JPH08120116A - Crystalline synthetic resin composition - Google Patents

Abstract

PURPOSE: To obtain the subject composition useful as fibers, etc., having extremely improved transparency and increased mechanical strength by blending a crystalline synthetic resin with an alkali metal carboxylate, a basic Al salt of a cyclic organic phosphoric ester, etc. CONSTITUTION: This crystalline synthetic resin composition is obtained by blending (A) 100 pts.wt. of a crystalline synthetic resin (e.g. ethylene/propylene random copolymer) with (B) 0.01-5 pts.wt. of at least one of an alkali metal carboxylate (e.g. lithium aliphatic monocarboxylate), (C) 0.01-5 pts.wt. of at least one basic Al salt of a cyclic organic phosphoric ester of formula I (R1 is H or a 1-4C alkyl; R2 and R3 are each H, a 1-12C alkyl or a cycloalkyl) and (D) 0.001-5 pts.wt. of at least one of a polyhydric alcohol higher fatty acid partial ester and/or an amine compound of formula II (R4 is an alkyl or an alkanoyl; R5 is a 2-3C alkylene; (n) is 1-10) ]e.g. N,N bis(2-hydroxyethyl) laurylamine].

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 synthetic resin containing a basic polyvalent metal salt of an alkali metal compound and a cyclic organic phosphate and a higher fatty acid partial ester of a polyhydric alcohol. And / or a crystalline synthetic resin composition having improved transparency, mechanical properties and the like, which is prepared by blending a specific amine compound.

[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 have slow crystallization rates 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.

For this purpose, it is known to add a crystal nucleating agent or a crystallization accelerator, and it has been conventionally known that 4
-Tert-butylbenzoic acid aluminum salt, carboxylic acid metal salt 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.

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 of using an acidic organic phosphoric acid ester compound and an aliphatic carboxylic acid metal salt in combination has been proposed. Further, in JP-A-3-43437, when a cyclic organic phosphoric acid ester metal salt is used, the heat after irradiation is increased. 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 upon immersion in water.

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, Japanese Patent Laid-Open No. 1-104638,
JP-A-1-104639 and JP-A-1-104647 propose to use a basic aluminum salt of an aromatic phosphodiester in order to improve the processability and heat resistance of a high-rigidity propylene resin. However, when such a compound was used, the transparency improving effect 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. JP-A-5-156078 proposes that the transparency of a crystalline synthetic resin is improved by using an alkali metal carboxylate in combination with the basic aluminum salt. However, such a composition is still unsatisfactory from the viewpoint of improving transparency.

[0009]

SUMMARY OF THE INVENTION The present inventors have made various studies in view of the present situation, and as a result, have found that an alkali metal organic carboxylic acid salt, a basic aluminum salt of a cyclic organic phosphoric acid ester, and a crystalline synthetic resin can be used. The inventors have found that the addition of a higher fatty acid partial ester of a polyhydric alcohol and / or a specific amine compound significantly improves transparency and also increases mechanical strength, and has reached the present invention.

That is, the present invention relates to (a) 0.01 to 5 parts by weight of at least one alkali metal carboxylate, and (b) a compound represented by the following general formula (I), relative to 100 parts by weight of the crystalline synthetic resin. 0.01 to 5 parts by weight of a cyclic organic phosphate ester basic aluminum salt, and (c) a higher fatty acid partial ester of a polyhydric alcohol and / or an amine compound represented by the following general formula (II): The present invention provides a crystalline synthetic resin composition containing 0.001 to 5 parts by weight of at least one kind.

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Examples of the alkali metal constituting the alkali metal carboxylate of 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 the component (a) used in the present invention is a salt of the above alkali metal and a 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 cyclic organic phosphate ester basic polyvalent metal salt compound represented by, the alkyl group having 1 to 4 carbon atoms represented by R ₁ is methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, isobutyl. And so on. Examples of the alkyl group having 1 to 12 carbon atoms represented by R ₂ and R ₃ include methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, tert-butyl, amyl, tert-amyl, hexyl, heptyl, octyl, Isooctyl, tertiary octyl, 2-ethylhexyl, nonyl, isononyl, decyl, isodecyl, undecyl, dodecyl,
Examples thereof include tertiary dodecyl and the like, and particularly preferably an alkyl group having 1 to 5 carbon atoms. Further, examples of the cycloalkyl group represented by R ₂ and R ₃ include a cyclopentyl group, a cyclohexyl group, and an α-methylcyclohexyl group.

Therefore, examples of the compound represented by the general formula (I) used in the present invention include the following compounds.

[0017]

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[0018]

[Chemical 4]

[0019]

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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.

As the higher fatty acid partial ester of polyhydric alcohol which is the component (c) used in the present invention, glycerin monolaurate, glycerin monomyristyrate,
Glycerin monopalmitate, glycerin monostearate, glycerin monobehenate, glycerin fatty acid ester such as glycerin monooleate, diglycerin monolaurate, diglycerin monomyristylate, diglycerin monopalmitate, diglycerin monostearate, etc. Diglycerin fatty acid ester, sorbitan fatty acid ester, propylene glycol fatty acid ester, sucrose fatty acid ester, pentaerythritol fatty acid ester, trimethylolpropane fatty acid ester, polyoxyethylene glycerin fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyethylene glycol fatty acid ester, polypropylene Examples thereof include glycol fatty acid ester.

As the alkyl group R ₄ of the specific amine compound represented by the general formula (II) used in the present invention,
Examples thereof include linear or branched alkyl groups having 8 to 30 carbon atoms, and specific examples thereof include lauryl group, myristyl group, palmityl group, stearyl group and behenyl group.

Similarly, the alkanoyl group has 8 carbon atoms.
Examples include linear or branched alkanoyl groups of up to 30 and specifically include lauroyl group, myristoyl group, palmitoyl group, stearoyl group, behenoyl group and the like. The alkylene group for R ₅ is an ethylene group,
Examples thereof include a trimethylene group and a propylene group.
Furthermore, n in the general formula (II) is preferably 1.

More specifically, when R ₄ is an alkyl group, N, N-bis (2-hydroxyethyl) laurylamine, N, N-bis (2-hydroxyethyl) myristylamine, N, N-bis (2-Hydroxyethyl) palmitylamine, N, N-bis (2-hydroxyethyl)
N, N-bis (2-hydroxyethyl) aliphatic amines such as stearylamine, N, N-bis (2-hydroxyethyl) oleylamine, N, N-bis (2-hydroxyisopropyl) laurylamine, N, N- Bis (2-hydroxyisopropyl) myristylamine, N, N-bis (2-hydroxyisopropyl) palmitylamine,
Examples are N, N-bis (2-hydroxyisopropyl) aliphatic amines such as N, N-bis (2-hydroxyisopropyl) stearylamine and N, N-bis (2-hydroxyisopropyl) oleylamine, and R ₄ is alkanoyl. In the case of a group, N, N-bis (2-hydroxyethyl) laurylamide, N, N-bis (2-hydroxyethyl) myristylamide, N, N-bis (2-hydroxyethyl) palmitylamide, N, N -Bis (2-hydroxyethyl) stearylamide, N, N-bis (2-
Hydroxyethyl) behenylamide, N, N-bis (2
-Hydroxyethyl) oleylamide, N, N-bis (2-hydroxyethyl) aliphatic amide, N, N-bis (2-hydroxyisopropyl) laurylamide, N,
N-bis (2-hydroxyisopropyl) myristylamide, N, N-bis (2-hydroxyisopropyl) palmitylamide, N, N-bis (2-hydroxyisopropyl) stearylamide, N, N-bis (2-hydroxy) Examples include N, N-bis (2-hydroxyisopropyl) aliphatic amides such as isopropyl) oleylamide.

These amine compounds are crystalline resins 100
The amount is 0.001 to 5 parts by weight, and more preferably 0.01 to 3 parts by weight. If it is less than this, the effect of addition is not recognized, and if it is used more than this, the effect does not change so much and it is economically disadvantageous.

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

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. Useful in cases. Further, 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. 3-1957551 and the like.

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

Further, 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.

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 oxidation stability and the light stability, and in particular,
By using a phenol-based antioxidant and / or an organic phosphorus-based antioxidant together, it is possible to prevent coloring during heating and deterioration of mechanical properties.

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-β- (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'-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, 1,3,5-
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 Tributyl-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 these phenolic antioxidants added is usually 0.001 to 100 parts by weight of the synthetic resin.
It is 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-di-tert-butylphenyl) phosphite, di (tridecyl) pentaerythritol diphosphite, distearylpentaerythritol diphosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite Bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, bis (2,4,6-tri-tert-butylphenyl) pentaerythritol diphosphite, tetra (tridecyl) isopropylidene Phenol 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) butanetriphospha , 2,2'-methylenebis (4,6-ditertiarybutylphenyl) octylphosphite, 2,2'-methylenebis (4,6-ditertiarybutylphenyl) 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 -Examples include oxides.

The amount of the organic phosphorus-containing compound added is usually 0.001 to 5 parts by weight, preferably 0.01 to 3 parts by weight, based on 100 parts by weight of the synthetic resin.

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, 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-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- 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, in the crystalline synthetic resin composition of the present invention, other nucleating agents such as aluminum-p-tertiary butyl benzoate, dibenzylidene sorbitol, bis (4-methylbenzylidene) sorbitol, etc. may be added, if necessary. , Addition of hydrotalcites, aliphatic carboxylic acid salts of alkaline earth metals, lauryl alcohol, alkyl alcohols such as stearyl alcohol, pigments, dyes, fillers, foaming agents, flame retardants, lubricants, processing aids, etc. You can

[0042]

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

Example 1 After blending the compounds shown in Table 1 for 5 minutes with a mixer, pellets were prepared using an extruder under the conditions of a temperature of 230 ° C. and a rotation speed of 20 rpm. Using the pellets, injection molding machine, 250 ℃, mold temperature 6
Molding was performed at 0 ° 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.

[0044]

[Table 1]

[0045]

[Table 2]

Example 2 After blending the formulations shown in Table 3 with a mixer for 5 minutes, pellets were prepared using an extruder under the conditions of a temperature of 230 ° C. and a rotation speed of 20 rpm. Using the pellets, injection molding machine, 250 ℃, mold temperature 6
Molding was performed at 0 ° 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.

[0047]

[Table 3]

[0048]

[Table 4]

(Example 3) After blending the formulations shown in Table 5 for 5 minutes with a mixer, pellets were prepared using an extruder under the conditions of a temperature of 240 ° C and a rotation speed of 20 rpm. 250 ℃, mold temperature 60 by injection molding machine
Molded at ℃, to make a test piece 1 mm thick. 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.

[0050]

[Table 5]

[0051]

[Table 6]

[0052]

When the alkali metal carboxylate and the cyclic organic phosphate ester basic aluminum salt are used in combination, the transparency of the crystalline synthetic resin is improved to some extent.
The effect is not satisfactory, and the effect of improving the transparency of the crystalline synthetic resin is not recognized when the partial higher fatty acid ester of polyhydric alcohol or the glycol amine compound is used alone. Further, even if an alkaline earth metal carboxylate is used instead of the alkali metal carboxylate, the transparency improving effect is small.

On the other hand, a partial higher fatty acid of a polyhydric alcohol having no transparency improving effect in a combined system of an alkali metal carboxylate having a transparency improving effect of a crystalline synthetic resin and a cyclic organic phosphate ester basic aluminum salt The composition of the present invention in which an ester or glycol amine compound is used in combination synergistically has significantly improved transparency, and it is clear that the effect of the present invention is extremely specific.

[Procedure amendment]

[Submission date] December 2, 1994

[Procedure Amendment 1]

[Document name to be amended] Statement

[Name of item to be corrected] 0015

[Correction method] Change

[Correction content]

Further, the general formula (I) of the component (b) of the present invention is
Cyclic organic phosphoric acid ester basic aluminum represented in
In the salt , examples of the alkyl group having 1 to 4 carbon atoms represented by R ₁ 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, peptyl, octyl, Isooctyl, tertiary octyl, 2-ethylhexyl, nonyl, isononyl, decyl, isodecyl, undecyl, dodecyl,
Examples thereof include tertiary dodecyl and the like, and particularly preferably an alkyl group having 1 to 5 carbon atoms. In addition, R ₂ and R ₃
Examples of the cycloalkyl group represented by include a cyclopentyl group, a cyclohexyl group, and an α-methylcyclohexyl group.

[Procedure Amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0028

[Correction method] Change

[Correction content]

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

[Procedure 3]

[Document name to be amended] Statement

[Correction target item name] 0044

[Correction method] Change

[Correction content]

[0044]

[Table 1]

[Procedure amendment 4]

[Document name to be amended] Statement

[Correction target item name] 0047

[Correction method] Change

[Correction content]

[0047]

[Table 3]

Front page continuation (72) Inventor Junji Shibasaki 5-2-13 Shirahata, Urawa-shi, Saitama Asahi Denka Kogyo Co., Ltd.

Claims (1)

[Claims] 1. To 100 parts by weight of a crystalline synthetic resin,
(A) At least one kind of alkali metal carboxylate.
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), and (c) a higher fatty acid of a polyhydric alcohol. A crystalline synthetic resin composition comprising a partial ester and / or 0.001 to 5 parts by weight of at least one amine compound represented by the following general formula (II). Embedded image