JP3107645B2 - Propylene resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a propylene resin composition having high rigidity and impact resistance, and excellent in processability and quality stability.

[0002]

2. Description of the Related Art Conventionally, to improve the impact resistance of polypropylene, a soft material such as amorphous ethylene-propylene rubber (hereinafter abbreviated as EPR) produced by using a vanadium catalyst is mixed with polypropylene. Was done by that. However, due to poor compatibility between polypropylene and EPR, a small amount of addition does not provide a sufficient effect of improving impact resistance, and a large amount of addition improves impact resistance, but decreases rigidity. There was a problem of doing.

On the other hand, as a method for obtaining a soft material composed of a polypropylene resin, various methods have been proposed in which a crystalline polyolefin component and an ethylene propylene copolymer component are simultaneously produced by polymerization. However, although the copolymer obtained by the above method is obtained in the form of particles,
Its fluidity is poor, especially when the polymer particles obtained from the polymerization tank are left to accumulate, because they solidify and become agglomerated by the load, causing troubles in the storage and transfer processes, and also complicated There was a problem that operation was required. Further, the polymer particles exhibit a fluidity at a relatively low temperature, for example, around room temperature, but have a relatively high temperature, for example, at 50 to 70 ° C., so that they adhere to the fluid at a relatively high temperature, for example, 50 to 70 ° C., and have a low fluidity. Had the disadvantage of doing so.

The inventors of the present invention have conducted various studies to solve the above problems, and as a result, it has been found that particles of a propylene-based block copolymer containing a polybutene component, a polypropylene component and a propylene-ethylene copolymer component are excellent. Have already been proposed (Japanese Patent Application No. 4-8).
No. 5487).

[0005]

Means for Solving the Problems The present inventors have conducted further studies on the above-mentioned propylene-based block copolymer, and as a result, have found that the above-mentioned propylene-based block copolymer is melt-kneaded with an organic peroxide to form a decomposition product. By mixing the material with polypropylene, it is possible to improve the physical properties of polypropylene, combine excellent rigidity and impact resistance, and find that a propylene-based resin composition having processability and quality stability can be obtained, The present invention has been completed.

That is, the present invention relates to (1) polypropylene 1
(2) a block copolymer containing (2) a polybutene component, a polypropylene component, and a propylene-ethylene random copolymer component, wherein the polybutene component is 0.1% by weight.
01 to 5% by weight, 1 to 70% by weight of a polypropylene component, 25% of a propylene-ethylene random copolymer component
To 99.99% by weight, and the propylene-ethylene random copolymer component contains one monomer unit based on ethylene.
5 to 80 mol%, 85 monomer units based on propylene
Consisting of a random copolymer containing up to 20 mol%,
The ratio of components having a molecular weight of 10,000 or less is 1.0% by weight or less, and a decomposition product of a propylene-based block copolymer having a weight average molecular weight of 600,000 or more due to an organic peroxide is 1 to
A propylene-based resin composition comprising 60 parts by weight.

One component of the propylene resin composition of the present invention is polypropylene. Here, polypropylene is a homopolymer of propylene, 90 mol% or more of propylene and an α-olefin other than propylene, for example, ethylene, 1-butene, 1-pentene, 1-hexene,
A random copolymer or a block copolymer with at least 10 mol% of one or more of -heptene, 4-methyl-1-pentene and the like is generally used.

Next, the other component of the propylene-based resin composition of the present invention is a decomposition product of a specific propylene-based block copolymer by an organic peroxide. Here, the propylene-based block copolymer (hereinafter, simply referred to as “block copolymer”) comprises a polybutene component, a polypropylene component, and a propylene-ethylene copolymer component. The solidification of polymer particles obtained by polymerization when the polybutene component is replaced by another component, for example, a polyethylene component,
The fluidity at high temperatures is poor and cannot be the object of the present invention.

The proportions of the polybutene component, the polypropylene component and the propylene-ethylene random copolymer component in the block copolymer used in the present invention are 0.01 to 5% by weight for the polybutene component and 1 to 70% for the polypropylene component. % By weight, and the propylene-ethylene random copolymer component is 25 to 99.99% by weight.

In the present invention, the polybutene component is indispensable for improving the particle properties of the copolymer particles. In particular,
When the content of the polypropylene component is low, for example, 30
When the content is less than 10% by weight, the obtained copolymer particles tend to stick, but even in such a case, due to the presence of the polybutene component, the copolymer particles can have good fluidity. When the polybutene component is less than 0.01% by weight,
When the copolymer particles obtained by polymerization are left to accumulate, they are consolidated by the load, and the copolymer particles are further reduced to 50 to 50%.
When the temperature is 70 ° C., the fluidity is extremely poor, which is not preferable. On the other hand, when the polybutene component exceeds 5% by weight, the fluidity of the block copolymer particles is undesirably lowered. The ratio of the polybutene component is preferably in the range of 0.04 to 3% by weight in consideration of better fluidity of the block copolymer particles.

On the other hand, if the propylene component is less than 1% by weight, the mechanical strength and heat resistance of a molded article made of a propylene-based copolymer decrease. If the proportion of the polypropylene component exceeds 70% by weight, the impact resistance of the molded product is reduced, and the intended propylene resin composition cannot be obtained. The polypropylene component is preferably in the range of 3 to 60% by weight in consideration of mechanical strength, heat resistance, impact resistance, and the like. When the content is 30% by weight or less, flexibility and transparency are good.

Further, the content of the ethylene-propylene random copolymer component is 25 to 99.99% by weight. When the content of the above components is less than 25% by weight, the impact resistance is poor and 98.99.
If the amount is more than 10% by weight, the mechanical properties such as strength and heat resistance of the molded product are inferior, which is not preferable. The ethylene-propylene random copolymer component is preferably in the range of 40 to 97% by weight in consideration of impact resistance, strength and heat resistance.

The block copolymer used in the present invention includes:
Polybutene component, polypropylene component, propylene-ethylene random copolymer component in one or more,
As long as the physical properties of the propylene-based resin composition are not impaired, other α-olefins may be copolymerized and contained in a small amount, for example, in a range of 5 mol% or less.

The block copolymer used in the present invention comprises a so-called block copolymer in which at least two or more of a polybutene component, a polypropylene component and a propylene-ethylene random copolymer component are arranged in one molecular chain. It is conceivable that the molecular chain composed of each of the polybutene component, the polypropylene component and the propylene-ethylene random copolymer component is microscopically mixed to such an extent that mechanical mixing cannot attain.

The polybutene component in the block copolymer used in the present invention is used for preventing the block copolymer particles from caking.
In order to improve the fluidity at a high temperature, the isotacticity is preferably 0.90 or more. Poly 1-
The isotacticity of butene was measured by ¹³ C-NMR, and the polymer journal (Polymer) was used.
J.) 16 mm (1984), pages 716-726.

The content ratios of the monomer units based on ethylene and the monomer units based on propylene in the propylene-ethylene random copolymer component are as follows:
It is 15 to 80 mol%, preferably 15 to 60 mol%, more preferably 20 to 50 mol%, of a monomer unit based on ethylene. 85 to 20 monomer units based on propylene
Mol%, preferably 85 to 40 mol%, more preferably 80 to 50 mol%. When the content ratio of the monomer unit based on ethylene is less than 15 mol% and the content ratio of the monomer unit based on propylene exceeds 85 mol%, the flexibility and impact resistance of the molded product are not sufficient, which is preferable. Absent. On the other hand, the content ratio of the monomer unit based on ethylene is 8
When the content of the monomer unit based on propylene is more than 0 mol% and less than 20 mol%, the strength and heat resistance of the molded product are not sufficient, which is not preferable.

The block copolymer used in the present invention is obtained as a powder having excellent fluidity by polymerization. This is surprising considering that a conventional propylene-ethylene random copolymer having an ethylene content similar to that of the block copolymer used in the present invention can be obtained in a lump due to adhesion between particles.

In order to obtain the block copolymer in powder form,
It is necessary to reduce the amount of low molecular weight components. In the elution curve measured by gel permeation chromatography (hereinafter, abbreviated as "GPC"), the block copolymer used in the present invention generally contains a component having a molecular weight of 10,000 or less in a proportion of 1.0% by weight or less, Preferably, by setting the content to 0.6% by weight or less, a powdery state can be maintained. One of the methods for reducing the low molecular weight components of the block copolymer can be achieved by relatively increasing the weight average molecular weight. Weight average molecular weight of the block copolymer used in the present invention,
At least 600,000 or more, usually 800,000 or more, preferably 1
It is 100,000 or more, more preferably 1.3 to 7,000,000, and most preferably 1.5 to 3,000,000. In the present invention, the weight average molecular weight is a value measured by GPC and converted based on a calibration curve obtained with polystyrene.

The block copolymer used in the present invention is obtained in the form of a powder, and its average particle size is not particularly limited, but is usually preferably in the range of 100 to 1000 μm, particularly preferably in the range of 100 to 800 μm. Although the particle size distribution is not particularly limited, it is usually relatively narrow, and specifically, the particle size is 100 μm.
It is suitable that the proportion of the following powder is 1% by weight or less and the proportion of the powder having a particle diameter of 1000 μm or more, preferably 800 μm or more is 1% by weight or less.

The block copolymer used in the present invention may be obtained by any method. The following is a particularly preferred example of the method.

That is, the following components A and B, or C and / or D.A. Titanium compound B. Organoaluminum compound C. Electron donor D. In the presence of an iodine compound represented by the general formula (i) R-I (i) (where R is an iodine atom or an alkyl group having 1 to 7 carbon atoms or a phenyl group), propylene is added in an amount of 0.1 to 0.1 500g polymer / g
Preliminary polymerization is performed so as to be in the range of the Ti compound to obtain a catalyst-containing prepolymer, and then the polymerization of propylene and ethylene through the polymerization of 1-butene and the polymerization of propylene in the presence of the catalyst-containing prepolymer. A method in which a random copolymerization of the mixture is sequentially performed to obtain a high-molecular-weight powdery material is preferable.

As the titanium compound [A] used in the prepolymerization in the above method for producing a block copolymer, a titanium compound known to be used for polymerization of an olefin is employed without any limitation. As a method for producing this catalyst, a known method is employed without any limitation. For example, JP-A-56-155206, JP-A-56-136806, JP-A-57-34103, JP-A-58-8706, JP-A-58-830
06, 58-138708, 58-183709, 59-206408, 59-21
9311, 60-81208, 60-81209, 60-186508, 60-19
2708, 61-211309, 61-271304, 62-15209, 62-1
1706, 62-72702, 62-104810, etc. are adopted. Specifically, for example, a method of co-grinding titanium tetrachloride with a magnesium compound such as magnesium chloride, co-milling titanium halide with a magnesium compound in the presence of an electron donor such as alcohol, ether, ester ketone or aldehyde. A method of pulverizing, or a method of contacting a titanium halide, a magnesium compound and an electron donor in a solvent may be used.

As the titanium compound, well-known α, β, γ or δ-titanium trichloride is preferably used in addition to the above-mentioned supported catalyst. Preparation methods of these titanium compounds, for example, JP-A-47-34478, 50-126590, 50-11439
4, 50-93888, 50-123091, 50-74594, 50-10419
1, 50-98489, 51-136625, 52-30888, 52-35283
Etc. are adopted.

Next, as the organoaluminum compound [B], a compound known to be used for polymerization of an olefin is employed 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-
Trialkylaluminums such as n-octylaluminum and tri-ndecylaluminum; diethylaluminum monohalides such as diethylaluminum monochloride and diethylaluminum bromide; alkylaluminum halides such as methylaluminum sesquichloride, ethylaluminum sesquichloride and ethylaluminum dichloride And the like. Other alkoxy aluminums such as monoethoxy diethyl aluminum and diethoxy monoethyl aluminum can be used.

Further, as the electron donor [C], a compound known to be used for improving the stereoregularity of an olefin is employed without any limitation. For example, alcohols such as methanol, ethanol, propanol, butanol, pentanol, hexanol, octanol, isopropyl alcohol, isoamyl alcohol; phenols such as phenol, cresol, cumylphenol, xylenol, and naphthol; acetone, methyl ethyl ketone, acetophenone, benzophenone Ketones such as;
Aldehydes such as acetaldehyde, propionaldehyde and benzaldehyde; methyl formate, methyl acetate,
Ethyl acetate, vinyl acetate, methyl propionate, ethyl propionate, methyl butyrate, ethyl butyrate, ethyl valerate, ethyl stearate, ethyl acrylate, methyl methacrylate, ethyl benzoate, methyl toluate, methyl anisate, phthalic acid Organic acid esters such as ethyl, methyl carbonate and butyrolactone; silicate esters such as ethyl silicate and phenyltriethoxysilane; ethers such as methyl ether, ethyl ether, isopropyl ether, isoamyl ether, tetrahydrofuran, anisole and diethylene glycol dimethyl ether Oxygen-containing electron donors such as amides such as acetic acid amide, benzoic acid amide and maleic acid amide; amines such as methylamine, ethylamine, piperidine, pyridine and aniline; Tolyl, nitriles such as benzonitrile; nitrogen-containing electron donors such as isocyanate: sulfur-containing electron donor: and the like and phosphorus-containing electron donors may be mentioned.

In the present invention, when an iodine compound [D] represented by the general formula (i) is used in addition to the titanium compound [A], the organoaluminum compound [B] and the electron donor [C], It is often preferred because the amount of the low molecular weight polymer having a molecular weight of 10,000 or less is remarkably reduced and there is an advantage that high fluidity can be imparted to the block copolymer.

Specific examples of the iodine compound which can be suitably used in the present invention are as follows. For example, iodine, methyl iodide, ethyl iodide, propyl iodide, butyl iodide, iodobenzene, toluene and p-iodide.
Particularly, methyl iodide and ethyl iodide are preferred.

The amount of each of the components [A] and [B] and, if necessary, [C] and / or [D] used varies depending on the type of catalyst and the conditions of prepolymerization. The optimum usage amount may be determined in advance according to each of these conditions. An example of a generally preferred range is as follows.

That is, the use ratio of the organoaluminum compound [B] is 0.1 to 100, preferably 0.1 to 20 in terms of Al / Ti (molar ratio) with respect to the titanium compound [A]. The proportion of the electron donor [C] used is 0.01 to 100, preferably 0.01 to 10, as [C] / Ti (molar ratio) with respect to the titanium compound [A].
Are each suitable. The proportion of the iodine compound [D] used as required is 0.1 to 100 in terms of I / Ti (molar ratio) with respect to the titanium compound [A].
Preferably, the range of 0.5 to 50 is suitable.

The prepolymerization in the present invention is an important factor in controlling the particle properties of the obtained block copolymer. The polymer obtained by the prepolymerization for polymerizing propylene in the presence of the catalyst component varies depending on the prepolymerization conditions and the like, but is generally from 0.1 to 500 g / g · Ti compound, preferably from 1 to 100 g / g · Ti compound. It is enough to choose from a range. Propylene used in the prepolymerization is suitable for controlling the particle properties of the block copolymer obtained by using a monomer of propylene alone, but, for example, in a range that does not adversely affect the physical properties of the block copolymer. Mixing up to 5 mol% of other α-olefins, such as ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 4-methylpentene-1 and the like is acceptable. It is also possible to make hydrogen coexist at each prepolymerization stage.

The prepolymerization is usually preferably carried out by slurry polymerization. As a solvent, a saturated aliphatic hydrocarbon or aromatic hydrocarbon such as hexane, heptane, cyclohexane, benzene or toluene is used alone, or a mixed solvent thereof. Can be used. The prepolymerization temperature is-
Temperatures between 20 and 100C, especially between 0 and 60C are preferred. 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. it is about ² G. The prepolymerization may be performed in any of batch, semi-batch, and continuous methods.

After the completion of the prepolymerization, it can be directly subjected to the polymerization of 1-butene described below. After washing with the above-mentioned solvent, it can be subjected to the polymerization of 1-butene.

The main polymerization is carried out after the preliminary polymerization. In the main polymerization, first, 1-butene is polymerized in the presence of the catalyst-containing prepolymer obtained by the above prepolymerization, then propylene is polymerized, and then propylene-ethylene random copolymerization is performed.

In the present invention, the catalyst used in the main polymerization may be the same catalyst component used in the preliminary polymerization and a combination thereof, or may be used after being chemically modified in the main polymerization step. The catalyst components used in the prepolymerization can be used as they are, but it is generally preferable to add and adjust the components other than the titanium compound during the main polymerization.

As the organoaluminum compound used in the main polymerization, those used in the above-mentioned preliminary polymerization can be used. The amount of the organoaluminum compound used is 1 to 10 in terms of Al / Ti (molar ratio) based on titanium atoms in the catalyst-containing prepolymer.
00, preferably 2 to 500.

Further, as the electron donor to be used if necessary, the compounds described above can be employed without any limitation. The amount of the electron donor used in the main polymerization is 0.001 to [C] / Ti (molar ratio) based on Ti atoms in the catalyst-containing prepolymer.
1000, preferably 0.1 to 500. Furthermore, the iodine compound used if necessary is 0.1 / (in molar ratio) I / Ti with respect to titanium atoms in the catalyst-containing prepolymer.
It is 1-100, preferably 0.5-50.

In the main polymerization in the present invention, first, 1-butene is obtained by mixing the catalyst-containing prepolymer, an organoaluminum compound,
If necessary, the reaction is carried out in the presence of an electron donor and / or a catalyst component of an iodine compound. Although the polymerization of 1-butene may be carried out by gas phase polymerization, it is generally preferable to carry out solution polymerization in the above-mentioned solvent or slurry polymerization in a 1-butene medium. The polymerization temperature is preferably from -20 to 100C, particularly preferably from 0 to 60C. The polymerization time may be appropriately determined depending on the temperature and the amount of polymerization, but may be generally selected from the range of 15 minutes to 3 hours. The polymerization pressure is not particularly limited,
In the case of solution polymerization, the pressure is generally from atmospheric pressure to about 5 kg / cm ² G.

Other conditions for the polymerization of 1-butene may be appropriately selected and carried out as long as the effects of the present invention are achieved. In general, the obtained block copolymer has a high molecular weight and a molecular weight of 10,000 or less. It is preferable to select each condition so that the amount of the polymer is 1.0% by weight or less. Further, each condition can be selected so that the tacticity is 0.90 or more in mm (triad). It is sufficient to select the polymerization amount of 1-butene to be 0.1 to 500 g / g · Ti compound, preferably 1 to 200 g / g · Ti compound. The polymerization conditions may be determined in advance so that the polybutene component is in the range of 0.01 to 5% by weight in the obtained block copolymer.

The block copolymer obtained in the present invention becomes particles excellent in anti-caking property and fluidity at 50 to 70 ° C., and therefore, the most preferred embodiment is that 1-butene is a homopolymer. . However, α-olefins other than 1-butene, for example, ethylene, propylene, 3-methylbutene, and 4-methyl-1 as long as the properties are not adversely affected.
It is permissible to carry out copolymerization in a state where pentene, 1-hexene and the like are mixed. The allowable amount varies depending on various polymerization conditions, but it is generally preferable to select the other α-olefin so as to have a mixing ratio of 5 mol% or less. The polymerization of 1-butene can be carried out in the presence of hydrogen as a molecular weight regulator, if necessary.

Following the polymerization of 1-butene, polymerization of propylene is carried out. The polymerization of propylene may be carried out by supplying a mixture of propylene and up to 5 mol% of an acceptable α-olefin. The polymerization of propylene can be carried out in the same manner as the polymerization of 1-butene described above. When the polymerization conditions of the propylene are exemplified, the polymerization temperature is preferably as low as possible in order to increase the bulk specific gravity of the block copolymer. For example, the polymerization temperature is preferably 80 ° C. or less, and more preferably 20 to 70 ° C. It is suitable.
If necessary, hydrogen can also be allowed to coexist as a molecular weight regulator. Furthermore, the polymerization may be any method such as slurry polymerization, gas phase polymerization, and solution polymerization using propylene itself as a solvent. The simplicity of the process, and also the reaction rate,
Considering the particle properties of the resulting block copolymer, slurry polymerization using propylene itself as a solvent is the most preferred embodiment. The polymerization method may be any of a batch system, a semi-batch system, and a continuous system, and the polymerization may be performed in two or more stages under different conditions.

Next, propylene-ethylene random copolymerization is performed. In the propylene-ethylene random copolymerization, the monomer unit based on propylene is 20 to 85 mol%, preferably 40 to 85 mol%, and the monomer unit based on ethylene is 15 to 80 mol%, preferably 15 to 60 mol%.
Propylene and ethylene may be mixed and used so as to be in the range of mol%. For this purpose, it is preferable to select the mixing ratio of propylene and ethylene so that the ethylene concentration in the gaseous state is 7 to 50 mol%, preferably 10 to 40 mol%. As other conditions, the same conditions as in the above-described polymerization of propylene can be adopted.

After completion of the main polymerization, the monomer can be evaporated from the polymerization system to obtain a particulate polymer.

The other component of the propylene-based resin composition in the present invention is a decomposition product of the above-described block copolymer by an organic peroxide. As the organic peroxide, known compounds can be used without any limitation. Typical examples thereof include, for example, ketone peroxides such as methyl ethyl ketone peroxide, methyl isobutyl ketone peroxide, and cyclohexanone peroxide; isobutyryl peroxide , Lauroyl peroxide, diacyl peroxide such as benzoyl peroxide; hydroperoxide such as diisopropylbenzene hydroperoxide; dicumyl peroxide; 2,5-dimethyl-2,5-di- (t-butylperoxy) hexane , 1,3-bis- (t-butylperoxy-isopropyl) -benzene, di-t-butyl peroxide, 2,5-dimethyl-2,5-di- (t-
Dialkyl-parts such as butylperoxy) -hexane-3
Oxide; 1,1-di-t-butylperoxy-3,
3,5-trimethylcyclohexane, 2,2-di- (t
Peroxyketals such as -butylperoxy) -butane; alkyl peresters such as t-butylperoxy-pivalate and t-butylperoxybenzoate;
Percarbonates such as butyl peroxyisopropyl carbonate and the like can be mentioned.

The amount of the above-mentioned organic peroxide is not particularly limited, but is generally 0.001 to 5 parts by weight, more preferably 0.002 to 5 parts by weight, per 100 parts by weight of the block copolymer.
It is preferably in the range of 3 parts by weight.

Further, when melting with the above-mentioned organic peroxide, a compound having two or more radically polymerizable groups in one molecule (hereinafter, also referred to as a cross-linking agent) may be present. As the cross-linking agent, a known compound can be employed without any limitation. Specifically, divinyl compounds such as divinylbenzene; diallyl compounds such as diallyl phthalate, diallyl terephthalate, diallyl isophthalate, diallyl tartrate, diallyl epoxysuccinate, diallyl maleate and diallyl carbonate; P-quinone dioxime; Oxime compounds such as P-dibenzoylquinone dioxime; maleimide compounds such as phenylmaleimide; di- or triallyl esters of cyanuric acid or isocyanuric acid such as triallyl cyanurate and triallyl isocyanurate; ethylene glycol methacrylate, diethylene glycol Acrylic acid and methacrylic acid ester compounds such as dimethacrylate and pentaerythritol triacrylate;
Oligomers having a double bond in the main chain or side chain such as 2-polybutadiene; and polymers having a double bond in the main chain or side chain such as syndiotactic-1,2-polybutadiene can be exemplified.

The amount of the crosslinking agent is not particularly limited, but is generally 0.01 to 20 parts by weight, more preferably 0.02 to 10 parts by weight, based on 100 parts by weight of the block copolymer. Is preferred.

The kneading of the above-mentioned block copolymer and organic peroxide and, if necessary, the crosslinking agent is generally carried out at a temperature not lower than the melting point of the block copolymer and the decomposition temperature of the organic peroxide. This is performed using a known kneading device. For example, screw extruders, Banbury mixers,
A method of kneading at 160 to 330 ° C, preferably 170 to 300 ° C, using a mixing roll or the like can be adopted. The melt-kneading can also be performed under a stream of an inert gas such as nitrogen gas. Prior to melt kneading, premixing can be performed using a known mixing device, for example, a tumbler, Henschel mixer or the like.

The amount of the component (1) and the component (2) in the propylene resin composition of the present invention is 1 to 60 with respect to 100 parts by weight of the component (1). Parts by weight. When the component (2) is less than 1 part by weight, the effect of improving impact resistance is not exhibited. On the other hand, when the amount of the component (2) exceeds 60 parts by weight, the effect of improving the impact resistance not only reaches a peak, but also the rigidity decreases, which is not preferable. Considering the balance between the rigidity of the resulting propylene-based resin composition and the effect of improving the impact resistance, component 100 of (1)
The component (2) is preferably 3 to 55 parts by weight based on part by weight.

For the mixing of the component (1) and the component (2), the above-described method of melt-kneading the block copolymer and the organic peroxide can be employed as it is.

The propylene-based resin composition obtained in the present invention can be appropriately mixed with other resins and known additives such as an antioxidant, a light stabilizer and an antistatic agent. In the present invention, in addition to the above-mentioned components, an inorganic filler is added in an amount of 1 to 70 parts by weight, preferably 3 to 60 parts by weight, based on 100 parts by weight of the propylene-based resin composition, whereby rigidity is improved. In addition, the dimensional stability can be improved. Known inorganic fillers such as calcium carbonate, magnesium carbonate, magnesium sulfate, talc, clay, silica, glass fiber, carbon fiber, potassium titanate whisker, and wollastonite can be used without any limitation.

[0051]

The propylene resin composition of the present invention has both excellent rigidity and impact resistance, and has good processability and quality stability. For this reason, the propylene-based resin composition of the present invention can be used, for example, in automobile parts, home electric parts, and various miscellaneous goods fields, with high rigidity required in response to expansion of applications, thinning of products, and responding to increase in size. And can be used as impact resistant material.

[0052]

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 measuring method used in the following examples will be described.

1) The weight average molecular weight and the ratio of the molecular weight of 10,000 or less were measured by GPC (gel permeation chromatography). Waters GPC-15
O-dichlorobenzene as solvent at 135 ° C.
I went in. The column used was Tosoh TSK gel.
GMH6-HT, gel size 10-15μ. The calibration curve shows that the weight average molecular weight is 950, 290 as a standard sample.
It was prepared using 0, 10,000, 50,000, 4.98 million, 2.7 million and 6.75 million polystyrene.

2) A method for measuring the proportions of the monomer units based on ethylene and the monomer units based on propylene in the propylene-ethylene random copolymer component and a method for measuring the ratio of the polybutene component ¹³ C-NMR spectrum chart Was calculated.
That is, the respective proportions of the monomer units based on ethylene and the monomer units based on propylene in the propylene-ethylene random copolymer component are first determined by the polymer (P
polymer, Vol. 29 (1988), p. 1848, and then the assignment of peaks was determined, followed by the method described in Macromolecules, Vol. 10, (1977) p. 773. The respective proportions of the monomer units based on ethylene and the monomer units based on propylene were calculated.

Next, the weight and ratio of the polybutene component were calculated from the integrated intensity ratio of the peak derived from methyl carbon in the monomer unit and the peak derived from methyl carbon in the polybutene component based on propylene.

3) Measurement of isotacticity of poly 1-butene Measurement was carried out by ¹³ C-NMR, and the results were obtained from Polymer Journal (Polymer J.) Vol. 16 (1984) 71.
The measurement was performed based on pages 6 to 726.

4) Particle size distribution Aperture 75, 125, 250, 355, 500, 71
About 0.1 g of a polymer particle was charged into a sieve having a diameter of 0.1180 μm, and the mixture was classified with a sieve shaker for 10 minutes.

5) Dropping seconds at 70 ° C. An outlet having a diameter of 10 mm is provided at the center of the bottom and a height of 175 m
m, the inner diameter of the upper cylindrical part is 68 mm, and the height of the cylindrical part is 60
100 ml of polymer particles, which were previously kept at 70 ° C., were placed in a metal funnel having a shape of mm, and the polymer particles were discharged while applying a vibration of 2 mm width in the lateral direction, and the time required for discharging the entire amount was measured. did.

6) Evaluation of solidification property After the completion of the polymerization, about 100 g of polymer particles separated from the monomer were obtained.
Was placed in a 500 cc beaker having a diameter of 8 cm and a height of 15 cm, and allowed to stand at room temperature for one week to observe the state. The criteria were based on the following five ranks.

A: There is almost no change from before the standing, and there is no consolidation at all.

B: A state where the bottom is in a solidified state, but is loosened when an impact is applied. C: A state in which the entire part is consolidated when an impact is applied. D: A state in which the entire part is loosened when an impact is applied. A state in which the whole is not loosened even when an impact is applied. E: A state in which it is extremely solidified and does not move as a lump. 7) Measured according to MI JIS K7210.

8) Flexural modulus Conducted according to ASTM D-790.

9) Izod Impact Strength (20 ° C.) Measured at 20 ° C. according to ASTM D-256.

Production Examples 1-1 to 1-6 (Preliminary polymerization) A 1-liter glass autoclave reactor equipped with a stirrer was sufficiently replaced with nitrogen gas, and 400 ml of heptane was charged. Reactor temperature 2
Keeping at 0 ° C., 0.18 mmol of diethylene glycol dimethyl ether, 22.7 mmol of ethyl iodide, 18.5 mmol of diethylaluminum chloride, and titanium trichloride (“TOS-1” manufactured by Marubeni Solvay Chemical Co., Ltd.)
7 ") After adding 22.7 mmol, propylene was continuously introduced into the reactor for 30 minutes so as to be 3 g per 1 g of titanium trichloride. The temperature during this period was kept at 20 ° C. After stopping the supply of propylene, the inside of the reactor was sufficiently replaced with nitrogen gas, and the obtained titanium-containing polypropylene was washed four times with purified heptane. As a result of the analysis, 2.9 g of propylene was polymerized per 1 g of titanium trichloride.

(Main Polymerization) Step 1: Polymerization of 1-Butene After sufficiently replacing a 1-liter stainless steel autoclave reactor equipped with a stirrer with nitrogen gas, 400 ml of heptane was charged. The temperature in the reactor was maintained at 20 ° C., and 18.15 mmol of diethyl aluminum chloride was added.
1, diethylene glycol dimethyl ether 0.18m
mol, 22.7 mmol of ethyl iodide, and 22.7 mmol of titanium-containing polypropylene obtained by pre-polymerization as titanium trichloride. Then, 1-butene was continuously added for 2 hours so as to be 15 g per 1 g of titanium trichloride. It was introduced into the reactor. The temperature during this period was kept at 20 ° C.
After stopping the supply of 1-butene, the inside of the reactor was replaced with nitrogen gas to obtain a titanium-containing poly-1-butene polymer. As a result of the analysis, 14 g of 1-butene was polymerized per 1 g of titanium trichloride.

Step 2: Polymerization of Propylene and Copolymerization of Propylene Ethylene To a 2-liter autoclave with N ₂ substitution, 1 liter of liquid propylene and 0.70 mmol of diethylaluminum chloride were added, and the internal temperature of the autoclave was adjusted to 70 ° C. The temperature rose. 0.087 mmol of titanium-containing poly 1-butene polymer was added as titanium trichloride, and propylene was polymerized at 70 ° C for 60 minutes. No hydrogen was used during this time. Next, the internal temperature of the autoclave was rapidly reduced to 55.
C. At the same time, a mixed solution of 0.50 mmol of ethylaluminum sesquiethoxide (Et ₃ Al ₂ (OEt) ₃ ) and 0.014 mmol of methyl methacrylate was added, ethylene was supplied, and the ethylene gas concentration in the gas phase was changed to
The copolymerization of propylene and ethylene was carried out at 55 ° C. for 120 minutes so as to be 15 mol%. During this time, the ethylene gas concentration was 15 m while checking with a gas chromatograph.
ol% was retained. No hydrogen was used during this time. After completion of the polymerization, unreacted monomers were purged to obtain a particulate polymer. No adhesion to the inside of the polymerization tank or to the stirring blade was observed at all. The yield was 140 g and the polymerization ratio of the whole polymer was 7
370 g-polymer / g-titanium trichloride.

Separately, as a result of the polymerization of propylene alone, 1 g of titanium trichloride was obtained at 70 ° C. for 60 minutes.
Each time, 1030 g of propylene was polymerized. As a result, the polybutene component in the block copolymer was 0.1%.
It turns out that 9 wt% and the polypropylene component are 14 wt%. The results are shown in Table 1.

Next, 1,3-bis- (t-butylperoxyisopropyl) benzene as an organic peroxide and divinylbenzene as a crosslinking agent were added to 30 kg of the obtained polymer at the ratios shown in Table 2. Further, 0.1 phr of an antioxidant was added, mixed with a Henschel mixer for 3 minutes, and melt-kneaded with a φ65 mm single screw extruder at 230 ° C. to obtain pellets.

Production Examples 2 and 3 The same operation as in Production Example 1 was carried out except that the polymerization amount of 1-butene in Production Example 1 was changed to 3 g and 50 g per 1 g of titanium trichloride. went. The results are shown in Table 1. Furthermore, it melt-kneaded with the amount of organic peroxide shown in Table 2 in the same manner as in Production Example 1.

Production Examples 4 and 5 The same operation as in Production Example 1 was carried out except that the polymerization of propylene was carried out at 60 ° C. for 10 minutes and at 60 ° C. for 30 minutes. In a separate polymerization experiment, the polymerization rate of propylene at this time was 240 g-P
P / g-TiCl ₃ and 540 g-PP / g-TiCl ₃
Met. The results are shown in Table 1. Furthermore, it melt-kneaded with the amount of organic peroxide shown in Table 2 in the same manner as in Production Example 1.

Comparative Production Examples 1 and 2 The same operation as in Production Example 1 was carried out except that the polymerization of 1-butene was changed to 0.3 g and 600 g per 1 g of titanium trichloride in the main polymerization of Production Example 1. The results are shown in Table 1. Furthermore, it melt-kneaded with the amount of organic peroxide shown in Table 2 in the same manner as in Production Example 1.

Comparative Production Example 3 The same operation as in Production Example 1 was carried out except that the hydrogen gas concentration in the polymerization of ethylene propylene in Production Example 1 was changed to 14 mol%. The results are shown in Table 1. Furthermore, it melt-kneaded with the amount of organic peroxide shown in Table 2 in the same manner as in Production Example 1.

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[Table 1]

[0075]

[Table 2]

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[Table 3]

Examples 1 to 12 Pellets obtained in Production Examples 1-1 to 1-6 were mixed with a melt flow index of 40 g / 10 minutes and ethylene units of 3.
7 mol% of an ethylene-propylene random copolymer was weighed at a ratio shown in Table 3 so as to make a total amount of 500 g, and kneaded at 230 ° C. with a pravender.

Using the pellets as a raw material, 50 TO
Using an N injection molding machine, four pieces of a flexural modulus test piece and four Izod impact test pieces were collected. In addition, a test piece for MI measurement was cut out from the Izod impact test piece. This operation was repeated five times to produce a total of 20 test pieces. Using this test piece, a bending elastic modulus test and an impact test were performed, and MI was measured. Table 3 shows the results.

Examples 13 to 16, Comparative Examples 1 to 4 The polymers produced in Production Examples 1 to 5 and Comparative Production Examples 1 to 3 were mixed with an ethylene-propylene random copolymer in the same manner as in Example 1. Table 3 shows the physical properties.

Comparative Examples 5-7 MI produced using a vanadium catalyst was 9 g / 10
In minutes, an ethylene-propylene rubber having an ethylene unit of 88 mol% and an ethylene-propylene random copolymer having an MI of 40 g / min and an ethylene unit of 3.7 mol% have a total amount of 500 g in a ratio shown in Table 3. And weighed at 230 ° C. with a lavender. Hereinafter, a test was performed in the same manner as in Example 1. The results are shown in Table 3.

Comparative Example 8 Comparative Example 5 was the same as Comparative Example 5 except that an ethylene propylene rubber having an MI of 1 g / 10 minutes and an ethylene unit of 83 mol% was used as the ethylene propylene rubber. The operation was performed in the same manner as in Example 5, and the results are shown in Table 3.

Comparative Example 9 In Comparative Example 5, instead of ethylene propylene rubber,
MI produced using a vanadium catalyst is 0.5 g /
The procedure was performed in the same manner as in Comparative Example 5 except that the ethylene propylene diene rubber was used in which the ethylene unit was 75 mol% and the ethylidene norbornene unit was 10 mol% in 10 minutes. The results are shown in Table 3.

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[Table 4]

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[Table 5]

Claims (1)

(57) [Claims] (1) Polypropylene
100 parts by weight (2) A block copolymer containing a polybutene component, a polypropylene component, and a propylene-ethylene random copolymer component, wherein the polybutene component is 0.01 to 5% by weight and the polypropylene component is 1 to 70% by weight. % Of the propylene-ethylene random copolymer component is from 25 to 99.99% by weight, and the propylene-ethylene random copolymer component is from 15 to 80 mol% of a monomer unit based on ethylene, and is contained in propylene. The composition is composed of a random copolymer containing 85 to 20 mol% of a monomer unit based on the above, and the proportion of components having a molecular weight of 10,000 or less is 1.0% by weight or less, and the weight average molecular weight is 600,000 or more. A propylene-based resin composition comprising 1 to 60 parts by weight of a decomposition product of a propylene-based block copolymer with an organic peroxide.