JP3151064B2 - Propylene resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION The present invention relates to mechanical strength, flexibility,
The present invention relates to a propylene-based resin composition having excellent processability and quality stability.

[0002]

2. Description of the Related Art Conventionally, a soft material made of a polyolefin resin is obtained by mixing amorphous ethylene-propylene rubber (hereinafter abbreviated as "EPR") or the like produced using a vanadium catalyst with polypropylene. It is manufactured by.

Recently, various methods have been proposed for obtaining a soft material by simultaneously producing a crystalline polyolefin component and an ethylene propylene copolymer component by polymerization. However, although the copolymer obtained by the above method can be obtained in the form of particles, its fluidity is poor, especially when the polymer particles obtained from the polymerization tank are left to deposit, they solidify due to the load and become massive. For this reason, there is a problem that a trouble is caused in the storage and transfer steps, and a complicated operation is required. Further, the polymer particles have a relatively low temperature, for example, 50 to 70 ° C. because they show fluidity at a relatively low temperature, for example, around normal temperature, but contain a large amount of an amorphous polymer portion.
, There is a disadvantage that the adhesiveness becomes remarkable and the fluidity decreases.

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]

As a result of further studies on the propylene-based block copolymer, the present inventors have found that the propylene-based block copolymer has a high mechanical strength and a good flexibility represented by elongation. The inventors succeeded in obtaining a resin composition, and have proposed the present invention.

That is, the present invention provides (1) a polybutene component,
A block copolymer containing a polypropylene component and a propylene-ethylene random copolymer component, wherein the polybutene component is 0.01 to 5% by weight, the polypropylene component is 1 to 70% by weight, and the propylene-ethylene random copolymer component is 25 to 98.9% by weight, and the propylene-ethylene random copolymer component contains 15 to 80 mol% of a monomer unit based on ethylene and 85 to 20 mol% of a monomer unit based on propylene. The ratio of the component composed of a polymer and having a molecular weight of 10,000 or less is 1.0
100% by weight of a decomposition product of a propylene-based block copolymer with an organic peroxide having a weight-average molecular weight of 600,000 or more (2) 0.05 to 2 parts by weight of a crystal nucleating agent It is a resin composition.

In the present invention, the propylene-based block copolymer (hereinafter, simply referred to as "block copolymer") as a raw material comprises a polybutene component, a polypropylene component and a propylene-ethylene copolymer component. If the polybutene component is replaced by another component, for example, a polyethylene component, the polymer particles obtained by polymerization have poor solidifying properties and high-temperature fluidity, and cannot be a raw material intended in 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 essential for improving the particle properties of the polymer particles. In particular, when the content of the polypropylene component described later is small, for example, when the content is 30% by weight or less, the obtained polymer particles tend to stick, but even in such a case, the presence of the polybutene component makes it possible to obtain a good fluidity weight. It can be a united particle. When the polybutene component is less than 0.01% by weight, when the polymer particles obtained by polymerization are left to accumulate, they solidify due to the load, and the copolymer particles are further reduced to 50 to 50% by weight.
When the temperature is 70 ° C., the fluidity is extremely poor, which is not preferable. On the other hand, when the content of the polybutene component exceeds 5% by weight, the fluidity of the block copolymer is rather lowered, which is not preferable. 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 polymer particles.

On the other hand, if the propylene component is less than 1% by weight, the strength and heat resistance of the molded article made of the block copolymer are reduced. 70% by weight of polypropylene component
If the ratio exceeds the above range, the low-temperature impact resistance of the molded article is reduced, and the intended propylene-based 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, low-temperature impact resistance, and the like, and when it is 30% by weight or less, flexibility and transparency become particularly good.

Further, the content of the ethylene-propylene random copolymer component is 25 to 99.99% by weight. When the content of the above component is less than 25% by weight, flexibility such as elongation and low-temperature impact resistance are inferior. In consideration of flexibility, strength and heat resistance, the ethylene-propylene random copolymer component is preferably in the range of 40 to 97% by weight.

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

The content ratio of each of the monomer units based on ethylene and the monomer units based on propylene in the propylene-ethylene random copolymer component is 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. The weight average molecular weight in the present invention 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 from 100 to 1,000 μm, particularly preferably from 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 the polymerization of olefins 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, known α, β, γ, or δ-titanium trichloride can be suitably 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 the polymerization of 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 proportion of the organoaluminum compound [B] used is 0.1 to 100, preferably 0.1 to 20 in terms of Al / Ti (molar ratio) 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 within a range that does not adversely affect the physical properties of the block copolymer, for example, 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.

In the prepolymerization, slurry polymerization is generally 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. 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 used for 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 prepolymerization 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 aforementioned prepolymerization 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.

The main polymerization of the present invention is carried out in the presence of 1-butene in the presence of the catalyst-containing prepolymer, an organoaluminum compound, and, if necessary, an electron donor and / or a catalyst component of an iodine compound. The polymerization of 1-butene may be carried out by gas phase polymerization, but is generally carried out by solution polymerization or 1-butene in the above-mentioned solvent.
Slurry polymerization in a butene medium may be performed. 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, it is generally at 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 having excellent anti-caking properties 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, the 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 using propylene and ethylene itself as a solvent, gas phase polymerization, and solution polymerization. Considering the simplicity of the process, the reaction rate, and 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 first component of the propylene-based resin composition of the present invention is a decomposition product of the above block copolymer by an organic peroxide. This decomposition product is obtained by melt-kneading the above-described block copolymer with an organic peroxide. As the organic peroxide, known compounds can be used without any limitation. Typical examples thereof include 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-butylperoxy)
Dialkyl peroxide such as -hexane-3; 1,1
Peroxyketals such as -di-t-butylperoxy-3,3,5-trimethylcyclohexane, 2,2-di- (t-butylperoxy) -butane; t-butylperoxy-pivalate, t-butyl Alkyl peresters such as peroxybenzoate; and percarbonates such as t-butyl peroxyisopropyl carbonate.

The amount of the 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 the above organic peroxide is melted, a compound having two or more radically polymerizable groups in one molecule (hereinafter, also simply referred to as a crosslinking agent) may be present. The presence of the cross-linking agent can cross-link the molecular chains of the block copolymer, thereby improving heat resistance.

As the crosslinking agent, known compounds 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 liquid 1,2-polybutadiene; syndiotactic-1,
Examples thereof include polymers having a double bond in the main chain or side chain, such as 2-polybutadiene.

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. Is carried out using a kneading device. Generally, it is preferable to knead at 170 to 330 ° C.

As the nucleating agent which is the other component of the propylene resin composition of the present invention, a known compound can be employed without any limitation. For example, metal salts of aromatic monocarboxylic acids such as benzoic acid, toluic acid and p-tert-butylbenzoic acid; 1,3,2,4-di (benzylidene)
Di (benzylidene) sorbitols such as sorbitol, 1,3,2,4-di (p-methylbenzylidene) sorbitol; bis (4-tert-butylphenyl) phosphate
Metal salts of aromatic phosphoric acid compounds such as sodium and methylene (2,4-tert-butylphenyl) sodium phosphate; and talc.

The amount of the above crystal nucleating agent is from 0.05 to 2.0 based on 100 parts by weight of the decomposition product of the block copolymer.
It is in the range of 0 parts by weight, and preferably in the range of 0.1 to 1.0 parts by weight. When the amount of the crystal nucleating agent is less than the above range, sufficient mechanical strength and flexibility cannot both be satisfied, and when the amount is more than the above range, the mechanical strength and flexibility are rather reduced. Not preferred.

The compounding time of the crystal nucleating agent is not limited at all. For example, it may be added to a decomposition product of the block copolymer after decomposition with an organic peroxide. Decomposition with an organic peroxide may be carried out by mixing at the time of mixing with the combined organic peroxide.

The propylene 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 decomposition product of the block copolymer. Thereby, rigidity and 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.

[0052]

The propylene-based resin composition of the present invention has improved mechanical strength and flexibility by blending a crystal nucleating agent, and has excellent workability. further,
It is considered that the fluidity of the particles of the block copolymer, which is the raw material, is extremely excellent. However, the dispersion of physical properties such as flexural modulus, tensile strength, and tensile elongation is small, and the quality is excellent.

Accordingly, the propylene-based resin composition of the present invention can be used in a wide range of fields such as automobile parts, household electric parts, building construction materials, medical equipment and the like.

[0054]

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 has a weight average molecular weight of 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 proportion of the monomer unit based on ethylene and the proportion of the monomer unit 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 A measurement was carried out by ¹³ C-NMR, and the results were reported in Polymer Journal (Polymer J.), 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 Approximately 100 g of polymer particles separated from the monomer after completion of the polymerization
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 in which the bottom is in a solidified state, but is loosened when an impact is applied. C: A state in which the whole is consolidated, but is completely loosened when an impact is applied. D: A state in which the whole is consolidated. 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 becomes in a lump and does not move. 7) Flexural modulus The test was performed in accordance with ASTM D-790.

8) Tensile strength and tensile elongation Measured according to JIS K7113.

9) Vicat softening temperature Measured under the condition of a load of 250 g according to JIS K7206.

Production Example 1 (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 above-mentioned 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.

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.

Production Example 4 The same operation as in Production Example 1 was carried out except that the polymerization of propylene in Production Example 1 was changed to 60 ° C. for 10 minutes. In a separate polymerization experiment, the polymerization rate of propylene at this time was 240 g-PP / g-TiCl ₃ . The results are shown in Table 1.

Production Example 5 The same operation as in Production Example 1 was carried out except that in the polymerization of propylene in Production Example 1, the ethylene gas concentration in the gas phase was adjusted to 5 mol%. The results are shown in Table 1.

Production Example 6 The same procedure as in Production Example 1 was carried out except that the polymerization of propylene was carried out at 70 ° C. for 5 hours and the copolymerization of propylene and ethylene was carried out at 55 ° C. for 60 minutes. The operation was performed. In a separate polymerization experiment, the polymerization magnification at this time was
It was _{5100g-PP / g-TiCl 3} . The results are shown in Table 1.

Comparative Production Example 1 The same operation as in Production Example 1 was carried out except that the polymerization of 1-butene was not carried out in the main polymerization of Example 1. Table 1 shows the results
It was shown to.

Comparative Production Example 2 The same operation as in Production Example 1 was carried out except that the polymerization of 1-butene was changed to 600 g per 1 g of titanium trichloride in the main polymerization of Example 1. The results are shown in Table 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 Example 1 was changed to 14 mol%. The results are shown in Table 1.

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[Table 1]

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[Table 2]

Examples 1 to 12 To 30 kg of the block copolymer produced in Production Example 1, 1,3-bis- (t-butylperoxyisopropyl) benzene as an organic peroxide, divinylbenzene as a crosslinking agent, and Sodium 2,2-methylenebis (4,6-di-tertbutylphenyl) phosphate, p-tert-aluminum benzoate, and 1.
3,2,4-di (p-methylbenzylidene) sorbitol was added at the ratio shown in Table 2, and 3 was added using a 100 L supermixer.
After mixing for 1 minute, the mixture was melt-kneaded at 230 ° C. with a φ65 mm single screw extruder to obtain pellets.

Using these pellets as raw materials, bending test pieces and tensile test pieces were prepared using a 50 TON injection molding machine. The number of these test pieces was 20, respectively.

The flexural modulus was measured using a bending test piece, and the tensile speed was measured at 200 mm /
The tensile strength and the tensile elongation were measured in seconds, and the Vicat softening point was measured using a bending test piece. The measurement of the above-mentioned flexural modulus, tensile strength, tensile elongation and Vicat softening temperature was performed for 20 samples, and the average value and the coefficient of variation were determined. The results are shown in Table 2.

Examples 13 to 18 Using the block copolymers produced in Production Examples 2 to 6, a test was conducted in the same manner as in Example 1. The results are shown in Table 2.

Comparative Examples 1 to 12 Using the block copolymers produced in Production Examples 1 to 6 and Comparative Production Examples 1 to 3, tests were conducted in the same manner as in Example 1. The results are shown in Table 2.

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[Table 3]

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[Table 4]

Continuation of the front page (56) References JP-A-3-54238 (JP, A) JP-A-63-90552 (JP, A) JP-A-62-241947 (JP, A) JP-A-62-236852 (JP) , A) JP-A-60-92341 (JP, A) JP-A-51-47946 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C08L 53/00

Claims (1)

(57) [Claims] 1. A block copolymer comprising (1) a polybutene component, a polypropylene component, and a propylene-ethylene random copolymer component, wherein the polybutene component is 0.1%.
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%,
Decomposition products of a propylene-based block copolymer having a weight-average molecular weight of 600,000 or more and a ratio of components having a molecular weight of 10,000 or less being 1.0% by weight or less.
100 parts by weight (2) A propylene-based resin composition comprising 0.05 to 2 parts by weight of a nucleating agent.