JPH083364A - Crystalline synthetic resin composition - Google Patents

Abstract

(57) [Summary] (Modified) [Objective] To provide a crystalline synthetic resin composition having improved transparency, mechanical properties and the like. [Structure] At least 0.01 to 5 parts by weight of a dibenzylidene sorbitol derivative represented by the following general formula (I) and 100 parts by weight of a crystalline synthetic resin and the following general formula (II) or ( A crystalline synthetic resin composition comprising 0.01 to 5 parts by weight of at least one metal salt of an aromatic organic phosphate represented by III). (In the formula, R ₁ , R ₂ , R ₃ and R ₄ represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. Provided that at least one of R ₁ and R ₂ or R ₃ and R ₄ is alkyl. It represents a group.) (In the formula, R ₅ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R ₆ , R ₇ , R ₈ , R ₉ and R ₁₀ are each a hydrogen atom and an alkyl group having 1 to 12 carbon atoms. And M ₁ and M ₂ represent an alkali metal atom, an alkaline earth metal atom, a zinc atom or an aluminum atom,
p represents 1 or 2, q represents 0 when M ₁ and M ₂ are alkali metal atoms, alkaline earth metal atoms or zinc atoms, and 1 or 2 when M ₁ and M ₂ are aluminum atoms. Represent )

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 containing a specific dibenzylidene sorbitol derivative and a metal salt of an aromatic organophosphate ester, which is transparent. The present invention relates to a crystalline synthetic resin composition having improved mechanical properties and the like.

[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 a slow crystallization rate after heat-melt molding, and therefore have a molding cycle. There is a defect that the property is low and that shrinkage occurs due to progress of crystallization after heat molding. In addition, 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
-Aluminum tert-butylbenzoate, metal carboxylates such as sodium adipate, etc. have been used.

Among these crystal nucleating agents, compounds having particularly large effects are disclosed in JP-A-58-1736, JP-A-59-184252, JP-A-5-140466 and JP-A-5-156078. The metal salts of cyclic phosphoric acid esters of alkylidene bisphenols described in US Pat.

Further, Japanese Patent Laid-Open No. 50-139150,
JP-A-51-22740 proposes dibenzylidene sorbitol, but due to the problem of compatibility with resins, JP-A-53-117044 and JP-A 58-58.
-17135, JP-A-3-102242 and the like propose dibenzylidene sorbitol derivatives having a substituent on the benzene nucleus.

Attempts have also been made to combine these compounds to improve their effects. For example, in JP-A-62-209151, a crystalline propylene polymer is added to a cyclic phosphate ester. Metal salt and bis (4
-Alkylbenzylidene) sorbitol is proposed to be used in combination, and in JP-A-2-102242, a crystalline propylene-based polymer is used in combination with an aromatic phosphoric acid ester metal salt and a dibenzylidene-sorbitol-based compound. Have been proposed for use.

However, the improvement effect by the combination described in these publications is not yet satisfactory in practical use, and further improvement has been demanded particularly from the viewpoint of improving the transparency of the crystalline synthetic resin.

[0009]

[Means for Solving the Problems] In view of the present situation, the inventors of the present invention have made various studies and as a result, added a specific dibenzylidene sorbitol derivative and a metal salt of an aromatic organic phosphoric acid ester to a crystalline synthetic resin. The inventors have found that by doing so, the transparency is greatly improved and the mechanical strength is also increased, and the present invention has been completed.

That is, in the present invention, 0.01 to 5 parts by weight of at least one dibenzylidene sorbitol derivative represented by the following general formula (I) and the following general formula ( The present invention provides a crystalline synthetic resin composition containing 0.01 to 5 parts by weight of at least one metal salt of an aromatic organic phosphate represented by II) or (III). Hereinafter, the crystalline synthetic resin composition of the present invention will be described in detail.

[0011]

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[0012]

[Chemical 4]

In the general formula (I), R ₁ , R ₂ , R ₃ and R ₄
Examples of the alkyl group having 1 to 4 carbon atoms represented by are methyl, ethyl, propyl, isopropyl, butyl, isobutyl, secondary butyl, tertiary butyl, and the like.
Of these, those which are both methyl groups are preferable.

Examples of the dibenzylidene sorbitol derivative used in the present invention include the compounds shown below.

[0015]

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[0016]

[Chemical 6]

[0017]

[Chemical 7]

[0018]

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The amount of these dibenzylidene sorbitol derivatives added is 0. 0, based on 100 parts by weight of the crystalline synthetic resin.
The amount is 01 to 5 parts by weight, preferably 0.05 to 3 parts by weight. Here, when the addition amount is less than 0.01 parts by weight, almost no effect is observed, and when it is used in an amount of more than 5 parts by weight, the effect is not improved, and the coloring property is adversely affected. May occur.

In the general formulas (II) and (III), the alkyl group having 1 to 4 carbon atoms represented by R ₅ is methyl, ethyl, propyl, isopropyl,
Butyl, secondary butyl, isobutyl, etc.
1 carbon atom represented by R ₆ , R ₇ , R ₈ , R ₉ and R ₁₀
Examples of the alkyl group of ~ 12 include methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, tert-butyl,
Amyl, tertiary amyl, hexyl, heptyl, octyl,
Isooctyl, tertiary octyl, 2-ethylhexyl, nonyl, isononyl, decyl, isodecyl, undecyl,
Examples include dodecyl and third dodecyl.

Examples of the metal salt of an aromatic organic phosphoric acid ester used in the present invention include the compounds shown below.

[0022]

[Chemical 9]

[0023]

[Chemical 10]

[0024]

[Chemical 11]

[0025]

[Chemical 12]

[0026]

[Chemical 13]

[0027]

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[0028]

[Chemical 15]

[0029]

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[0030]

[Chemical 17]

The metal salt of these aromatic organic phosphates can be produced by a conventional method, and the production method is not particularly limited.

The amount of the metal salt of the aromatic organic phosphate ester added is 0.0 with respect to 100 parts by weight of the crystalline synthetic resin.
It is 1 to 5 parts by weight, preferably 0.05 to 3 parts by weight. Here, when the addition amount is less than 0.01 parts by weight, almost no effect is observed, and when it is used in an amount of more than 5 parts by weight, the effect is not improved, and the coloring property is adversely affected. May occur.

When a metal salt other than the alkali metal is used among the metal salts of these aromatic organic phosphoric acid esters, it is preferable to use an alkali metal compound together. Examples of these alkali metal compounds are alkali metal carboxylates, alkali metal β-diketonates or alkali metal β-ketoacetic acid ester salts, and the alkali metals constituting these include lithium, sodium, potassium and the like. , An aliphatic monocarboxylic acid salt of an alkali metal, particularly an aliphatic monocarboxylic acid salt of lithium is preferable, and an aliphatic monocarboxylic acid salt having 8 to 20 carbon atoms is particularly preferable.

Examples of the carboxylic acid which constitutes 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.

Examples of the β-diketone which constitutes the alkali metal β-diketonate include acetylacetone, pivaloylacetone, palmitoylacetone, benzoylacetone, pivaloylbenzoylacetone and dibenzoylmethane.

Further, as the β-ketoacetic acid ester which constitutes the alkali metal β-ketoacetic acid ester salt, for example,
Examples thereof include ethyl acetoacetate, octyl acetoacetate, lauryl acetoacetate, stearyl acetoacetate, ethyl benzoyl acetate, and lauryl benzoyl acetate.

The alkali metal carboxylate, alkali metal β-diketonate or alkali metal β-ketoacetic acid ester salt is added in an amount of 0.01 to 5 parts by weight per 100 parts by weight of the crystalline synthetic resin, and particularly, , 0.05 ~
3 parts by weight is preferred.

Examples of the crystalline synthetic resin used in the present invention include low density polyethylene, linear low density polyethylene, high density polyethylene, polypropylene, syndiotactic polypropylene, polybutene-1, poly-.
Α-Olefin polymers such as 3-methylbutene, ethylene / propylene block or random copolymers; thermoplastic linear polyesters such as polyethylene terephthalate, polybutylene terephthalate, polyhexamethylene terephthalate; polyphenylene sulfide; polycaprolactone, polyhexamethylene azide Linear polyamide such as poamide; polystyrene, syndiotactic polystyrene, poly (alkylstyrene), poly (halogenated styrene), poly (alkoxystyrene), poly (vinyl benzoate) and polystyrene such as copolymers thereof Examples thereof include polymers.

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, medical use such as syringes and infusion bags, or food sterilization for radiation sterilization or paintability. In order to improve the surface characteristics, 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 (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) butyric acid] glycol ester, 4,4'-butylidene bis (6-tertiary) 3-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-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 the phenolic antioxidant added is 0.001 to 100 parts by weight of the crystalline synthetic resin.
It is 5 parts by weight, preferably 0.01 to 3 parts by weight.

Examples of the organophosphorus antioxidant which can be used in the present invention include trisnonylphenyl phosphite,
Tris (mono and dinonylphenyl) phosphite,
Tris (2,4-ditert-butylphenyl) phosphite, di (tridecyl) pentaerythritol diphosphite, distearyl pentaerythritol diphosphite, bis (2,4-ditert-butylphenyl) pentaerythritol diphosphite , Bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, bis (2,4,6-tri-tert-butylphenyl) pentaerythritol diphosphite, tetra (tridecyl) isopropylidenedi Phenol 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) 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 these organic phosphorus-containing compounds added is 0.001 to 5 parts by weight, preferably 0.01 to 3 parts by weight, per 100 parts by weight of the crystalline 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 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 nonionic, cationic or anionic antistatic agents, aluminum-p-tertiary butyl benzoate, sodium benzoate and the like. Nucleating agents, hydrotalcites, alkaline earth metal aliphatic carboxylates, pigments, dyes, fillers, foaming agents, flame retardants,
Lubricants, processing aids and the like can be added.

[0051]

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 The formulations shown in Table 1 were mixed using a Henschel mixer for 7 minutes at a rotation speed of 1100 rpm, and then pelletized using an extruder under the conditions of a temperature of 250 ° C. and a rotation speed of 25 rpm. Created. Using these pellets, test pieces having a thickness of 1 mm and 3 mm at 250 ° C., and test pieces for a bending test according to JIS standard were prepared. The haze value (HV, 1 mm and 3 mm) was measured according to JIS K7105, and the bending strength and elastic modulus were measured according to JIS K7203. The crystallization temperature (CD) was measured when the pellet was melted at 250 ° C. for 10 minutes and then cooled at 5 ° C./minute. Table of the results
Shown in 2.

[0053]

[Table 1]

[0054]

[Table 2]

Example 2 Using the formulations shown in Table 3, the haze value (HV) was measured and the bending test was conducted in the same manner as in Example 1. The results are shown in Table-4.

[0056]

[Table 3]

[0057]

[Table 4]

Example 3 Using the formulations shown in Table 5, bending tests and crystallization temperature measurements were carried out in the same manner as in Example 1. The results are shown in Table-6.

[0059]

[Table 5]

[0060]

[Table 6]

(Results) As is apparent from the examples, when the metal salt of the aromatic organic phosphate or the sorbitol compound is used alone in the crystalline synthetic resin, the transparency and mechanical properties of the crystalline synthetic resin are improved. Although it shows an effect of improving strength to some extent, the effect is still insufficient. Further, even if a nucleating agent other than the present invention was used in combination, the synergistic effect was hardly shown.

On the other hand, only when the metal salt of the aromatic organic phosphoric acid ester or the specific sorbitol compound is used in combination, these act synergistically, and the transparency and mechanical strength of the crystalline synthetic resin are increased. It was found that

[0063]

EFFECT OF THE INVENTION A crystalline synthetic resin composition having excellent transparency and mechanical properties can be obtained by blending the crystalline synthetic resin with a specific sorbitol compound and a metal salt of an aromatic organic phosphoric acid ester.

Claims (1)

[Claims] 1. To 100 parts by weight of a crystalline synthetic resin,
0.01 to 5 parts by weight of at least one dibenzylidene sorbitol derivative represented by the following general formula (I), and a metal of an aromatic organic phosphate represented by the following general formula (II) or (III) At least one kind of salt 0.01
A crystalline synthetic resin composition containing 5 to 5 parts by weight. Embedded image Embedded image