JPH08120129A - Propylene resin composition and its molded article - Google Patents

Abstract

PURPOSE: To obtain the subject composition having balanced rigidity and impact resistance and excellent scratch resistance and fabricability and useful for automobile part, etc., by using a polypropylene and a polyolefin having respective specific physical properties in combination. CONSTITUTION: The objective composition is produced by using (A) 47-70wt.% of a polypropylene containing >=98.0wt.% of a fraction insoluble by xylene extraction at 25 deg.C, having an isotactic pentad fraction of >=96.5wt.% and an average isotactic chain length of >=90 and containing >=10wt.% in total of fractions having an isotactic chain length of >=300 by column fractionation in combination with e.g. (B) 5-20wt.% of a polyolefin resin having an (η1 /η2 ) ratio of 4-20 (η1 is kinetic viscosity at 190 deg.C and a frequency of 10<-1> rad/sec and η2 is the viscosity at 10rad/sec), a crystallization peak temperature Tcp of 110-130 deg.C measured by differential scanning calorimetry, a (Tmp/Tcp) ratio of 1.1-1.5 (Tmp is melting peak temperature), a Tmp/(Tmp-Tmc) ratio of 3.0-9.8 and a crystal structure exhibiting a-axis orientation in the diffraction pattern by X-ray diffraction.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION The present invention is particularly applicable to electric / electronic parts,
The present invention relates to a propylene-based resin composition which is suitably used in the field of packaging materials, engineering plastic substitutes and the like, and which is excellent in balance between rigidity and impact resistance, scratch resistance and secondary processability.

[0002]

2. Description of the Related Art Propylene-based resins are generally inexpensive, and their characteristics are lightness, transparency, mechanical strength,
Utilizing properties such as heat resistance and chemical resistance, it is widely used for industrial materials such as automobile parts, electric / 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 blending ethylene-propylene block copolymer with ethylene-propylene rubber and a nucleating agent (Japanese Patent Publication No. 60-3420).
Alternatively, a method of blending ethylene-propylene rubber, ethylene copolymer and an inorganic filler (JP-A-4-275351, JP-A-5-5051, JP-A-5-98097, JP-A-5-98098, etc.) ) Etc. have been proposed.

[0003]

However, although the above methods all improve some of the properties, the heat resistance and the rigidity are still insufficient.
There is also a problem that the secondary workability such as vacuum forming is poor. The present invention has been made in view of such circumstances, and an object thereof is to provide a propylene-based resin composition having excellent balance between rigidity and impact resistance, scratch resistance, and secondary workability.

[0004]

Means for Solving the Problems As a result of intensive studies, the present inventors have found that the above object can be achieved by using a combination of polypropylene and polyolefin having specific physical properties, and based on this finding, The invention was completed. That is, (A) polypropylene having the following physical properties (i) to (iv) 45 to 70% by weight, (i) xylene extraction insoluble portion at 25 ° C. 98.0% by weight or more (ii) isotactic pentad fraction 96.5%
Above (iii) Average isotactic chain length of 90 or more (iv) Total amount of fractions with an isotactic average chain length of 300 or more by column fractionation method 10
% By weight or more (B) 5 to 20% by weight of a polyolefin resin having the following physical properties (v) to (vii), (v) a temperature 190 ° C., a dynamic viscosity η _{1 at} a frequency of 10 ⁻¹ rad / sec, and a frequency of 10 rad. Ratio (η ₁ / η ₂ ) to the dynamic viscosity η ₂ at 4 / sec 4 to 20 (vi) Crystallization peak temperature Tcp by differential scanning calorimetry (DSC) is 110 to 130 ° C., and melting peak temperature Tmp And Tcp ratio (Tmp / Tcp) is 1.1 to
1.5 and Tmp / (Tmp-Tcp) is 3.
0 to 9.8 (vii) is a crystal structure showing a-axis orientation in a diffraction diagram by an X-ray diffraction method (C) rubber-like polymer 3 to 15% by weight, (D) precipitated calcium carbonate, hydrous silicic acid And at least one inorganic filler selected from the group consisting of hydrous calcium silicate and 5 to 30% by weight, and (E) at least one inorganic filler selected from the group consisting of talc, mica and potassium titanate. ~ 30
Weight% (however, (A) + (B) + (C) + (D) +
(E) = 100% by weight) is provided. Hereinafter, the present invention will be described in detail.

The polypropylene (A) (hereinafter referred to as "PP") in the present invention is a propylene homopolymer or a random or block copolymer of propylene and ethylene and / or an α-olefin having 4 to 12 carbon atoms. Examples of the α-olefin include butene-1,
4-methylpentene-1, hexene-1, octene-1
And the like. The PP of the present invention is required to have the following physical properties. That is, (i) the xylene extraction insoluble portion (hereinafter referred to as “XI”) at 25 ° C. is 98.0% by weight or more, preferably 98.5% by weight or more, and more preferably 99.0% by weight or more. XI is 98.0
If it is less than wt%, the rigidity and scratch resistance are poor. XI
Was measured by once dissolving polypropylene in ortho-xylene at 135 ° C. and then cooling to 25 ° C. to precipitate a 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 98.0%, 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 used as 1, 2, 4
-Dissolve in a mixed solvent of trichlorobenzene / deuterated benzene by heating to 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. 1A is a spectrum of a methyl group region in polypropylene, and b is an enlarged view of the spectrum. The spectrum is measured with a pentad unit, that is, five adjacent methyl groups as one unit, and the absorption peak differs depending on the isotacticity of the methyl group (there are 10 types such as mmmm, mmmr structurally). Correspondence between the absorption peak and isotacticity is shown in b of FIG.

On the other hand, as a theory of polymerization, 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 of the degree of disorder in the isotactic chain σ : Probability of forming meso compounds with the same end as polymerized end by end-dominated polymerization (Bernoulli process) ω: The ratio of α sites Theoretical calculation of 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.

[0010]

[Table 1] However, β = α (1-α)

Next, the average chain length (N) definition formula described in the J. C. Randall reference; N = Meso chain number / Meso unit number is applied, and actually calculated by the following formula. be able to. N = 1 + (A ₁ + A ₂ + A ₃ ) /0.5 (A ₄ + A ₅ +
A ₆ + A ₇ )

Further, (iv) 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 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 the xylene-extracted insoluble portion is dissolved in para-xylene at a temperature of 130 ° C., then Celite is added, the temperature is lowered to 30 ° C. at a temperature lowering rate of 10 ° C./hour, and adhered to Celite. Then, the method is to fill the column with slurry celite, raise the temperature stepwise every 30 ° C. to 2.5 ° C. with paraxylene as a developing solution, and fractionate polypropylene by fractions. For more information, see MasahiroKakugo et al; Macromolecules, vo
l.21, p314-319 (1988). The N _f of the separated polypropylene is measured by the above N measuring method.

Polymerization of PP of the present invention is carried out by a slurry method carried out in the presence of an inert hydrocarbon 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. The temperature condition is room temperature to 130 ° C., preferably 50 to 90 ° C., pressure 2 to 50 k
It is performed under the condition of g / 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 step reaction and then propylene and α-olefin are copolymerized in the second step reaction. For example, JP-B-36-15284 and JP-B-38-14834 are disclosed. JP-A-53-35788, JP-A-53-35789, and JP-A-56-55416.

As an example of the catalyst for obtaining PP 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,
Further, in the general formula: Ti Xa · Yb (wherein X represents a halogen atom of Cl, Br, I, Y represents an electron-donating compound, a represents 3 or 4 and b represents an integer of 3 or less). An improved polymerization catalyst obtained by treating with the indicated titanium compound, washing with a halogen-containing compound, and then washing with a hydrocarbon is mentioned.

Ti Xa in the above formula is, for example, RPSCo.
utts, et al, Advan.Organometal.Chem., 9 , 135 (1970), 4th Edition New Experimental Chemistry Lecture 17 Inorganic and chelate complexes Maruzen of the Chemical Society of Japan (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.

Next, the (B) polyolefin resin in the present invention includes polyethylene, polypropylene, an ethylene-propylene random copolymer, ethylene and 4 to 10 carbon atoms.
12 are α-olefin copolymers, ethylene-butene-propylene terpolymers, and the like.

The polyolefin resin of the present invention has a ratio (η ₁ / η) of (v) a temperature of 190 ° C., a dynamic viscosity η _{1 at} a frequency of 10 ^-1 rad / sec and a dynamic viscosity η ₂ at a frequency of 10 rad / sec. ₂ ) needs to be 4 to 20. η ₁ / η ₂ is preferably 4 to 15, and particularly 5
-15 are suitable. When η ₁ / η ₂ is less than 4, the anisotropy becomes large and M. D / T. D balance becomes poor. on the other hand,
When it exceeds 20, gel or fish eyes are increased and the commercial value is lowered, which is not preferable. Note that the dynamic viscosity is the deformation of an object or the vibration of an external force (angular frequency).
It represents the viscoelastic behavior observed when it is applied to the sample, and the measuring method is described in, for example, The Society of Rheology, Japan; Course / Rheology, pages 78 to 119 (published by Kobunshi Publishing Co., Ltd., 1992). Has been done.

The polyolefin resin of the present invention is
(vi) The crystallization peak temperature Tcp by differential scanning calorimetry (DSC) is 110 to 130 ° C., and the melting peak temperature Tmp to Tcp ratio (Tmp / Tcp) is 1.1 to.
1.5 and Tmp / (Tmp-Tcp) is 3.
It is necessary to be 0 to 9.8. Tcp is preferably 112-127 ° C., especially 113-125.
C is preferred. When Tcp is less than 110 ° C., the mechanical strength has large anisotropy. On the other hand, if it exceeds 130 ° C, mechanical strength such as impact strength becomes insufficient, which is not preferable.

When Tmp / Tcp is less than 1.1, flexibility and impact strength are insufficient. On the other hand, when it exceeds 1.5, the mechanical strength becomes anisotropic and the balance is deteriorated.
When Tmp / (Tmp-Tcp) is less than 3.0, the mechanical strength is anisotropic. On the other hand, if it exceeds 9.8, flexibility and impact strength are lowered, which is not preferable.
The DSC measurement method for Tcp and Tmp is as follows. For polyethylene resin, Tcp is 19
After raising the temperature to 0 ℃, hold for 5 minutes, and then decrease the temperature at 10 ℃
It is a crystallization peak temperature when the temperature is lowered to 30 ° C. under the condition of / min, and Tmp is 190 at a heating rate of 10 ° C./min again.
It is the melting peak temperature when the temperature is raised to ℃. Also,
In the case of a propylene-based resin, Tcp is a crystallization peak temperature when the temperature is raised to 230 ° C., held for 5 minutes, and then lowered to 30 ° C. at a temperature lowering rate of 20 ° C./minute, and Tmp is again measured. It is the melting peak temperature when the temperature is raised to 230 ° C. at a temperature rising rate of 20 ° C./min.

Further, the polyolefin resin of the present invention is required to have a crystal structure exhibiting a-axis orientation in (vii) X-ray diffraction diffractogram. Polyolefin X
There are many studies on the analysis of the crystal structure by the line diffraction method,
For example, “Polymer”, Vol. 14, No. 158, pp. 379-388, “Journal of the Chemical Society of Japan”, Vol. 82, No. 12, pp. 1575-1577, etc. 2 is an example of an X-ray diffraction diagram of polypropylene having an a-axis orientation, and the longitudinal direction corresponds to the film drawing direction (MD). In this figure, the meridian direction corresponds to the a-axis, and a diffraction image (a pair of upper and lower white lines in the horizontal direction) showing the orientation in this direction is clearly shown. On the other hand, FIG. 3 shows an example of polypropylene having no a-axis orientation, and its diffraction image has a ring shape because the crystal has no orientation. If a polyolefin resin having no such a-axis orientation is used, the effect of improving secondary workability cannot be seen.

Specific examples of the polyolefin resin of the present invention include, for example, polypropylene obtained by irradiation treatment with ionizing radiation such as electron beam or gamma ray in a vacuum or an inert gas atmosphere, and porous δ type titanium trichloride as a catalyst. Examples of the polypropylene, silica or alumina carrier obtained by using the transition metal oxide such as chromium or molybdenum and high density polyethylene using a solid catalyst obtained by firing at high temperature are mentioned. Among these,
It is preferable that the melt tension at a temperature of 230 ° C. is 10 g or more from the viewpoint of secondary workability.

The rubbery polymer (C) in the present invention is not particularly limited, and examples thereof include natural rubber, butadiene rubber, isoprene rubber, chloroprene rubber, styrene-butadiene rubber hydrogenated product, styrene-ethylene / butene-styrene. Block copolymer, styrene-isoprene rubber hydrogenated product, styrene-ethylene / isoprene-styrene block copolymer hydrogenated product, acrylic rubber, butyl rubber, ethylene-propylene rubber, ethylene-propylene-non-conjugated diene rubber, ethylene-butadiene rubber Examples include hydrogenated products. Among these, ethylene-propylene rubber,
Ethylene-butadiene rubber hydrogenated product, styrene-ethylene / butene-styrene block copolymer and styrene-
Ethylene / isoprene-styrene block copolymer hydrogenated products are preferred.

The component (D) in the present invention is at least one inorganic filler selected from the group consisting of precipitated calcium carbonate, hydrous silicic acid and hydrous aluminum silicate, and among them, precipitated calcium carbonate is preferred. The average particle size of these fillers is usually 4 μm or less, preferably about 1 μm, and particularly preferably 0.05 to 1 μm.

The component (E) is at least one inorganic filler selected from the group consisting of talc (magnesium silicate), mica and potassium titanate. Of these, talc is preferred.

The above fillers may be treated with an organic titanate-based or aluminum-based coupling agent, a fatty acid, a fatty acid metal salt, a fatty acid ester or the like. Further, a modified polypropylene graft-treated with an unsaturated carboxylic acid represented by maleic anhydride, acrylic acid, itaconic acid or the like or an anhydride thereof may be used together with the organic peroxide.

The composition ratio of the component (A) in the resin composition of the present invention is 45 to 70% by weight, preferably 48 to 67% by weight, and particularly preferably 50 to 65% by weight.
When the proportion of the component (A) is less than 45% by weight, the rigidity, scratch resistance and secondary workability are deteriorated. On the other hand, if it exceeds 70% by weight, impact resistance is lowered, which is not preferable. The composition ratio of the component (B) is 5 to 20% by weight, preferably 7 to 18% by weight, and particularly preferably 9 to 16% by weight. If the proportion of the component (B) is less than 5% by weight, the secondary workability is poor. on the other hand,
If it exceeds 20% by weight, the appearance of the molded product is deteriorated, which is not preferable. The composition ratio of the component (C) is 3 to 15% by weight, preferably 4 to 13% by weight, and particularly preferably 5 to 10% by weight. If the proportion of the component (C) is less than 3% by weight, the impact resistance decreases. On the other hand, if it exceeds 15% by weight, rigidity and scratch resistance are deteriorated, which is not preferable. The composition ratio of the component (D) is 5 to 30% by weight, preferably 8 to 28% by weight, and particularly preferably 10 to 25% by weight. If the proportion of the component (D) is less than 5% by weight, the impact resistance will decrease. On the other hand, 3
If it exceeds 0% by weight, the secondary workability is poor and the impact resistance is also reduced, which is not preferable. The composition ratio of the component (E) is 5 to 5.
30% by weight, preferably 6 to 25% by weight, particularly 7
-20% by weight is preferred. If the proportion of the component (E) is less than 5% by weight, the rigidity will decrease. On the other hand, if it exceeds 30% by weight, the secondary workability is deteriorated, which is not preferable.

Further, the resin composition of the present invention may contain a nucleating agent commonly used in the art. Examples of these nucleating agents include carboxylic acid metal salts, dibenzylidene sorbitol derivatives, phosphate metal salts, inorganic fillers such as talc and calcium carbonate. Specific examples include sodium benzoate, aluminum adipate, pt-butyl benzoic acid aluminum salt, sodium thiophenecarboxylate, 1,3,3.
2,4-dibenzylidene sorbitol, 1,3,2,4
-Di- (p-methylbenzylidene) sorbitol, 1,
3-p-chlorobenzylidene-2,4-p-methylbenzylidene sorbitol, potassium-bis- (4-t-butylphenyl) phosphate, sodium-bis-
(4-t-butylphenyl) phosphate, sodium-2,2-ethylidene-bis (4,6-t-butylphenyl) phosphate and the like can be mentioned. These nucleating agents may be used alone or in combination of two or more. The amount of the nucleating agent added is generally 0.05 to 0.5% by weight,
Preferably 0.08 to 0.4% by weight, especially 0.1 to
0.35% by weight is preferred.

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 composition is a film, a sheet, a tube, a well-known melt molding method and compression molding method.
It can be molded into a bottle and used alone, or can be used as a laminated body by laminating other materials.

As the lamination method, a so-called dry laminate molding method, a coextrusion lamination method, a coextrusion method, a coextrusion method An injection molding method, a co-extrusion pipe molding method, etc. are mentioned. The multilayer laminate thus obtained can be formed into a molded body by a method of reheating and stretching using a molding method such as vacuum molding, pressure molding, stretch blow molding or the like. further,
The resin composition 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, a pigment, a plasticizer, and a softening agent. You may mix | blend etc. suitably in the range which does not impair the objective of this invention.

[0031]

The present invention will be described in more detail with reference to the following examples. In addition, the measuring method of each physical property is shown below. [MFR] According to JIS K7210, using a melt indexer manufactured by Takara, temperature 230 ° C, load 2.16
It was measured under the condition of kg. [Flexural Modulus] Based on JIS K7203. [Izod impact strength] In accordance with JIS K7110,
It was measured with a notch. [Scratch resistance] A conical toe needle (manufactured by Sapphire, JIS K6719 standard) in which a vertical load is applied to a test piece (150 × 80 mm, thickness 0.5 mm) using a surface property measuring device (14S / D manufactured by HEIDEN) The minimum load at which the surface is damaged when the product is scratched was measured.

The following two items were evaluated as secondary processing characteristics. [Holding time] 2 sheets fixed on the frame (400 x 400 mm)
The sheet was placed in an oven heated to 00 ° C., and the time when the sheet once hung down was returned to its original state and kept in that state was measured. The longer the holding time, the better the secondary workability in general. [Uniform spreadability] 30 in an oven heated to 220 ° C
Hold the sheet held for 2 seconds, and use the box mold (opening size: 300
X200 mm, bottom size: 280 x 180 mm) was vacuum formed, and the presence or absence of unevenness in thickness and wrinkles of the formed product was visually observed to judge the quality. In addition, a production example of the used PP 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 made by T.
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 300 parts of toluene.
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.
And washed three times.

[0035] 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 Under a nitrogen atmosphere, 2.0 g of the prepolymerized solid catalyst prepared by the above method, 11.4 g of triethylaluminum, and 6.84 g of dicyclopentyldimethoxysilane were put into an autoclave with an internal volume of 60 liters equipped with a stirrer, Next, 18 kg of propylene and hydrogen were charged so that the concentration would be 13,000 mol ppm based on propylene, the temperature was raised to 75 ° C., and polymerization was carried out for 1 hour. Then, unreacted propylene was removed to terminate the polymerization. As a result, MFR is 0.7 g /
10 minutes polypropylene (hereinafter referred to as "PP1")
I got

As a comparative example, 6.0 g of AA-type titanium trichloride manufactured by Tosoh Akzo Co., Ltd. and 23.5 g of diethylaluminum chloride were used as catalyst components, and 18 kg of propylene and 8000 mol ppm of hydrogen relative to propylene were used. Charge it and raise the temperature to 70 ° C.
Polymerized in the same manner as above, MFR 0.8 g / 1
Polypropylene (hereinafter referred to as "PP2") having 0 minutes was used.

XI, IP, N and N _f of the above PP were measured. The results are shown in Table 2. In addition, IP
The measurement conditions of are as follows. Measuring device JNM-GSX400 manufactured by JEOL Ltd. Measurement mode: Proton decoupling method Pulse width: 8.0 μs Pulse repetition time: 5.0 s Cumulative number of times: 20000 Solvent: 1,2,4-trichlorobenzene /
Mixed solvent of heavy benzene (75/25% by volume) Internal circulation: Hexamethyldisiloxane Sample concentration: 300 mg / 3.0 ml Solvent measurement temperature: 120 ° C

[0039]

[Table 2]

As a polyolefin resin, polypropylene powder having an MFR of 0.6 g / 10 min was placed in a multilayer film bag (polyethylene and ethylene-vinyl alcohol copolymer) and purged with nitrogen, and then an electron beam irradiation device (Nisshin High 5Mra as irradiation dose using voltage
What was d-irradiated and then heat-treated at 130 ° C. for 60 minutes (hereinafter referred to as “XPP”), a polypropylene having an MFR of 2.8 g / 10 minutes polymerized using a δ type titanium trichloride catalyst (hereinafter “PP3”). Polyethylene (hereinafter referred to as “PE1”) having an MFR (measured at a temperature of 190 ° C. and a load of 2.16 kg) of 1.5 g / 10 minutes, which was polymerized using a chromium trioxide catalyst. For comparison, polypropylene having a MFR of 2.9 g / 10 minutes polymerized using a titanium trichloride-based catalyst (hereinafter referred to as “PP
4 ”) and polyethylene having an MFR of 1.7 g / 10 min polymerized using a magnesium chloride-supported catalyst (hereinafter referred to as“ PE2 ”).

The dynamic viscosity ratio (η ₁ / η
₂ ), Tmp, Tcp, Tmp / (Tmp-Tcp) and the presence or absence of a-axis orientation are shown in Table 3. The dynamic viscosity is A
ASTM D4065-90, ASTM D4440-8
Compliant with 4, Mechanical Spectrometer manufactured by Rheometric
It measured using Model RMS-800. Crystallization temperature and melting temperature are measured by PERKIN-ELMER DSC measuring device (7Series
Thermal Analysis System) was used. The a-axis orientation was 50K using an X-ray diffractometer (RAD-II) manufactured by Rigaku Corporation.
Irradiation was performed with point focus for 1 hour under conditions of V and 40 mA, and a diffraction pattern was measured with a wide-angle X-ray flat camera.

[0042]

[Table 3]

The rubber polymer has a propylene content of 32.
% Ethylene-propylene rubber (hereinafter "EP
R ”), ethylene-butadiene rubber hydrogenated product having a butadiene content of 19% by weight (hereinafter referred to as“ hydrogenated EBR ”), Asahi Kasei's“ Tuftec H1051 ”(hereinafter referred to as“ SEBS ”) and Kuraray's“. Septon 2
023 ”(hereinafter referred to as“ SEPS ”) was used. Also,
Precipitated calcium carbonate surface-treated with unsaturated fatty acid as component (D) (CALSHITEC Stavigot manufactured by Shiraishi Calcium Co., Ltd.
-15A, average particle size 0.15 μm (hereinafter referred to as “precipitated calcium”), hydrous silicic acid (manufactured by Tokuyama Corporation, Fineseal average particle size 0.05 μm) (hereinafter referred to as “silicic acid”) and hydrous calcium silicate Fluorite classified by Tokuyama Co., Ltd. (average particle diameter 4 μm) (hereinafter referred to as “Keical”) was used. (E) Talc as a component (MION W, manufactured by Hayashi Kasei)
HITE # 5000S, average particle size 2.8 μm, mica (Marietta Inc., Szolite average particle size 20 μm) and potassium titanate (Otsuka Chemical Co., Tesmo fiber diameter 0.
2 to 0.5 μm, fiber length 10 to 20 μm) (hereinafter “T
Called ").

Examples 1 to 14 and Comparative Examples 1 to 9 PP, polyolefin resin and two types of inorganic fillers whose types and amounts are shown in Table 4 and di-t-butyl-p-as a stabilizer. Cresol 0.05 part by weight, pentaerythrityl-tetrakis [3- (3,5-
Di-t-butyl-4-hydroxyphenyl) propionate] 0.10 parts by weight and calcium stearate 0.10 parts by weight are mixed and mixed using a super mixer (SMV20 type) manufactured by Kawata Manufacturing Co., Ltd. Pelletization was performed using a twin-screw extruder (AS30 type). Each of the obtained pellets was manufactured by Toshiba Machine Co., Ltd. injection molding machine (I
S-170FII) was used to prepare each test piece at a temperature of 220 ° C. and a mold cooling temperature of 50 ° C. The test piece thus obtained was allowed to stand in a thermostatic chamber at a relative humidity of 50% and a temperature of 23 ° C. for 2 days, and then the flexural modulus, Izod impact strength (notched) and scratch resistance were measured. Secondary workability is 600 mm width for each pellet
A sheet having a thickness of 0.5 mm was produced by using the T-die extruder, and the sheet was evaluated. The above results are shown in Table 5.

[0045]

[Table 4]

[0046]

[Table 5]

[0047]

Industrial Applicability The resin composition of the present invention is excellent in the balance between rigidity and impact resistance, scratch resistance and secondary processability, and thus is particularly useful in the fields of automobile parts, electric / electronic parts, packaging materials and the like. is there.

[Brief description of drawings]

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

FIG. 2 is a diagram showing an example of an X-ray diffraction image of polypropylene having an a-axis orientation.

FIG. 3 is a diagram showing an example of an X-ray diffraction image of polypropylene having no a-axis orientation.

[Explanation of symbols]

 a Spectrum diagram b Enlarged view of a

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical display location C08K 3/26 KED 3/34 KEF C08L 23/08 23/16 LCY 53/00 LLV LLY // ( C08L 23/10 23:02 21:00) B29K 23:00

Claims (4)

[Claims] 1. (A) 45 to 70% by weight of polypropylene having the following physical properties (i) to (iv), (i) 98.0% by weight or more of xylene extraction insoluble portion at 25 ° C. (ii) Isotactic pen Tad fraction 96.5%
Above (iii) Average isotactic chain length of 90 or more (iv) Total amount of fractions with an isotactic average chain length of 300 or more by column fractionation method 10
% By weight or more (B) 5 to 20% by weight of a polyolefin resin having the following physical properties (v) to (vii), (v) a temperature 190 ° C., a dynamic viscosity η _{1 at} a frequency of 10 ⁻¹ rad / sec, and a frequency of 10 rad. Ratio (η ₁ / η ₂ ) to the dynamic viscosity η ₂ at 4 / sec 4 to 20 (vi) Crystallization peak temperature Tcp by differential scanning calorimetry (DSC) is 110 to 130 ° C., and melting peak temperature Tmp And Tcp ratio (Tmp / Tcp) is 1.1 to
1.5 and Tmp / (Tmp-Tcp) is 3.
0 to 9.8 (vii) is a crystal structure showing a-axis orientation in a diffraction diagram by an X-ray diffraction method (C) rubber-like polymer 3 to 15% by weight, (D) precipitated calcium carbonate, hydrous silicic acid And at least one inorganic filler selected from the group consisting of hydrous calcium silicate and 5 to 30% by weight, and (E) at least one inorganic filler selected from the group consisting of talc, mica and potassium titanate. ~ 30
Weight% (however, (A) + (B) + (C) + (D) +
(E) = 100% by weight). 2. The (B) rubber-like polymer is ethylene-propylene rubber, ethylene-butadiene rubber hydrogenated product, styrene-ethylene / butene-styrene block copolymer and styrene-ethylene / isoprene-styrene block copolymer water. The propylene-based resin composition according to claim 1, which is at least one selected from the group consisting of additives. 3. A sheet obtained by molding the propylene-based resin composition according to claim 1 or 2. 4. A molded article obtained by injection molding the propylene-based resin composition according to claim 1 or 2.