JP2794783B2 - Polypropylene resin composition - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a polypropylene-based resin composition, and more particularly, to a softened polypropylene which can be used by injection molding and can provide industrial products having good performance. The present invention relates to a resin composition.

[Prior Art] Conventionally, ethylene propylene rubber (EPM) is often used for softening a polypropylene resin. But,
Usually EPM is based on 100 parts by weight of polypropylene resin composition.
Unless 40 to 50 parts by weight are blended, there is a current situation that a softening composition that can be used for various kinds of industrial products as desired cannot be obtained.

[Problems to be Solved by the Invention] The present invention is embodied in a polypropylene resin, and can be softened with a relatively small amount of blend as compared with the case of EPM. An object of the present invention is to provide a high-quality polypropylene-based composition.

[Means for Solving the Problems] In view of the above-mentioned conventional technical problems, the present inventors have conducted intensive studies on softening of polypropylene-based resin. A) 30-80% by weight of polypropylene-based resin, and b) hexene- 1. It has been found that a soft polypropylene resin composition can be obtained by blending 20 to 70% by weight of an α-olefin polymer in which any one of octene-1 and decene-1 is 60 mol% or more. Reached the present invention.

 Hereinafter, the present invention will be described in detail.

As the a) polypropylene resin used in the present invention, commercially available polypropylene homopolymers, random copolymers of ethylene and propylene, block copolymers of ethylene and propylene are preferably used, and among them, block copolymers of ethylene and propylene are preferable.

The main constituent components of b) α-olefin polymer used in the present invention are hexene-1 octene-1 and decene-1.
These components can be used in any combination, but specific examples of the polymer include polyhexene-1, polyoctene-1, polydecene-1, and hexene-1, octene-1, and decene-1. An α-olefin copolymer in which any one of the constituents is at least 60 mol%.

As other constituent components of the α-olefin copolymer, other α-olefins having 6 to 20 carbon atoms, for example, 4-methylpentene-1, heptene-1,4,4-dimethyl-pentene-1, nonene -1, undecene-1, dodecene-1,
Tridecene-1, tetradecene-1, pentadecene-
1, hexadecene-1, octadecene-1, nonadecene-1, eicosene-1, and the like. These other components can be used in any combination.
The content of other components in the olefin copolymer is 40
Mol% or less.

When blended as a composition, an α-olefin polymer component obtained by blending these copolymers may be used.

The preferred molecular weight of these α-olefin polymers is 10,0
It is from 00 to 500,000, particularly preferably from 100,000 to 400,000.

These α-olefin polymers can be produced by a so-called Ziegler-Natta type catalyst.

As the transition metal compound component of the Ziegler-Natta catalyst, a titanium compound and a composition thereof are particularly preferable.
Particularly preferred examples of the titanium compound or its composition include, for example, titanium tetrachloride, a titanium trichloride composition obtained by reducing titanium tetrachloride with various reducing agents (eg, aluminum hydrogen, titanium, organic aluminum, etc.) (for example, TiCl ₃ .nAlCl ₃ ), a titanium trichloride composition obtained by subjecting the titanium trichloride composition to an electron donating compound, for example, an organic acid ester, an ether, a phosphoric amide, or the like; After reduction with ether treatment and Lewis acid treatment, a titanium trichloride composition, a reaction product of magnesium oxychloride and alkyl aluminum dichloride (a compound obtained by further reacting these with a siloxane compound if desired), or Using magnesium chloride as a carrier, an electric donor compound (organic acid ester, Supported titanium catalyst component which contains, as essential components, phenols, amines, organic acid amides, ethers, water) and a halogen-containing titanium compound (eg, titanium tetrachloride, titanium trichloride, alkoxytitanium trichloride, etc.). .

As the organometallic compound organism which is another component of the Ziegler-Natta catalyst, organometallic compounds of Groups 1 to 3 of the periodic table are suitable, and among them, organometallic compounds of Group 3 metals, particularly aluminum, are preferable. Used. Normal,
Examples of preferably used organoaluminum compounds include (a) trialkylaluminums such as trimethylaluminum, triethylaluminum, triisobutylaluminum, and tri-n-hexylaluminum;
(B) dialkylaluminum halides such as diethylaluminum chloride, di-n-propylaluminum chloride and diisobutylaluminum chloride;
Dialkylaluminum hydrides such as diethylaluminum hydride and diisobutaluminum hydride;
(D) alkylaluminum sesquichlorides such as methylaluminum sesquichloride, ethylaluminum sesquichloride, n-propylaluminum sesquichloride, isobutylaluminum sesquichloride, (e) alkylaluminums such as methylaluminum dichloride, ethylaluminum dichloride, isopropylaluminum dichloride Dialkylaluminum alkoxides or aryloxides such as dihalide, (f) diethylaluminum ethoxide, diethylaluminum isopropoxide, di-n-propylaluminum-2,6-di-t-butylphenoxide, (t) dimethylaluminumtrimethylsiloxy And diethylaluminum trimethylsiloxide. Alternatively, a reaction product of these organic aluminum with water or a secondary amine or an organic acid ester may be used. These organoaluminum compounds may be used in combination of two or more.

Preferred polymerization conditions for b) the α-olefin polymer used in the present invention include a polymerization temperature of 0 to 200 ° C, particularly preferably 20 to 150 ° C, and a polymerization pressure of 0 to 150 kg / cm ² · G, particularly preferably 0 to 50 kg. / cm ² · G, polymerization time 0.1 to 10 hours, particularly preferably 0.5 to 2 hours. There is no particular restriction on the polymerization mode, and (a) n-hexane, n-heptane, n-heptane
A slurry method or a solution method using an inert solvent such as octane, toluene, benzene, or cyclohexane, or (ii) a slurry method or a melting method in which an α-olefin serves as a solvent without substantially adding a solvent is used. Can be In addition, hydrogen and / or an alkyl zinc compound can be used as a molecular weight agent for the polymer.

The polypropylene resin composition of the present invention comprises: a) 40 to 80% by weight of a polypropylene resin, preferably 30 to 80% by weight.
And b) 20 to 60% by weight of the α-olefin polymer, preferably 20 to 70% by weight. a) Polypropylene resin
If the amount is less than 30% by weight, the obtained resin composition cannot be formed into a pellet shape, which is not preferable. If it exceeds 80% by weight, the flexural modulus becomes too high, which is not preferable.

In the production of the polypropylene resin composition of the present invention, in a range that does not significantly increase the flexural modulus,
Fillers such as talc, silica and glass fiber can be used. If necessary, a heat stabilizer, an ultraviolet absorber, a coloring agent, and the like can be used. Furthermore, partial cross-linking can be performed by treating with an organic peroxide.

In producing the polypropylene-based resin composition of the present invention, a Banbury mixer, a kneader blender, an intermixer, a continuous mud continuous machine, and an extruder can be used.

[Examples] Hereinafter, the present invention will be described in more detail with reference to examples.
In the examples, parts and% indicate parts by weight and% by weight, respectively, unless otherwise specified.

In this example, the polystyrene equivalent averaging molecular weight of the polymer was measured at 135 ° C. in a trichlorobenzene solvent using a 15-type gel permeation chromatograph manufactured by Waters. In addition, hexene in the copolymer in the present Example
1 content is JNM-FX100 type carbon-13 NMR manufactured by JEOL Ltd.
Using ( ¹³ C-NMR), the area ratio of the spectrum determined by the Lindemann and Adams calculation formula, or the A-302 infrared spectrophotometer (IR) manufactured by JASCO Corporation,
Attention was paid to peaks derived from each component, and the peak was determined using a calibration curve prepared from a known sample prepared in advance using a polymer blend.

In this example, the flexural modulus was measured according to JIS K7203, and the Izod impact strength was measured according to JIS K7110 (with a V notch). Note that NB in Table 1 means non-break (no break).

Example 1 A. Production of α-Olefin Polymer Into a 5-flask previously purged with nitrogen, 300 g of dehydrated and purified n-hexane 3 and dehydrated and purified hexene 1 (Dialen-6, manufactured by Mitsubishi Kasei Corporation) were charged. Triisobutylaluminum 15 mmol, supported Ti catalyst (Japanese
0.3 mmol) was prepared and stirred at 30 ° C for 1 hour. Thereafter, 10 ml of isopropyl alcohol was added to stop the polymerization reaction, and then the solvent was removed by blowing steel into the polymerization reaction solution, followed by drying with a roll at 100 ° C. The yield of the polymer was 140 g, and the number average molecular weight in terms of polystyrene was 119,000.
).

B. Measurement of physical properties of composition Using PHX and Mitsubishi Noblen BC-2 (polypropylene resin, manufactured by Mitsubishi Yuka Co., Ltd.), using a formulation shown in Table 1, using a 250 cc plastmill (manufactured by Toyo Seiki) at 150 ° C.
After kneading for minutes, the sheets were sheeted with a cold roll.
The obtained sheet was formed into a square pellet, a sample piece was prepared by injection molding, and the physical properties were measured. The results are shown in Table 1.

The composition of this example shows a low flexural modulus, which indicates that it is a good soft material.

Comparative Example-1 B. Physical Properties of Composition In Example-1B, JSR EP02P (EP
M, manufactured by Nippon Synthetic Rubber Co., Ltd.), and physical properties were measured in the same manner as in Example 1. The results are shown in Table 1. When EPM is used instead of PHX, the bending modulus is about 50% higher, which is not preferable.

Example 2 A. Production of α-olefin-based polymer In Example 1A, 195 ml of hexene-1 and 195 ml of decene-1 (dialen 10,
Polymerization was carried out in the same manner as in Example 1A, except that 95 ml of the product (Mitsubishi Kasei) was used. The yield of the polymer was 151 g, the number average molecular weight in terms of polystyrene was 127,000, and hexene-1 was determined by ¹³ C-NMR.
The content was 63% mol (this polymer is called PHD).

B. Physical properties of composition In Example 1B, physical properties were measured in the same manner as in Example 1B except that PHD was used instead of PHX. Table-Results
1 is shown.

It turned out that it was a favorable soft material like Example-1.

Examples-3, 4 and Comparative Examples-2-4 B. Physical properties of composition In Example-1B, physical properties were measured in the same manner as in Example-1B, except that each component was used at a ratio shown in Table-1. did. The results are shown in Table 1.

Examples-3 and 4 exhibited lower flexural modulus than Comparative Example-2, and were good.

Example-5 A. Production of α-olefin-based polymer In Example-1A, instead of hexene-1 300 ml, hexene-1 270 ml and 4-methylpentene-1 30 were used.
Polymerization was carried out in the same manner as in Example 1A, except that (Mitsui Petrochemical) was used. The yield of the polymer was 138 g, the number average molecular weight in terms of polystyrene was 115,000, and the hexene-1 content by IR method (measured by an infrared spectrophotometer) was 87 mol% (this polymer is referred to as PHMP).

B. Physical Properties of Composition In Example 1B, physical properties were measured in the same manner as in Example 1B, except that PHMP was used instead of PHX. Table 1 shows the results.

As in Example 1, it was found that this example was a good soft material.

[Effects of the Invention] According to the present invention, a good soft polypropylene-based resin composition is obtained, and is useful for various industrial articles such as automobile bumpers, spoilers, motorcycle helmets, and home appliance housings.

──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Kenya Makino 2-11-24 Tsukiji, Chuo-ku, Tokyo Japan Synthetic Rubber Co., Ltd. (56) References JP-A-53-98353 (JP, A) (58) Field surveyed (Int.Cl. ⁶ , DB name) C08L 23/10 C08L 23/18

Claims (1)

(57) [Claims] 1. An α-olefin polymer comprising 30% to 80% by weight of a) a polypropylene resin, and b) at least 60% by mole of any one of hexene-1, octene-1 and decene-1. A polypropylene resin composition comprising 70% by weight.