JP3369719B2 - Crystalline synthetic resin composition - Google Patents

Description

Description: BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a crystalline synthetic resin composition, and more particularly, to a crystalline α-olefin polymer containing a glycerin metal salt and a hydrotalcite compound. The present invention relates to a crystalline synthetic resin composition having improved transparency and mechanical properties. 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 low crystallization rates after heat-melt molding. For this reason, the molding cycleability is low, and shrinkage occurs due to the progress of crystallization after heat molding . In addition, these crystalline synthetic resins have disadvantages of insufficient strength and poor transparency because large crystals are generated. [0003] All of these disadvantages are derived from the crystallinity of the synthetic resin, and are known to be eliminated if the crystallization temperature of the synthetic resin can be increased and fine crystals can be rapidly formed. I have. It is known to add a nucleating agent or a crystallization accelerator for this purpose.
A metal salt of a carboxylic acid such as aluminum tertiary butyl benzoate, sodium adipate, sodium bis (4-
Tert-butylphenyl) phosphate, sodium-2,
2'-methylenebis (4,6-di-tert-butylphenyl)
Acidic phosphate metal salts such as phosphates, and polyhydric alcohol derivatives such as dibenzylidene sorbitol and bis (4-methylbenzylidene) sorbitol have been used. However, there has not been obtained a compound which sufficiently satisfies transparency and mechanical strength when added to a synthetic resin. It is known that a hydrotalcite compound is added to a synthetic resin as a hydrochloric acid supplement for a chlorine-containing resin or a deactivator for a metal catalyst used in the production of an olefin resin. 60-6023
No. 8 proposes to use a sorbitol-based compound, an antioxidant, hydrotacite and the like in combination with a propylene polymer which has not been treated with a catalyst residue.
No. 51 proposes to use an aluminum salt of p-butylbenzoic acid and hydrotalcite in combination with a propylene-based polymer containing Mg and halogen as a catalyst residue. However, hydrotalcite has no specific effect compared to other catalyst deactivators, and its effect is still insufficient. For this reason, a crystalline synthetic resin composition having excellent transparency and mechanical properties has been strongly demanded. The present inventors have made various studies in view of the present situation, and as a result, have found that crystalline α-olefin
By the emission polymer adding a specific metal salt of glycerin and hydrotalcite compounds, significantly improve transparency, yet it was reached the present invention that also increases the mechanical strength. That is, the present invention relates to a crystalline α-olefin polymerization
(A) 0.01 to 5 parts by weight of an alkaline earth metal salt or zinc salt of glycerin (hereinafter, also abbreviated as glycerin metal salt) and (b) at least one kind of hydrotalcite compound per 100 parts by weight of the body . An object of the present invention is to provide a crystalline synthetic resin composition containing from 0.01 to 5 parts by weight. Hereinafter, the crystalline synthetic resin composition of the present invention will be described in detail. In the alkaline earth metal salt or zinc salt of glycerin, examples of the alkaline earth metal include magnesium, calcium, barium and strontium, and among these metal salts, the zinc salt is most preferred. The number of metal atoms constituting the glycerin metal salt: the number of glycerin molecules (hereinafter referred to as a molar ratio) is usually 1:
1, but is not limited to this. The alkaline earth metal salt and zinc salt of glycerin used in the present invention can be easily produced by, for example, a dehydration reaction between glycerin and a metal oxide or hydroxide. The particle size, crystal form, or presence or absence of water of crystallization of the glycerin metal salt is not particularly limited.
The particle size is preferably 100 microns or less, particularly 50 microns or less, and the water content is preferably 5% or less, particularly preferably 3% or less. The amount of the glycerin metal salt added depends on the amount of the crystalline α-
The amount is 0.01 to 5 parts by weight, preferably 0.05 to 3 parts by weight, based on 100 parts by weight of the olefin polymer . If the amount is less than 0.01 part by weight, there is almost no effect, and if the amount is more than 5 parts by weight, no improvement in performance is observed, and there is a possibility that a disadvantage such as adverse effect on coloring property may be caused. The hydrotalcite compound used in the present invention is a magnesium-aluminum or magnesium-zinc-aluminum complex salt compound represented by the following general formula (I). ## STR1 ## The hydrotalcite compound used in the present invention may be a natural product or a synthetic product. As the synthesis method, JP-B-46-2280,
JP-B-50-30039, JP-B-51-2912
9 and JP-A-61-174270. Further, in the present invention, it can be used without being limited by the crystal structure, the crystal particle diameter, the presence or absence of crystallization water and the amount thereof. Further, the surface of the hydrotalcite compound may be made of a higher fatty acid such as stearic acid, a higher fatty acid metal salt such as an alkali metal oleate, an organic metal sulfonate such as an alkali metal dodecylbenzenesulfonate, a higher fatty acid amide, or the like. Those coated with higher fatty acid esters or waxes can also be used. The addition amount of these hydrotalcite compounds is 0.01 to 10 parts by weight, preferably 0.05 to 5 parts by weight, based on 100 parts by weight of the crystalline α-olefin polymer . When the hydrotalcite compound is used in an amount of less than 0.01 part by weight, almost no effect is obtained, and when it is used in an amount of more than 10 parts by weight, the effect is not increased, and a drawback such as giving a large color to the synthetic resin may be caused. is there. The crystalline α-olefin used in the present invention
Examples of the polymer include low-density polyethylene, linear low-density polyethylene, high-density polyethylene, polypropylene, syndiotactic polypropylene, polybutene-1, poly-3-methylbutene, an ethylene / propylene block, and a random copolymer. α-olefin
Polymers and the like can be mentioned. [0021] In particular, the present invention is useful when applied to polypropylene, ethylene / propylene copolymer and polypropylene resin, such as those of the propylene polymer and mixtures with other α- olefin polymer. 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. No. 37148, 63-
Nos. 37152, 63-90552 and 63
-210152, 63-213547,
JP-A-63-243150, JP-A-63-243152, JP-A-63-260943, and JP-A-63-2609.
44, 63-264650, JP-A-1-
178541, 2-49047, 2-
Nos. 102242, 2-251548, 2
-279746, JP-A-3-195751 and the like can also be suitably used. [0022] In the present invention, a method of adding the components is not particularly restricted, a method generally used, for example, sintered
A method of dry blending a crystalline α-olefin polymer powder or pellets with an additive powder, a masterbatch containing a high concentration of each component is prepared, and this is mixed with a crystalline α-O
A method of adding to the refin polymer can be used. In addition, the crystalline synthetic resin composition of the present invention can be formed into various molded products, fibers, biaxially stretched films, sheets, and the like by well-known processing methods such as extrusion molding, injection molding, vacuum molding, blow molding, and cross-linking foam molding. Can be used. The composition of the present invention may be used for various post-treatments, for example, for medical use such as a syringe and an infusion bag, or for use in sterilization by radiation such as a food packaging use, or paintability. To improve surface properties,
It can also be used for applications in which low-temperature plasma treatment or the like is performed after molding. The crystalline synthetic resin composition of the present invention may further comprise, if necessary, a phenolic antioxidant, an organic phosphorus antioxidant such as organic phosphite or phosphonite,
By adding a light stabilizer such as a thioether-based antioxidant, an ultraviolet absorber or a hindered amine compound, the oxidation stability and the light stability can be further improved.
By using a phenolic antioxidant and / or an organic phosphorus antioxidant in combination, it is possible to prevent coloring during heating and a decrease in mechanical properties. The phenolic antioxidants usable in the present invention include, for example, 2,6-di-tert-butyl-p-cresol, 2,6-diphenyl-4-octadecyloxyphenol, 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-ditert-butyl-4
-Hydroxyphenoxy) -s-triazine, 2,2 ′
-Methylenebis (4-methyl-6-tert-butylphenol), bis [3,3-bis (4-hydroxy-3-tert-butylphenyl) butylic acid] glycol ester, 4,4'-butylidenebis (6- Tributyl-m
-Cresol), 2,2′-ethylidenebis (4,6-
Di-tert-butylphenol), 1,1,3-tris (2-
Methyl-4-hydroxy-5-tert-butylphenyl) butane, bis [2-tert-butyl-4-methyl-6- (2-
Hydroxy-3-tert-butyl-5-methylbenzyl) phenyl] terephthalate, 1,3,5-tris (2,6
-Dimethyl-3-hydroxy-4-tert-butylbenzyl) isocyanurate, 1,3,5-tris (3,5-
Di-tert-butyl-4-hydroxybenzyl) isocyanurate, 1,3,5-tris (3,5-di-tert-butyl-4)
-Hydroxybenzyl) -2,4,6-trimethylbenzene, 1,3,5-tris [(3,5-di-tert-butyl-
4-hydroxyphenyl) propionyloxyethyl]
Isocyanurate, tetrakis [methylene-3-
(3 ', 5'-di-tert-butyl-4'-hydroxyphenyl) propionate] methane, 2-tert-butyl-4-methyl-6- (2-acryloyloxy-3-tert-butyl-5-methylbenzyl ) Phenol, 3,9-bis (1,1-dimethyl-2-hydroxyethyl) -2,
4,8,10-Tetraoxaspiro [5.5] undecane-bis [β- (3-tert-butyl-4-hydroxy-5
-Butylphenyl) propionate] and triethylene glycol bis [β- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate]. The addition amount of these phenolic antioxidants is based on 100 parts by weight of the crystalline α-olefin polymer .
It is 0.001 to 5 parts by weight, preferably 0.01 to 3 parts by weight. The organic phosphorus antioxidants usable in the present invention include, for example, 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-di-tert-butylphenyl) octyl phosphite, 2,2'-methylene bis (4,6-di-tert-butylphenyl) octadecyl phosphite, 2,2'-methylene bis (4,6-di-tert-butylphenyl) fluorophosphite, tetrakis (2,4-di-tert-butylphenyl) biphenylenediphosphonite, 9,10-dihydro-9-oxa-10phosphaphenanthrene-10 -Oxides and the like. The addition amount of the organic phosphorous compound, forming
0.0 parts by weight based on 100 parts by weight of the crystalline α-olefin polymer.
The amount is from 0.01 to 5 parts by weight, preferably from 0.01 to 3 parts by weight. Examples of thioether antioxidants include thiodipropionic acid dilauryl, dimyristyl,
And dialkylthiodipropionates such as myristylstearyl and distearyl esters, and β-alkylmercaptopropionates of polyols such as pentaerythritol tetra (β-dodecylmercaptopropionate). As the ultraviolet absorber, for example, 2,4
-Dihydroxybenzophenone, 2-hydroxy-4-
2-hydroxybenzophenones such as methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, and 5,5′-methylenebis (2-hydroxy-4-methoxybenzophenone); 2- (2-hydroxy-5
-Methylphenyl) benzotriazole, 2- (2-hydroxy-5-tert-octylphenyl) benzotriazole, 2- (2-hydroxy-3,5-ditert-butylphenyl) -5-chlorobenzotriazole, 2- (2-
Hydroxy-3-tert-butyl-5-methylphenyl)-
5-chlorobenzotriazole, 2- (2-hydroxy-3,5-dicumylphenyl) benzotriazole,
2,2′-methylenebis (4-tert-octyl-6-benzotriazolyl) phenol, 2- (2-hydroxy-
2- (3-tert-butyl-5-carboxyphenyl) benzotriazole such as polyethylene glycol ester
(2-hydroxyphenyl) benzotriazoles; phenyl salicylate, resorcinol monobenzoate, 2,4-di-tert-butylphenyl-3,5-di-tert-butyl-4-hydroxybenzoate, hexadecyl-
Benzoates such as 3,5-di-tert-butyl-4-hydroxybenzoate; substituted oxanilides such as 2-ethyl-2'-ethoxyoxanilide and 2-ethoxy-4'-dodecyloxanilide; ethyl-α -Cyano-β,
β-diphenyl acrylate, methyl-2-cyano-3
And cyanoacrylates such as -methyl-3- (p-methoxyphenyl) acrylate. Light stabilizers such as hindered amine compounds include, for example, 2,2,6,6-tetramethyl-4
Piperidyl stearate, 1,2,2,6,6-pentamethyl-4-piperidyl stearate, 2,2,6
6-tetramethyl-4-piperidyl benzoate, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1,2,2,6,6-pentamethyl-
4-piperidyl) sebacate, tetrakis (2,2,
6,6-tetramethyl-4-piperidyl) butanetetracarboxylate, tetrakis (1,2,2,6,6-
Pentamethyl-4-piperidyl) butanetetracarboxylate, bis (1,2,2,6,6-pentamethyl-
4-piperidyl) di (tridecyl) -1,2,3,4
-Butanetetracarboxylate, bis (1,2,2,
6,6-pentamethyl-4-piperidyl) -2-butyl-2- (3,5-ditert-butyl-4-hydroxybenzyl) malonate, 1- (2-hydroxyethyl) -2,
2,6,6-tetramethyl-4-piperidinol / diethyl succinate polycondensate, 1,6-bis (2,2,6,6
-Tetraethyl-4-piperidylamino) hexane / dibromoethane polycondensate, 1,6-bis (2,2,6,6
-Tetramethyl-4-piperidylamino) hexane /
2,4-dichloro-6-morpholino-s-triazine polycondensate, 1,6-bis (2,2,6,6-tetramethyl-4-piperidylamino) hexane / 2,4-dichloro-6- Trioctylamino-s-triazine polycondensate,
1,5,8,12-tetrakis [2,4-bis (N-butyl-N- (2,2,6,6-tetramethyl-4-piperidyl) amino) -s-triazin-6-yl]- 1,
5,8,12-tetraazadodecane, 1,5,8,12
-Tetrakis [2,4-bis (N-butyl-N- (1,
2,2,6,6-pentamethyl-4-piperidyl) amino) -s-triazin-6-yl] -1,5,8,12
-Tetraazadodecane, 1,6,11-tris [2,4
-Bis (N-butyl-N- (2,2,6,6-tetramethyl-4-piperidyl) amino) -s-triazine-6
-Ylamino] undecane, 1,6,11-tris [2,4-bis (N-butyl-N- (1,2,2,6,
Hindered amine compounds such as 6-pentamethyl-4-piperidyl) amino) -s-triazin-6-ylamino] undecane. In addition, the crystalline synthetic resin composition of the present invention may contain, if necessary, a nonionic, cationic or anionic antistatic agent, aluminum-p-tert-butylbenzoate, dibenzylidenesorbitol, bis ( 4-
Add other nucleating agents such as methylbenzylidene) sorbitol, metal salts of alkylene bisphenol phosphates, aliphatic carboxylate salts of alkaline earth metals, pigments, dyes, fillers, blowing agents, flame retardants, lubricants, processing aids, etc. be able to. The present invention will be described in more detail with reference to the following examples. However, the present invention is not limited in any way by these examples. Example 1 The following formulation was mixed with a Henschel mixer at a rotational speed of 11
After mixing at 00 rpm for 7 minutes, the temperature was 250 ° C. and the number of revolutions was 2
Pellets were prepared using an extruder under the condition of 5 rpm. Using the pellets, test pieces having a thickness of 1 mm and 3 mm and a test piece for a bending test according to JIS were prepared at 250 ° C. The haze value (HV, 1 mm and 3 mm) was measured in accordance with JIS K7105,
Flexural strength and elastic modulus were measured in accordance with 7203. The results are shown in Table 1. (Blending) 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-di-tert-butylphenyl) phosphite 0.1 parts by weight zinc glycerin (molar ratio 1: 1) ...
······ 0.3 parts by weight test compound (Table-1)
..... 0.1 parts by weight [Table 1] Example 2 A test similar to that of Example 1 was performed using the following formulation. The results are shown in Table-2. (Blending) Propylene homopolymer (melt flow rate 2 g / 1
100 minutes by weight tetrakis [methylene-3- (3 ', 5'-di-tert-butyl-4'-hydroxyphenyl) propionate] methane 0.1 parts by weight tris (2,4-di-tert-butylphenyl) phosphite 0.1 parts by weight zinc glycerin (molar ratio 1: 1) ...
.......... 0.3 parts by weight of test compound (Table-2)
..... 0.1 parts by weight [Table 2] Example 3 A bending test was performed in the same manner as in Example 1 using the following compound. The results are shown in Table-3. (Blending) 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-di-tert-butylphenyl) phosphite 0.1 parts by weight hydrotalcite 1 ...
······ 0.1 parts by weight of test compound (Table-3)
... 0.2 parts by weight [Table 3] As is clear from the examples, the crystalline α-O
When a metal salt of glycerin and a catalyst deactivator other than those specified in the present invention are used in combination with the refin polymer, the effect of improving the transparency and mechanical properties is insufficient, and the crystal other than the present invention its combined effect is not observed little if the agent or crystallization accelerator was used in combination with hydrotalcite compounds, in particular insufficient effect of improving the mechanical properties. On the other hand, when used in combination with a metal salt of glycerin and a hydrotalcite compound, they act synergistically to significantly improve the transparency and mechanical strength of the crystalline α-olefin polymer. I do. The transparency, mechanical properties and the like are remarkably improved by adding a metal salt of glycerin and a hydrotalcite compound to the crystalline α-olefin polymer .

────────────────────────────────────────────────── ─── Continuation of the front page (56) References JP-A-3-39351 (JP, A) JP-A-2-75641 (JP, A) JP-A-7-278449 (JP, A) JP-A-7-278 278448 (JP, A) (58) Field surveyed (Int. Cl. ⁷ , DB name) C08L 101/00-101/16 C08L 23/02-23/24 C08K 3/24-3/26 C08K 5/05 -5/057 CA (STN)

Claims (1)

(57) Claims: (1) at least one kind of alkaline earth metal salt or zinc salt of glycerin (a) in an amount of 0.01 to 5 parts by weight based on 100 parts by weight of a crystalline α-olefin polymer; Part and / or at least one hydrotalcite compound (b).
A crystalline synthetic resin composition containing from 0.01 to 5 parts by weight.