JPH01101356A - Ethylene-propylene block copolymer composition having high rigidity and high melt viscoelasticity - Google Patents

Abstract

PURPOSE:To obtain the title composition having excellent rigidity and high- temperature rigidity, by compounding a specific crystalline ethylene-propylene block copolymer with a specific amount of a phosphate compound. CONSTITUTION:The objective composition can be produced by compounding (A) 100pts.wt. of a crystalline ethylene-propylene block copolymer having an ethylene content of 3-20wt.% and composed of (A1) 60-95wt.% of a polymer having an ethylene content of 0-1wt.%, produced by polymerizing propylene or propylene and ethylene in >=3 steps, giving a polymer in each polymerization step having mol.wt. satisfying the formula I and having an isotactic pentad fraction (p) and MFR satisfying the formula II and (A2) 40-5wt.% of a polymer having an ethylene content of 10-100wt.% and produced by polymerizing ethylene or ethylene and propylene in >=1 step with (B) 0.01-1pt.wt. of a phosphate compound of formula III (R is H, etc.).

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a highly rigid and highly melt viscoelastic ethylene-propylene block copolymer composition. More specifically, the present invention relates to a highly rigid and highly melt viscoelastic ethylene-propylene block copolymer composition that provides a molded article with significantly superior rigidity and heat resistance.

[Prior art] Generally, propylene polymers have excellent processability, chemical resistance,
Because it has electrical and mechanical properties, it is processed into injection molded products, blow molded products, films, sheets, fibers, etc. and used for various purposes. However, sheets manufactured by processing propylene polymers tend to sag quickly during heat forming for secondary processing, and the processing conditions range is narrow, resulting in poor forming efficiency, and wide sheets suffer from the aforementioned sagging. Moreover, there are other problems such as the thickness of the secondary processed product tends to be uneven, and overlapping wrinkles are likely to occur. For this reason, only small molded products can be manufactured. Further, when a propylene polymer is used for blow molding, there are the following problems.

That is, (1) the parison sags significantly during molding, resulting in uneven wall thickness of the molded product; For this reason, it can only be applied to the production of small products.■ If a high molecular weight propylene polymer is used to prevent the above-mentioned sagging, there is a risk of poor fluidity, load holes during molding, large energy loss, and mechanical troubles. In addition, the molded product becomes severely rough and loses its commercial value.

On the other hand, depending on the specific use of the propylene polymer, the properties of the propylene polymer, especially its impact resistance, may not be sufficient, and it may not be suitable for molded products that are subjected to mechanical shock or that are used at low temperatures. The problem is that it is difficult to use it for molded products. In general, there is an incompatible relationship between rigidity and impact resistance of plastic materials, such as rigidity and lTi1 thermal rigidity, and it is often extremely difficult to improve the former and the latter at the same time. In order to expand the demand for practical applications and increase demand, it is necessary not only to have the above-mentioned impact resistance, but also to have rigidity (rigidity and heat resistance rigidity).
There is a need to further improve this. By improving these physical properties, other general-purpose resins such as high impact polystyrene (HIPS) resin or ABS
It becomes possible to use propylene-based polymers in application fields where resins are used. Several proposals have been made regarding improving the impact resistance of propylene polymers. In particular, a method of block copolymerizing propylene with ethylene is well known. The resulting crystalline ethylene-propylene block copolymer has a problem in that, while its low-temperature impact resistance is significantly improved compared to a propylene homopolymer, its rigidity is reduced.

For this reason, for the purpose of improving the secondary processability, blow moldability, and rigidity of the above-mentioned sheets related to propylene polymers, Japanese Patent Application Laid-Open No. 149711/1989 filed by the same applicant as the present application has been published. A crystalline ethylene-propylene block copolymer having a specific molecular weight distribution that is polymerized in the presence of a specific catalyst is disclosed. In addition, in order to improve the rigidity, aluminum pt-butylbenzoate or 1.3
, 2φ4-dibenzylidene sorbitol and the like are often blended with organic nucleating agents.

[Problems to be Solved by the Invention] However, the crystalline ethylene-propylene block copolymer having a specific molecular weight distribution obtained by polymerizing in the presence of a specific catalyst as disclosed in JP-A-62-149711, The secondary processability and blow moldability of the composite sheet are practically satisfactory, and although the rigidity has been considerably improved, it is still not fully satisfactory. Aluminum pt-butylbenzoate or l.3 is added to a crystalline ethylene-propylene block copolymer having a specific molecular weight distribution
．． 2◆ Sheets using crystalline ethylene-propylene block copolymer compositions containing organic nucleating agents such as 4-dibenzylidene sorbitol have a high degree of rigidity and heat resistance, although the effect of improving rigidity is considerable. It is still not fully satisfactory when used in applications that require rigidity.

The present inventors solved the above-mentioned problems with propylene-based polymer compositions containing the various nucleating agents described above, namely, the secondary processability and blow moldability of the sheet when it is made into a sheet.
We conducted extensive research to solve the problems of rigidity and heat resistance. As a result, a phosphate compound represented by the following general formula [I1 (hereinafter referred to as compound A) was added to a crystalline ethylene-propylene block copolymer having a specific molecular weight distribution and a specific isotactic pentad fraction. It was discovered that a composition obtained by blending the above-mentioned propylene polymer compositions could solve the problems of the propylene-based polymer compositions described above, and the present invention was completed based on this knowledge.

(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 purpose of the present invention is to Crystalline ethylene-
An object of the present invention is to provide a propylene block copolymer composition.

[Means for solving problems] The present invention has the following configuration.

The polymer (A) produced in the polymerization step (I) mainly containing propylene with an ethylene content of 0 to 1% by weight or propylene obtained by polymerizing propylene and ethylene in three or more stages is 60% of the total polymer amount. ~95% by weight, and then a polymer (B ) is 40 to 511% by weight of the total polymer amount, and the ethylene content is 3 to 20% by weight of the total polymer amount, the copolymer comprising: The molecular weight of each polymer produced in each polymerization step of step (I) is the melt flow rate (MFR; 23
The amount of molten resin discharged for 10 minutes at 0°C and when a load of 2.16 kg is applied is expressed by the following formula (1) MFR+,; MFRMF of the polymer produced at the nth stage
R,1,: indicates the MFR of the polymer produced in the (n+1)th stage), and the polymer produced in the polymerization step (1) (
A) The relationship between isotactic pentad fraction (P) and melt flow rate (MFR) is 1.00≧P≧0.
015 Q ogM F R+ 0.955% of a phosphate compound (hereinafter referred to as compound) represented by the following general formula [I] was added to 10,021 parts of a crystalline ethylene-propylene block copolymer having a value of 0.955. 01~l
A high-rigidity, high-melt viscoelastic ethylene-propylene block copolymer composition comprising:

(However, in the formula, R represents hydrogen or an alkyl group having i to t8 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 an ethylene A polymerization process mainly consisting of propylene having a content of 0 to 131% by weight, or propylene and ethylene polymerized in three or more steps (the polymer (A) produced by the process is 60 to 95% of the total polymer content). % by weight, and then the polymer produced in the polymerization step (II) mainly consisting of ethylene or ethylene and propylene polymerized in one or more stages with an ethylene content of 10 to 100% by weight.
B) is 40 to 5% by weight of the total polymer amount, and the ethylene content is 3 to 20% by weight of the total polymer amount, the polymerization step ( The molecular weight of each polymer produced in each polymerization step of I) is expressed as the melt flow rate (MFR) value by the following formula (1): MFR,l; MFRMF of the polymer produced in the n-th stage
R, , , indicates the MFR of the polymer produced at the (n+1)th stage. ) and which is produced in the polymerization step (I).
A) The relationship between the isotactic pentad fraction (P) and the melt flow rate (MFR) is 1.00≧P≧0.
It is a crystalline ethylene-propylene block copolymer with a Q ogM F R+ of 0.955. Such a crystalline ethylene-propylene block copolymer is disclosed in Japanese Patent Application Laid-Open No. 62-149 filed by the same applicant as the present application.
It is manufactured by the manufacturing method described in No. 711. That is, the reaction product (V )
The solid product obtained by reacting with titanium tetrachloride (i
i), and a solid product (iii
) with an organoaluminum compound (i) and an aromatic carboxylic acid ester (iv) (e.g. ethyl benzoate, p-
methyl toluate, ρ-ethyl toluate, p-2-ethylhexyl toluate, etc.), the molar ratio iv/1ii of the aromatic carboxylic acid ester (iv) and the solid product (iii) = 0.1 Produced in the polymerization step (1) mainly consisting of propylene with an ethylene content of 0 to 1% by weight, or propylene and ethylene polymerized in three or more stages in the presence of a catalyst with a concentration of ~10.0%. The polymer (A) is polymerized so that it accounts for 60 to 9511% by weight of the total polymer, and then the ethylene content is 10%.
The polymer (B) produced in the polymerization step (II) mainly consisting of ethylene or ethylene and propylene in one or more steps of ~100% by weight accounts for 40 to 5f [% by weight] of the total polymer amount. It can be obtained by block copolymerization such that the ethylene content is 3 to 20% of the total polymer amount. In this case, one stage means one section of continuous or temporary supply of these monomers. In the polymerization step (1) of the present invention, the polymer produced in the polymerization step (1) is Butene-1,4-methylpentene-11 styrene or non-conjugated dienes may be used in addition to 1% by weight or less of ethylene, as long as the above-mentioned P value can be maintained in the composite (A).

However, in order to maintain high rigidity and heat-resistant rigidity of the crystalline ethylene-propylene block copolymer of the present invention, homopolymerization of propylene is desirable and easy to carry out. Combine (
The ratio of the amount of A) is 60 to 60 to the crystalline ethylene-propylene block copolymer that is the final product.
95% by weight, preferably 75-90% by weight. In addition, in the polymerization step (II) of the present invention, the ethylene content is 10 to 100% by weight, preferably 20 to 70ffl%.
The ratio of the amount of polymer (B) in the polymerization step (II) is as follows:
5 to 40% by weight based on the propylene block copolymer, preferably lO to 25! i amount%. Also, in this polymerization step (II), a small amount of other α-olefins or non-conjugated dienes can also be used in combination, as in the case of polymerization step (1). However, the final polymer waste, excluding the soluble polymer dissolved in the polymerization solvent,
) must be in the range of 3 to 20% by weight of the total polymer. Therefore, if propylene alone is polymerized in an amount of 70% by weight of the total polymer in the polymerization step (I), Since the amount of ethylene block copolymerized in the polymerization step (II) is limited to 20% by weight or less, in that case, the remaining 10 to 27% by weight is propylene or propylene and other α-olefins other than ethylene. However, if 80% by weight of propylene is polymerized in the polymerization step (1), only 20% by weight of ethylene can be polymerized in the polymerization step (■).

As mentioned above, within the limits of the stage in which ethylene can be polymerized and the ethylene content in the total polymer, ethylene can be used alone or with ethylene and propylene or other polymers in the polymerization step (n). The melt flow rate of the crystalline ethylene-propylene block copolymer of the present invention obtained as above can be mixed with an α-olefin to carry out the block copolymerization of the present invention in one step or in multiple steps. (MFR) is usually 0.01 to 10
0g/10 minutes, but especially for sheet molding and blow molding, the MFR value is 0.05 to 10g/10
minutes, preferably 0.10 to 5.0 g/10 minutes. Incidentally, the molecular weight difference between the polymers produced in the polymerization step (1) mainly containing propylene, when expressed as an MFR value, needs to be within the range of the above-mentioned formula (1). ) is less than 1.0, the high melt viscoelasticity that is the objective of the present invention cannot be obtained.Although there is no upper limit to the value, in specific embodiments of the present invention, , 3.0 or more is difficult. Here, isotactic pentad fraction (P) is Macromolecules, Volume 6, No. 6, 1
January-December, pages 925-926 (1973) [
Mac-romolecules, Vol-6*N
ap, November-Deceggber.

925-926 (1973)], that is, the isotactic fraction in pentad units in the molecular chain of a propylene-based polymer measured using the method published in I"e-NMR. In other words, The fraction means the fraction of propylene monomer units in which six consecutive propylene monomer units are isotactic bonded.
"Determination of the attribution of spectral peaks in measurements using C-NMR," Macromolecules, Vol. 8, No. 5, September-October, pp. 687-689 (1975)
[Macromolecules, Vol. 8
．． ! '&i5eSeptember-Octobe
r, 687-689 (1975)]; Incidentally, a 270 MHz FT-NMR device was used for IC-NMR measurements in the Examples described below.
Through 27,000 cumulative measurements, the signal detection limit was improved to 0.001 in terms of isotactic pentad fraction. The requirements for the above relational expression between isotactic pentad fraction (P) and melt flow rate (M, FR) are that the fraction P of propylene polymers with low MFH generally decreases, so As a system polymer, the constituent requirement is to limit the lower limit of P corresponding to its MP'H. Then, the P is minutes □-
Because it is! , OO is the upper limit. The MFR mentioned above is JI
Compliant with 7210, 230℃, load 1i2.16kg
Measure with.

The aforementioned ethylene content is measured by infrared absorption spectroscopy. Further, the polymerization ratio between the polymerization step (I) and the polymerization step (II) is determined as follows. That is, copolymers with varying reaction ratios of ethylene/propylene are prepared in advance, and a calibration curve is created using this as a standard sample using infrared absorption spectroscopy to determine the reaction amount ratio of ethylene/propylene in the polymerization step (II). , roughly calculated from the ethylene content of the entire copolymer. In addition, in order to obtain the value of the relational expression of the above-mentioned formula (1), the M F R of each polymer produced in each polymerization step of the 1st polymerization step (1) is calculated as follows: The polymerization step (1) consists of three stages of polymerization. Taking the case as an example, it is as follows.

MFR,; MFR of the polymer polymerized in the first stage (this book
) MFR2; MFR of the polymer polymerized in the second stage (*l
) MFR3; MFR of the polymer polymerized in the third stage (*1
) MFR,. 2; MFR M F R+ of all polymers produced in the first stage and the second stage; 2. a; MFR W of the total polymer produced in the first stage of the first stage; Polymerization process (1) of the polymer produced in the first stage
(Book 2) W2; Ratio of the polymer produced in the second stage to the total polymer produced in the polymerization step (I) (Book 2) W,; Proportion of the polymer produced in the third stage Ratio of the resulting polymer to the total polymer produced in the polymerization step (1) (*2) W, +W2+W3=1.0 *1; Measured by sampling.

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

M P” R 2 and M F R 3 are determined by the following relational expression.

In addition, the crystalline ethylene-propylene block copolymer used in the present invention is a normal crystalline propylene polymer, that is, a crystalline propylene homopolymer, and contains 70% by weight or more of a propylene component, within a range that does not impair the effects of the present invention. propylene and ethylene, butene-11 pentene-1,
Crystalline random copolymer or crystalline block copolymer with one or more α-olefins such as 4-methyl-pentene-1, hexene-11 octene-1, propylene and vinyl acetate or acrylic acid ester or a saponified product of the copolymer,
゛Copolymers of propylene and unsaturated silane compounds, copolymers of propylene and unsaturated carboxylic acids or their anhydrides, reaction products of the copolymers with metal ion compounds, etc., or crystalline propylene polymers. It can also be used as a mixture of a modified propylene polymer obtained by modifying the polymer with an unsaturated carboxylic acid or its derivative, a silane-modified propylene polymer obtained by modifying a crystalline propylene polymer with an unsaturated silane compound, etc. , various synthetic rubbers (
For example, ethylene-propylene copolymer rubber, ethylene-propylene-nonconjugated diene copolymer 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, medium density polyethylene, high density polyethylene,
Polyolefins other than propylene polymers such as ultra-high molecular weight polyethylene, polybutene, poly-4-methylpentene-1, polystyrene, styrene-acrylonitrile copolymers, acrylonitrile-butadiene-styrene copolymers, polyamides, polyethylene terephthalate,
It is also possible to use a mixture of polybutylene terephthalate, polycarbonate, polyvinyl chloride, fluororesin, etc.).

Compound A used in the present invention includes aluminum hydroxy-di-phenyl phosphate, aluminum hydroxy-bis(p-methylphenyl) phosphate, aluminum hydroxy-bis(p-ethylphenyl) phosphate, aluminum hydroxy-bis(p-n-propylphenyl) phosphate, aluminum hydroxy-bis(p-1-propylphenyl) phosphate, aluminum hydroxy-bis(p-n-butylphenyl) phosphate, aluminum hydroxide Oxy-bis(p-i-butylphenyl) phosphate, aluminum hydroxy-bis(p-s-butylphenyl) phosphate, aluminum hydroxy-bis(p-t-butylphenyl) phosphate, aluminum hydroxy- Bis(p-
n-amylphenyl) phosphate, aluminum hydroxy-bis(p-1-amylphenyl) phosphate, aluminum hydroxy-bis(p-s-amylphenyl) phosphate, aluminum hydroxy-bis(p-t- amyl phenyl) phosphate, aluminum hydroxy-bis(p-hexylphenyl) phosphate, aluminum hydroxy-bis(p-n-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-nonylphenyl) phosphate,
p-dodecylphenyl) phosphny, 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(ρ-octoxyphenyl) phosphate, Aluminum hydroxy-bis(p-butoxyphenyl) phosphate −
Examples include cyclohexylphenyl) phosphate, aluminum hydroxy-bis(p-biphenylyl) phosphate, and aluminum hydroxy-bis(p-phenoxyphenyl) phosphate, particularly aluminum hydroxy-bis(p-phenoxyphenyl) phosphate. Butylphenyl) phosphate is preferred, and these phosphate compounds can of course be used alone, or two or more phosphate compounds can be used in combination. The compound A
The blending ratio is 0.01 to 1 part by weight, preferably 0.05 to 0.5 parts by weight, per 100 parts by weight of the above-mentioned crystalline ethylene-propylene block copolymer. 0.
If less than 1 part by weight is added, the effect of improving stiffness and heat resistance stiffness will not be sufficiently exhibited, and 1! Although it is possible to exceed 1 part, it is not only impractical, but also uneconomical since no further improvement in the above-mentioned effects can be expected.

The composition of the present invention includes various additives that are usually added to propylene polymers, such as phenol-based, thioether-based, phosphorus-based antioxidants, light stabilizers, clarifying agents, nucleating agents, Lubricants, antistatic agents, antifogging agents, antiblocking agents, non-drip agents, pigments, metal deactivators <tS harm inhibitors), radical generators such as peroxides, dispersants such as metal soaps, or Neutralizing agents, inorganic fillers (e.g. 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 ) or coupling agents (e.g., silane-based, titanate-based, boron-based, aluminate-based, zircoaluminate-based, etc.). , valves, waste paper, synthetic fibers, natural fibers, etc.) can be used in combination without impairing the purpose of the present invention. In particular, when an inorganic filler is used in combination, the rigidity and heat-resistant rigidity are further improved, so it is preferable to use the inorganic filler in combination.

The composition of the present invention is prepared by adding predetermined amounts of Compound A and the various additives usually added to propylene polymers to the crystalline ethylene-propylene block copolymer according to the present invention using a conventional mixing device. For example, mix using a Hensel mixer (trade name), super mixer, ribbon blender, Pan Bali mixer, etc., and use a regular single screw extruder, twin screw extruder, Brabender or roll, etc.
Melt kneading temperature 170°C to 300°C, preferably 200°C
It can be obtained by melt-mixing pelletizing at C to 250'C. The obtained composition is used to produce a desired molded article by various molding methods such as injection molding, extrusion molding, and blow molding.

[Function] In the present invention (1) the phosphate compound represented by compound A is disclosed in Japanese Patent Publication No. 41-18303 and
Similar to the phosphate compound disclosed in Japanese Patent No. 3-105550, it is generally known that it acts as a nucleating agent to improve rigidity and heat-resistant rigidity. however,
Said Japanese Patent Publication No. 41-16303 and Japanese Patent Application Laid-open No. 1983-
Compound A, which is a basic aluminum salt of a phosphate compound (aluminum normal salt) disclosed in Japanese Patent No. 105550, is converted into a crystalline compound having a specific molecular weight distribution and a specific isotactic pentad fraction according to the present invention. By blending it with the ethylene-propylene block copolymer, a surprising synergistic effect that could not be predicted from a single combination of a conventional common J, +1 nucleating agent is exhibited, resulting in a composition with significantly superior rigidity and heat-resistant rigidity. was found to be obtained.

[Effects of the Invention] Compared to conventionally known crystalline ethylene-propylene block copolymer compositions containing various nucleating agents, the composition of the present invention has (1) significantly superior rigidity and heat-resistant rigidity; ing. (2) Not only can the molded product be made thinner, contributing to WL savings, but also the cooling rate during molding is faster, which increases the molding speed per unit time and improves productivity. I can contribute. (3) It is now possible to use polypropylene resin in applications for which high impact polystyrene (HIPS) resin, ABS resin, etc. have traditionally been 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 manufacturing sheets for secondary processing and blow molded products.

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

The evaluation method used in Examples and Comparative Examples was as follows.

l) Secondary processability of the sheet (thermal vacuum formability): A sheet with a medium size of 60 cm and a thickness of 0.4 cm was made by extrusion molding using the obtained pellets, and the heat vacuum formability of the sheet was modeled. In order to evaluate the sheet 40c x 40
Cut it into 0cm pieces, fix it tightly in a 40ccm x 40cm frame, and place it in a constant temperature room at 200°C. Eventually, the sheet fixed to the frame will heat up and the center of the frame will begin to sag, and at a certain point it will begin to return to its original position due to heat contraction. After that, it starts to droop again. At this time, (a) the amount of sagging just before the sheet starts to return is measured as the maximum amount of sagging (sagging).

(b) Measure the amount of deformation (w) at which the sheet returns to its original position from the point where it sagged to its maximum, and calculate (the amount of deformation/maximum amount of sagging) x, ioo as the maximum amount of return - (%) Record as.

(C) Measure the time (seconds) from the point where the sheet returns to its maximum until it hangs down again at 10+w+, and use this as the holding time.

A material with good secondary processability (vacuum formability) of a sheet according to the above evaluation method refers to a material with minimum droop, maximum return, and long holding time.

2) Stiffness: Using the obtained pellets, the width is 80 Il! I
A sheet with a thickness of 0.4 m and a thickness of 0.4 mm was created by extrusion molding,
Measurement of Young's modulus using the sheet (ASTM 08B2
(according to ASTM D 8) and tensile yield strength measurement (ASTM D 8
The rigidity was evaluated by performing the following method (based on 82). A highly rigid material is one that has a high Young's modulus and a high tensile yield strength.

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

3) Heat resistance rigidity: length + 30f using the obtained pellets
flI*, width 13 mm, thickness 6.5 mm test piece was created by injection molding method, and the heat distortion temperature was measured using the test piece (based on JIS 7207; 4.6 kgf/cm2 load). Heat resistance rigidity was evaluated. A material with high heat resistance and rigidity is one that has a high thermal deformation temperature.

4) Impact resistance: width 60 cl using the obtained pellets
m.

A sheet with a thickness of 0.4 m + m was created by extrusion molding,
Specified test pieces were prepared using the sheet, and impact resistance was evaluated by measuring punching impact strength (based on ASTM 0781). A material with excellent impact resistance is one that has high punching impact strength.

Production Examples 1 to 3 (Production Examples of Crystalline Ethylene-Propylene Block Copolymers Used in Examples and Comparative Examples) (1) Preparation of Catalyst n-hexane 6Q, diethylaluminium monochloride (D E A C) 5. 0 mol and 12.0 mol of diisoamyl ether were mixed at 25°C for 5 minutes and reacted at the same temperature for 5 minutes to obtain reaction product liquid (V) (molar ratio of diisoamyl ether/DEAC 2.4). . 40 moles of titanium tetrachloride was placed in a reactor purged with nitrogen and heated to 35°C.
After adding the entire amount of the reaction product solution (v) dropwise to this solution over a period of 3 hours, the temperature was kept at the same temperature for 30 minutes, the temperature was raised to 75°C, and the temperature was further increased for 1 hour.
After reacting for an hour, cool to room temperature (20°C), remove the supernatant, add 30 (i) of n-hexane, and remove the supernatant by decantation, which is repeated 4 times to obtain a solid product (it).
1.9 kg was obtained. The total amount of this solid product (11) is n
- 1.6 kg of diisoamyl ether and 3.5 kg of titanium tetrachloride suspended in hexane 30Q at 20°C.
was added at room temperature for about 5 minutes and reacted at 65°C for 1 hour. After the reaction was completed, the mixture was cooled to room temperature, the supernatant was removed by decantation, 30Q n-hexane was added, and the mixture was stirred for 15 minutes. After repeating the operation of leaving the mixture still and removing the supernatant liquid five times, it was dried under reduced pressure to obtain a solid product (iii).

(2) Pretreatment of catalyst In a tank with an internal volume of 50Q, 4011 n-hexane, 850 g of diethylaluminium monochloride, and 3.8 g of the above solid product (iii) 3608% I)-) methyl ruylate
Next, while stirring and maintaining the temperature at 30°C, a pretreatment process was carried out by supplying professional and ren gas at 1803/H for 2 hours.

(3) ii Polymerization method Add the catalyst slurry pretreated with n-hexane 26Q/H1 to the polymerization vessel 1 as Production Example 1 at 240d/H1, Production Example 2 at 240fnQ/H, and Production Example 3 at 120wdl/H and P-). Methyl tolyate was continuously fed in an amount of Ig per gram of solid product (iii) in the catalyst slurry. The temperature of polymerization vessel 1 was 70°C in Production Examples 1 to 3, the temperature of polymerization vessel 2 was 70°C in Production Example 1, 60°C in Production Example 2 and 70°C in Production Example 3, and the temperature of polymerization vessel 3 was 70°C in Production Example 3. 70°C as Production Example 1, 50°C as Production Example 2, and 70°C as Production Example 3. Also, the pressure of the polymerization vessel I was 6 kg/cw+ as Production Example 1.
2G, Production Example 2 Toshil"4kg/c+a2G OyoUal
The pressure of the polymerizer 3 was 6 kg/cm2G for Production Example 3, 8 kg/cm2G for Production Examples 1 to 3.The pressure of the polymerization vessel 3 was 10kg/cs2G for Production Example 1, and 12kg/cs2G for Production Example 2 As Example 3, propylene was supplied and adjusted to each polymerization vessel so that the amount was 10 kg/cm2G. ! ! Example 10 Polymerization vessel 1
The hydrogen concentration in the gas phase of 3 to 3 was supplied so that it was 5.9 mol % only to polymerizer 1, and 0.9 mol% in polymerizer 2 and 3.
It was 65 mol%, o, oe9-il%.

The hydrogen concentration in the gas phase of polymerization vessels 1 to 3 in Production Example 2 is as follows:
When only 1 was supplied so that the amount was 14.5 mol %, the amounts in polymerizer 2.3 were 1.0 mol % and 0.10 mol %, respectively. In addition, the hydrogen concentration in the gas phase of polymerizers 1 to 3 in Production Example 3 was 0.41 mol% and 0.046 mol% in polymerizer 2 and 3, respectively.
It was mol%. Furthermore, the analytical values of the polymerization ratio and melt flow rate (MFR) of each polymerization vessel were as shown in Table 1. In addition, the liquid level in polymerization vessels 1 to 3 was drawn out using a control valve so that the liquid level was 80%.

Next, the slurry containing polymer particles extracted from the polymerization vessel 3 was degassed at 60°C in a falling pressure tank at 0.5kg/c+s2G and transferred to the polymerization vessel 4 by a pump. At a temperature of 60°C, ethylene was supplied at a rate of 600 g/H, and the gas composition of the gas phase was changed to 2 ethylene/H.
Propylene and hydrogen were supplied so that (ethylene + propylene) = 0.40, and the polymerization reaction was continued. The slurry that came out of the polymerization vessel 4 was passed through a degassing tank, and then the catalyst was deactivated with methanol. , neutralization with a 20% by weight aqueous sodium hydroxide solution, washing with water, separation, and drying to obtain about 6.5 kg/h of white copolymer powder.

The analysis results of the copolymer are shown in Table 1.

In addition, in Table 1, the first stage, second stage, third stage of polymerization step (I) and polymerization step (II) are the above-mentioned polymerization vessel 1, polymerization vessel 2, polymerization vessel 3 and polymerization vessel 1, respectively. This corresponds to the polymerization in vessel 4. In addition, all polymerization vessels 1 to 4 had an internal volume of 1500.

Examples 1 to 3, Comparative Examples 1 to 9 Each melt flow rate (MFR), each isotactic pentad fraction CP) and ethylene content manufactured in Production Examples 1 to 3 shown in Table 2 below Aluminum hydroxy-bis(
Predetermined amounts of pt-butylphenyl) phosphate and other additives were placed in a Hensel mixer (trade name) at the mixing ratios listed in Table 2 below, and after stirring and mixing for 3 minutes, The mixture was melt-kneaded using a single-screw extruder at 200°C to form pellets. Further, as Comparative Examples 1 to 9, powdered crystalline ethylene having each melt flow rate, each isotactic pentad fraction, and ethylene content manufactured in Production Examples 1 to 3 shown in Table 2 below.
100 parts by weight of the propylene block copolymer and the second
Example 1
Pellets were obtained by melt-kneading according to 3.

The sheet used for the sheet secondary processability, rigidity and impact resistance tests was prepared by extrusion molding the obtained pellets at a resin temperature of 250°C. Moreover, the test piece used for the heat resistance rigidity test was prepared by injection molding the obtained pellet at a resin temperature of 250°C and a mold temperature of 50°C.

Using the obtained sheets and test pieces, the sheet's secondary processability, rigidity, heat-resistant rigidity, and impact resistance were evaluated according to the test methods described above. These results are shown in Table 2.

Examples 4 to 6, Comparative Examples 10 to 18 Each melt flow rate (MFR), each isotactic pentad fraction (P) and ethylene content manufactured in Production Examples 1 to 3 shown in Table 3 below To 100 parts of a powdery crystalline ethylene-propylene block copolymer having and other additives in the mixing ratios listed in Table 3 below in a Hensel mixer (trade name), stirred and mixed for 3 minutes, and then heated at 200°C in a single-screw extruder with a diameter of 40 m. The mixture was melted and mixed into pellets. Also, Comparative Examples 1O to 18
100 weight of powdered crystalline ethylene-propylene block copolymers having each melt flow rate, each isotactic pentad fraction, and ethylene content prepared in Production Examples 1 to 3 shown in Table 3 below. A predetermined amount of each of the additives listed in Table 3 below was added to the mixture, and the mixture was melt-kneaded in accordance with Examples 4 to 6 to obtain pellets.

The sheet used for the sheet secondary processability, rigidity and impact resistance tests was prepared by extrusion molding the obtained pellets at a resin temperature of 250°C. Moreover, the test piece used for the heat resistance rigidity test was prepared by injection molding the obtained pellet at a resin temperature of 250°C and a mold temperature of 50°C.

The resulting pieces and test pieces were used to evaluate the sheet's secondary processability, rigidity, heat-resistant rigidity, and impact resistance using the test methods described above. These results are shown in Table 3.

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

Compound A Nialuminum hydroxy-bis(pt-
(butylphenyl) phosphate nucleating agent 1: pt-butylaluminum benzoate nucleating agent 2: l.3,2.4-dibenzylidene sorbitol nucleating agent 3: Sodium-bis(pt-butylphenyl) Phosphate [manufactured by Adeka Argus Chemical; MAR
K NA-10UF] Nucleating agent 4 Nialuminum-bis(pt-butylphenyl) phosphate Nucleating agent 5 Nialuminum-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 comethane phosphorus antioxidant l: Tetrakis(2,4-di-t-butylphenyl) -4,4'- Biphenylene-diphosphonite phosphorous antioxidant 2: Bis(2,4-di-t-butylphenyl)-pentaerythritol-siphosphite Ca-5t nickel stearate lucium Inorganic filler: Talc (average Particle size: 2 to 3μ) Examples and comparative examples listed in Table 2 are crystalline ethylene-propylene block copolymers having various melt flow rates and isotactic pentad fractions as pro- and pyrene-based polymers. This is the case when . As can be seen from Table 2, Examples 1 to 3 are compounds in which Compound A is blended with a crystalline ethylene-propylene block copolymer having a molecular weight distribution and an isotactic pentad fraction within the range of the present invention. Examples 1 to 3 and Comparative Examples 1 to 3 (in which an organic nucleating agent was added to a crystalline ethylene-propylene block copolymer having a molecular weight distribution and an isotactic pentad fraction within the range of the present invention). When compared with the sheet without blending), Examples 1 to 3 and Comparative Examples 1 to 3 have the same degree of secondary processability, but Comparative Examples 1 to 3 have no improvement effect on stiffness and heat resistance stiffness. A crystalline ethylene-propylene block copolymer having a molecular weight distribution and an isotactic and pentad fraction within the range of the present invention, which are not yet sufficient, and further improve the stiffness and heat resistance stiffness of Comparative Examples 1 to 3. Comparing Examples 1 to 3 with Comparative Examples 4 to 9, in which an organic nucleating agent consisting of a compound other than Compound A was blended with the organic nucleating agent, Comparative Examples 4 to 9 showed a considerable improvement in stiffness and heat resistance stiffness, but the results were still insufficient. On the contrary, Examples 1 to 3 were significantly superior in rigidity and heat-resistant rigidity, and it can be seen that a remarkable synergistic effect was observed by blending Compound A. In particular, it is clear that Comparative Example 7, in which a positive aluminum salt of Compound A (-basic aluminum salt) according to the present invention is blended, does not exhibit the effects of the present invention, and this is confirmed by the aforementioned Japanese Patent Publication No. 41-16303. No. 53-105550 and JP-A-53-105550 do not mention this at all. That is, the stiffness and heat-resistant stiffness obtained in the present invention are based on crystalline ethylene having an isotactic pentad fraction within the range limited in the present invention.
It can be said that this is a unique effect that can only be seen when Compound A is blended with a propylene block copolymer. Also,
By blending Compound A in Examples 1 to 3, which are compositions of the present invention, there was no decrease in impact resistance due to improvement in rigidity, and the impact resistance was in no way inferior to Comparative Examples 1 to 9. It was confirmed that there was no

Table 3 shows the propylene polymer used in Table 2,
Furthermore, talc is used as an inorganic filler,
In this case, the same effect as described above was confirmed.

This shows that the composition of the present invention has better sheet fabrication properties, stiffness, and heat-resistant stiffness compared to conventionally known compositions made by blending a nucleating agent with a crystalline ethylene/propylene block copolymer. It was found that the composition of the present invention was significantly superior in terms of the above, and the remarkable effects of the composition of the present invention were confirmed. -1 or more

Claims (6)

[Claims] (1) The polymer (A) produced in the polymerization process (I) mainly consisting of propylene with an ethylene content of 0 to 1% by weight or propylene and ethylene polymerized in three or more stages is a total polymer. 60 to 95% by weight of the ethylene content, followed by ethylene containing 10 to 100% by weight, or polymers produced in the ethylene-based polymerization step (II) obtained by polymerizing ethylene and propylene in one or more stages. A crystalline ethylene-propylene block copolymer in which the polymer (B) is 40 to 5% by weight of the total polymer amount, and the ethylene content is 3 to 20 weight% of the total polymer amount, and the polymerization The molecular weight of each polymer produced in each polymerization step of step (I) is determined by the melt flow rate (MFR; 23
The amount of molten resin discharged for 10 minutes when a load of 2.16 kg at 0°C is applied is expressed by the following formula (1) log (MFR_n/MFR_n_+_1)...
・(1) (However, MFR_n; MFRMF of the polymer produced in the nth stage
R_n_+_1; M of the polymer produced at the n+1st stage
Indicates FR. ), and the relationship between the isotactic pentad fraction (P) and melt flow rate (MFR) of the polymer (A) produced in the polymerization step (I) is 1.00≧P≧0
．． 0.01 to 1 part by weight of a phosphate compound represented by the following general formula [I] (hereinafter referred to as compound A) to 100 parts by weight of a crystalline ethylene-propylene block copolymer having a log MFR of 0.015 log MFR + 0.955. A highly rigid and highly melt viscoelastic ethylene-propylene block copolymer composition. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [I] (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.) (2) Melt flow rate (MFR) of crystalline ethylene-propylene block copolymer is 0.05 to 10 g/1
0 minutes. The highly rigid and highly melt viscoelastic ethylene-propylene block copolymer composition according to claim 1. (3) In general formula [I], R is an alkyl group having 1 to 9 carbon atoms, claim (1) or (
The highly rigid and highly melt viscoelastic ethylene-propylene block copolymer composition according to any one of items 2). (4) The compound according to claim 1 or 2, wherein aluminum hydroxy-bis-(p-t-butylphenyl) phosphate is blended as compound A. Highly rigid and highly melting viscoelastic ethylene-propylene block copolymer composition. (5) Claim No. 1 containing an inorganic filler
) or (2), the highly rigid and highly melt viscoelastic ethylene-propylene block copolymer composition. (6) Inorganic fillers such as talc, mica, clay, wollastonite, zeolite, asbestos, calcium carbonate, aluminum hydroxide, magnesium hydroxide, silicon dioxide, titanium dioxide, zinc oxide, magnesium oxide,
Claim (5) uses one or more selected from zinc sulfide, barium sulfate, calcium silicate, glass fiber, carbon fiber, carbon black, potassium titanate, and metal fiber. Highly rigid and highly melt viscoelastic ethylene/propylene block copolymer composition.