is known that all of these drawbacks are derived from the crystallinity of the synthetic resin and can be solved if the crystallization temperature of the synthetic resin can be raised and fine crystals can be rapidly produced.

For this purpose, it has been known to add a crystal nucleating agent or a crystallization accelerator, and it has been conventionally known that 4-
Aluminum salt of tert-butylbenzoate, metal salt of carboxylic acid such as sodium adipate, sodium bis (4-tert-butylphenyl) phosphate, sodium-2,
2'-methylenebis (4,6-di-tert-butylphenyl)
Acid phosphate metal salts such as phosphates, polyhydric alcohol derivatives such as dibenzylidene sorbitol, bis (4-methylbenzylidene) sorbitol and the like have been used.

Among these compounds, JP-A-58-1
The metal salt of a cyclic phosphoric acid ester of alkylidene bisphenol described in Japanese Patent No. 736, No. 59-184252 and the like has a great effect and is widely used. Further, JP-A-6-65270 proposes to improve the performance as a nucleating agent by a substituent of alkylidene bisphenol, and a metal normal salt of bis (3-methyl-4,6-di-tert-butylphenyl) phosphate is proposed. Is used.

Attempts have been made to improve the effect by using these compounds in combination with other metal compounds. For example, JP-A-63-69853.
In the publication, 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 hydrotalcites 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 of using a cyclic organophosphate metal salt and a metal salt of a periodic table group of an aliphatic carboxylic acid in combination, and JP-A-3-79649 and JP-A-3-81368 disclose methods. A method has been proposed in which an acidic organic phosphoric acid ester compound and an aliphatic carboxylic acid metal salt are used in combination, and in JP-A-3-43437, when a cyclic organic phosphoric acid ester metal salt is used, hot water after irradiation with radiation is used. 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.

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.

Further, in JP-A-1-104638, JP-A-1-104639 and JP-A-1-104647, aromatic phosphodiesters are used to improve the processability and heat resistance of high-rigidity propylene resins. It has been proposed to use a basic aluminum salt, but when such a compound is used, the effect of improving transparency is hardly recognized. It has been considered that such a basic aluminum salt is not effective in improving the transparency of the crystalline synthetic resin. JP-A-5-156078 proposes to improve the transparency of a crystalline synthetic resin by using an alkali metal carboxylate in combination with this basic aluminum salt. However, such a composition is still unsatisfactory from the viewpoint of improving transparency.

[0009]

Means for Solving the Problems As a result of various studies conducted by the present inventors in view of the present situation, it has been found that an alkali metal carboxylate and a basic aluminum salt of a cyclic organic phosphate are added to a crystalline synthetic resin. According to the present invention, the inventors have found that the transparency is greatly improved and the mechanical strength is also increased, and the present invention has been achieved.

That is, the present invention is based on the crystalline synthetic resin 100.
0.01 to 5 parts by weight of (a) an alkali metal carboxylate, and (b) at least one of a cyclic organic phosphate ester basic aluminum salt represented by the following general formula (I), based on parts by weight. A crystalline synthetic resin composition containing 0.01 to 5 parts by weight is provided. Less than,
The crystalline synthetic resin composition of the present invention will be described in detail.

[0011]

Embedded image

Examples of the alkali metal constituting the alkali metal carboxylate as the component (a) used 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,
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- 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 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, xylic acid, ethylbenzoic acid,
Aromatic mono- or polycarboxylic acids such as 4-tertiary-butylbenzoic acid, salicylic acid, phthalic acid, trimellitic acid and pyromellitic acid can be mentioned.

The alkali metal carboxylic acid salt of component (a) used in the present invention is a salt of the above-mentioned alkali metal and carboxylic acid, and can be produced by a conventionally known method.
Among these alkali metal carboxylates of component (a), an alkali metal aliphatic monocarboxylic acid salt, particularly a lithium aliphatic monocarboxylic acid salt is preferable, and an aliphatic monocarboxylic acid salt having 8 to 20 carbon atoms is particularly preferable. Carboxylates are preferred.

The amount of the alkali metal carboxylate added is 0.01 to 5 with respect to 100 parts by weight of the crystalline synthetic resin.
Parts by weight, particularly preferably 0.05 to 3 parts by weight.

Further, the general formula (I) of the component (b) of the present invention is
In the basic aluminum salt of a cyclic organic phosphate represented by the following formula, the number of carbon atoms represented by R ₁ and R ₂ is 1 to 1.
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. And particularly preferably an alkyl group having 1 to 5 carbon atoms. Further, as the cycloalkyl group, cyclopentyl, cyclohexyl, α-
Examples include methylcyclohexyl. Examples of the compound represented by the general formula (I) used in the present invention include the compounds shown below.

[0017]

Embedded image

[0018]

[Chemical 4]

[0019]

Embedded image

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

The particle size of the above cyclic organic phosphate basic aluminum salt is not particularly limited, and for example, those having an average particle size of 0.01 to 50 μm can be used, but a uniform dispersion is possible. In order to achieve the above, it is preferable to pulverize and use the fine particles having an average particle diameter of 10 microns or less, particularly 3 microns or less.

The amount of the cyclic organic phosphate ester basic aluminum salt added is 0.01 to 5 parts by weight, and preferably 0.03 parts by weight, based on 100 parts by weight of the crystalline synthetic resin.
~ 3 parts by weight.

The ratio of the alkali metal carboxylate as the component (a) and the cyclic organic phosphoric acid ester basic aluminum salt as the component (b) is not particularly limited, but the ratio (a) is particularly preferable.
The effect of the present invention is remarkable when the addition amount of the alkali metal carboxylate as the component is equal to or more than the addition amount of the cyclic organic phosphate ester basic aluminum salt as the component (b).

The crystalline synthetic resin used in the present invention is, 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 and polyhexamethylene adipamide, syndiotactic Examples include tic polystyrene.

Particularly when the present invention is applied 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 for. Further, the present invention is stereoregularity such as isotactic or syndiotactic of these polypropylene resins, isotactic pentad fraction, intrinsic viscosity, density, molecular weight distribution,
It can be applied regardless of the melt flow rate, the rigidity, etc., for example, JP-A-63-37148 and 63.
-37152, 63-90552, 6
3-210152, 63-213547, 63-243150, 63-24315.
No. 2, gazette 63-260943, gazette 63-26.
0944, 63-264650, JP-A-1-178541, 2-49047, 2-102242, 2-251548.
It can also be suitably used for polypropylene resins such as those described in JP-A-2-279746 and JP-A-3-1957751.

In the present invention, the method of adding each component is not particularly limited, and a generally used method, 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 the master batch to the crystalline synthetic resin, and the like 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 known processing methods such as blow molding and cross-linking foam molding.

In addition, the composition of the present invention is used for various post-treatments, for example, for sterilization by radiation for medical use or food packaging, or for improving surface properties such as paintability. In addition, it can be used for applications such as low temperature plasma treatment after molding.

The crystalline synthetic resin composition of the present invention also comprises
Add phenolic antioxidants, organophosphorus antioxidants such as organic phosphites or phosphonites, thioether antioxidants, UV absorbers or light stabilizers such as hindered amine compounds as necessary to improve their oxidation stability and light resistance. The stability can be further improved, and particularly when a phenol-based antioxidant and / or an organic phosphorus-based antioxidant is used in combination, coloring and deterioration of mechanical properties during heat processing can be prevented.

Examples of the phenolic antioxidant which can be used in the present invention include 2,6-di-tert-butyl-p-cresol, 2,6-diphenyl-4-octadecyloxyphenol and 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-ditert-butyl-4-hydroxyphenoxy) -s-triazine, 2,2 '-Methylenebis (4-methyl-6-tert-butylphenol), bis [3,3-bis (4-hydroxy-3-tert-butylphenyl) butyric acid] glycol ester, 4,4'-butylidenebis (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, 1,3,5-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) bropionyloxyethyl] isocyanurate, tetrakis [methylene-
3- (3,5-Ditert-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 these phenolic antioxidants added is usually 0.00 based on 100 parts by weight of the crystalline synthetic resin.
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-ditertiarybutylphenyl) phosphite,
Di (tridecyl) pentaerythritol diphosphite, distearyl pentaerythritol diphosphite, bis (2,4-ditert-butylphenyl) pentaerythritol diphosphite, bis (2,6-di-tert-butyl-4-methyl) Phenyl) pentaerythritol diphosphite, bis (2,4,6-tri-tert-butylphenyl) pentaerythritol diphosphite, tetra (tridecyl) isopropylidene diphenol diphosphite, tetra (tridecyl) -4,4'- n-butylidene bis (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-butylphen Nyl) octyl phosphite, 2,2'-methylenebis (4,6-di-tert-butylphenyl) octadecylphosphite, 2,2'-methylenebis (4,6-di-tert-butylphenyl) fluorophosphite, tetrakis ( 2,4-di-tert-butylphenyl) biphenylene diphosphonite, 9,10-dihydro-9-oxa-10 phosphaphenanthrene-10-oxide and the like can be mentioned.

The amount of these organic phosphorus-containing compounds added is usually 0.001 to 5 relative to 100 parts by weight of the crystalline synthetic resin.
Parts by weight, preferably 0.01 to 3 parts by weight.

Examples of the thioether antioxidant include dilauryl thiodipropionate, dimyristyl,
Examples thereof include dialkylthiodipropionates such as myristyl stearyl and distearyl esters, and β-alkylmercaptopropionic acid esters of polyols such as pentaerythritol tetra (β-dodecylmercaptopropionate).

Examples of the ultraviolet absorber include 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-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-tertiary octyl-6-benzotriazolyl) phenol, 2- (2-hydroxy-
2-tert-butyl-5-carboxyphenyl) benzotriazole such as polyethylene glycol ester
(2-Hydroxyphenyl) benzotriazoles; phenyl salicylate, resorcinol monobenzoate, 2,4-ditert-butylphenyl-3,5-ditert-butyl-4-hydroxybenzoate, hexadecyl-
Benzoates such as 3,5-ditertiary 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
Examples include cyanoacrylates such as -methyl-3- (p-methoxyphenyl) acrylate.

Examples of light stabilizers such as hindered amine compounds include 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) butane tetracarboxylate, 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
-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 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-second 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,
Examples thereof include hindered amine compounds such as 6-pentamethyl-4-piperidyl) amino) -s-triazin-6-ylamino] undecane.

In addition, if necessary, the crystalline synthetic resin composition of the present invention may contain other nucleating agents such as aluminum-p-tert-butylbenzoate, dibenzylidene sorbitol and bis (4-methylbenzylidene) sorbitol. Antistatic agents such as partial esters of polyhydric alcohols and diethanolstearylamine, hydrotalcites, aliphatic carboxylates of alkaline earth metals, alkyl alcohols such as lauryl alcohol and stearyl alcohol, pigments, dyes, fillers , Foaming agents, flame retardants, lubricants, processing aids and the like can be added.

[0037]

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

Reference Example: Synthesis Example of Compound No. 1, 2.
2'-methylenebis (3-methyl-4,6-di-tert-butylphenyl) phosphate sodium salt 10.72 g
(0.02 mol) was dissolved in methanol, and while stirring at 40 ° C, aluminum trichloride hexahydrate 2.41 g (0.02 mol) was obtained.
1 mol) was added dropwise as a 50 ml aqueous solution over 30 minutes. After completion of dropping, the mixture was stirred under reflux of methanol for 4 hours, cooled to room temperature, 3N aqueous sodium hydroxide solution was added, and p
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) After mixing the components in the proportions shown in Table 1 for 5 minutes with a mixer, the temperature was 230 ° C and the rotation speed was 20.
Pellets were made using an extruder under conditions of 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 (haze value) of this test piece was measured according to the method of ASTM D-1003-61. The results are shown in Table-2.
Shown in

[0040]

[Table 1]

[0041]

[Table 2]

(Example 2) After mixing the components at a ratio shown in Table 3 for 5 minutes with a mixer, the temperature was 230 ° C and the rotation speed was 20.
Pellets were made using an extruder under conditions of 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 (haze value) of this test piece was measured in the same manner as in Example 1. The results are shown in Table-4.

[0043]

[Table 3]

[0044]

[Table 4]

(Embodiment 3) After mixing the components at a ratio shown in Table 5 for 5 minutes with a mixer, the temperature was 240 ° C. and the rotation speed was 20.
Pellets were prepared using an extruder under the conditions of rpm, 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 haze (haze value) was measured in the same manner as in Example 1. The results are shown in Table-6.

[0046]

[Table 5]

[0047]

[Table 6]

[0048]

When the alkali metal carboxylate and the cyclic organic phosphate ester basic aluminum salt are used in combination,
By using 2,2′-alkylidene bis (3-methyl-4,6-alkyl-substituted phenyl) phosphate and a basic salt of aluminum, 2,2′-alkylidene bis (4,6-alkyl-substituted phenyl) phosphate is obtained. It is possible to obtain a crystalline synthetic resin composition which is superior in transparency as compared with the use of a basic salt of aluminum.

Claims (1)

[Claims] 1. To 100 parts by weight of a crystalline synthetic resin,
(A) At least one kind of alkali metal carboxylate.
A crystalline synthetic resin composition to which 0.01 to 5 parts by weight and (b) 0.01 to 5 parts by weight of at least one cyclic organophosphate ester basic aluminum salt represented by the following general formula (I) are added. Embedded image