JP2562915B2 - High rigidity and high melt viscoelasticity ethylene-propylene block copolymer composition - Google Patents

Description

TECHNICAL FIELD The present invention relates to a high-rigidity high-melt viscoelasticity ethylene-propylene block copolymer composition. More specifically, it relates to a high-rigidity and high-melting viscoelasticity ethylene-propylene block copolymer composition capable of obtaining a molded article having extremely excellent rigidity and heat resistance rigidity.

[Prior Art] Generally, propylene-based polymers have excellent processability, chemical resistance, electrical properties and mechanical properties. Therefore, they are processed into injection-molded products, blow-molded products, films, sheets, fibers, etc. It is used for purposes. However, a sheet produced by processing a propylene-based polymer quickly sags during heat molding for secondary processing, has a narrow range of processing conditions, is inferior in molding efficiency, and has a large sag described above in a wide sheet. In addition, the thickness of the secondary processed product is likely to be uneven, and overlapping wrinkles are likely to occur. Therefore, only small molded products can be manufactured.
Further, when the propylene polymer is used for blow molding, there are the following problems. That is, since the parison droops significantly during molding, the thickness of the molded product becomes uneven. Therefore, it can only be applied to the manufacture of small products. When a high molecular weight propylene-based polymer is used to prevent the above-mentioned sagging, the fluidity is poor, the load during molding is large,
There is a risk of large energy loss and mechanical trouble, and the surface roughness of the molded product is severe and the commercial value is lost.

On the other hand, depending on various specific uses of the propylene-based polymer, the properties of the propylene-based polymer, particularly impact resistance, may not be sufficient, and the molded product may be subjected to mechanical impact or used at low temperature. However, it is difficult to use for molded products. In general, the rigidity and heat resistance of a plastic material are incompatible with impact resistance, and it is often extremely difficult to improve and improve the former and the latter at the same time. In order to increase the specific applications of the propylene-based polymer and the demand, it is required to further improve not only the above-mentioned impact resistance but also the rigidity surface (referred to as rigidity and heat-resistant rigidity). By improving these physical properties, it becomes possible to use a propylene-based polymer in an application field in which another general-purpose resin such as a high impact polystyrene (HIPS) resin or an ABS resin is used. Several proposals have been made to improve the impact resistance of propylene-based polymers. In particular, a method of block copolymerizing propylene with ethylene is well known. The obtained crystalline ethylene-propylene block copolymer has a problem that the low-temperature impact resistance is remarkably improved as compared with the propylene homopolymer, but the rigid surface is reduced.

Therefore, in order to improve the secondary processability, blow moldability, and rigidity of the above-mentioned sheet related to the propylene-based polymer, the Japanese Patent Application Laid-Open No. 62-149711 filed by the same applicant as the present application has been disclosed. A crystalline ethylene-propylene block copolymer having a specific molecular weight distribution obtained by polymerization in the presence of a specific catalyst is disclosed. Further, in order to improve the rigidity, the propylene-based polymer has p-
Aluminum t-butyl benzoate or 1,3,2,4
-It is common practice to incorporate organic nucleating agents such as dibenzylidene solybitol.

[Problems to be Solved by the Invention] However, the crystalline ethylene-propylene block copolymer having a specific molecular weight distribution obtained by polymerization in the presence of the specific catalyst disclosed in JP-A-62-149711. The secondary workability and blow moldability of the combined sheet are sufficiently satisfactory for practical use, and although the rigidity is considerably improved, they are not yet sufficiently satisfactory. In addition, the crystalline ethylene-propylene block copolymer having a specific molecular weight distribution obtained by polymerization in the presence of the specific catalyst is added with p-
Aluminum t-butyl benzoate or 1,3,2,4
-A sheet using a crystalline ethylene-propylene block copolymer composition prepared by blending an organic nucleating agent such as dibenzylidene sorbitol requires a high degree of rigidity and heat resistance although the effect of improving the rigidity is considerably recognized. When it is used for the intended use, it is not yet fully satisfactory.

The present inventors have the above-mentioned problems regarding the propylene-based polymer composition containing the above-mentioned various nucleating agents, that is, the secondary processability, blow moldability, rigidity and heat resistance of the sheet when the sheet is formed. Researched in earnest to solve the problem. As a result, the crystalline ethylene-propylene block copolymer having a specific molecular weight distribution and a specific isotactic pentad fraction has a phosphate compound represented by the following general formula [I] (hereinafter referred to as compound A).
It was found that the composition containing the above can solve the problems of the above-mentioned propylene-based polymer composition,
The present invention has been completed based on this finding.

(However, in the formula, R represents hydrogen or an alkyl group having 1 to 18 carbon atoms, an alkoxy group, a cycloalkyl group, a phenyl group, or a phenoxy group.) As is clear from the above description, the object of the present invention is a sheet. It is an object of the present invention to provide a crystalline ethylene-propylene block copolymer composition capable of obtaining a molded product which is remarkably excellent in secondary processability and blow moldability of the sheet and rigidity and heat resistance.

[Means for Solving the Problems] The present invention has the following configurations.

The polymer (A) produced in the polymerization step (I) mainly composed of propylene having an ethylene content of 0 to 1% by weight or propylene and ethylene which are polymerized in three or more steps is 60% of the total amount of the polymer. To 95% by weight, and then ethylene having an ethylene content of 10 to 100% by weight, or a polymer (B) produced in the polymerization step (II) mainly composed of ethylene obtained by polymerizing ethylene and propylene in one or more steps (B). ) Is 40 to 5% by weight of the total amount of polymer, and the ethylene content is 3 to 20% by weight of the total amount of polymer, which is a crystalline ethylene-propylene block copolymer. ) The molecular weight of each polymer produced in each polymerization step is expressed by the following formula (1) as a melt flow rate (MFR; discharge amount of molten resin for 10 minutes when a load of 2.16 kg at 230 ° C. is added). (However, MFR _n ; MFR of the polymer produced in the nth stage, MFR _{n + 1} ; MFR of the polymer produced in the _{n +} 1th stage) is satisfied, and in the polymerization step (I) The relationship between the isotactic pentad fraction (P) and the melt flow rate (MFR) of the resulting polymer (A) is 1.00 ≧ P ≧ 0.015logM
0.01 to 1 part by weight of a phosphate compound represented by the following general formula [I] (hereinafter referred to as compound A) was added to 100 parts by weight of a crystalline ethylene-propylene block copolymer having FR + 0.955. A high-rigidity, high-melting viscoelasticity ethylene-propylene block copolymer composition comprising:

(In the formula, R represents hydrogen or an alkyl group having 1 to 18 carbon atoms, an alkoxy group, a cycloalkyl group, a phenyl group or a phenoxy group.) The crystalline ethylene-propylene block copolymer used in the present invention is ethylene. The polymer (A) produced in the polymerization step (I) mainly composed of propylene having a content of 0 to 1% by weight or propylene and ethylene polymerized in three or more steps is 60 to 60% of the total amount of the polymer. Polymer (B) produced in a polymerization step (II) mainly composed of ethylene or ethylene obtained by polymerizing ethylene and propylene in one or more steps, which is 95% by weight and then has an ethylene content of 10 to 100% by weight. Is 40 to 5% by weight of the total polymer amount,
And a crystalline ethylene-propylene block copolymer having an ethylene content of 3 to 20% by weight based on the total amount of the polymer, wherein the molecular weight of each polymer produced in each polymerization step of the polymerization step (I) is a melt. Flow rate (MFR) value as the following formula (1) (However, MFR _n ; MFR of the polymer formed in the nth stage; MFR _{n + 1} ; MFR of the polymer formed in the _{n +} 1th stage) is satisfied, and in the polymerization step (I) The relationship between the isotactic pentad fraction (P) and the melt flow rate (MFR) of the resulting polymer (A) is 1.00 ≧ P ≧ 0.015logM
It is a crystalline ethylene-propylene block copolymer having FR + 0.955. Such a crystalline ethylene-propylene block copolymer is produced by the production method described in Japanese Patent Application Laid-Open No. 62-149711 filed by the same applicant as the present application. That is, the organoaluminum compound (i)
(Eg, triethylaluminum, diethylaluminum monochloride) or the reaction product (v) of an organoaluminum compound (i) with an electron donor (eg, diisoamyl ether, ethylene glycol monomethyl ether) is reacted with titanium tetrachloride. A solid product (iii) obtained by further reacting the obtained solid product (ii) with the above-mentioned electron donor (eg, anhydrous aluminum chloride, titanium tetrachloride, vanadium tetrachloride, etc.)
In combination with an organoaluminum compound (i) and an aromatic carboxylic acid ester (iv) (for example, ethyl benzoate, methyl p-toluate, ethyl p-toluate, 2-ethylhexyl p-toluate, etc.), Molar ratio of carboxylic acid ester (iv) and solid product (iii) i
Polymerization step (I) mainly composed of propylene having an ethylene content of 0 to 1 wt% or propylene obtained by polymerizing propylene and ethylene in three or more steps in the presence of a catalyst having v / iii = 0.1 to 10.0. The polymer (A) produced in step 1) is polymerized in an amount of 60 to 95% by weight based on the total amount of the polymer, and then ethylene or ethylene and propylene having an ethylene content of 10 to 100% by weight are polymerized in one or more steps. The polymer (B) produced in the polymerization step (II) mainly composed of ethylene is 40 to 5% by weight of the total amount of polymer, and the ethylene content is 3 to 20% by weight of the total amount of polymer. Thus, it can be obtained by block copolymerization. One step in this case means one section of continuous or temporary supply of these monomers. In the polymerization step (I) of the present invention, as long as the polymer (A) produced in the polymerization step (I) can maintain the above-mentioned P value, 1-% by weight or less of ethylene is added to butene-1,4-methyl. Penten-
1, styrene or non-conjugated dienes can be used in combination. However, in order to maintain the rigidity and the heat resistance of the crystalline ethylene-propylene block copolymer of the present invention at a high level, homopolymerization of propylene is desirable and easy to carry out, and therefore it is preferable. The ratio of the amount of the polymer (A) in the polymerization step (I) of the present invention is 60 to 95% by weight, preferably 75 to 90% by weight based on the crystalline ethylene-propylene block copolymer which is the final product. % By weight. Further, in the polymerization step (II) of the present invention, the ethylene content is 10 to 100% by weight, preferably 20 to 70% by weight, and the ratio of the amount of the polymer (B) in the polymerization step (II) is the final 5 to 40% by weight, preferably 10 to 25% by weight, based on the crystalline ethylene-propylene block copolymer which is the product obtained
% By weight. Also in this polymerization step (II), a small amount of other α-olefin or non-conjugated dienes and the like can be used together, as in the case of the polymerization step (I).
However, the ethylene content in the finally obtained polymer (excluding the soluble polymer eluted in the polymerization solvent) must be within the range of 3 to 20% by weight based on the total amount of the polymer. Therefore, when only 70% by weight of propylene is polymerized in the polymerization step (I), the amount of ethylene to be block copolymerized in the polymerization step (II) is limited to 20% by weight or less. , In which case the remaining 10-27% by weight is propylene or other alpha excluding propylene and ethylene.
-Olfines must be block copolymerized.
However, when 80% by weight of propylene is polymerized in the polymerization step (I), only 20% of ethylene is polymerized in the polymerization step (II).
It is possible to polymerize by weight%. As described above, the polymerization step (II) is within the limits of the stage in which ethylene can be polymerized and the ethylene content in the whole polymer.
In ethylene, the block copolymer of the present invention can be carried out in one step or in multiple steps by mixing ethylene alone or ethylene and propylene or other α-olefin. Melt flow rate (MFR) of the crystalline ethylene-propylene block copolymer of the present invention obtained as described above
Is usually 0.01 to 100 g / 10 minutes, especially for sheet molding,
For blow molding, those having an MFR value of 0.05 to 10 g / 10 minutes, preferably 0.10 to 5.0 g / 10 minutes are used. Incidentally, the molecular weight difference between the polymers produced in the polymerization step (I) mainly containing propylene, when expressed as an MFR value, needs to be within the range of the above formula (1). If the value on the left side of () is less than 1.0, the high melt viscoelasticity aimed at by the present invention cannot be obtained. Although the upper limit of the numerical value is not limited, it is difficult to set it to 3.0 or more in a specific embodiment of the present invention. here,
Isotactic Pentad Fraction (P) is Macromolecules, Vol. 6, No. 6, November-December, pp. 925-926 (1973) [Macromolecules, Vol.6, No.6, November −De
Cember, 925-926 (1973)], that is, the isotactic fraction in the pentad unit in the propylene-based polymer molecular chain, which is measured using ¹³ C-NMR. In other words, the fraction means the fraction of propylene monomer units in which five propylene monomer units are continuously isotactically bonded. The determination of the attribution of the peak of the spectrum in the measurement using ¹³ C-NMR described above is
Macro Molecules, Volume 8, Issue 5, September-October, 687
~ 689 (1975) [Macromolecules, Vol.8, No.5, Septe
mber-October, 687-689 (1975)]. By the way, FT is used for measurement by ¹³ C-NMR in Examples described later.
-Using a NMR 270 MHz apparatus, the signal detection limit was improved to 0.001 in terms of isotactic pentad fraction by integrating measurement of 27,000 times. Isotactic pentad fraction (P) and melt flow rate (MF
The requirement of the relational expression with R) is that the fraction P of a propylene polymer having a low MFR generally decreases, so that the lower limit of P corresponding to the MFR should be limited as the propylene polymer to be used. Is a constituent requirement. And the P
Is a fraction, so 1.00 is the upper limit. The above MFR is JISK
According to 7210, measure at 230 ℃, load 2.16kg. The above ethylene content is measured by an infrared absorption spectrum method.
Further, the polymerization ratio between the polymerization step (I) and the polymerization step (II) is determined as follows. That is, a copolymer having a changed ethylene / propylene reaction ratio was prepared in advance, and a calibration curve was prepared by the infrared absorption spectrum method using this as a standard sample to determine the reaction amount ratio of ethylene / propylene in the polymerization step (II). Further, it is calculated from the ethylene content of all the copolymers. In order to obtain the value of the relational expression of the above-mentioned expression (1),
MFR of each polymer produced in each polymerization step of the polymerization step (I)
The following is an example of the case where the polymerization step (I) comprises three steps of polymerization.

MFR ₁ ; MFR of polymer polymerized in the first stage (* 1) MFR ₂ ; MFR of polymer polymerized in the second stage (* 1) MFR ₃ ; MFR of polymer polymerized in the third stage (* 1) MFR _{1 + 2} ; M of all polymers produced in the first and second stages
FR MFR _{1 + 2 + 3} ; MFR W ₁ of all the polymers produced in the first step, the second step and the third step; produced in the polymerization step (I) of the polymer produced in the first step Ratio to total polymer (* 2) W ₂ ; Ratio of polymer formed in second stage to total polymer formed in polymerization step (I) (* 2) W ₃ ; Generated in third stage Ratio of polymer to total polymer produced in polymerization step (I) (* 2) W ₁ + W ₂ + W ₃ = 1.0 * 1; Sampling and actual measurement.

* 2: The titanium content in the polymer is analyzed and calculated by the fluorescent X-ray method.

MFR ₂ and MFR ₃ are calculated by the following relational expressions.

The crystalline ethylene-propylene block copolymer used in the present invention contains a normal crystalline propylene-based polymer, that is, a crystalline propylene homopolymer, and 70% by weight or more of a propylene component, as long as the effects of the present invention are not impaired. Propylene and ethylene, butene-1, pentene-1,4
-Methyl-pentene-1, hexene-1, octene-1
, A crystalline random copolymer or a crystalline block copolymer with one or more α-olefins, a copolymer of propylene and vinyl acetate or an acrylic ester, or a saponified product of the copolymer. , A copolymer of propylene and an unsaturated silane compound, a copolymer of propylene and an unsaturated carboxylic acid or an anhydride thereof, a reaction product of the copolymer and a metal ion compound, or a crystalline propylene-based polymer. It is also possible to use a modified propylene-based polymer obtained by modifying the polymer with an unsaturated carboxylic acid or a derivative thereof, or a mixture of a silane-modified propylene-based polymer obtained by modifying the crystalline propylene-based polymer with an unsaturated silane compound, and the like. , Various synthetic rubbers (for example, ethylene-propylene copolymer rubber, ethylene-propylene-non-conjugated diene copolymer Combined rubber, polybutadiene, polyisoprene, polychloroprene, chlorinated polyethylene, chlorinated polypropylene, styrene-butadiene rubber, acrylonitrile-butadiene rubber, styrene-butadiene-styrene block copolymer, styrene-isoprene-styrene block copolymer , Styrene-ethylene-
Butylene-styrene block copolymer, styrene-propylene-butylene-styrene block copolymer, etc.) or thermoplastic synthetic resin (for example, ultra low density polyethylene, low density polyethylene, linear low density polyethylene,
Polyolefins other than propylene-based polymers such as medium density polyethylene, high density polyethylene, ultra high molecular weight polyethylene, polybutene, poly-4-methylpentene-4,
Polystyrene, styrene-ocrylonitrile copolymer,
Acrylonitrile-butadiene-styrene copolymer, polyamide, polyethylene terephthalate, polybutylene terephthalate, polycarbonate, polyvinyl chloride,
It is also possible to use a mixture of fluororesin).

Examples of the compound A used in the present invention include aluminum hydroxy-di-phenyl phosphate, aluminum hydroxy-bis (p-methylphenyl) phosphate, aluminum hydroxy-bis (p-ethylphenyl) phosphate, aluminum hydroxy. -Bis (pn-propylphenyl) phosphate,
Aluminum hydroxy-bis (pi-propylphenyl) phosphate, aluminum hydroxy-
Bis (pn-butylphenyl) phosphate, aluminum hydroxy-bis (pi-butylphenyl) phosphate, aluminum hydroxy-bis (ps-butylphenyl) phosphate, aluminum hydroxy-bis ( pt-butylphenyl) phosphate, aluminum hydroxy-bis (p-
n-aluminumphenyl) phosphate, aluminum hydroxy-bis (p-i-amylphenyl) phosphate, aluminum hydroxy-bis (ps-amylphenyl) phosphate, aluminum hydroxy-bis (pt-) Amylphenyl) phosphate, aluminum hydroxy-bis (p-hexylphenyl) phosphate, aluminum hydroxy-
Bis (pn-octylphenyl) phosphate, aluminum hydroxy-bis (p-2-ethylhexylphenyl) phosphate, aluminum hydroxy-bis (pt-octylphenyl) phosphate, aluminum hydroxy-bis ( p-nonylphenyl) phosphate, aluminum hydroxy-bis (p-dodecylphenyl) phosphate, aluminum hydroxy-bis (p-tridecylphenyl) phosphate, aluminum hydroxy-bis (p-
Hexadecylphenyl) phosphate, aluminum hydroxy-bis (p-octadecylphenyl) phosphate, aluminum hydroxy-bis (p-methoxyphenyl) phosphate, aluminum hydroxy-bis (p-ethoxyphenyl) phosphate, aluminum Hydroxy-bis (p-propoxyphenyl) phosphate, aluminum hydroxy-bis (p-butoxyphenyl) phosphate, aluminum hydroxy-bis (p-octoxyphenyl) phosphate, aluminum hydroxy-bis (p- Cyclohexylphenyl) phosphate, aluminum hydroxy-bis (p-biphenylyl) phosphate and aluminum hydroxy-bis (p
-Phenoxyphenyl) phosphate and the like, and aluminum hydroxy-bis (pt-butylphenyl) phosphate is particularly preferred. These phosphate compounds can be used alone or in combination of two or more. The compounding ratio of the compound A is 0.01 to 1 part by weight, preferably 0.05 to 0.5 part by weight, based on 100 parts by weight of the crystalline ethylene-propylene block copolymer. If the amount is less than 0.01 parts by weight, the effect of improving rigidity and heat resistance will not be sufficiently exerted, and if it exceeds 1 part by weight, further improvement of the above effects cannot be expected and it is not practical. It is uneconomical again.

In the composition of the present invention, various additives usually added to propylene-based polymers such as phenol-based, thioether-based, phosphorus-based antioxidants, light stabilizers, clarifying agents, nucleating agents, Lubricants, antistatic agents, anti-fog agents, anti-blocking agents, anti-drop agents, pigments, heavy metal deactivators (copper damage inhibitors), radical generators such as peroxides, dispersants such as metal soaps or medium Additives, inorganic fillers (eg talc, mica, clay, wollastonite, zeolite,
Asbestos, calcium carbonate, aluminum hydroxide, magnesium hydroxide, silicon dioxide, titanium dioxide, zinc oxide, magnesium oxide, zinc sulfide, barium sulfate, calcium silicate, glass fiber, carbon fiber, carbon black, potassium titanate, metal fiber Etc.) or a coupling agent (for example, silane-based, titanate-based, boron-based, aluminate-based, zircoaluminate-based, etc.) surface-treated inorganic filler or organic filler (for example, wood powder, (Pulp, waste paper, synthetic fiber, natural fiber, etc.) can be used together as long as the object of the present invention is not impaired. In particular, when an inorganic filler is used in combination, the rigidity and heat-resistant rigidity are further improved.

The composition of the present invention is obtained by adding the compound A to the above-mentioned crystalline ethylene-propylene block copolymer according to the present invention.
In addition, a predetermined amount of each of the above-mentioned various additives which are usually added to the propylene-based polymer is mixed by using an ordinary mixing device such as a Henschel mixer (trade name), a super mixer, a ribbon blender, a Banbury mixer, and the like. Screw extruder, twin screw extruder, brabender or roll,
It can be obtained by melt-kneading pelletizing at a melt-kneading temperature of 170 ° C to 300 ° C, preferably 200 ° C to 250 ° C.
The obtained composition is used for production of a target molded article by various molding methods such as an injection molding method, an extrusion molding method, and a blow molding method.

[Action] In the present invention, the phosphate compound represented by Compound A is disclosed in JP-B-41-16303 and JP-A-53-10555.
It is generally known that it acts as a nucleating agent to improve the rigidity and the heat resistance rigidity like the phosphate compound disclosed in Japanese Patent Laid-Open Publication No. However, the aforementioned Japanese Patent Publication No. 41-
Compound A, which is a monobasic aluminum salt of a phosphate-based compound (aluminum normal salt) disclosed in JP-A No. 16303 and JP-A No. 53-105550, has a specific molecular weight distribution and a specific isotactic content according to the present invention. By blending with a crystalline ethylene-propylene block copolymer having a tic pentad fraction, a surprising synergistic effect that cannot be predicted from the formulation of a conventionally known nucleating agent is exerted,
It has been found that a composition having remarkably excellent rigidity and heat resistance can be obtained.

[Effects of the Invention] The composition of the present invention is (1) significantly superior in rigidity and heat resistance as compared with a conventionally known crystalline ethylene-propylene block copolymer composition containing various nucleating agents. ing. (2) Not only can it contribute to resource saving by reducing the thickness of the molded product, but also because the cooling rate during molding is faster, the molding rate per unit time can be increased, which also contributes to improved productivity. it can. (3) Polypropylene resin can be used in applications where high-impact polystyrene (HIPS) resin, ABS resin, etc. were conventionally used, and the applications of polypropylene resin can be expanded.
(4) Since the sheet has excellent secondary processability and blow moldability, it can be suitably used for producing a secondary processing sheet and a blow molded product.

EXAMPLES Hereinafter, the present invention will be specifically described with reference to Examples, Comparative Examples, and Production Examples, but the present invention is not limited thereto.

The evaluation methods used in Examples and Comparative Examples were as follows.

1) Secondary workability of sheet (heated vacuum formability): A sheet having a width of 60 cm and a thickness of 0.4 mm was prepared by extrusion molding using the obtained pellets, and the heat vacuum formability of the sheet was evaluated as a model. Cut the sheet into 40 cm x 40 cm,
Fix it tightly in a frame of cm x 40 cm and put it in a thermostatic chamber at 200 ° C. Eventually, the sheet fixed to the frame is heated and the central part of the frame starts to hang down, and at some point, it begins to return to the original position due to heat contraction. After that, it begins to hang down again. At this time, (a) the sag amount immediately before the sheet starts to return is measured as the maximum sag amount (mm).

(B) The amount of deformation (mm) at which the sheet droops to the maximum and returns to the original position in the direction of the original position is measured, and (the amount of deformation /
Record the maximum amount of droop) x 100 as the maximum amount of return (%).

(C) Measure the time (seconds) from the point where the sheet returns to the maximum until it hangs down again by 10 mm, and use it as the holding time.

Secondary workability (vacuum formability) of the sheet by the above evaluation method
A material having a good value is a material having a minimum sag, a maximum return, and a long holding time.

2) Rigidity: width 60 cm, thickness 0.4 m using the obtained pellets
A sheet of m was prepared by an extrusion molding method, and Young's modulus (based on ASTM D 882) and tensile yield strength (based on ASTM D 882) were measured using the sheet to evaluate rigidity. A high-rigidity material means a material having high Young's and tensile yield strength.

In the Examples and Comparative Examples, two types of test pieces, MD (vertical; extrusion direction) and TD (horizontal (direction perpendicular to the extrusion direction)) of the sheet were prepared, and Young's modulus and tensile yield were used using the test pieces. The strength was measured and the average value was shown.

3) Heat resistance rigidity: length of 130mm using the obtained pellets,
A test piece having a width of 13 mm and a thickness of 6.5 mm was prepared by an injection molding method, and the heat resistance was evaluated by measuring the heat distortion temperature using the test piece (in accordance with JIS K 7207; 4.6 kgf / cm ² load). . A material having high heat resistance and rigidity means a material having a high heat distortion temperature.

4) Impact resistance: width 60 cm, thickness using the obtained pellets
A 0.4 mm sheet is prepared by extrusion molding, and a prescribed test piece is prepared using the sheet, and the punching impact strength is measured (AS
According to TM D 781), the impact resistance was evaluated. A material having excellent impact resistance means a material having high punching impact strength.

Production Examples 1 to 3 (Production Example of Crystalline Ethylene-Propylene Block Copolymer Used in Examples and Comparative Examples) (1) Preparation of Catalyst n-Hexane 6, Diethylaluminum Monochloride (DEAC) 5.0 Mol, Diisoamyl Ether 12.0 mol to 2
Mix for 5 minutes at 5 ° C. and react for 5 minutes at the same temperature to produce reaction solution (v) (diisoamyl ether / DEAC molar ratio 2.
4) got. 40 mol of titanium tetrachloride was placed in a reactor purged with nitrogen and heated to 35 ° C, and the whole amount of the above reaction product liquid (v) was added dropwise to this in 3 hours, then kept at the same temperature for 30 minutes, and kept at 75 ° C.
The reaction mixture was heated to room temperature for 1 hour, cooled to room temperature (20 ° C), the supernatant was removed, n-hexane 30 was added, and the supernatant was removed by decantation was repeated 4 times to obtain a solid product. (Ii) Obtained 1.9 kg. With the total amount of this solid product (ii) suspended in n-hexane 30, 1.6 kg of diisoamyl ether and 3.5 kg of titanium tetrachloride were added at room temperature for about 5 minutes, and the mixture was heated to 65 ° C. And reacted for 1 hour. After completion of the reaction, the mixture was cooled to room temperature, the supernatant was removed by decantation, 30 n-hexane was added, and the mixture was stirred for 15 minutes,
The operation of leaving still and removing the supernatant liquid was repeated 5 times, and then dried under reduced pressure to obtain a solid product (iii).

(2) Pretreatment of catalyst In a tank having an internal volume of 50, n-hexane 40, diethylaluminum monochloride 850 g, and the above solid product (iii) 3
Charge 60g and 3.8g of methyl p-toluate, then 30 ℃
Propylene gas was supplied at 180 g / H for 2 hours while maintaining and stirring at 2, for pretreatment.

(3) Polymerization method n-Hexane 26 / H in the polymerization vessel 1 and 240 ml / H as the production example 1 of the catalyst slurry pretreated were used as the production example 2
40 ml / H and 120 ml / H as Preparation Example 3 and 1 g of solid product (iii) in the catalyst slurry with methyl p-toluate.
Each of them was continuously fed so that the amount was 1 g. The temperature of the polymerization vessel 1 was 70 ° C. in Production Examples 1 to 3, the temperature of the polymerization vessel 2 was 70 ° C. in Production Example 1, 60 ° C. in Production Example 2 and Production Example 3
Is 70 ° C., the temperature of the polymerization vessel 3 is 70 ° C. as a production example, 50 ° C. as a production example 2 and 70 ° C. as a production example 3, and the pressure of the polymerization vessel 1 is 6 kg / cm ² G as a production example 1. As 2
4 kg / cm ² G and 6 kg / cm ² G as Production Example 3, the pressure of the polymerization vessel 2 is 8 kg / cm ² G in Production Examples 1 to 3, and the pressure of the polymerization vessel 3 is 10 kg / cm ² G as Production Example 1. Propylene was supplied to each of the polymerization vessels so as to be 12 kg / cm ² G as Production Example 2 and 10 kg / cm ² G as Production Example 3, respectively. Polymerizer 1 of Production Example 1
When the hydrogen concentrations in the gas phase portions of 3 to 3 were supplied so that only the polymerization reactor 1 had a hydrogen concentration of 5.9 mol%, the polymerization reactors 2 and 3 had a hydrogen concentration of 0.65 mol% and 0.069 mol%, respectively. Polymerizers 1 to 3 of Production Example 2
When the hydrogen concentration in the gas phase part was supplied only to Polymerizer 1 to 14.5 mol%, Polymerizers 2 and 3 were 1.0 mol% and 0.10 mol%, respectively. Moreover, the polymerization vessels 1 to 3 of Production Example 3
When the hydrogen concentration in the gas phase part was supplied so that only the polymerization reactor 1 had a concentration of 2.1 mol%, the polymerization reactors 2 and 3 had a hydrogen concentration of 0.41 mol% and 0.046 mol%, respectively. The analysis values of the polymerization ratio and melt flow rate (MFR) of each polymerization vessel were as shown in Table 1. The liquid level in the polymerization vessels 1 to 3 is
It was taken out with a control valve so that it would be 80%.

Then, the slurry containing the polymer particles extracted from the polymerization vessel 3 was transferred to the polymerization vessel 4 by a degassing pump at 60 ° C. and 0.5 kg / cm ² G in a pressure drop tank. The hydrogen concentration in the gas phase of the polymerization vessel 4 is 10 mol%, the temperature is 60 ° C., and ethylene is supplied at 600 g / H.
Gas phase gas composition is ethylene / (ethylene + propylene)
The polymerization reaction was continued by supplying propylene and hydrogen so that the ratio was 0.40. The slurry discharged from the polymerization vessel 4 is passed through a degassing tank, and the catalyst is further deactivated with methanol, followed by neutralization with a 20% by weight aqueous sodium hydroxide solution, washing with water, separation, and drying to obtain a white mixture. About 6.5 kg / H of polymer powder
I got it. The results of analysis of the copolymer are shown in Table 1.

In Table 1, the first stage of the polymerization step (I),
The second stage, the third stage and the polymerization step (II) correspond to the polymerization in the polymerization vessel 1, the polymerization vessel 2, the polymerization vessel 3 and the polymerization vessel 4, respectively. All of the polymerization vessels 1 to 4 had an inner volume of 150.

Examples 1 to 3 and Comparative Examples 1 to 9 Each melt flow rate (MFR), each isotactic pentad fraction (P) and ethylene content produced in Production Examples 1 to 3 shown in Table 2 below. To 100 parts by weight of a powdery crystalline ethylene-propylene block copolymer having a compound (A), aluminum hydroxide-bis (pt-butylphenyl) phosphate as compound A and a predetermined amount of each of other additives are added to the second component described below. The mixture was put in a Henschel mixer (trade name) at the blending ratio shown in the table, stirred and mixed for 3 minutes, and then melt-kneaded at 200 ° C. with a single-screw extruder having a diameter of 40 mm to form pellets. Also, powdery crystalline ethylene-propylene blocks having respective melt flow rates, respective isotactic pentad fractions and ethylene contents produced in Production Examples 1 to 3 shown in Table 2 below as Comparative Examples 1 to 9. A predetermined amount of each of the additives shown in Table 2 below was mixed with 100 parts by weight of the copolymer, and melt-kneaded according to Examples 1 to 3 to obtain pellets.

A sheet used for secondary workability, rigidity and impact resistance test of the sheet was prepared by subjecting the obtained pellets to extrusion molding at a resin temperature of 250 ° C. In addition, the test pieces used for the heat resistance rigidity test were obtained by pelletizing the pellets at a resin temperature of 250 ° C and a mold temperature of 50
Prepared by injection molding at ° C.

Using the obtained sheet and test piece, the secondary workability, rigidity, heat resistance and impact resistance of the sheet were evaluated by the above-mentioned test method. The results are shown in Table 2.

Examples 4 to 6 and Comparative Examples 10 to 18 Melt flow rates (MFR), isotactic pentad fractions (P), and ethylene contents produced in Production Examples 1 to 3 shown in Table 3 below. To 100 parts by weight of a powdery crystalline ethylene-propylene block copolymer having a compound (A), aluminum hydroxy-bis (pt-butylphenyl) phosphate as the compound A, and fine particle talc having an average particle size of 2 to 3 μm as the inorganic filler. And each of the specified amounts of other additives were added to the Henschel mixer (trade name) in the blending ratios shown in Table 3 below, and the mixture was stirred and mixed for 3 minutes, then at 200 ° C in a single screw extruder with a diameter of 40 mm. It was melt-kneaded and pelletized. In addition, powdery crystalline ethylene-propylene block having each melt flow rate, each isotactic pentad fraction and ethylene content produced in Production Examples 1 to 3 shown in Table 3 below as Comparative Examples 10 to 18 A predetermined amount of each of the additives shown in Table 3 below was added to 100 parts by weight of the copolymer, and the mixture was melt-kneaded in accordance with Examples 4 to 6 to obtain pellets.

A sheet used for secondary workability, rigidity and impact resistance test of the sheet was prepared by subjecting the obtained pellets to extrusion molding at a resin temperature of 250 ° C. In addition, the test pieces used for the heat resistance rigidity test were obtained by pelletizing the pellets at a resin temperature of 250 ° C and a mold temperature of 50
Prepared by injection molding at ° C.

Using the obtained sheet and test piece, the secondary workability, rigidity, heat resistance and impact resistance of the sheet were evaluated by the above-mentioned test method. The results are shown in Table 3.

The compounds and additives relating to the present invention shown in Tables 2 to 3 are as follows.

Compound A: Aluminum hydroxy-bigger (pt-butylphenyl) phosphate Nucleating agent 1: p-t-Butyl aluminum benzoate Nucleating agent 2: 1,3,2-Dibenzylidene sorbitol Nucleating agent 3: Sodium-bis (pt-butylphenyl)
Phosphate [Adeka Argus Chemical Co., Ltd .; MARK
NA-10UF] Nucleating agent 4: Aluminum-bis (pt-butylphenyl) phosphate Nucleating agent 5: Aluminum-2,2'-methylene-bis (4-,
6-di-t-butylphenyl) phosphate nucleating agent 6: aluminum hydroxy-2,2'-methylene-bis (4,6-di-t-butylphenyl) phosphate phenolic antioxidant 1: 2 , 6-di-t-butyl-p-
Cresol phenolic antioxidant 2: tetrakis [methylene-3-
(3 ', 5'-di-t-butyl-4'-hydroxyphenyl) propionate] methanephosphorus antioxidant 1: tetrakis (2,4-di-t-butylphenyl) -4,4'-biphenylene- Di-phosphonite Phosphorus antioxidant 2: Bis (2,4-di-t-butylphenyl) -pentaerythritol-diphosphite Ca-St: Calcium stearate Inorganic filler: Talc (average particle size 2-3μ ) The examples and comparative examples shown in Table 2 are the cases where a crystalline ethylene-propylene block copolymer having each melt flow rate and each isotactic pentad fraction was used as the propylene-based polymer. As can be seen from Table 2, Examples 1 to 3 are prepared by compounding Compound A with a crystalline ethylene-propylene block copolymer having a molecular weight distribution and an isotactic pentad fraction within the scope of the present invention. Yes, Examples 1-3 and Comparative Examples 1-
In comparison with No. 3 (a crystalline ethylene-propylene block copolymer having a molecular weight distribution and an isotactic pentad fraction within the scope of the present invention, an organic nucleating agent is not mixed), 1-3 and Comparative Example 1
Although the sheet Nos. 3 to 3 have the same degree of secondary workability, Comparative Examples 1 to 3 are still insufficient in the effect of improving the rigidity and the heat resistance rigidity. Furthermore, in order to improve the rigidity and heat resistance of Comparative Examples 1 to 3, crystalline ethylene-propylene block copolymers having a molecular weight distribution and an isotactic pentad fraction within the scope of the present invention are added to compounds other than Compound A. Comparing Comparative Examples 4 to 9 and Examples 1 to 3 in which an organic nucleating agent made of a compound is mixed, Comparative Examples 4 to 9 are not yet sufficient although the effect of improving rigidity and heat resistance is considerably observed. It is understood that 1 to 3 are remarkably excellent in rigidity and heat resistance rigidity, and that by adding the compound A, a remarkable synergistic effect is recognized. In particular, it is clear that the effect of the present invention is not exhibited in Comparative Example 7 in which the aluminum normal salt of the compound A (monobasic aluminum salt) according to the present invention is blended, which means that the above Japanese Patent Publication No. 41-16303.
Nothing is described in Japanese Patent Application Laid-Open No. 05-105550. That is, the rigidity and heat-resistant rigidity obtained in the present invention are not obtained when compound A is blended with a crystalline ethylene-propylene block copolymer having an isotactic pentad fraction within the range limited in the present invention. It can be said that this is a unique effect. In addition, when the compound A is blended in Examples 1 to 3 which are the compositions of the present invention, the impact resistance is not decreased due to the improvement of the rigidity, and the impact resistance is higher than that of Comparative Examples 1 to 9. It was confirmed that there was no difference.

Table 3 shows that the propylene polymer used in Table 2 was used in combination with talc as an inorganic filler, and the same effect as described above was confirmed for this.

From this, the composition of the present invention has a secondary processability of a sheet and rigidity and heat resistance as compared with a composition obtained by compounding a conventionally known crystalline ethylene-propylene block copolymer with a nucleating agent. It was found that the composition of the present invention was remarkably excellent, and the remarkable effect of the composition of the present invention was confirmed.

Claims (6)

(57) [Claims] 1. A polymer (A) produced in a polymerization step (I) mainly comprising propylene having an ethylene content of 0 to 1% by weight, or propylene obtained by polymerizing propylene and ethylene in three or more steps. Produced in the ethylene-based polymerization step (II), which is 60 to 95% by weight of the amount of the polymer, and then has ethylene content of 10 to 100% by weight, or ethylene obtained by polymerizing ethylene and propylene in one or more steps. The polymer (B) is 40 to 5% by weight of the total amount of polymer,
A crystalline ethylene-propylene block copolymer having an ethylene content of 3 to 20% by weight based on the total amount of the polymer, wherein the molecular weight of each polymer produced in each polymerization step of the polymerization step (I) is Melt flow rate (MFR; discharge amount of molten resin for 10 minutes when a load of 2.16 kg at 230 ° C) is calculated as the following formula (1) (However, MFR _n ; MFR of the polymer produced in the nth stage, MFR _{n + 1} ; MFR of the polymer produced in the _{n +} 1th stage) is satisfied, and in the polymerization step (I) The relationship between the isotactic pentad fraction (P) and the melt flow rate (MFR) of the resulting polymer (A) is 1.00 ≧ P ≧ 0.015logM
0.01 to 1 part by weight of a phosphate compound represented by the following general formula [I] (hereinafter referred to as compound A) was added to 100 parts by weight of a crystalline ethylene-propylene block copolymer having FR + 0.955. A high-rigidity, high-melting viscoelasticity ethylene-propylene block copolymer composition comprising: (In the formula, R represents hydrogen or an alkyl group having 1 to 18 carbon atoms, an alkoxy group, a cycloalkyl group, a phenyl group or a phenoxy group.) 2. A high-rigidity, high-melting viscoelastic ethylene according to claim 1, wherein the crystalline ethylene-propylene block copolymer has a melt flow rate (MFR) of 0.05 to 10 g / 10 minutes. Propylene block copolymer composition. 3. In the general formula [I], R has 1 to 9 carbon atoms.
The high-rigidity high-melting viscoelasticity ethylene-propylene block copolymer composition according to any one of claims (1) and (2), which is an alkyl group of. 4. A compound according to claim 1, which comprises aluminum hydroxy-bis- (pt-butylphenyl) phosphate as compound A. The high-rigidity high-melting viscoelasticity ethylene-propylene block copolymer composition described. 5. A high-rigidity and high-melting viscoelasticity ethylene-propylene block copolymer composition according to any one of claims (1) and (2), which comprises an inorganic filler. Stuff. 6. As an inorganic filler, talc, mica, clay, wollastonite, zeolite, asbestos, calcium carbonate, aluminum hydroxide, magnesium hydroxide, silicon dioxide, titanium dioxide, zinc oxide, magnesium oxide, zinc sulfide, sulfuric acid. Use of one or more selected from barium, calcium silicate, glass fiber, carbon fiber, carbon black, potassium titanate and metal fiber. High rigidity and high rigidity according to claim (5). Melt viscoelastic ethylene-propylene block copolymer composition.