JP3369007B2 - Propylene resin composition - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION The present invention is particularly applicable to mechanical parts, electric
The present invention relates to a propylene-based resin composition having excellent rigidity, impact resistance, heat resistance and surface hardness, which is preferably used in the fields of electronic parts, packaging materials, engineering plastic substitutes and the like.

[0002]

Polypropylene is generally inexpensive and
In addition, by taking advantage of its characteristics such as lightness, transparency, mechanical strength, heat resistance, and chemical resistance, automobile parts, electricity,
It is widely used for industrial materials such as electronic parts and various packaging materials. In recent years, as the functionality of products has been improved or the cost has been reduced, it has been strongly demanded to improve the characteristics of these materials. As a method for improving the rigidity, impact resistance, heat resistance, etc. of polypropylene, for example, a method of compounding ethylene-propylene block copolymer with ethylene-propylene rubber and a nucleating agent (Japanese Examined Patent Publication No. 60-3420) or ethylene -Method of blending propylene rubber, ethylene copolymer and inorganic filler (JP-A-4-275351, JP-A-5-5051, JP-A-5-98097, JP-A-5-98098, etc.), etc. Is proposed.

[0003]

However, although the above methods all improve some of the properties, the heat resistance and the rigidity are still insufficient.
The present invention has been made in view of such circumstances, and an object of the present invention is to provide a propylene resin composition having excellent rigidity, impact resistance, heat resistance, and surface hardness.

[0004]

As a result of intensive studies, the inventors of the present invention have found that the above object can be achieved by using a propylene block copolymer having specific physical properties and a propylene homopolymer in combination. The present invention has been completed based on this finding. That is, the present invention includes (A)
(i) to (iv) polypropylene part (a) having physical properties, and (i) xylene extraction insoluble part (XI) 9 at 25 ° C.
8.0 wt% or more (ii) Isotactic pentad fraction (IP) 9
6.5% or more (iii) Isotactic average chain length (N) 90 or more (iv) Total amount of each fraction having an isotactic average chain length (N _f ) of 300 or more by column fractionation method
Copolymer part of propylene and ethylene and / or α-olefin having 4 to 12 carbon atoms satisfying all of the following conditions (v) to (viii) of 10% by weight or more (b) (v) Average by two-site model Propylene content (FP)
20 to 80 mol% (vi) 2 sites copolymer produced in the active sites of polymerization preferentially propylene in the model propylene content _(P P) 65 to 90 mol% of _{(P H) (vii) P} H is co Ratio (P _f1 ) in polymer 0.4
0-0.90 (viii) Two-site model blockiness (CSD)
Propylene block copolymer consisting of 1.8 to 5.0
30 to 60 wt%, (B) Propylene homopolymer having the following physical properties (ix) to (xii) 20 to 40 wt%, (ix) Xylene extraction insoluble part (XI) 9 at 25 ° C
8.0% by weight or more (x) isotactic pentad fraction (IP) 96.
5% or more (xi) Isotactic average chain length (N) 90 or more (xii) Total amount of fractions with an isotactic average chain length (N _f ) of 300 or more by column fractionation method
10 wt% or more (C) ethylene-α-olefin copolymer 1 to 10 wt%, (D) styrene rubber polymer 2 to 15 wt% and (E) talc 5 to 30 wt% [however, (A) +
(B) + (C) + (D) + (E) = 100% by weight]. Hereinafter, the present invention will be described in detail.

The (A) propylene block copolymer (hereinafter referred to as "BPP") in the present invention is a copolymer of polypropylene part (a) with propylene and ethylene and / or α-olefin having 4 to 12 carbon atoms. It is a block copolymer composed of part (b). The BPP of the present invention is the first
It is necessary that the polypropylene part (a) produced in the reaction of the stage has the following physical properties. That is, (i) the xylene extraction insoluble part (hereinafter referred to as “XI”) at 25 ° C. is 9
It is 8.0% by weight or more, preferably 98.5% by weight or more, and more preferably 99.0% by weight or more. XI
Is less than 98.0% by weight, rigidity and heat resistance are poor. The XI was measured by a method in which polypropylene was once dissolved in 135 ° C. orthoxylene and then cooled to 25 ° C. to precipitate the polymer.

Further, (ii) the isotactic pentad fraction (hereinafter referred to as "IP") needs to be 96.5% or more, preferably 96.8% or more, and particularly 97.0%.
% Or more is preferable. If the IP is less than 96.5%, the rigidity and heat resistance are poor, which is not preferable. The IP is
It is an isotactic fraction in a pentad unit in a polypropylene molecular chain measured by nuclear magnetic resonance ( ¹³ C-NMR) spelttle with isotope carbon. The measurement method is A. Zambelli; Macromolecules, 6 , 925 (1973), 8 , 6
87 (1975) and according to the method described in the 13, 267 (1980).

Further, (iii) the isotactic average chain length (hereinafter referred to as "N") must be 90 or more, preferably 100 or more, and particularly preferably 110 or more. When N is less than 90, rigidity and heat resistance are poor. Note that N is
It represents the average length of the isotactic portion of the methyl group in the polypropylene molecule, and its measurement method is
JCRandall; Polymer SequenseDistribution, Academic
Press, New York, 1977, Chapter 2). Specifically, polypropylene is 1,2,4-
It is dissolved in a mixed solvent of trichlorobenzene / deuterated benzene by heating at a temperature of 130 ° C. so that the polymer concentration becomes 10% by weight. This solution is put into a glass sample tube of 10 mmΦ, and ¹³ C-NMR spectrum is measured by the same method as for IP. An example of this spectrum diagram is shown in FIG. Figure 1
A is a spectrum of a methyl group region in polypropylene, and b is an enlarged view of the spectrum. The spectrum shows pentad units, that is, 5 adjacent methyl groups.
It is measured with the individual as one unit, and the isotacticity of the methyl group (1mm such as mmmm, mmmr structurally
The absorption peak varies depending on the number of types). 1b
Shows the correspondence between the absorption peak and isotacticity.

On the other hand, as a polymerization theory, Shan-Nong et al; P
There is a two-site model described in olymer Journal, vol.15, No.12, p859-868 (1983). That is, there are two types of active species at the time of polymerization, that is, the catalyst side and the polymer terminal, the catalyst side is called catalyst-controlled polymerization, and the other is called terminal-controlled polymerization (for details, see Furukawa Junji; Taka Molecular Essence and Topics 2, "Polymer Synthesis", P7
3 (Published by Kagaku Doujin Co., Ltd. (1986)). According to the above-mentioned literature, the two-site model is, after all, α: the probability that the D- and L-forms are added to the polymerization end by the catalyst-controlled polymerization (enantiomorphic process), that is, an index σ of the degree of disorder in the isotactic chain. ： Probability that a meso compound with the same end as the polymerization end is formed by the end-dominated polymerization (Bernoulli process) ω: The ratio of the α sites is theoretically calculated from 10 types of isotactic strengths with different isotacticity in pentad units. it can. Then, α, σ, and ω are obtained by the method of least squares so that the intensity measured by NMR and the theoretical intensity match, and each pentad unit is obtained by the following equation.

[0009]

[Table 1] However, β = α (1-α)

Next, the average chain length (N) definition formula described in the above-mentioned J C. Randall reference; N = Meso chain number / Meso unit number be able to. N = 1 + (A ₁ + A ₂ + A ₃ ) /0.5 (A ₄ + A ₅ +
A ₆ + A ₇ )

Further, the total amount of those having an isotactic average chain length (hereinafter referred to as “N _f ”) of 300 or more in each fraction by the (iV) column fractionation method is 10% by weight of the whole.
It is necessary to be the above, preferably 30% by weight or more, particularly preferably 50% by weight. If N _f is 300 or more but the total amount is less than 10% by weight, the effect of improving rigidity, surface hardness and heat resistance is poor. Here, the column fractionation method means that after the xylene-extracted insoluble portion is dissolved in para-xylene at a temperature of 130 ° C., Celite is added, the temperature is lowered to 30 ° C. at a temperature lowering rate of 10 ° C./hour, and the mixture is attached to Celite. The method is to fill the column with slurry celite, raise the temperature stepwise every 30 ° C. to 2.5 ° C. using paraxylene as a developing solution, and separate polypropylene by fractions. For more information, see Masahiro Kaku
go et al; Macromolecules, vol. 21, p314-319 (1988). The N _f of the separated polypropylene is measured by the above N measuring method.

Further, in the BPP of the present invention, it is necessary that the propylene-α-olefin copolymer (b) produced in the second stage reaction satisfies all the following conditions. Here, the two-site model of the propylene-α-olefin copolymer will be described by taking the propylene-ethylene copolymer as an example. FIG. 2 shows an example of a nuclear magnetic resonance ( ¹³ C-NMR) spectrum of isotope carbon of a propylene-ethylene copolymer. In the spectrum, 10 peaks shown in (1) to (10) appear due to the difference in chain distribution (arrangement of ethylene and propylene). The name of this chain is Carman, C, J, et al; M.
acromolecules, Vol.10, p536-544 (1977),
The name is shown in FIG. Such a chain can be expressed as a reaction probability (P) assuming a reaction mechanism of copolymerization, and the relative intensity of each peak of (1) to (10) when the overall peak intensity is 1 is P. It can be expressed as a probability equation by Bernoulli statistics with the parameter. For example, in the case of (1) Sαα, if the propylene unit is the symbol p and the ethylene unit is the symbol e, then the possible chain is [p
There are three types, ppp], [ppee], and [eppe], which are represented by reaction probabilities (P) and are added together. The remaining peaks (2) to (10) can be obtained by formulating equations in the same manner and optimizing P so that the peak intensity actually measured and those 10 equations are closest to each other. . The two-site model is a model that assumes this reaction mechanism. HNCHENG; Jounal of Applied P
olymer Sience, Vol.35 p1639-1650 (1988). That is, in the model of copolymerizing propylene and ethylene using a catalyst, polymerized preferentially ethylene and propylene content (P _P) of the copolymer generated at the active sites of polymerization preferentially propylene (P _H) Assuming two of the propylene content (P _P ') of the copolymer produced at active sites,
Further, when the ratio of P _H in the copolymer (P _f1 ) is used as a parameter, the probability equation shown in Table 2 below is obtained.

[0013]

[Table 2]

Next, the three parameters of P _P , P _P 'and P _f1 should be optimized so that the relative intensity of the ¹³ C-NMR spectrum described above and the stochastic equation shown in Table 2 match. Required by.

(I) Average propylene content (FP) of the present invention
Is calculated by the following equation using the above three parameters. _{FP = P P × P f1 +} P P '× (1-P f1) FP sought (mol%) The above formula is 20 to 80 mol%, preferably 25 to 75 mol%, more preferably 3
It is 0 to 70 mol%. If the FP is less than 20 mol%, the appearance of the molded product is significantly deteriorated. On the other hand, if it exceeds 80 mol%, the impact resistance decreases, which is not preferable.

Among the above parameters, (ii) P _P
Is 65 to 90 mol%, preferably 68 to 88 mol%, and particularly preferably 70 to 85 mol%. P _P is 6
If it is less than 5 mol%, the rigidity and heat resistance will be reduced. on the other hand,
If it exceeds 90 mol%, impact resistance is impaired, which is not preferable.

Further, (iii) P _f1 is 0.40 to 0.90.
And 0.45 to 0.85 is preferable, and especially 0.
48 to 0.82 is preferable. When P _f1 is less than 0.40, the rigidity and heat resistance decrease. On the other hand, if it exceeds 0.90, impact resistance is impaired, which is not preferable.

Finally, (iv) block property (CSD) is
This is the reactivity ratio of ethylene and propylene, and this definition is in accordance with the method of "Polymerization 1 reaction analysis," p. 5-13, edited by Kobunkai, published by Baifukan (1975). That is, it is expressed by the following equation using the intensity ratio (Ri) of each peak in the spectrum of FIG. CSD = [(0.5 × R7 + 0.25 × R6 + 0.5 × R3) × R1] /
[0.5 × (R2 + R3)] ^{2 The} CSD obtained by the above formula is 1.8 to 5.0 and 2.0
˜4.5 is preferable, and 2.5 to 4.0 is particularly preferable. If the CSD is less than 1.8, the rigidity and heat resistance will decrease. On the other hand, when it exceeds 5.0, impact resistance at low temperature is impaired, which is not preferable.

Propylene-α in BPP of the present invention
The proportion of the olefin copolymer (b) is not particularly limited, but is preferably 3 to 50% by weight, and particularly 10 to 4
0 wt% is preferred. The polymerization of BPP of the present invention is carried out by a slurry method carried out in the presence of an liquefied α-olefin solvent such as hexane, heptane, kerosene or the like or a liquefied α-olefin solvent such as propylene, a gas phase polymerization method without a solvent, etc. At room temperature to 130 ° C., preferably 50 to 90 ° C., and a pressure of ^{2 to} 50 kg / cm ² . As the reactor in the polymerization step, those usually used in the technical field can be appropriately used, and examples thereof include a stirred tank reactor, a fluidized bed reactor, a circulation reactor, and a continuous type, a semi-batch type, or a batch type. Either method may be used. Specifically, it can be obtained using a known multistage polymerization method. That is, it is a method in which propylene is polymerized in the first stage reaction and then propylene and α-olefin are copolymerized in the second stage reaction.
-15284, Japanese Patent Publication No. 38-14834, Japanese Patent Laid-Open No. 53-35788
JP-A-53-35789, JP-A-56-55416 and the like.

The BPP of the present invention cannot be obtained with a known Ziegler-Natta catalyst such as a titanium trichloride catalyst or a magnesium chloride-supporting titanium-type catalyst.
As an example of the catalyst for obtaining the BPP of the present invention, a solid catalyst containing a magnesium compound, a titanium compound, a halogen-containing compound and an electron-donating compound as essential components can be used, and further a compound represented by the general formula: Ti Xa · Yb (wherein X is Is a halogen atom of Cl, Br, I, Y is an electron-donating compound, a is 3 or 4, and b is an integer of 3 or less), and then washed with a halogen-containing compound. And an improved polymerization catalyst obtained by further washing with a hydrocarbon.

Ti Xa in the above formula is, for example, RPSCo.
utts, et al, Advan.Organometal.Chem., 9 , 135 (1970), 4th Edition New Experimental Chemistry Course 17 Inorganic and chelate complexes Maruzen (1991) p.35, HKKakkoen, et al, J. Organ
As described in Omet. Chem., 453 , 175 (1993), etc., it is generally known that an electron-donating compound easily forms a complex. X is a halogen atom of Cl, Br, I, of which Cl is preferred. a is 3 or 4, but is preferably 4. Examples of Y generally include oxygen-containing compounds, nitrogen-containing compounds, phosphorus-containing compounds and sulfur-containing compounds. Examples of the oxygen-containing compound include alcohols, ethers, esters, acid halides, acid anhydrides and the like. These electron donating compounds may be used alone or in combination of two or more.
Among these, esters are preferable, and phthalates are particularly preferable. B of Y is
When a is 3, b is preferably 1 to 3 and when a is 4, 1 or 2 is preferable, and particularly preferably, a is 4 and b is 1.

The propylene homopolymer (B) in the present invention is polypropylene having excellent stereoregularity.
It is necessary to have the physical properties of (ix) to (xii). (ix) Xylene extraction insoluble part (XI) 9 at 25 ° C
8.0% by weight or more (x) isotactic pentad fraction (IP) 96.
5% or more (xi) Isotactic average chain length (N) 90 or more (xii) Total amount of fractions with an isotactic average chain length (N _f ) of 300 or more by column fractionation method
10 wt% or more These physical properties are described in detail in the section of (A) BPP. Melt flow rate of component (B) (JIS K7
According to No. 210, there is no particular limitation regarding (measured under condition 14 in Table 1), but it is 10 when considering the balance between rigidity and formability.
It is advisable to use the one having an amount of -60 g / 10 min.

The ethylene-α-olefin copolymer (C) according to the present invention is used in the presence of a Ziegler catalyst, a Phillips catalyst, a metallocene catalyst or the like at a pressure of 200 kg / cm in a gas phase flow method, a slurry method, a solution method or the like. ^It can be obtained by ^two or more high-pressure polymerization methods. The copolymerization ratio of the α-olefin is usually at most 30 mol%, preferably 25 mol%, particularly preferably 5 to 15 mol%. Specific examples of α-olefins include 1-butene and 3
-Methyl-1-butene, 3-methyl-1-pentene, 4
-Methyl-1-pentene, 4,4-dimethyl-1-pentene, vinylcyclopentane, vinylcyclohexane and the like can be mentioned. These α-olefins may be used alone or in combination of two or more.

The styrene-based rubber polymer (D) in the present invention generally has a hard segment polystyrene block and a soft segment rubber block, and the polystyrene block has a rubber elasticity by forming physical crosslinking points. It is also called a styrene thermoplastic elastomer. Examples of the soft segment include polybutadiene (B), polyisobutadiene (I), polyolefin (ethylene / butylene: EB, ethylene / propylene: EP, etc.) and the like. Depending on how the hard segment polystyrene (S) block and the soft segment are arranged, they are roughly classified into a linear type and a radial type. Specific examples of the component (D) of the present invention include S
BS, SIS, SEBS, SEPS, etc. are mentioned.
These may be used alone or in combination of two or more.

Further, (E) talc in the present invention is also referred to as magnesium silicate, and is produced by a dry method in which natural ore is roughly crushed and classified and refined, and is widely used as a filler in the field of synthetic resins and synthetic rubbers. Is. Examples of use are described, for example, in JP-A-53-79938, JP-A-55-120642 and JP-A-56-141341. The average particle size of the talc is generally 5 μm
It is below, 0.3-3.0 micrometers is preferable and especially 0.
It is preferably 4 to 2.8 μm. Further, those treated with an organic titanate coupling agent, a silane coupling agent, an aluminum coupling agent, a fatty acid, a fatty acid metal salt, a fatty acid ester or the like may be used for the purpose of improving the dispersibility or adhesiveness of talc. .

The composition ratio of the component (A) in the resin composition of the present invention is 30 to 60% by weight, and 33 to 57% by weight.
Is preferable, and 40 to 55% by weight is particularly preferable.
If the proportion of the component (A) is less than 30% by weight, the rigidity and heat resistance will decrease. On the other hand, if it exceeds 60% by weight, the impact resistance decreases. The composition ratio of the component (B) is 20 to 40% by weight, preferably 23 to 38% by weight, and particularly preferably 25 to 35% by weight. If the proportion of the component (B) is less than 20% by weight, the rigidity and heat resistance will decrease. On the other hand, if it exceeds 40% by weight, the impact resistance decreases. The composition ratio of the component (C) is 1 to 10% by weight, preferably 1.5 to 9% by weight,
In particular, 2 to 8% by weight is suitable. Ratio of component (C) is 1
If it is less than wt%, the impact resistance is lowered. On the other hand, 10% by weight
If it exceeds, the rigidity and heat resistance will be impaired. The composition ratio of the component (D) is 2 to 15% by weight, preferably 3 to 13% by weight, and particularly preferably 4 to 11% by weight. If the proportion of the component (D) is less than 2% by weight, the impact resistance will decrease. On the other hand, if it exceeds 15% by weight, the rigidity and heat resistance decrease. The composition ratio of the component (E) is 5 to 30% by weight, preferably 10 to 28% by weight, and particularly preferably 15 to 25% by weight. When the proportion of the component (E) is less than 5% by weight, the rigidity and heat resistance are poor. On the other hand, if it exceeds 30% by weight, the impact resistance is lowered and the mold is contaminated due to bleed-out, which is not preferable.

The resin composition of the present invention is prepared by a known mixing method,
For example, it can be obtained by mixing each component using a ribbon blender, a tumbler, a Henschel mixer, and the like, and further melt-mixing using a kneader, a mixing roll, a Banbury mixer, an extruder, and the like. The temperature during melt mixing is usually 170 to 280 ° C, preferably 190 to 260 ° C.
Should be done in. The obtained resin composition may be formed into a film, sheet, tube, bottle or the like by a known melt molding method and compression molding method, and used alone or laminated with other materials to be used as a laminate. it can.

Further, the BPP of the present invention includes additives commonly used by those skilled in the art, such as an antioxidant, a weather resistance stabilizer, an antistatic agent, a lubricant, an antiblocking agent, an antifogging agent, and the like.
A pigment, a plasticizer, a softening agent and the like may be appropriately added within a range that does not impair the object of the present invention.

[0029]

EXAMPLES The present invention will now be described in more detail with reference to examples. In addition, the measuring method of each physical property is shown below. [MFR] In accordance with JIS K7210, a melt indexer manufactured by Takara Co. was used. [Ethylene content] CJ Carman et al; Macromolecule
s, 10, 537 was based on ¹³ C-NMR method described in (1977). [Flexural Modulus] Based on JIS K7203. [Izod impact strength] In accordance with JIS K7110,
It was measured with a notch. [Drop weight impact strength] According to ASTM D3029-78, the weight is dropped from a height of 1 m, and the weight load is 100%.
The load when 50% of the 20 test pieces was broken was calculated while changing every g. The temperature was measured under the condition of -20 ° C. [Rockwell hardness] Measured with a scale R according to JIS K7202.

A production example of BPP used is shown below. (A) Preparation of solid catalyst 56.8 g of anhydrous magnesium chloride was added to anhydrous ethanol 1
00g, Idemitsu Kosan Vaseline oil (CP15N) 5
00 ml and Shin-Etsu Silicone Silicone Oil (KF
96) In a 500 ml mixed solution, under a nitrogen atmosphere,
Completely dissolved at 0 ° C. This mixture is T manufactured by Tokushu Kika Kogyo Co., Ltd.
The mixture was stirred for 3 minutes at 120 ° C. and 3000 revolutions / minute using a K homomixer. Then, the mixture was transferred into 2 liters of anhydrous heptane while maintaining stirring and cooling so as to maintain 0 ° C or lower. The obtained white solid was thoroughly washed with anhydrous heptane and vacuum dried at room temperature. White solid 3 obtained
0 g was suspended in 200 ml of anhydrous heptane, and 500 ml of titanium tetrachloride was added dropwise over 1 hour while stirring at 0 ° C. Next, when heating started to 40 ° C, 4.96 g of diisobutyl phthalate was added, and the temperature was raised to about 100 ° C by about 1
Raised in time. After reacting at 100 ° C. for 2 hours, a solid portion was collected by hot filtration. Titanium tetrachloride (500 ml) was added to the obtained solid portion, and the mixture was reacted at 120 ° C. for 1 hour under stirring, and then the solid portion was collected by hot filtration again, and 60 ° C.
1 liter of hexane 7 times, then hexane 1 at room temperature
Wash 3 times with liters.

(B) TiCl ₄ [C ₆ H ₄ (COO ⁱ C
Preparation of ₄ H ₉ ) ₂ ] To a solution of 1 liter of hexane containing 19 g of titanium tetrachloride, 27.8 g of diisobutyl phthalate was added dropwise over about 30 minutes while maintaining 0 ° C. After the dropping was completed, the temperature was raised to 40 ° C. and the reaction was performed for 30 minutes. After the reaction was completed, the solid portion was collected and washed with 500 ml of hexane 5 times to obtain the desired product.

(C) Preparation of polymerization catalyst component 20 g of the solid catalyst obtained in the above (a) was added to toluene 300
TiC obtained in (b) above at 25 ° C.
I ₄ [C ₆ H ₄ (COO ⁱ C ₄ H ₉ ) ₂ ] 5.2 g was treated for 1 hour to be supported. After the completion of loading, the solid portion was collected by hot filtration and 300 ml of toluene and 10 m of titanium tetrachloride.
re-suspended in 1 l, washed with stirring at 90 ° C. for 1 hour, and the solid portion was collected by hot filtration, and then the reaction product was mixed with 500 ml of 90 ° C. toluene 5 times and 500 ml of hexane at room temperature.
It was washed 3 times.

[0033] Under prepolymerization nitrogen atmosphere, in a content volume of 3-liter autoclave, n- heptane 500 ml, triethyl aluminum 6.0 g, dicyclopentyldimethoxysilane 3.9
g, and 10 g of the polymerization catalyst component obtained in (c) above were added and stirred at a temperature range of 0 to 5 ° C for 5 minutes. next,
Propylene was fed into the autoclave so that 10 g of propylene was polymerized per 1 g of the polymerization catalyst component, and 0 to 5 was added.
Prepolymerization was carried out in the temperature range of ° C for 1 hour. The resulting prepolymerized solid catalyst component was washed with 500 ml of n-heptane three times and used for the following main polymerization.

Main Polymerization (1) First-stage polymerization: 2.0 g of a prepolymerized solid catalyst prepared by the above method in an autoclave with a stirrer and an internal volume of 60 liters under a nitrogen atmosphere, and triethylaluminum 1
1.4 g, dicyclopentyldimethoxysilane 6.84
g, then 18 kg of propylene, and hydrogen were charged so that the concentration would be 13000 mol ppm with respect to propylene.
The temperature was raised to 70 ° C. and polymerization was carried out for 1 hour. Then, unreacted propylene was removed to terminate the polymerization. After the reaction,
The reaction product was sampled. (2) Second-stage polymerization; after completion of the first-stage polymerization, liquid propylene was removed and ethylene / propylene = 40/6 at a temperature of 75 ° C.
0 (molar ratio) mixed gas 2.2 Nm ³ / hour, hydrogen 20
Copolymerization was carried out for 40 minutes at a feed rate of N liter / hour. After the polymerization was completed, the unreacted gas was removed to terminate the polymerization. As a result, ethylene content was 9.7% by weight and MFR was 1
8.0 kg of a propylene-ethylene block copolymer (hereinafter referred to as "BPP1") having a weight of 7.8 g / 10 minutes was obtained.

Similarly, the amount of hydrogen charged during the first stage polymerization,
By adjusting the polymerization time and the amount of ethylene during the second stage polymerization, the ethylene content is 10.5% by weight and the MFR is 8.1 g / 1.
A propylene-ethylene block copolymer (hereinafter referred to as "BPP2") having 0 minutes and an ethylene content of 6.
Propylene-ethylene block copolymer having 8 wt% and MFR of 28.3 g / 10 minutes (hereinafter referred to as "BPP3").
I got). In addition, during the second-stage polymerization, the ethylene content was 8.4% by weight, the butene-1 content was 0.7% by weight, and the MFR was 16. A propylene-ethylene block copolymer (hereinafter referred to as "BPP4") having a weight of 7 g / 10 minutes was obtained.

Further, the following two types of BP are used for comparison.
P was used. Tosoh Akzo AA type titanium trichloride 6.6g, diethyl aluminum chloride 23.5g
Was used as a catalyst component, 18 kg of propylene and hydrogen were charged so that the concentration would be 8000 mol ppm based on propylene, the temperature was raised to 70 ° C., and the polymerization was carried out in the same manner as in BPP1. As a result, ethylene content was 9.8. Wt% and MFR
Of 18.2 g / 10 min (hereinafter referred to as “BPP5”), BPP1 except that the catalyst prepared in (a) above was used and the amount of hydrogen at the first stage polymerization was 9300 mol ppm. Polymerization was carried out in the same manner as above, with an ethylene content of 10.1% by weight and an MFR of 18.4 g / 1.
What was 0 minutes (hereinafter referred to as "BPP6") was obtained.

Regarding the polypropylene portion sampled at the end of the first-stage polymerization of the above copolymer, XI, I
P, N and N _f were measured. The results are shown in Table 3.
The IP measurement conditions are as follows. Measuring device JNM-GSX400 manufactured by JEOL Ltd. Measurement mode: Proton decoupling method Pulse width: 8.0 μs Pulse repetition time: 3.0 s Cumulative number of times: 20000 times Solvent: 1,2,4-trichlorobenzene /
Mixed solvent of heavy benzene (75/25 wt%) Internal circulation: Hexamethyldisiloxane sample concentration: 300 mg / 3.0 ml Solvent measurement temperature: 120 ° C

[0038]

[Table 3]

For each ethylene-propylene copolymer part obtained in the second step, FP, P _P , P _f1 and CSD were determined by analysis of NMR spectrum and two-site model.
I asked. The results are shown in Table 4.

[0040]

[Table 4]

(B) The above B as a propylene homopolymer
MFR polymerized using a PP catalyst is 25.1 g / 10
Minute polypropylene (hereinafter referred to as "PP1"), M
A polypropylene having an FR of 12.7 g / 10 minutes (hereinafter referred to as "PP2") and a polypropylene having an MFR of 7.0 g / 10 minutes (hereinafter referred to as "PP3") were used. For comparison, a polypropylene (hereinafter referred to as "PP4") having an MFR of 32.2 g / 10 minutes obtained by polymerization using AA type titanium trichloride manufactured by Tosoh Akzo Co., Ltd. and diethylaluminum chloride as a catalyst component, and the above Polymerization was carried out using the catalyst obtained by the operation (a) only in the preparation of the BPP catalyst, and polypropylene (hereinafter referred to as "PP5") having an MFR of 6.8 g / 10 min was used. XI, IP, N and N _f were measured for the above PP. The results are shown in Table 5. The measurement conditions are as described above.

[0042]

[Table 5]

(C) As an ethylene-α-olefin copolymer, an ethylene-butene-1 copolymer (manufactured by Mitsui Petrochemical Co .; Tuffmer A1085) (hereinafter referred to as "PEC-1") and an ethylene-propylene copolymer ( Mitsui Petrochemical Co., Ltd .; Tuffmer P) (hereinafter referred to as "PEC-2") was used. (D) Styrene-based rubber polymer, styrene-ethylene-butylene block copolymer (manufactured by Asahi Kasei; Tuftec H1052), and (E) talc having an average particle size of 2.6 μm (hereinafter referred to as “TALC-1”). And an average particle size of 11.0 μm (hereinafter “TALC-
A product obtained by treating both 2) with a silane coupling agent was used.

Examples 1 to 7 and Comparative Examples 1 to 6 BPP, PP, whose types and blending amounts are shown in Table 6,
Ethylene-α-olefin copolymer, styrene rubber polymer and talc, and 0.05 part by weight of di-t-butyl-p-cresol as a stabilizer, pentaerythrityl-tetrakis [3- (3,5-di- t-butyl-4-
Hydroxyphenyl) propionate] 0.10 part by weight and calcium stearate 0.10 part by weight are mixed, and a super mixer (SMV20 type) manufactured by Kawata Manufacturing Co., Ltd.
Using a twin-screw extruder (AS3 manufactured by Nakatani Machinery Co., Ltd.
Pelletization was carried out using (Type 0). Using an injection molding machine (IS-170FII) manufactured by Toshiba Kikai Co., Ltd., each of the obtained pellets was manufactured into a test piece at a temperature of 220 ° C and a mold cooling temperature of 50 ° C. The test piece thus obtained has a relative humidity of 50% and a temperature of 23 ° C
After being left for 2 days in a thermostatic chamber, the flexural modulus, Izod impact strength (with notch), deflection temperature under load and Rockwell hardness were measured. The results obtained are shown in Table 7.

[0045]

[Table 6]

[0046]

[Table 7]

[0047]

Since the resin composition of the present invention is excellent in rigidity, impact resistance, heat resistance and surface hardness, it is particularly useful for automobile parts, electric / electronic parts, packaging materials and the like.

[Brief description of drawings]

FIG. 1 is an example of a nuclear magnetic resonance spectrum in the methyl region of polypropylene.

FIG. 2 is an example of a nuclear magnetic resonance spectrum of an ethylene-propylene copolymer.

FIG. 3 is a diagram showing names of carbons derived from a chain distribution in polyolefin.

[Explanation of symbols]

a ・ ・ ・ Spectrum diagram b ... Enlarged view of a

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI C08L 23/12 C08L 23/12

Claims (4)

(57) [Claims] 1. A polypropylene part (a) having the following physical properties (i) to (iv); and (i) a xylene extraction insoluble part (XI) 9 at 25 ° C.
8.0 wt% or more (ii) Isotactic pentad fraction (IP) 9
6.5% or more (iii) Isotactic average chain length (N) 90 or more (iv) Total amount of each fraction having an isotactic average chain length (N _f ) of 300 or more by column fractionation method
Copolymer part of propylene and ethylene and / or α-olefin having 4 to 12 carbon atoms satisfying all of the following conditions (v) to (viii) of 10% by weight or more (b) (v) Average by two-site model Propylene content (FP)
20 to 80 mol% (vi) 2 sites copolymer produced in the active sites of polymerization preferentially propylene in the model propylene content _(P P) 65 to 90 mol% of _{(P H) (vii) P} H is co Ratio (P _f1 ) in polymer 0.4
0-0.90 (viii) Two-site model blockiness (CSD)
Propylene block copolymer consisting of 1.8 to 5.0
30 to 60 wt%, (B) Propylene homopolymer having the following physical properties (ix) to (xii) 20 to 40 wt%, (ix) Xylene extraction insoluble part (XI) 9 at 25 ° C
8.0% by weight or more (x) isotactic pentad fraction (IP) 96.
5% or more (xi) Isotactic average chain length (N) 90 or more (xii) Total amount of fractions with an isotactic average chain length (N _f ) of 300 or more by column fractionation method
10 wt% or more (C) ethylene-α-olefin copolymer 1 to 10 wt%, (D) styrene rubber polymer 2 to 15 wt% and (E) talc 5 to 30 wt% [however, (A) +
(B) + (C) + (D) + (E) = 100% by weight]. 2. The propylene resin composition according to claim 1, wherein the proportion of (b) in the component (A) is 3 to 50% by weight. 3. The α of the copolymer part (b) of the component (A).
-The propylene-based resin composition according to claim 1 or 2, wherein the olefin is ethylene and / or butene-1. 4. The solid catalyst, wherein the component (A) contains a magnesium compound, a titanium compound, a halogen-containing compound and an electron-donating compound as essential components, and further has the general formula: T
i Xa .Yb (wherein X is a halogen atom of Cl, Br, I, Y is an electron-donating compound, a is 3 or 4, and b is
Represents an integer of 3 or less), is washed with a halogen-containing compound, and is further washed with a hydrocarbon, and is then polymerized using an improved polymerization catalyst. Item 1. A propylene-based resin composition according to item 1.