JPH07278449A - Crystalline synthetic resin composition - Google Patents

Abstract

PURPOSE:To obtain a crystalline synthetic resin compsn. improved in transparency, mechanical properties, etc. CONSTITUTION:This crystalline synthetic resin compsn. is prepd. by compounding 100 pts.wt. crystalline synthetic resin with 0.01-5 pts.wt. at least one metal salt of a polyhydric alcohol of the formula and 0.01-5 pts.wt. at least one dibenzylidenesorbitol deriv. In the formula, A is a residue formed by removing hydroxyl groups from a tri- to hexahydric alcohol; Me is an alkaline earth metal or zinc; (m) is 0-4; and (n) is 1-3.

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, more specifically, a crystalline synthetic resin blended with a polyhydric alcohol metal salt and a dibenzylidene sorbitol derivative. The present invention relates to an improved crystalline synthetic resin composition.

[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
-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-50-1
No. 39150, No. 51-22740, No. 53-117044, No. 54-2834.
The dibenzylidene sorbitol derivatives described in JP-A No. 8 and JP-A-56-49739 are widely used because they have a large effect of improving the transparency of the resin, and these dibenzylidene sorbitol derivatives are added. In this case, the improvement of mechanical strength was still insufficient.

Therefore, JP-A-51-122150 proposes to use dibenzylidene sorbitol or dibenzylidene mannitol in combination with an organic carboxylic acid or an anhydride thereof, and JP-A-54-69155.
JP-A-58-104933 proposes to use dibenzylidene sorbitol in combination with a metal salt of a carboxylic acid, and JP-A-58-157841 discloses dibenzylidene sorbitol and a hydroxide of an alkali metal. It has been proposed to use an oxide, a carbonate or a hydroxide or oxide of an alkaline earth metal in combination, and JP-A-59-664.
No. 38, it is proposed to use 1,3,2,4-di (alkylbenzylidene) sorbitol and di (aluminum para-t-butylbenzoate) in combination, but the effect is still unsatisfactory in practical use. Was enough.

Therefore, there has been a strong demand for a crystal nucleating agent or a crystallization accelerator which is added to a crystalline synthetic resin to improve transparency and mechanical strength.

[0008]

[Means for Solving the Problems] In view of the present situation, the present inventors have conducted various investigations, and as a result, as a result of adding a polyhydric alcohol metal salt and a dibenzylidene sorbitol derivative to a crystalline synthetic resin, the transparency has been improved. Greatly improved,
Moreover, they have found that they also increase the mechanical strength and have reached the present invention.

That is, the present invention relates to (a) 0.01 to 5 parts by weight of at least one polyhydric alcohol metal salt represented by the following general formula (I) with respect to 100 parts by weight of a crystalline synthetic resin, and ( b) The present invention provides a crystalline synthetic resin composition containing 0.01 to 5 parts by weight of at least one dibenzylidene sorbitol derivative.

[0010]

[Chemical 3]

The dibenzylidene sorbitol derivative is preferably a compound represented by the following general formula (II).

[0012]

[Chemical 4]

The crystalline synthetic resin composition of the present invention will be described in detail below.

In the general formula (I), A represents a residue obtained by removing a hydroxyl group from a 3- to 6-valent alcohol, and examples of the 3- to 6-valent polyhydric alcohol which can provide the same include glycerin and penta. Examples thereof include erythritol, dipentaerythritol, sorbitol, and mannitol. Among them, a residue from glycerin is preferable, Me represents an alkaline earth metal atom or a zinc atom, and alkaline earth metals include magnesium, calcium, barium and the like. Among these metal atoms, zinc atom is preferable. In addition, the number of metal atoms constituting the polyhydric alcohol metal salt: the number of polyhydric alcohol molecules (hereinafter referred to as the molar ratio)
Is usually, but not limited to, 1: 1 or 1: 2.

The particle size, crystal form, or presence or absence of crystal water of the polyhydric alcohol metal salt are not particularly limited, but the particle size is preferably 100 microns or less, particularly 50 microns or less, and the water content is 5%. The following is particularly preferable, and 3% or less.

The polyhydric alcohol metal salt is added in an amount of 0.01 to 5 parts by weight based on 100 parts by weight of the crystalline synthetic resin.
It is preferably 0.05 to 3 parts by weight. Where 0.0
If it is used in an amount of less than 1 part by weight, the effect is almost nonexistent, and if it is used in an amount of more than 5 parts by weight, the performance is not improved, and there is a possibility that a drawback such as an adverse effect on the coloring property may occur.

The polyhydric alcohol metal salt can be easily produced by a dehydration reaction between the polyhydric alcohol and a metal oxide or hydroxide, but the production method is not particularly limited.

In the general formula (II), examples of the halogen atom represented by R ₁ and R ₂ include fluorine, chlorine, bromine and iodine, and examples of the alkyl group having 1 to 4 carbon atoms include methyl, Examples thereof include ethyl, propyl, isopropyl, butyl, sec-butyl and isobutyl, and examples of the alkoxy group include methoxy, ethoxy, propoxy, isopropoxy, butoxy, sec-butoxy, isobutoxy and the like.

Examples of the dibenzylidene sorbitol derivative of the component (b) used in the present invention include the compounds shown below.

[0020]

[Chemical 5]

[0021]

[Chemical 6]

[0022]

[Chemical 7]

[0023]

[Chemical 8]

[0024]

[Chemical 9]

[0025]

[Chemical 10]

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 of the dibenzylidene sorbitol derivative is less than 0.01 parts by weight, almost no effect is observed, while when it is used in an amount of more than 5 parts by weight, the effect is not improved and the coloring property is improved. There is a risk of causing defects such as adverse effects.

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 polyamides such as poamide; polystyrene, indiotactic polystyrene, poly (alkylstyrene), poly (halogenated styrene), poly (alkoxystyrene), poly (vinyl benzoate), and polystyrenes 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 a syringe and infusion bag, food sterilization such as radiation sterilization, and 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 phenolic antioxidants that 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, based on 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, in the crystalline synthetic resin composition of the present invention, a nonionic, cationic or anionic antistatic agent, aluminum-p-tertiary butyl benzoate, alkylene bisphenol phosphate metal salt, etc. may be added, if necessary. Other nucleating agents, hydrotalcites, aliphatic carboxylates of alkaline earth metals, pigments, dyes, fillers, foaming agents, flame retardants, lubricants, processing aids and the like can be added.

[0040]

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 following ingredients 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. With this pellet,
At 250 ° C., test pieces with a thickness of 1 mm and 3 mm, and a test piece for a bending test according to JIS standard were prepared. JI
According to SK7105, haze value (HV, 1 mm and 3 m
m) was measured, and bending strength and elastic modulus were measured according to JIS K7203.

The pellets were melted at 250 ° C. for 10 minutes and then cooled at 5 ° C./minute to obtain a crystallization temperature (C
D) was measured. The results are shown in Table-1.

(Compounding) Propylene homopolymer (melt flow rate 2 g / 10 min) ··· 100 parts by weight tetrakis [methylene-3- (3 ′, 5′-ditertiary butyl-4′-hydroxyphenyl) propionate] methane・ ・ ・ 0.1 parts by weight Tris (2,4-ditertiarybutylphenyl) phosphite ・ ・ ・ 0.1 parts by weight Calcium stearate ・ ・ ・ ・ ・ ・ ・ ・..... 0.1 part by weight No. 2 compounds: 0.1 part by weight polyhydric alcohol metal salt (Table-1)・ ・ ・ ・ ・ 0.2 parts by weight

[0044]

[Table 1]

Example 2 Example 1 using the following formulation
The same test was performed. The results are shown in Table-2.

(Compounding) Propylene homopolymer (melt flow rate 15 g / 10 minutes) 100 parts by weight Tetrakis [methylene-3- (3 ', 5'-di-tert-butyl-4'-hydroxyphenyl) propionate] methane 0.1 parts by weight tris (2,4-ditertiary butylphenyl) phosphite 0.1 parts by weight DHT-4A (synthetic hydrotalcite manufactured by Kyowa Chemical Industry Co., Ltd.)・ 0.1 parts by weight Glycerin Zn (molar ratio 1: 1) ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ 0.2 parts by weight Dibenzylidene sorbitol derivative (Table-2) ・ ・ ・ ・ ・... 0.1 parts by weight

[0047]

[Table 2]

Example 3 Example 1 was prepared using the following formulation.
The bending test and the crystallization temperature were measured by the same method as described above. The results are shown in Table-3.

(Compounding) High-density polyethylene: 100 parts by weight Tetrakis [methylene-3- (3 ', 5'-di-tert-butyl] -4'-Hydroxyphenyl) propionate] methane: 0.1 parts by weight Tris (2,4-ditertiarybutylphenyl) phosphite: 0.1 parts by weight Calcium stearate ...・ ・ ・ 0.1 parts by weight No. 2 compounds: 0.1 parts by weight Polyhydric alcohol metal salt (Table-2)・ ・ ・ ・ ・ 0.2 parts by weight

[0050]

[Table 3]

As is apparent from the examples, when the dibenzylidene sorbitol derivative or the polyhydric alcohol metal salt is used alone in the crystalline synthetic resin, the transparency and mechanical strength of the crystalline synthetic resin are improved to some extent. Although it shows an effect, the effect is still insufficient. Further, even if a nucleating agent other than those specified in the present invention is used in combination, its additive effect is hardly shown.

On the other hand, only when the dibenzylidene sorbitol derivative or the polyhydric alcohol metal salt is used in combination, these act synergistically and remarkably improve the transparency and mechanical strength of the crystalline synthetic resin. I understand.

[0053]

By adding a polyhydric alcohol metal salt and a dibenzylidene sorbitol derivative to a crystalline synthetic resin, a crystalline synthetic resin composition having excellent transparency and mechanical properties can be obtained.

Claims (3)

[Claims] 1. To 100 parts by weight of a crystalline synthetic resin,
(A) 0.01 to 5 parts by weight of at least one polyhydric alcohol metal salt represented by the following general formula (I) and (b) at least one of dibenzylidene sorbitol derivatives.
A crystalline synthetic resin composition containing 0 to 5 parts by weight. [Chemical 1] 2. The composition according to claim 1, wherein the dibenzylidene sorbitol derivative is a compound represented by the following general formula (II). [Chemical 2] 3. The composition according to claim 1, wherein the polyhydric alcohol metal salt is a metal glycerolate.