JPH10204232A - Polypropylene resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a resin composition excellent in transparency and stiffness, and free from the adhesion of dirt to a forming machine during a forming process. SOLUTION: This polypropylene resin composition is composed of 100 pts.wt. of a propylene-ethylene-butene-1 three dimensional copolymer obtained by the random polymerization of propylene, ethylene and butene-1 in the presence of a catalyst composed of (A) a solid titanium compound which contains magnesium, titanium and a halogen as essential components, (B) an organo aluminum compound and (C) t-butyl(ethyl)dimethoxysilane, and 0.05-0.5 pts.wt. of a nucleating agent such as a dibenzylidenesorbitol-based nucleating agent.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polypropylene resin composition comprising a propylene-ethylene-butene-1 terpolymer obtained by a specific polymerization catalyst and a nucleating agent. The present invention relates to a polypropylene resin composition capable of obtaining a molded article having excellent product appearance such as rigidity and transparency when molded.

[0002]

2. Description of the Related Art Conventionally, polypropylene has been widely used in the field of sheets and injections because of its lightness, high rigidity, excellent chemical resistance and transparency. However, depending on the application, these properties are not fully satisfied. For example, in fields competing with polystyrene, polyvinyl chloride and the like, further improvement in rigidity and transparency is required. As means for improving transparency and rigidity, Japanese Patent Application Laid-Open
As described in JP-A-4-88950, JP-A-58-215446 and JP-A-59-74158, there is a method of blending a propylene-ethylene random copolymer with a nucleating agent. The stiffness and stiffness have not yet reached satisfactory levels. Various means for solving such a problem have been proposed so far. For example, JP-A-59-164348 discloses that a terpolymer obtained by random copolymerization of propylene, ethylene and butene-1 is blended with a nucleating agent to have high transparency. A method for obtaining a molded article having excellent rigidity is disclosed. However, even in the resin composition obtained by this method, the balance between transparency and rigidity has not yet reached a satisfactory level.

[0003] On the other hand, polypropylene and propylene-based copolymers are generally produced using a catalyst comprising a titanium halide compound and an organoaluminum compound. However, when a large amount of these catalyst residues remain in the polymer. In this case, not only does the color tone of the molded product become yellow and the transparency is impaired, but also the problem of poor appearance occurs. In particular, when a large amount of chlorine atoms remain in the polymer, when the polymer is mixed with a metal soap such as calcium stearate, which is generally used as a processing aid or a chlorine scavenger, it reacts with chlorine atoms. As a result, fatty acids such as stearic acid are liberated to cause stains on molds and rolls at the time of molding, phenomena on eyes, and the quality of molded products is impaired.

[0004]

As described above, injection,
There has been a demand for a polypropylene-based resin composition which satisfies the balance of appearance and the like of a product while satisfying transparency and rigidity in the field of sheets.

[0005]

Means for Solving the Problems The present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, a nucleating agent was added to a terpolymer obtained using a specific catalyst system. The polypropylene-based resin composition can finely and uniformly regulate polypropylene crystals, and has very few substances that may impair the appearance of the product. Therefore, it has been found that the above-mentioned problems can be solved, and the present invention has been completed.

That is, the present invention relates to a catalyst comprising [A] a solid titanium compound containing magnesium, titanium and halogen as essential components, [B] an organoaluminum compound, and [C] t-butyl (ethyl) dimethoxysilane. Propylene, ethylene and butene-1 in the presence of
Propylene-ethylene- obtained by random copolymerization of
A polypropylene resin composition comprising 100 parts by weight of a butene-1 terpolymer and 0.05 to 0.5 parts by weight of a nucleating agent.

The details will be described below.

[0008] The terpolymer of the present invention is a random copolymer substantially composed of monomer units based on propylene, ethylene and butene-1. The monomer unit based on (hereinafter, also simply referred to as “ethylene unit”) is 1 to 6 mol%, and the monomer unit based on butene-1 (hereinafter, also simply referred to as “butene-1 unit”) is from 1 to 6 mol%. 6 mol%. That is, if the composition is out of the above range, the balance between transparency and rigidity in injection and sheet molding is not sufficiently exhibited, which is not preferable.
For example, one ethylene unit or one butene-1 unit
If the amount is less than 6 mol%, the molded article obtained using the same has poor transparency. On the other hand, when the ethylene unit exceeds 6 mol% or the butene-1 unit exceeds 6 mol%,
It is not preferable because the rigidity of the molded article is reduced. In consideration of the above-mentioned quality balance, a more preferable composition range is that the ethylene unit is 1.2 to 5.5 mol%, more preferably,
1.5 to 5 mol%, and butene-1 unit is 1.5 to 5 mol%.
It is in the range of 5.5 mol%, more preferably 2 to 5 mol%.

The terpolymer of the present invention has a small amount of catalyst residue remaining in the copolymer, has no roll contamination due to the release of fatty acids when metal soap is used as a chlorine scavenger, and has good color tone and appearance. Is also excellent. That is, in the terpolymer of the present invention, the remaining titanium atom is 3 ppm.
Or less, preferably 2 ppm or less. On the other hand, the concentration of chlorine atoms is 30 ppm or less,
pm or less. When the concentration of the titanium atom exceeds 3 ppm, the color tone of the obtained molded article is undesirably yellow. On the other hand, when the concentration of chlorine atoms exceeds 30 ppm, fatty acids are released from the added metal soap, and when molding into films and sheets, the stains of the apparatus are caused and the appearance of molded products is poor.

The concentrations of these atoms are values measured by the fluorescent X-ray method. These values for the terpolymer of the present invention are values for the terpolymer itself obtained by polymerization.

The terpolymer according to the present invention preferably has a small amount of a low molecular weight amorphous component represented by a low-temperature toluene-soluble content. The value of the low-temperature toluene-soluble component S (wt%) of the terpolymer of the present invention is expressed by the following formula in relation to the monomer unit E (mol%) based on ethylene: S ≦ 0.37 × E + 1.5 is preferably satisfied. In particular, when the low-temperature toluene-soluble content is within the range of the above relational expression, a molded article having good bleed whitening and good blocking resistance of the sheet can be obtained. A more preferred range is S ≦ 0.37 × E + 1.0, and still more preferably S ≦ 0.35 × E + 1.0.

The value of the low-temperature toluene-soluble component S (wt%) of the terpolymer according to the production method of the present invention is determined by completely dissolving the terpolymer in toluene at 100 ° C. 18
After cooling to ° C., the mixture was allowed to stand and the precipitated components were separated by filtration and toluene was completely evaporated from the toluene solution to obtain a toluene-soluble content, which was obtained from the following equation.

S = (amount of soluble matter (g) / amount of terpolymer used (g)) × 100 Furthermore, the terpolymer obtained by the production method of the present invention is obtained by gel permeation chromatography. It is preferable that the molecular weight distribution represented by the ratio (Mw / Mn) of the weight average molecular weight (Mw) and the number average molecular weight (Mn) measured by (GPC) is 4.0 or more. Particularly when Mw / Mn is 4.0 or more, the melt tension is high, the workability is good, and the rigidity of the molded body is more excellent.

The titanium compound [A] used in the present invention
Is a solid titanium compound having high catalytic activity and containing titanium, magnesium and halogen as essential components. As such a titanium compound having a high catalytic activity, a titanium halide, particularly a titanium tetrachloride in which various magnesium compounds are supported, is suitably used. As a method for producing this catalyst, a known method is employed without any limitation. For example, a method of co-milling titanium tetrachloride with a magnesium compound such as magnesium chloride, a method of co-milling a titanium halide and a magnesium compound in the presence of an electron donor such as alcohol, ether, ester, ketone or aldehyde, or And a method of contacting a titanium halide, a magnesium compound and an electron donor in a solvent. A method for producing such a titanium compound is described in, for example,
Nos. 55206, 56-136806 and 57-3
4103, 58-8706, 58-83006, 58-138708, 58-183709, 59-
206408, 59-219311, 60-812
08, 60-81209, 60-186508, 60-192708, 61-211309, 61-
271304, 62-15209, 62-1170
6, 62-72702, 62-104810, and the like.

As the organoaluminum compound [B], a compound known to be used for polymerization of olefins can be used without any limitation. For example, trimethyl aluminum, triethyl aluminum, tri-n propyl aluminum, tri-n butyl aluminum, tri-i butyl aluminum, tri-n hexyl aluminum, tri-
n-octyl aluminum, trialkyl aluminums such as tri-n-decyl aluminum, ethyl aluminum dichloride, ethyl aluminum sesquichloride,
Diethyl aluminum chloride, diethyl aluminum bromide, diethyl aluminum iodide, diisobutyl aluminum chloride, di-n-propyl aluminum chloride, ethyl aluminum dibromide, ethyl aluminum diiodide, isobutyl aluminum dichloride, isobutyl aluminum dibromide, isobutyl aluminum diiodide, etc. Halogen containing alkyl aluminums can be used. Further, alkoxyaluminums such as monoethoxydiethylaluminum and diethoxymonoethylaluminum can also be used.

As the component [C] of the present invention, t-butyl (ethyl) dimethoxysilane is used. Compounds other than t-butyl (ethyl) dimethoxysilane are not preferred because the transparency and rigidity of the obtained terpolymer are not sufficiently improved.

The terpolymer of the present invention can be obtained by subjecting a terpolymer of propylene, ethylene and butene-1 to random copolymerization in the presence of the above-mentioned catalyst component. In order to further reduce the soluble component and improve the particle properties of the polymer particles obtained by the polymerization, the titanium compound [A] is prepolymerized with propylene or another α-olefin prior to performing the ternary random copolymerization. Is effective. The conditions for the prepolymerization are not particularly limited, but it is more preferable that the prepolymerization is performed under the following conditions. That is, [A] titanium compound [B] organoaluminum compound [D] general formula [I] R ¹ _n Si (OR ² ) _4-n [I] (where R ¹ and R ² are the same or different carbons) Number 1
To 20 hydrocarbon groups. And (E) a general formula [II] R ³ I [II] (where R ³ is an iodine atom or a hydrocarbon group having 1 to 20 carbon atoms) The method of prepolymerizing 0.1 to 50 g of propylene or another α-olefin per 1 g of [A] titanium compound in the presence of an iodine compound represented by the formula (1) is preferable.

As the organoaluminum compound [B] used in the prepolymerization, the compounds described above can be used as they are.

The amount of the organoaluminum compound [B] used in the prepolymerization is not particularly limited, but is generally 1 to 100 in terms of Al / Ti (molar ratio) to Ti atoms in the titanium compound. Is more preferable, and 3-1
It is preferably 0.

Further, as the organosilicon compound [D], the compound represented by the above general formula [I] can be employed without any limitation, but other than the t-butyl (ethyl) dimethoxysilane used in the ternary random copolymerization. The use of the compound is a more preferred embodiment because it is possible to prevent mutual adhesion of the obtained terpolymer particles and to further improve the particle properties.

In the above formula, the hydrocarbon group having 1 to 20 carbon atoms represented by R ¹ and R ² includes a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group and a sec-butyl group. Pentyl group, isopentyl group, neopentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, and cyclopentyl group, alkyl-substituted cyclopentyl group, cyclohexyl group, alkyl-substituted cyclohexyl group, t-
Examples include a butyl group, a t-amyl group, a phenyl group, and an alkyl-substituted phenyl group.

Examples of the organosilicon compound preferably used in the present invention are as follows. For example, trimethylmethoxysilane, trimethylethoxysilane, di-t
-Butyldimethoxysilane, di-t-amyldimethoxysilane, dicyclohexyldimethoxysilane, di (2-methylcyclopentyl) dimethoxysilane, di (3-methylcyclopentyl) dimethoxysilane, di (2-ethylcyclopentyl) dimethoxysilane, di (2 3-dimethylcyclopentyl) dimethoxysilane, di (2,4-
Dimethylcyclopentyl) dimethoxysilane, di (2,
5-dimethylcyclopentyl) dimethoxysilane, di (2,3-diethylcyclopentyl) dimethoxysilane, di (2,3,4-trimethylcyclopentyl) dimethoxysilane, di (2,3,5-trimethylcyclopentyl) dimethoxysilane, di ( 2,3,4-triethylcyclopentyl) dimethoxysilane, di (tetramethylcyclopentyl) dimethoxysilane, di (tetraethylcyclopentyl) dimethoxysilane, di (2-methylcyclohexyl) dimethoxysilane, di (3-methylcyclohexyl) dimethoxysilane, (4-methylcyclohexyl) dimethoxysilane, di (2-ethylcyclohexyl) dimethoxysilane, di (2,3-dimethylcyclohexyl) dimethoxysilane, di (2,4-dimethylcyclohexyl) dime Kishishiran, di (2,5-dimethylcyclohexyl) dimethoxysilane, di (2,6
Dimethylcyclohexyl) dimethoxysilane, di (2,
3-diethylcyclohexyl) dimethoxysilane, di (2,3,4-trimethylcyclohexyl) dimethoxysilane, di (2,3,5-trimethylcyclohexyl)
Dimethoxysilane, di (2,3,6-trimethylcyclohexyl) dimethoxysilane, di (2,4,5-trimethylcyclohexyl) dimethoxysilane, di (2,4
6-trimethylcyclohexyl) dimethoxysilane, di (2,3,4-triethylcyclohexyl) dimethoxysilane, di (2,3,4,5-tetramethylcyclohexyl) dimethoxysilane, di (2,3,4,6-tetra Methylcyclohexyl) dimethoxysilane, di (2,
3,5,6-tetramethylcyclohexyl) dimethoxysilane, di (2,3,4,5-tetraethylcyclohexyl) dimethoxysilane, di (pentamethylcyclohexyl) dimethoxysilane, di (pentaethylcyclohexyl) dimethoxysilane, t-amyl Methyldimethoxysilane, cyclopentylmethyldimethoxysilane, cyclopentylethyldimethoxysilane, cyclopentylisobutyldimethoxysilane, dicyclopentyldimethoxysilane, cyclohexylmethyldimethoxysilane, cyclohexylethyldimethoxysilane, cyclohexylisobutyldimethoxysilane, diphenyldimethoxysilane, phenylmethyldimethoxysilane, ethyltrimethoxysilane Methoxysilane, ethyltriethoxysilane, methyltrimethoxysilane, - propyltriethoxysilane, decyltriethoxysilane, phenyltrimethoxysilane, methyltriethoxysilane, ethyltriethoxysilane, t- butyl triethoxysilane, n- butyl triethoxysilane, cyclopentene trimethoxysilane,
Examples thereof include cyclohexyltrimethoxysilane, cyclopentyltriethoxysilane, cyclohexyltriethoxysilane, phenyltriethoxysilane, ethyl silicate, butyl silicate and the like.

The amount of the organosilicon compound used in the prepolymerization is not particularly limited, but is generally 0.1 / Si (Ti molar ratio) with respect to the Ti atom in the titanium compound.
To 100, and preferably 0.5 to 10.

Further, in the prepolymerization, it is preferable to use an iodine compound [E] in order to further reduce the low-temperature toluene-soluble content of the obtained terpolymer.

The iodine compound [E] has the general formula [II]
Is employed without any limitation. R ³ in the general formula [II] is an iodine atom or a hydrocarbon group having 1 to 20 carbon atoms. In the case of a hydrocarbon group, R ³ is a carbon atom such as an alkyl group, an alkenyl group, an alkynyl group or an aryl group. It is a hydrogen group. Specific examples of the iodine compound that can be suitably used in the present invention include, for example, iodine, methyl iodide, ethyl iodide, propyl iodide, butyl iodide, benzene iodide, p-iodide toluene and the like. Among them, iodine, methyl iodide, ethyl iodide and the like are preferable.

The amount of the iodine compound used in the prepolymerization is not particularly limited, but generally it is preferably 0.1 to 100 (molar ratio) with respect to the Ti atom in the titanium compound. It is preferably from 0.5 to 50.

The above components used in the prepolymerization may be added sequentially or may be used as a mixture. The order of addition in the case of sequential addition is not particularly limited.

The polymerization amount of propylene or α-olefin in the prepolymerization is 0.1 to 50 per gram of the titanium compound.
g, preferably in the range of 1 to 20 g.
A range from 10 to 10 g is preferred. Examples of the α-olefin other than propylene used in the prepolymerization include linear α-olefins such as ethylene, butene-1, pentene-1, and hexene-1.
In addition to olefins, branched α-olefins such as 3-methylbutene-1, 4-methylpentene-1, vinylcycloalkane and the like can be mentioned. In addition, the propylene or α-
It is also possible to use two or more olefins simultaneously. It is also possible to make hydrogen coexist in the preliminary polymerization.

In the prepolymerization, slurry polymerization is usually preferably applied. As a solvent, a saturated aliphatic hydrocarbon or an aromatic hydrocarbon such as hexane, heptane, cyclohexane, benzene or toluene is used alone, or a mixed solvent thereof is used. Can be used. The prepolymerization temperature is generally preferably −20 to 100 ° C., particularly preferably 0 to 60 ° C.,
When the prepolymerization is carried out in multiple stages, the prepolymerization may be carried out under different temperature conditions in each stage. The pre-polymerization time may be appropriately determined according to the pre-polymerization temperature and the amount of polymerization in the pre-polymerization, and the pressure in the pre-polymerization is not limited, but in the case of slurry polymerization, generally, the pressure is from atmospheric pressure to 5 kg / cm ^2. It is about. The prepolymerization may be performed in any of batch, semi-batch, and continuous methods. At the end of the prepolymerization, it is preferable to wash a saturated aliphatic hydrocarbon or an aromatic hydrocarbon such as hexane, heptane, cyclohexane, benzene, and toluene alone or with a mixed solvent. Is preferred.

In the present invention, in the ternary random copolymerization of propylene, ethylene and butene-1, when the above prepolymerization is carried out, the obtained prepolymerization catalyst, [B] organoaluminum compound and [C] t-butyl (ethyl) ) Dimethoxysilane

[0031]

Embedded image

The main polymerization is carried out in the presence of

In the above production method, by using the t-butyl (ethyl) dimethoxysilane as a catalyst component, the obtained terpolymer is not subjected to a treatment such as extraction, separation, and washing with a solvent after polymerization. Even in this case, the low-temperature toluene-soluble component shows a low value in the above range. In addition, the terpolymer obtained by such a method, after polymerization, extraction with a solvent, separation, even when not performing post-treatment such as washing,
The concentration of atoms shows the above-mentioned low value.

The polymerization conditions for the main polymerization in the present invention are not particularly limited as long as the effects of the present invention are recognized, and known methods can be employed. Generally, the following conditions are preferred.

The amount of the organoaluminum compound [B] to be used is not particularly limited, but is generally 1 to 1 in terms of Al / Ti (molar ratio) with respect to the Ti atoms in the titanium compound obtained by the preliminary polymerization.
It is preferably 0 to 1000, more preferably 20 to 5
Preferably it is 00.

The amount of t-butyl (ethyl) dimethoxysilane [C] used is not particularly limited, but is generally 0.1 to 1000 in terms of Si / Ti (molar ratio) with respect to Ti atoms of the titanium compound. It is preferably, and more preferably 1 to 100. The order of addition of the components used in the main polymerization is not particularly limited. A mixture of an organoaluminum compound and an organosilicon compound may be used.

The polymerization temperature is 20 to 200 ° C., preferably 5 to 200 ° C.
The temperature is 0 to 150 ° C, and hydrogen can be allowed to coexist as a molecular weight regulator. The polymerization can also be applied to slurry polymerization, solventless polymerization, and gas phase polymerization, and may be any of a batch system, a semi-batch system, and a continuous system, and is further performed by dividing the polymerization into two or more stages under different conditions. You can also.

The melt flow rate of the terpolymer used in the present invention differs depending on the type of the molded product, but when used for sheet molding, it is 0.1 to 20 g.
/ 10 minutes, preferably 0.5 to 10 g / 10 minutes, and more preferably 1.0 to 5 g / 10 minutes. When used for injection molding, 5.0 to 100 g / 10
Min, preferably 10 to 80 g / min, more preferably 20 to 60 g / 10 min. 0.1 g / 10 min for sheet molding, 5.0 g / 10 min for injection molding
When the amount is less than 20 g / 10 min for sheet molding and more than 100 g / 10 min for injection molding, the melt tension is inferior and the moldability tends to decrease.

As the nucleating agent used in the present invention, those which have been widely used for improving transparency and rigidity can be used without any limitation. The effect of improving transparency, rigidity, etc. differs depending on the type of nucleating agent used, but when a nucleating agent is blended with the terpolymer used in the present invention, the nucleating agent is blended with a known terpolymer. The transparency rigidity and the like can be remarkably improved as compared with the case where the above method is adopted. In addition, the nucleating agent addition amount shows a remarkable improvement effect with an addition amount smaller than that used in the prior art.

The nucleating agent used is a dibenzylidene sorbitol-based nucleating agent such as dibenzylidene sorbitol, bis (p-methyldibenzylidene) sorbitol, bis (p-ethyldibenzylidene) sorbitol; disodium hydrogen phosphate, phosphorus Inorganic nucleating agents such as sodium dihydrogen oxide, magnesium oxide, titanium oxide, zinc oxide, calcium carbonate, sodium carbonate, calcium silicate, magnesium silicate, magnesium sulfate, barium sulfate, talc, kaolin, alumina, silica, clay, etc. Organic carboxylate nucleating agents such as sodium acetate, sodium benzoate, sodium pt-butyl benzoate, sodium hydrogen phthalate, sodium stearate, calcium stearate, magnesium stearate, sodium palmitate; bisphosphate (4-t-bu Tylphenyl) sodium,
Sodium salts of phosphoric acid esters such as sodium 2,2'-methylenebis (4,6-di-t-butylphenyl) phosphate and sodium 2,2'-methylenebis (4,6-di-t-butylphenyl) phosphate Nucleating agents and the like.
Among these nucleating agents, those particularly preferred for improving transparency and rigidity are dibenzylidene sorbitol nucleating agents. These nucleating agents can be used in combination of two or more.

The amount of the nucleating agent added to the terpolymer is 0.05 to 0.5 parts by weight. 0.05 added
If the amount is less than the weight part, rigidity and transparency improvement effect cannot be obtained,
If the amount is more than 0.5 part by weight, the effect is not improved, and problems such as contamination of the mold at the time of molding, whitening of the bleed of the molded product, and increase in odor are not preferred. The addition amount of the nucleating agent is preferably 0.1 to 0.4 parts by weight, more preferably 0.1 to 0.4 parts by weight.
15 to 0.30 parts by weight.

The addition of the nucleating agent is not particularly limited, but the terpolymer and a predetermined amount of the nucleating agent are stirred and mixed with a ribbon blender, a tumbler mixer, a Henschel mixer, a super mixer or the like, and then the mixture is mixed. Using a roll, Banbury mixer, extruder, etc.
C., preferably at 180 to 250.degree. In the polyolefin-based resin composition of the present invention, if necessary, an antioxidant, a light stabilizer, an antistatic agent, an antifogging agent, a chlorine scavenger such as a metal soap, or a dispersant may impair the object of the present invention. It can be added in a range that does not exist.

The resin composition of the present invention is suitably used for a sheet requiring transparency and rigidity and for injection molding. More specifically, medical instruments such as disposable syringes, blood transfusion bags, and blood collection instruments; packages of foods and plants, various cases such as clothes cases and containers for storing clothing; cups and packaging containers for retort foods Containers for microwave ovens; containers for juices, tea drinks, cosmetics, medicines, shampoos, etc. cans, bottles, etc .; seasoning containers and caps for miso, soy sauce, etc .; water, rice, bread, pickles, etc. It is suitable as a material for food cases and containers; refrigerators and other miscellaneous goods; stationery; electric and mechanical parts;

[0044]

The polypropylene resin composition comprising the terpolymer obtained by using the specific catalyst system of the present invention and a nucleating agent can control polypropylene crystals finely and uniformly, and have an external appearance of the product. Since the amount of substances that cause deterioration of the product is extremely small, the transparency and rigidity of the sheet and the injection molded body are excellent, and the quality of the product appearance due to the occurrence of stains and eyes on the molding machine during molding is impaired. Nothing. Therefore, the propylene resin composition of the present invention can be suitably used as a material for various sheets and injection molded articles having high transparency and high rigidity.

[0045]

EXAMPLES The present invention will be described below with reference to examples and comparative examples, but the present invention is not limited to these examples. The measurement method used in the following examples will be described.

(1) Melt flow rate (hereinafter referred to as MFR)
This is based on ASTM D-790.

(2) Ethylene and butene-1 content Measured by infrared spectroscopy.

(3) Amount of soluble matter in low-temperature toluene 1 g of the polymer was added to 100 cc of toluene, and the temperature was raised to 100 ° C. with stirring. The stirring was further continued for 30 minutes to completely dissolve the polymer. , 2
Left for 4 hours. The precipitate was separated by filtration, and a soluble matter was obtained by completely distilling the toluene solution.

The amount of low-temperature toluene-soluble matter (% by weight) = (toluene-soluble matter (g) / 1 g of polymer) × 100.

(4) Measurement of Residual Titanium Concentration and Chlorine Concentration in Polymer About 10 g of polymer was press-molded at 230 ° C. to form a disk-shaped sheet, and then a fully automatic X-ray fluorescence analyzer manufactured by Rigaku Corporation. The measurement was performed using the system 3080.

(5) Young's modulus Tensile Young's modulus was used as an index of rigidity of a sheet molded product.

According to JIS K6758, the Young's modulus in the resin flow direction was measured.

(6) Flexural Modulus The flexural modulus was used as an index of the rigidity of the injection molded article.

The measurement was performed according to JIS K7203.

(7) Roll dirt The roll dirt in the sheet forming is removed for 8 hours after continuous forming.
It was determined visually.

The resin composition of the present invention is suitably used for sheets requiring transparency and rigidity and for injection molding.

(8) Stain on the mold After 2,000 shots of continuous molding, it was judged visually.

(9) The haze was measured using a haze meter in accordance with JIS6714.

Ternary Copolymer Production Example 1 [Preparation of Titanium Compound] The titanium component was prepared according to the method of Example 1 in JP-A-58-83006. That is, 0.95 g of anhydrous magnesium chloride (10 mm
ol), decane 10 ml, and 2-ethylhexyl alcohol 4.7 ml (30 mmol) were heated and stirred at 125 ° C. for 2 hours. 0.55 g of phthalic anhydride in this solution
(6.75 mmol) was added, and the mixture was further stirred and mixed at 125 ° C. for 1 hour to obtain a homogeneous solution. After cooling to room temperature, 40 ml of titanium tetrachloride (0.
36 mol) over 1 hour.
Thereafter, the temperature of the mixed solution was raised to 110 ° C. over 2 hours. When the temperature reached 110 ° C., 0.54 ml of diisobutyl phthalate was added, and the mixture was kept under stirring at 110 ° C. for 2 hours. After completion of the reaction for 2 hours, the reaction mixture was filtered to collect a solid part, and the solid part was resuspended in 200 ml of TiCl4, and then heated again at 110 ° C. for 2 hours. After completion of the reaction, a solid portion was collected again by hot filtration, and sufficiently washed with decane and hexane until no free titanium compound was detected in the washing solution. The composition of the solid Ti catalyst was 2.1% by weight of titanium, 57% by weight of chlorine, 18.0% of magnesium, and 21.9% by weight of diisobutyl phthalate.

[Preliminary polymerization] Inner volume 1 liter with N2 substitution
200 ml of purified n-hexane, 50 mmol of triethylaluminum, 10 mmol of diphenyldimethoxysilane, 50 mmol of ethyl iodide, and 5 mmol of solid Ti catalyst component in terms of Ti atom were charged into the autoclave, and then 3 g of propylene was added to 1 g of the solid catalyst component. For 30 minutes continuously into the autoclave as described above. The temperature during this period was kept at 15 ° C. After 30 minutes, the reaction was stopped, and the inside of the autoclave was sufficiently replaced with N2.
The solid part of the obtained slurry was washed four times with purified n-hexane to obtain a titanium-containing polypropylene. As a result of the analysis, 2.1 g of propylene was polymerized per 1 g of the solid Ti catalyst component.

[Main polymerization] A polymerization tank having an internal volume of 2 m3 was charged with 545 kg of propylene and 55 kg of butene-1.
After introducing 612 mmol of triethylaluminum, 306 mmol of t-butyl (ethyl) dimethoxysilane, and hydrogen gas, the internal temperature of the polymerization vessel was raised to 55 ° C.
Then, ethylene gas was introduced, and 1.5 mmol of titanium-containing polypropylene was charged as Ti atoms to initiate polymerization. The temperature of the polymerization tank was raised to 70 ° C., and the polymerization was carried out for 2 hours while supplying ethylene so as to keep the ethylene gas concentration in the gas phase constant during the polymerization. After completion of the polymerization, unreacted propylene and butene-1 were purged to obtain a white granular copolymer. The obtained copolymer was dried at 70 ° C. for 1 hour. The ethylene content of the obtained copolymer is 3.5 mol%, the butene-1 content is 3.6 mol%, and the MFR is 2.
It was 2 g / 10 minutes. The results are shown in Table 1.

Ternary Copolymer Production Examples 2 to 6 In the main polymerization of Ternary Copolymer Production Example 1, the amounts of hydrogen gas, ethylene gas, and butene-1 introduced were changed as shown in Table 1 Content, butene-1 content and M
A terpolymer of FR was produced. The results are shown in Table 1.

Ternary Copolymer Production Comparative Examples 1 to 4 Instead of t-butyl (ethyl) dimethoxysilane used in the main polymerization of terpolymer production example 1, silane compounds shown in Table 1 and ethylene gas were introduced. The terpolymer was produced by changing the amount and the amount of hydrogen gas introduced. The silane compounds used and the results are shown in Table 1.

Preparation Example 5 of Ternary Copolymer [Preliminary polymerization] 200 ml of purified n-hexane, 50 mmol of diethylaluminum chloride, and titanium trichloride manufactured by Marubeni Solvay Co., Ltd. After inserting 5 g, propylene was continuously introduced into the autoclave for 30 minutes so that the amount of propylene was 3 g per 1 g of the solid catalyst component. The temperature during this period is 15
C. was maintained. After 30 minutes, the reaction was stopped, and the inside of the autoclave was sufficiently replaced with N2. The solid part of the obtained slurry was washed four times with purified n-hexane to obtain a titanium-containing polypropylene. As a result of the analysis, 2.1 g of propylene was polymerized per 1 g of the titanium trichloride catalyst component.

[Main polymerization] 555 kg of propylene and 45 kg of butene-1 were charged into a polymerization tank having an inner volume of 2 m3, and 612 mmol of diethylaluminum chloride was added.
Further, hydrogen gas was introduced, and the temperature of the polymer layer was raised to 55 ° C. Then, after introducing ethylene gas, 20 g of titanium-containing polypropylene was charged in terms of titanium trichloride, and polymerization was started. The temperature of the polymerization tank was raised to 70 ° C., and the polymerization was carried out for 2 hours while supplying ethylene so as to keep the ethylene gas concentration in the gas phase constant during the polymerization. After the completion of the polymerization, unreacted propylene was purged to obtain a white granular random copolymer. The obtained copolymer was dried at 70 ° C. for 1 hour. The ethylene content of the obtained copolymer was 3.6 mol%, the butene-1 content was 3.6 mol%, and the MFR was 2.1.
g / 10 minutes. The results are shown in Table 1.

Comparative Example 6 for Production of Terpolymer Co.
A terpolymer having an FR of 31 g / 10 min was produced. The results are shown in Table 1.

[0067]

[Table 1]

Example 1 (Sheet evaluation) [Granulation] To 100 parts by weight of the terpolymer of Production Example 1 was added 2,6-di-t-butyl-p as an antioxidant.
-0.1 part by weight of cresol, 0.05 part by weight of calcium stearate as a chlorine supplement, 1,3 as a nucleating agent
0.25 parts by weight of 2,4-di (paramethylbenzylidene sorbitol (Gerol MD, manufactured by Shin Nihon Rika Co., Ltd.) was added and mixed for 5 minutes with a Henschel mixer. Then, using an extrusion granulator having a screw diameter of 65 mmφ. The mixture was extruded at 230 ° C., and the pellet was granulated to obtain a raw material pellet.

[Preparation of Sheet] A non-stretched sheet was prepared using the granulated pellets by the following method. The raw material pellets are heated at a die temperature of 2 using a T-die film forming machine with a screw diameter of 40 mm
Melt extrusion was performed at 30 ° C., and the resultant was cooled with a cooling roll having a surface temperature of 20 ° C. to obtain a non-oriented sheet having a thickness of 0.5 mm. At the same time as observing the state of roll contamination of the cooling roll at this time, physical properties of the obtained sheet were measured 24 hours after molding. The results are shown in Table 2.

Examples 2 and 3 In Example 1, the amount of 1,3,2,4-di (paramethylbenzylidenesorbitol) added as a nucleating agent was 0.10.
The same procedure as in Example 1 was carried out except that the parts by weight (Example 2) and 0.15 parts by weight (Example 3) were used. The results are shown in Table 2.

Example 4 In Example 1, methylene bis (2,4-di-t-butylphenol) acid phosphate aluminum salt (NA21, instead of 1,3,2,4-di (paramethylbenzylidenesorbitol) was used as a nucleating agent. The procedure was performed in the same manner as in Example 1 except that Asahi Denka)) was used. Table 2 shows the results.

Example 5 In Example 1, 1,3,2,4-di (hydroxy-di (t-butylbenzoic acid) aluminum (YK, manufactured by Asahi Denka) instead of 1,3,2,4-di (para-methylbenzylidenesorbitol)) Was performed in the same manner as in Example 1 except that was used. Table 2 shows the results.

Examples 6 and 7 Instead of Production Example 1 of the terpolymer used in Example 1, Production Example 2 of the terpolymer (Example 6) or Production Example 3 of the terpolymer was used (Example 6). Example 7 was carried out in the same manner as in Example 1 except that Example 7) was used. The results are shown in Table 2.

Examples 8 and 9 Instead of terpolymer preparation example 1 used in Example 5, terpolymer preparation example 2 (Example 8) or terpolymer preparation example 3 (Example Example 9 was carried out in the same manner as in Example 5, except that Example 9) was used. The results are shown in Table 2.

Examples 10 and 11 Instead of terpolymer production example 1 used in Example 4, terpolymer production example 2 (Example 10) or terpolymer production example 3 (implementation) Example 4 except that Example 11) was used.
The same was done. The results are shown in Table 2.

[0076]

[Table 2]

Comparative Examples 1 to 5 Production was carried out in the same manner as in Example 1 except that Comparative Example 1 was used except that the nucleating agents and the amounts added were as shown in Table 3. The results are shown in Table 3.

Comparative Examples 6 to 13 The same procedures as in Example 1 were carried out except that the types and amounts of the terpolymer and the nucleating agent were changed as shown in Table 3. The results are shown in Table 3.

[0079]

[Table 3]

Example 12 (Evaluation of Injection Molded Article) [Granulation] Except that the terpolymer used in the granulation of Example 1 was changed to the ternary copolymer of Production Example 4 of terpolymer Obtained pellets according to the granulation of Example 1.

[Preparation of Injection Molded Body] Using the granulated pellets, an injection molded body was prepared by the following method. The raw material pellet was injection molded at a cylinder temperature of 230 ° C. and a mold temperature of 60 ° C. to prepare a test piece of 60 × 60 × 1 mm, which was used as a sample for haze measurement. The flexural modulus is JISK7203.
A sample piece was prepared according to -1982. The physical properties of the obtained injection molded articles were measured 48 hours after molding. The results are shown in Table 4.

Examples 13 to 22 The same procedures as in Example 12 were carried out except that the terpolymer, the nucleating agent and the amounts added were as shown in Table 4. The results are shown in Table 4.

[0083]

[Table 4]

Comparative Examples 14 to 26 The same procedures as in Example 12 were carried out except that the terpolymer used, the nucleating agent and the amounts added were as shown in Table 5. Table 5 shows the results.

[0085]

[Table 5]

[Brief description of the drawings]

FIG. 1 is a flowchart showing a typical polymerization procedure of a propylene-ethylene-butene-1 terpolymer used in the present invention.

[Procedure amendment]

[Submission date] February 3, 1997

[Procedure amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0041

[Correction method] Change

[Correction contents]

The amount of the nucleating agent to be added to the terpolymer is from 0.05 to 0.5% based on 100 parts by weight of the terpolymer.
5 parts by weight. If the addition amount is less than 0.05 part by weight, the rigidity and the effect of improving transparency cannot be obtained, and if the addition amount is more than 0.5 part by weight, the effect is not improved, and contamination of the mold during molding,
Problems such as bleeding of the molded article and increase in odor are undesirable. The added amount of the nucleating agent is preferably 0.1 to 0.1.
4 parts by weight, more preferably 0.15 to 0.30 part by weight.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification symbol FI // C08F 4/658 C08F 4/658

Claims (1)

[Claims] 1. A solid titanium compound containing magnesium, titanium, and a halogen as essential components;
Propylene-ethylene-butene-1 ternary copolymer obtained by random copolymerization of propylene, ethylene and butene-1 in the presence of a catalyst comprising an organoaluminum compound and [C] t-butyl (ethyl) dimethoxysilane A polypropylene resin composition comprising 100 parts by weight of coalescing and 0.05 to 0.5 part by weight of a nucleating agent.