JPS6090238A - Propylene polymer composition - Google Patents

Abstract

PURPOSE:A composition, obtained by incorporating crystalline polypropylene polymer before passing through a step of removing catalyst residues therefrom with a sorbitol based compound and an oxidation inhibitor, etc., and capable of giving molded articles having excellent transparency. CONSTITUTION:A composition obtained by incorporating (A) 100pts.wt. crystalline polypropylene polymer with <=300ppm.wt., preferably <=200ppm.wt. catalyst residue content obtained by polymerizing propylene in the presence of a Ziegler type complex catalyst supported on a halogen-containing magnesium compound as a catalyst carrier before passing through a step of substantially removing the catalyst residue with (B) 0.01-1pts.wt. sorbitol based compound expressed by the formula, (C) 0.001-0.5pts.wt. phenolic or phosphorous acid ester based oxidation inhibitor and (D) 0.01-1pts.wt. compound selected from (i) a metallic salt of a (hydroxy)fatty acid of a metal selected from Groups I and II in the periodic table, (ii) a salt of an alkylated lactic acid of a metal selected from Groups I and IIin the periodic table and (iii) hydrotalcite.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to highly transparent improved pyrene polymer compositions.

Tactical polypropylene is easily used in a wide range of fields due to its excellent practical performance, but because it is crystalline, its transparency may be poor and its commercial value may be impaired.

In order to improve this drawback, various methods of adding nucleating agents have been tried. For example, aluminum salts of aromatic carboxylic acids, metal salts of aromatic phosphates, and condensates of polyhydric alcohols and aldehydes are known.

In particular, condensates of polyhydric alcohols and aldehydes (hereinafter referred to as DAS)
) is known to have a large effect on improving the transparency of propylene polymers (Japanese Patent Publication No. 51-22740, No. 5
5-12460,% 1985-30449, 56-3
0450 and 56-45934).

On the other hand, propylene polymers are produced using Ziegler-Natsuta catalysts in gas phase, liquid phase, or in a solvent such as hebutane. This catalyst will remain in the propylene polymer, but if a large amount remains, it will have a significant adverse effect on the practical performance of the propylene polymer. Therefore, the propylene polymer containing the M medium component is usually treated with alcohol, etc. to deactivate it, convert this component into a water-soluble form, and remove it. However, recently, research has progressed to improve nuclear catalysts. The amount of polypropylene produced per unit amount of catalyst has dramatically improved, and as a result, the amount of residual catalyst has become extremely small, and progress has been made to the point where it is actually possible to omit the step of removing catalyst residue outside the system, reducing manufacturing costs. It is becoming possible to make a major contribution to

However, when DAS was added to obtain a transparent molded article using the propylene polymer produced in this way, a problem arose in that the desired transparency was not achieved.

As a result of intensive research into this problem, the present inventor discovered that a molded product with extremely excellent transparency could be obtained by combining compounds with a specific structure, and thus led to the present invention. .

That is, the present invention is a crystalline propylene polymer composition characterized by comprising each of the following components t1) to t4).

(1) Obtained using a Ziegler complex catalyst using a halogen-containing magnesium compound as a catalyst carrier,
A crystalline propylene polymer that has not yet been subjected to a substantial catalyst residue removal step, the catalyst residue content of which is 30%.
100 parts by weight of propylene polymer with a concentration of 0 ppm or less (2) 0.01 to 1 part by weight of a sorbitol compound represented by the following formula 11 ()to-CH)t CH2-0)I (in the formula, t is an integer of 1 or 0.R is a group selected from a hydrogen atom, an alkyl group having 1 to B carbon atoms, an alkoxy group, and a hydroxyl group, and may be different in the same compound.nl and n are θ (3) Phenolic antioxidant or their phosphite antioxidant 0.001 to 0.5 measuring part (4) Shown in (i) to (110) below. at least one of the compounds
Seeds, 0.01 to 1 part by weight (i) Fatty acid or hydroxy fatty acid metal salt of Group 1 or Group 1 of the Periodic Table (11) Alkylated lactate metal salt of Group 1 or Group 1 of the Periodic Table (11) Hydrotalcite The composition of the present invention has a high degree of transparency and is therefore ideal for medical instruments, food containers, and various packaging materials.

In terms of moldability, the propylene polymer (formula 11) used in the present invention has a melt flow rate (MFR) of 0.
Those having a root degree of 1 to 100 f/10 are preferable, and the effects of the present invention are significantly exhibited in crystalline ones. The catalyst used includes one containing titanium trichloride as an active ingredient supported on a carrier such as magnesium chloride. The residual amount of this catalyst in the polymer is 300 ppm by weight.
It is necessary to do the following. If more than this remains, the transparency will hardly be improved. Preferably 200 pp by weight
m or less.

Post-treatment of the propylene polymer after polymerization is not particularly limited, and it may be sufficient to simply remove unreacted monomers and, in some cases, remove the solvent used. Also, a small amount of water,
Those brought into contact with alcohol, epoxy compounds, etc. are more preferred.

In addition to a propylene homopolymer, the present propylene polymer contains a majority (preferably 70% by weight or more) of propylene and other α-olefins (e.g., ethylene,
Random or block copolymers with -methylpentene-1, hexene-1, etc.) are suitable. A random type copolymer is more preferable for this copolymer.

Further, as an example of the sorbitol compound as the component (2) used in the present invention, for example, lXm and n are each 1.1.
．． 1, and examples of R include hydrogen, paramethyl, paraethyl, para-n-butyl, methoxy, and chlorine. The amount added is Kamimachi (11 propylene polymers 1
0.01 to 1 part by weight, preferably o
, i −o,s parts by weight.

If it is more than 1 part by weight, it is not only uneconomical but also causes problems such as bleeding, making it unsuitable for obtaining the composition of the present patent.

Examples of the component (3) used in the present invention include phenolic antioxidants such as 2,6-di-t-butyl-hydroxytoluene, 1,1.3-)lis(2-methyl-4
-Hydroxy-5-t-butylphenyl)butane, tetrakis[methylene-3-(3,5-di-t-y'thyl-4-hydroxyphenyl)globionate]methane, 1
,3,5-trimethyl-2,4,6-tris(3,5-
di-t-butyl-4-hydroxybenzyl)benzene,
n-ophtatecyl-β-(4'-hydroxy-35'
-di-t-butylphenol)gropionate, tris(3,5-di-t-phthyl-4-hydroxybenzyl)
Isocyanurate, 1.3.5-tris-(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)isocyanurrR1d, t-α-tocopherol.

In addition, in the case of phosphite-based antioxidants, 4.4'-
Ptylidene bis(3-methyl-6-t-butylphenyl-di-tridecyl)phosphite, 1.1.3-
) Lis(2-methyl-4-ditridecylphosphite-5-t-butylphenyl)butane, tetrakis(2,
Examples include 4-c-t-butylphenyl)-4,4'-biphenylenecthuosphite, tris(2,4-di-t-butylphenyl)phosphite, and tri(mono- and di-nonylphenyl)phosphite. The amount added is 0.001 to 0.5 parts by weight, preferably 0.01
~0.3 parts by weight. If the amount is less than this, it is insufficient to obtain a molded product having the effects of this patent, and if it is too much, problems such as bleeding and coloring may occur, which is not preferable.

Further, as examples of the above component (4), examples of (i) include Li, Na, KXCa, and Zn salts of stearic acid;
- Li and Ca salts of hydroxystearic acid, Na and Ca salts of lauric acid, etc. (An example of in is stearyl lactate Ca salt.

The amount of component (4) added is 0.01 to 1 part by weight,
Preferably it is 0.05 to 0.3 parts by weight.

If it is more than this, the problem of bleeding is likely to occur.

The composition of the present invention may include other components such as sulfur-based antioxidants, benzophenone, triazole-based ultraviolet absorbers, hindered amine-based light stabilizers, benzoate-based and Ni-based light stabilizers, and more. Further, depending on the purpose, lubricants, antistatic agents, nucleating agents, pigments, dispersants, peroxides, copper damage inhibitors, etc. can be added. Hindered amine light stabilizers and amine antistatic agents may further improve the transparency that is the object of this patent.

The above four components used in the present invention can be mixed using a conventional mixing method. That is, the propylene polymer powder of component (1) is blended with the remaining components (2) or 4), and other components as necessary, mixed with a Henschel mixer etc., and then melt-kneaded with an extruder. Obtain the desired composition. The pellet is then subjected to compression, injection, extrusion, film molding, etc. to obtain a molded product with excellent transparency. Also, 4
The two components may be directly molded without kneading, or
It is also possible to add the above component (2) in the form of a masterbatch.

Examples and comparative examples of this patent are shown below.

Example 1 +1) A catalyst consisting of titanium trichloride supported on magnesium chloride (Ti content = 3.5% by weight) and triethylaluminum were polymerized in heptane, and then centrifuged. After removing heptane and soluble components, dry homopolypropylene powder (MFR=
2r/10 min, residual catalyst = 80 ppm) 100
Add components (2) to (4) listed in Table 1 to parts by weight,
After mixing with a super mixer, a 30mm diameter extruder (230
Pelletized at ℃ setting). The pellets were put into an injection molding machine to make an injection molded sheet of 100 x 100 x 1 m thick (set at 280°C). J I the haze of this sheet
S- was evaluated in accordance with 6714. The results are shown in Table 1.

Comparative examples were also evaluated in the same manner.

The compound abbreviations in the table are as follows.

ECI: 1,3,2,4-dibenzylidene sorbitol gelol manufactured by EC Chemical Co., Ltd. MD: 1,3,2,4-di(manufactured by Shin Nihon Rika Co., Ltd.)
(paramethylbenzylidene) Tulpitou TPNC: ICI
1,1.3-) Lis(2-methyl-4-hydroxy-5-t-butylphenyl)butane Bl (T: 2,6-di-t-butyl-hydroxytoluene manufactured by Yoshitomi Pharmaceutical Co., Ltd. RAlolo: Chipa Tetrakis [methylene-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate comethane Mark 522A manufactured by Niadeka Argus Chemical Co., Ltd.], 1゜3-tris(2-methyl-4- Ditridecylphosphite-5-t-butylphenyl)butane PBKS Nitto Kagaku Co., Ltd. Calcium stearate 5tLi
Lithium nistearate C86: Nitto Kasei Co., Ltd. M12-hydroxy-calcium stearate OHL: Nitto Kasei Co., Ltd. Lithium 12-hydroxy-stearate DHT: Kyowa Kagaku Kogyo Co., Ltd. No1 hydrotalcite LS7
70: Sankyo Co., Ltd. bis(2,2,6,6-tetramethyl-
4-piperidyl) sebacate DMTP: Yoshitomi Pharmaceutical Co., Ltd. dimyristyl thiodiglopionate AMS310 Nilion Co., Ltd. N,N'-bis(2-hydroxyethyl)alkyl (CI2-C18) amine C8L: Musashino Chemical Research Institute Co., Ltd. stearyl lactic acid Calcium (blank below) Example 2 Homopolypropylene polymerized using the same catalyst as in Example 1 was centrifuged to remove heptane and soluble components,
A powder that is brought into contact with a small amount of water vapor and then dried (
MFR=af/lo minute, residual catalyst=80 ppm)
is +1) component, and (2) to (4) listed in Table 2 are added to this.
The ingredients were added and pelletized in the same manner as in Example 1. The pellets were subjected to an electric press molding machine (heating at 230° C. for 10 minutes) to form a sheet having a thickness of III+. The haze of this sheet was measured. Comparative examples were also evaluated in the same manner. The results are shown in Table 2.

(Margin below) inkstone Regret

Claims (1)

[Scope of Claims] A propylene polymer composition comprising each of the following components (1) to 4). (1) Obtained using a Ziegler-type complex catalyst using a halogen-containing magnesium compound as a catalyst carrier,
A crystalline propylene polymer that has not yet been subjected to a substantial catalyst residue removal step, the catalyst residue content of which is 30%.
100 parts by weight of a propylene polymer having a concentration of 0 ppm or less (2) 0.
01 to 1 part by weight (HO-CH)/. CH2-OH ([I) In the formula, t is an integer of 1 or 0. R is a group selected from hydrogen, a halogen atom, an alkyl group having 1 to 8 carbon atoms, an alkoxy group, and a hydroxyl group, and may be different in the same compound. m and n are integers of 0 to 5. ) (3) 0.001 to 0.5 parts by weight of a phenolic antioxidant or their phosphite antioxidant (4) At least one of the compounds shown in (i) to (iii) below, 0.01 to 1 part by weight (1) Fatty acid or hydroxy fatty acid metal salt of Group 1 or Group 1 of the Periodic Table (ii) Alkylated lactate metal salt of Group 1 or Group II of the Periodic Table (iii) Hydrotalcite