JPS63213547A - High-rigidity and high-melt viscoelastic ethylene-propylene block copolymer composition - Google Patents

Abstract

PURPOSE:To obtain the titled composition, having remarkably improved rigidity and high temperature rigidity, by blending a specific crystalline ethylene- propylene block copolymer with a specific amount of a specified phosphate based compound. CONSTITUTION:A composition obtained by blending (A) 100pts.wt. crystalline ethylene-propylene block copolymer, consisting of (A1) 60-95wt.% polymer, prepared by polymerizing propylene with 0-1wt.% ethylene content or propylene with ethylene in three or more stages and having the molecular weight, expressed in terms of melt flow rate (MFR) value and satisfying formula I (MFRn is MFR of the polymer formed in the n-th stage) and relation between the isotactic pentad fraction (P) and the MFR expressed by formula II and (A2) 40-5wt.% polymer with 10-100wt.% ethylene content prepared by polymerizing ethylene or ethylene with propylene in one or more stages and having 3-20wt.% ethylene content based on the total polymer with (B) 0.01-1pt.wt. phosphate based compound expressed by formula III (R1 is 1-4C alkylidene; R2 and R3 are H; M is mono--trivalent metal; n is 1-3).

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a high-rigidity, high-melt viscoelastic ethylene-propylene block copolymer composition. The present invention relates to a melt viscoelastic ethylene-propylene block copolymer composition.

(Conventional technology) In general, 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 obtained using propylene polymers tend to sag quickly during heat forming for secondary processing, the range of processing conditions is narrow, the molding efficiency is poor, and wide sheets suffer from the aforementioned sagging. There are various problems such as that the thickness of the secondary processed product tends to be uneven and that overlapping wrinkles tend to occur. For this reason, the current situation is that 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, blow molding can only be applied to small products.

■If a high-molecular-weight propylene polymer is used to prevent the above-mentioned sagging, it will result in poor fluidity, a large load during molding, large energy loss, the risk of mechanical troubles, and rough skin of the molded product, which will severely reduce the product value. There are other problems.

On the other hand, depending on the various specific uses of the propylene polymer, the properties of the propylene polymer, especially its impact resistance, may not be sufficient, and the properties of the propylene polymer may not be sufficient for molding that is subjected to mechanical impact or used at low temperatures. The problem is that it is difficult to use for products. In general, there is an incompatible relationship between rigidity and impact resistance of plastic materials, such as rigidity and heat resistance.
It is often extremely difficult to improve and improve the former and the latter at the same time. In order to find specific uses for propylene-based polymers and to expand demand, it is desired to further improve not only the above-mentioned impact resistance but also rigidity. By improving these physical properties, propylene-based polymers can be used in application fields where other general-purpose resins, such as high-impact polystyrene (HIPS) resins or ABS resins, are used. Several proposals have been made regarding improving the impact resistance of propylene polymers.

A well-known method is to block copolymerize propylene with ethylene. The resulting 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-based polymers, Japanese Patent Application No. 60-283728 filed by the same applicant as the present application specifies An ethylene-propylene block copolymer having a specific molecular weight distribution that is polymerized in the presence of a catalyst has been proposed. Additionally, it is common practice to blend organic nucleating agents such as aluminum pt-butylbenzoate or 1,3,2,4-dibenzylidene sorbitol into propylene polymers for the purpose of improving rigidity. There is.

(Problems to be Solved by the Invention) However, using the ethylene-propylene block copolymer having a specific molecular weight distribution obtained by polymerizing in the presence of a specific catalyst as proposed in the above-mentioned Japanese Patent Application No. 60-283728, Although the sheet's secondary processability and blow moldability are sufficiently satisfactory in practical terms, the rigidity, although considerably improved, is still not fully satisfactory.

In addition, aluminum p-t-butylbenzoate or
・3. Ethylene-propylene block copolymer compositions containing 2,4-dibenzylidene sorbitol and the like have a considerable improvement in stiffness, but are used in applications that require high stiffness and heat-resistant stiffness. It is still not completely satisfactory.

The present inventors have conducted extensive research in order to solve the above-mentioned problems regarding propylene-based polymer compositions containing the various nucleating agents described above. As a result, a phosphate compound represented by the following general formula (1) (hereinafter referred to as Compound A) was added to an ethylene-propylene block copolymer having a specific molecular weight distribution and a specific isotactic limit fraction. It was discovered that a composition containing the above-mentioned propylene polymer compositions could solve the problems of the propylene polymer compositions described above, and based on this knowledge, the present invention was completed.

(However, if there is no expression in the formula, sulfur or an alkylidene group having 1 to 4 carbon atoms, Rt and R8 each represent hydrogen or a similar or alkyl group having 1 to 8 carbon atoms, and M is a monovalent to trivalent alkyl group. (n represents an integer of 1 to 3.) As is clear from the above description, the purpose of the present invention is to
It is an object of the present invention to provide an ethylene-propylene block copolymer composition which has excellent secondary processability and blow moldability, as well as rigidity and heat-resistant rigidity of the sheet when heated to K.

(Failure to solve the problem) The present invention has the following configuration.

The polymer (4) produced in the polymerization process (1) mainly containing propylene with an ethylene content of 0 to 1% by weight or propylene and ethylene in three or more stages is 60% of the total polymer amount. ~95% by weight and then ethylene content of 10 to 100% by weight, or a polymer produced in the polymerization step 1) consisting mainly of ethylene, which is obtained by polymerizing ethylene and propylene in one or more steps [F] ) is 40 to 5 M% of the total polymer amount, and the ethylene content is 3 to 20ii% of the total polymer amount, the M polymerization step (1 ).

The molecular weight of each 1 (combined) produced at each stage is melt flow rate (MFR; load at 230 °C 2, 16 & 9
The value of the discharge amount of molten resin for 10 minutes when adding is expressed by the following formula (1) MF Rn: MFRM of the polymer produced in the nth stage
FRn+1; M of the polymer produced at the n+1 stage
Indicates FR. ), and the polymer produced in the polymerization step (1) (
5) The relationship between isotactic pentad fraction (P) and melt flow rate (MFR) is 1.00≧P≧0.
For 100 parts by weight of a crystalline ethylene-propylene block copolymer having an MFR of 0.0151ogMFR+0.955,
A phosphate compound represented by the following general formula (1) (
Hereinafter, it will be referred to as compound A. ) in an amount of 0.01 to 1 part by weight.

(However, in the formula, R8 is absent or represents sulfur or an alkylidene group having 1 to 4 carbon atoms, R2 and R5 each represent hydrogen or the same or different alkyl group having 1 to 8 carbon atoms, and M
represents a monovalent to trivalent metal atom, and n represents an integer of 1 to 3.

) The ethylene-propylene block copolymer used in the present invention is produced using propylene having an ethylene content of 0 to 1% by weight, or propylene obtained by polymerizing propylene and ethylene in three or more stages. The polymer (A) produced in is 60 to 95% by weight of the total polymer amount,
Next, the polymer (B) produced in the polymerization step ('II) mainly composed of ethylene or ethylene with an ethylene content of 10 to 100% by weight, or ethylene and propylene polymerized in one or more stages, has a total polymer content of 10 to 100% by weight. 40~5Mjt% of
A crystalline ethylene-propylene block copolymer having an ethylene content of 3 to 20% by weight based on the total polymer amount, each of which is produced in each step of the polymerization step (1).
The molecular weight of the coalescing is expressed as the melt flow rate (MFR) value by the following formula (1) h4FRn: MFRMFR of the polymer produced in the nth stage
The MFR of the polymer produced at the n+1 stage is shown. ) and # the polymer produced in polymerization step (1) (
The relationship between the isotactic pentad fraction (g) and the melt flow rate (MFR) is 1.00≧P≧0.0
Crystalline ethylene with 151ogMFR+0.955
It is a propylene block copolymer. Such an ethylene-propylene block copolymer is produced by the production method described in Japanese Patent Application No. 60-283728 filed by the same applicant as the present application. That is, an organoaluminum compound (1) such as triethylaluminum, diethylaluminium monochloride, etc. or a reaction product (vl) of the organoaluminum compound (1) and an electron donor (4) such as diynamyl ether is mixed with titanium tetrachloride (vl).
A solid product (11) obtained by reacting K with Q, and a solid product (11) obtained by reacting an electron donor (g) with an electron acceptor, for example, titanium tetrachloride, is added with an organoaluminum compound ( 5) For example, triethylaluminum,
Diethylaluminum monochloride etc. and an aromatic carboxylic acid ester (Y), for example, in combination with methyl p-toluate, the molar ratio of the aromatic carboxylic acid ester (V) and the solid product (material) m/l-0,1 A polymerization process 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 an ethylene content of
) is polymerized so that the amount of polymer (A) produced is 60 to 95% by weight of the total polymer, and then the ethylene content is 1
The polymer (B) produced in the polymerization step (1) mainly composed of ethylene or ethylene and propylene in one or more stages, which is 0 to 100% by weight, is 40 to 5% by weight of the total polymer amount. It can be obtained by copolymerizing so that the ethylene content is 3 to 2011 L% of the total polymer amount. A stage in this case means one section of continuous or temporary feeding of these monomers. In the polymerization step (1) of the present invention, as long as the polymer (A) produced in the polymerization step Q) can maintain the above-mentioned P value, 1! In addition to ethylene, butene-1,4-methylbe/thene-1, styrene, or nonconjugated dienes can be used in combination in an amount of % or less. However, in order to maintain high rigidity and heat-resistant rigidity of the ethylene-propylene block copolymer of the present invention, homopolymerization of propylene is desirable and easy to carry out. Polymerization step (1) of the present invention
The ratio of the amount of polymer particles in ) is 60 to 95% by weight, preferably 75 to 90% by weight, based on the final product of the ethylene-propylene block copolymer. In addition, in the polymerization step (1) of the present invention, the ethylene content is 10 to 100% by weight, preferably 20 to 70M%, and the ratio of the amount of polymer Q3 in the 1st polymerization step is the final 5 to 40% by weight, preferably 1% to the ethylene-propylene block copolymer product obtained in
The amount is 0 to 25M%. Also, in this polymerization step (1), a small amount of other α-
Olefins or non-conjugated dienes, etc. can also be used in combination. However, the finally obtained polymer (However, it must be dissolved in the polymerization solvent. Therefore, if only propylene is polymerized in the polymerization step (1) in the total amount of 7011 (% by weight), the polymerization step Since the amount of ethylene to be block copolymerized in (1) is limited to 20% by weight or less, in that case, the remaining 10 to 27 -Olefins must be block copolymerized.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 (1). As mentioned above, ethylene can be used alone or mixed with propylene or other α-olefins, as long as the stage in which ethylene can be polymerized and the ethylene content in the total polymer are limited. The block copolymerization of the present invention can be carried out in one step or in multiple steps.The melt flow rate (MFR) of the ethylene-propylene block copolymer of the present invention obtained as described above is usually 0.01 to 1009/ 10 minutes, but especially for sheet molding and blow molding, the M
FR value is 0.05-10 g/l 0 min, preferably 0
．． 10 to 710 seconds is used. Incidentally, when the molecular weight difference between the polymers produced in the polymerization step (1) mainly containing propylene is expressed as an MFR value, it needs to be within the range of the above formula (1), and the formula ( The value on the left side of 1) is 1. If it is less than OK, the high melt viscoelasticity that is the objective of 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 specific embodiments of the present invention. Here, isotactic pentad fraction y) is Macromolecules, Volume 6, Issue 6, November ~
December, pp. 925-926 (1973 edition) (Mae
romolecules *Mo1.6. h 6 e
November-December, 925-9
26 (1973)), namely 1
It is an isotactic fraction in pentad units in a propylene polymer molecular chain measured using 3C-NMR. In other words, the fraction means the fraction of one propylene monomer unit in which five propylene monomer units are isotacticly bonded consecutively. The above-mentioned method for determining the attribution of spectral peaks in measurements using C-NMR is described in Macromolecules, Vol. 8, No. 5, September-October,
pp. 687-689 (1975 edition) (Maeromo
lecules * Mol , 8 t NIL 5
*September-October, 687-
689 (1975)) based on K. By the way, in the measurement by 13C-NMR in the examples described later, F'r-N
The signal detection limit was improved to 0.001 in isotactic pentad fraction by 27,000 cumulative measurements using MR's 270M field equipment. The requirements for the above relational expression between isotactic pentad fraction (P) and melt flow rate (MFR) are as follows: In general, propylene polymers with low MFH have a lower fraction P.
A constitutional requirement for the propylene polymer to be used is to limit the lower limit of P corresponding to its MFH. Since P is a fraction, the upper limit is 1.00. The MFR mentioned above is based on JIS K7210 and is 2.
Measured at 30°C and 1 load i2.16kg. The aforementioned ethylene content is measured by infrared absorption spectroscopy. Also,
Polymerization step (1) and polymerization step (1) are determined as follows. That is, copolymers with varying reaction ratios of ethylene/propylene are prepared in advance, and a calibration curve is created using infrared absorption spectroscopy using this as a standard sample, and the reaction amount ratio of ethylene/propylene in the polymerization step (1) is determined. , further calculated from the ethylene content of the entire copolymer. In addition,
In order to find the value of the relational expression of equation (1) above, the polymerization process (
The MFR of each polymer produced in each polymerization step of 1) is as follows, taking as an example the case where the polymerization step (1) consists of three stages of polymerization.

MFR,? MFR of the polymer polymerized in the first stage (*1) MFR,; MFR of the polymer polymerized in the second stage (*1
) MFH3: MFR of the polymer polymerized in the third stage (*1
) MFR++2; MFR of all polymers produced in the first stage and second stage MFR, +, +,; MFR of all polymers produced in the first stage, second stage and third stage Wl; in the first stage Polymerization step (I) of the produced polymer
Ratio to the total polymer produced in (*2) W2; Polymerization step (I) of the polymer produced in the first stage
Ratio to the total polymer produced in (*2) Wl i Polymerization process of the polymer produced in the first stage (1
) Ratio (*2) W, +Wt +Ws31.0 *1; Measured by sampling.

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

MFR, MFH3 was determined by the following relational expression.

In addition, the ethylene-propylene block copolymer used in the present invention may be a normal propylene-based polymer, that is, a homopolymer of propylene, propylene and ethylene, butene-1, pentene-14-), within a range that does not impair the effects of the present invention. f
Crystalline random copolymers or crystalline block copolymers with one or more a-olefins such as lupentene-1, xene-1, octene-1, propylene and vinyl acetate, acrylic esters, etc. copolymers or saponified products of said copolymers, copolymers of propylene and unsaturated carboxylic acids or their anhydrides, reaction products of core copolymers and metal ion compounds, etc., or propylene-based polymers. Modified propylene polymers modified with unsaturated carboxylic acids or derivatives thereof can be mixed and used, and various synthetic rubbers (e.g. ethylene-propylene copolymer rubber, ethylene-propylene-nonconjugated diene copolymer rubber) can be used. Polymer rubber, polyfridiene, polyisoprene, chlorinated polyethylene, chlorinated polypropylene, styrene-butadiene rubber, styrene-butadiene-styrene block copolymer, styrene-isoprene-styrene block copolymer, styrene-ethylene-butylene-styrene block copolymers, styrene-propylene-butylene-styrene block copolymers, etc.) or thermoplastic synthetic resins (e.g. polyethylene, polybutene, poly-4
- Polyolefins (excluding propylene polymers such as methylpentene-1, polystyrene, styrene-acrylonitrile copolymers, acrylonitrile-butadiene-styrene copolymers, polyamides, polyethylene terephthalate, polybutylene terephthalate, polyvinyl chloride, etc.) It can also be used as At this time, the mixture satisfies the above formula (1) and the above 1. OO≧P≧
0. 0151ogMFR+0.955'' (anything that satisfies this is fine.

Compound A used in the present invention includes sodium-2,
2'-methylene-bis-(4,6-di-t-butylphenyl)phosphate, sodium-2,2'-ethylidene-bis-(4,6-di-t-butylphenyl)phosphate, lithium- 2,2'-methylene-bis-(
4,6-di-t-butylphenyl) phosphate, lithium-2,2'-ethylidene-bis-(4°6-di-
t-butylphenyl) phosphate, sodium-2
,2'-ethylidene-bis-(4-i-7'robi-6
-t-7''F-ruphenyl)pho,<7x-),!
-t-butylphenyl)7 osphate, lithium-2
; Calcium-bis-(2,2'
-thiobis-(4-ethyl-6-t-butylphenyl)
phosphate], calcium-bis-(2,2'-thiobis-(4,6-sheet-t-7'f-ruphenyl)phosphate), magnesium-bis-[2,guthiobis-(4,6-sheet-t- 7'-tylphenyl) phosphate], magnesium-bis-(2,2'-thiobis-(
4-t-octylphenyl) phosphate], sodium-2,2'-butylidene-bis-(4,6-cymethylphenyl)phosphate, sodium-2,27
-Butylidene-bis-(4,6-di-t-butylphenyl)phosphate, sodium-2,2'-t-octylmethylene-bis-(4,6-di-methylphenyl)
Phosphate, sodium-2゜2'-t-octylmethylene-bis-(4,6-di-t-butylphenyl)
phosphate, calcium bis-(2,2'-methylene-bis-(4,6-)-t-butylphenyl) phosphate], magnesium-bis-(2,2'-methylene-bis-(4, 6-di-t-butylphenyl) phosphate], barium-bis-(2,2'-methylene-bis-(4,6-di-monophylphenyl)) 7 male 7
ate], sodium-2,2'-methylenebis-(4
-Methyl-6-t-7'-tylphenyl) phosphate, Sodium-2,2'-methylene-bis-(4-ethyl-6-t-butylphenyl)7 phosphate, Sodium (4,4'-dimethyl-6 ,6'-'sheet t-7'
Thiru-2,2'-piphenyl)phosphate, calcium-bis-((4,4'-dimethyl-6,6'-di-
t-butyl-2,2'-biphenyl)phosphate]
, sodium-2゜2'-ethylidene-bis-(4-s
-butyl-6-tert-propyl phenyl) phosphate,
Sodium-2,2'-methylene-bis-(4,6-cymethylphenyl)phosphate, sodium-2,
2'-methylene-bis-(4,6-cymethylphenyl)phosphate, potassium-2,2'-ethylidene-
Bis-(4,6-di-t-butylphenyl)phosphate, Calcilam-bis-(2,2'-ethylidene-bis-(4,6-di-t-butylphenyl)phosphate), Magnesium-bis -(2,2'-ethylidene-bis-(4,6-di-t-butylphenyl)phosphate], barium-his-(2,2'-ethylidene-bis-(4,6-di-t-t) -butylphenyl)phosphate), aluminum tris-(2,2'-methylene-
bis-('4.6-1-t-7" tylphenyl) phosphate], aluminum tris-(2,2'-ethylidene-bis-(4,6-di-t-7' tylphenyl)
phosphate] or a mixture of two or more of these. Particularly preferred is sodium-2,2'-methylene-bis-(4,6-di-t-butylphenyl)phosphate. The blending ratio of 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 above-mentioned crystalline ethylene-propylene block copolymer.
Parts by weight. If the amount is less than 0.01 parts by weight, the improvement effect on stiffness and heat resistance stiffness will not be sufficiently exhibited, and although it is possible to add more than 1 part by weight, it is impractical because no further improvement can be expected. It is not only economical but also uneconomical.

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, anti-drop agents, pigments, deactivators (copper inhibitors), radical generators such as peroxides, dispersants for metal soaps, etc. or neutralizing agents, inorganic fillers (e.g. talc, mica, clay, wollastonite, zeolite, asbestos, calcium carbonate, zinc bisulfide, barium sulfate, calcium silicate, glass fiber, carbon fiber, carbon black, potassium titanate) , metal fibers, etc.) or coupling agents (e.g., silane, titanate, boron, aluminate, zircoaluminate, etc.). The composition of the present invention can be used in combination with ethylene-based fibers according to the present invention, such as wood flour, pulp, waste paper, synthetic fibers, natural fibers, etc., to the extent that the object of the present invention is not impaired.
For the propylene block copolymer, predetermined amounts of the compound A and the above-mentioned additives that are usually added to the propylene-based monomer. ,
Mix using a Banbury mixer or the like, and melt-knead with a normal single-screw extruder, twin-screw extruder, Brabender T-roll, etc. at a temperature of 170°C to 300°C, preferably 200°C.
It can be obtained by melt-mixing pelletizing at 250'°C to 250'0°C. The obtained composition is used to produce a desired molded article by an individual molding method such as an injection molding method, an extrusion molding method, or a blow molding method. In particular, when the composition of the present invention is used for producing sheets for secondary processing and blow-molded products, the effects of the present invention become remarkable, and it is therefore preferable.

(Function) In the present invention, the phosphate compound represented by Compound A is generally known to act as a nucleating agent to improve rigidity and heat-resistant rigidity, as disclosed in JP-A-58-1736. However, the compound A=i
By blending it with the ethylene-propylene block copolymer having a specific molecular weight distribution and a specific isotactic pentad fraction (9) according to the present invention, surprising results that cannot be predicted from the blending of conventionally known nucleating agents can be obtained. A synergistic effect is exhibited, and a composition with extremely excellent stiffness and heat-resistant stiffness is obtained.

(Effects) The composition of the present invention has (1) significantly superior rigidity and heat-resistant rigidity compared to conventionally known compositions of ethylene-propylene block military combination compositions containing various heel nucleating agents; (2) Not only can the molded product be made thinner, which contributes to resource conservation, but also the cooling rate during molding is faster, so the molding speed per unit time can be increased, improving productivity. (3) It is now possible to use polypropylene resin in applications where high-impact polystyrene (I (IPS) resin, ABS resin, etc.) were conventionally used, and it is possible to expand the applications of polypropylene resin. .

〔Example〕

EXAMPLES The present invention will be specifically explained below 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.

■) Secondary processability of the sheet (heat vacuum formability): Using the obtained pellet, a sheet 1 with a width of 601 mm and a thickness of 0.4 fit was created by extrusion molding, and the heat vacuum formability of the sheet was modeled. In order to evaluate the sheet 40zx4
Cut it into 0n pieces, fix it in a 40alIX40cI11 frame in a taut state, 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 drooping just before the sheet starts to return is measured as the maximum amount of drooping (III).

(b) Deformation t (ff) t - where the sheet returned to its maximum from the point where it sagged to its maximum in the direction of its original position, and the amount of deformation returned to the maximum/maximum amount of droop x 100 is the maximum return! Record as (%).

(c) 10fn from the point where the seat returns to its maximum position! Measure the time (seconds) until it hangs down again and use it as the retention 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.

1) Type II: Using the obtained pellets, a width of 60 cm,
A sheet with a thickness of 0.4H was made by extrusion molding, and a specified test piece was prepared using the sheet, and the Young's modulus was measured (A
Stiffness was evaluated by measuring tensile yield strength (according to ASTM D 882) and tensile yield strength (according to ASTM D 882).

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.

heat resistance rigidity: length 130f using the obtained pellet
A test piece with a width of 13 ff and a thickness of 6.5 ff was made by injection molding, and the heat distortion temperature was measured using the test piece (J
According to IS K 7207; 4, 6 kti f /
d load) to evaluate heat resistance rigidity. A material with high heat resistance and rigidity is one that has a high heat deformation temperature.

■) Impact resistance: Using the obtained pellets, a sheet with a width of 603 mm and a thickness of 0.4 ff was made by extrusion molding, and a specified test piece was prepared using the sheet, and the punching impact strength was measured (ASTM Impact resistance was evaluated by performing the test (based on D781). 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 61 n-hexane, 5.0 mol of diethylaluminium monochloride (DEAC), Isoamyl ether12.
0 mol was mixed at 25°C for 5 minutes and reacted at the same temperature for 5 minutes to form the reaction product liquid (diisoamyl ether/D E
A molar ratio of A C of 2.4) was obtained. 40 moles of titanium tetrachloride was placed in a reactor substituted with 9 elements, heated to 35°C, and the entire amount of the reaction product liquid (6) was added dropwise thereto over 3 hours, kept at the same temperature for 30 minutes, and heated to 75°C. The temperature was raised to 20°C, and the reaction was continued for 1 hour. Cooled to room temperature (20°C), the supernatant liquid was removed, and n-
The operation of adding 301f hexane and removing the supernatant liquid with decane was repeated 4 times to obtain 1.9 to 1 solid product (1).
I got it. The entire amount of this solid product (1) was suspended in 301 tn-hexane, and 1.6 kq of diisoamyl ether and 8.5 kq f of titanium tetrachloride were added at 20°C over about 5 minutes at room temperature. The reaction was allowed to take place at °C for 1 hour. After the reaction was completed, it was cooled to room temperature, the supernatant liquid was removed by decantation, 301 n-hexane was added, stirred for 15 minutes, left to stand, and the supernatant liquid removed. After repeating this operation five times, the pressure was reduced. Drying under vacuum gave a solid product (2).

(2) Pretreatment of catalyst In a tank with an internal volume of 501 y, 401 y of n-hexane and 850 y of diethylaluminum monochloride were added.

The above solid product (7) was charged with 360 f% p-) methyl rulyate s, sy+, and then pretreated by supplying propylene gas r180 f/h for 2 hours while maintaining stirring at 30'C.

(3) Polymerization method Add the catalyst slurry pretreated with n-hexane 26 l/H1 to the polymerization vessel 1. 240 cod 1/H as Production Example 1, 240 m1/H as Production Example 2, and 120 m1/H as Production Example 3.
Methyl g//H and p-)ruylate were each continuously fed at a rate of 1 f/11 solid product in the catalyst slurry. Temperature gold production examples 1 to 3 in polymerization vessel 1
The temperature of polymerization vessel 2 was 70°C as production example 1.
60°C for C1 Production Example 2 and 70°C for Production Example 3
, the temperature of the polymerization vessel 3 was set to 70°C as Production Example 1, 50°C as Production Example 2, and 70°C as Production Example 3, and the pressure of the polymerization vessel 1 was set to 6 to 9/d (:,, Production Example 1). Example 2
as 4 kg/d G and as production example 3 6k
g/dG, x combined volume 2 pressure cracking examples 1 to 3 are all 8 kq
/ d G, the pressure of polymerization vessel 3 is 10 &
Propylene was supplied to each polymerization vessel and adjusted so as to be 12 kq/dG in Production Example 2 and 10 kg/dG in Production Example 3. The hydrogen concentration in the gas phase of polymerizers 1 to 3 in Production Example 1 was 0.65 mol% and 0.069 mol% in polymerizer 2 and 3, respectively. %Met. Manufacturing example 2
The hydrogen concentration in the gas phase of polymerizers 1 to 3 is 14 for polymerizer 1 only.
．． When the amount was supplied to be 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 production example 30 polymerizers 1 to 3 is as follows:
The analytical values of polymerization flow rate were as shown in Table 1. In addition, the control pulp was used to extract the liquid so that the liquid level in polymerization vessels 1 to 3 was 80%.

Next, the slurry containing polymer particles extracted from the polymerization vessel 3 was degassed in a drop pressure tank at 60°C and 10.5 kg/dG, and transferred to the polymerization vessel 4 by a pump. The hydrogen concentration in the gas phase of polymerization vessel 4 was 10 mol%, the temperature was 60°C, and the ethylene was 160%.
The polymerization reaction was continued by supplying propylene and hydrogen at a rate of 0f/H so that the gas composition of the gas phase became ethylene/(ethylene+propylene)-0.40. The slurry exiting the polymerization vessel 4 passes through a degassing tank, and after deactivating the catalyst with methanol, it undergoes the steps of neutralization with a 20% sodium hydroxide aqueous solution, washing with water, separation, and drying to produce a white color. Polymer powder was obtained at approximately 6, s#,/H. The analysis results of the copolymer are shown in Table 1.

In addition, in Table 1, the 1st stage, 2nd stage, 3rd stage of 1st polymerization process (1), and polymerization process (1) are the above-mentioned polymerization vessel 1, polymerization vessel 2, polymerization vessel 3, and polymerization vessel 3, respectively. Polymerization vessel 4
corresponds to the polymerization in

In addition, all of the polymerization vessels 1 to 4 used had an internal volume of 15 (l).

The results are shown in Table 1.

Examples 1 to 3, Comparative Examples 1 to 6 Each melt 70-rate (MFR), each isotactic pentad fraction (MFR) and ethylene content produced in Production Examples 1 to 3 shown in Table 2 below As compound A, sodium-2,2'-methylene-
Predetermined amounts of bis-(4,6-di-t-7'tylphenyl) phosphate and other additives were added to the
The mixture was put into a Hensel mixer (trade name) at the blending ratio shown in the table, stirred and mixed for 3 minutes, and then melted and mixed at 200''C using a single-screw extruder with a diameter of 4Qjfjl to form pellets. Comparative Examples 1 to 1 Powdered crystalline ethylene-propylene block copolymer 100 having each melt flow rate, each isotaph pentad fraction) and ethylene content produced in Production Examples 1 to 3 shown in Table 2 below as 6
Each predetermined f of the additives listed in Table 2 below is added to the weight part.
were blended and subjected to melt mixing treatment according to Examples 1 to 3 to obtain pellets.

The sheets used for the sheet secondary processability, rigidity and impact resistance tests were prepared by extrusion molding of 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 7 to 12 Each melt flow rate (MFR), each isotactic pentad fraction) and ethylene content manufactured in Production Examples 1 to 3 shown in Table 3 below Sodium-2,2'-methylene-bis-(4,e-di-t-butylphenyl) phosphate was added as Compound A to 100 parts by weight of a powdered crystalline ethylene-propylene block copolymer, and as an inorganic filler. Particulate talc with an average particle size of 2 to 3 μm and other additives were added to the prescribed fr' in the mixing ratio listed in Table 3 below in a Hensel mixer (trade name), stirred and mixed for 3 minutes, and then mixed with a diameter of 40 m'. The mixture was melt-kneaded at 200°C using a JF single-screw extruder to form pellets.

In addition, as Comparative Examples 7 to 12, powdered crystalline ethylene-propylene blocks having each melt flow rate, each isotactic pentad fraction, and ethylene content manufactured in Production Examples 1 to 3 shown in Table 3 below. Copolymer 1
Predetermined amounts of the additives listed in Table 3 below were added to 0x parts, and the mixture was melt-kneaded in accordance with Examples 4 to 6 to obtain pellets.

The sheet used for the secondary processability, repellency and impact resistance tests of the sheet 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 obtained sheets and test pieces were used to evaluate the sheet's secondary processability, rigidity, heat-resistant rigidity, and impact resistance according to 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; Sodium-2,2'-methylene-bis-(
4,6-di-t-butylphenyl) phosphate (manufactured by Adeka Argus Chemical ■; MARK NA-11) Nucleating agent 1ip-t-Butylbenzoate aluminum nucleating agent 2; 1, 3, 2, 4- Dibenzylidene sorbitol nucleating agent 3 Sodium bis-(4-t-butylphenyl) 7 osphate phenolic antioxidant 1i 2.6-di-1-butyl-
p-cresol phenolic antioxidant 2; Tetrakis (methylene-3
-(3',5'-di-t-butyl-4'-hydroxyphenyl)propionate comethane phosphorus antioxidant 1; tetrakis(2,4-di-t-butylphenyl)-4,4' -Biphenylene-diphosphonitophosphoric antioxidant 29bis(2,4-di-1-butylphenyl)-pentaerythritol 7osphite Ca-St; Calcium stearate inorganic loading Q1
Talc (average particle size 2 to 3μ) In the Examples and Comparative Examples listed in Table 2, each melt 70-
This is a case where crystalline ethylene-propylene block copolymers having various rates and isotactic pentad fractions are used. As seen from Table 2, Examples 1 to 3
is a crystalline ethylene-propylene block copolymer having a molecular weight distribution and an isotactic pentad fraction within the range of the present invention, and the compound At-blended. Examples 1 to 3 and Comparative Examples 1 to 3 (A crystalline ethylene-propylene block copolymer having a molecular weight distribution and an isotactic pentad fraction within the scope of the present invention,
(B) Rough comparison without using an organic nucleating agent shows that the sheets of Examples 1 to 3 and Comparative Examples 1 to 3 have the same degree of secondary processability, but Comparative Examples 1 to 3 have a lower rigidity. and the improvement effect of heat-resistant rigidity is still not sufficient. Furthermore, Comparative Examples 1 to
Organic nucleation consisting of a compound other than Compound A in a crystalline ethylene-propylene block copolymer having a molecular weight distribution and an isotactic pentad fraction within the range of the present invention in order to improve the rigidity and heat-resistant rigidity of No. 3. Comparing Comparative Examples 4 to 6 using agents and Examples 1 to 3, Comparative Example 4
Although the improvement effect of rigidity and heat-resistant rigidity is considerably recognized in ~6, it is still not sufficient, Examples 1-3 are significantly excellent in rigidity and heat-resistant rigidity, and a remarkable synergistic effect is recognized by using compound A. I understand. That is, the stiffness and heat-resistant stiffness obtained in the present invention are obtained when the compound Ai is used in a crystalline ethylene-propylene block copolymer having an isotactic pentad fraction within the range limited in the present invention. This can be said to be a unique effect.

In addition, in Examples 1 to 3, which are the compositions of the present invention, although the rigidity was improved by using Compound A, no decrease in impact resistance was observed, compared with Comparative Examples 1 to 6. It was confirmed that there was no inferiority in impact resistance.

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 indicates that the composition of the present invention is an ethylene-propylene block having a specific molecular weight distribution obtained by polymerizing in the presence of a specific catalyst proposed in Japanese Patent Application No. 60-283728 filed by the same applicant as the present application. It was found that the composition of the present invention is significantly superior in terms of secondary processability, stiffness, and heat resistance stiffness compared to a composition made by blending a nucleating agent with a copolymer, confirming the remarkable effects of the composition of the present invention. It was done.

that's all

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. Coalescing (B) is 40 to 5% by weight of the total polymer, and the ethylene content is 3 to 20% by weight of the total polymer
A crystalline ethylene-propylene block copolymer having a melt flow rate (MFR; when a load of 2.16 kg at 230°C is applied) of each polymer produced at each stage of the polymerization step (I). The following formula (1) log(MFR_n/MFR_n_+_1)≧1.0...
(1) (However, MFR_n: MFRMFR of the polymer produced in the nth stage
_n_+_1; MFR of the polymer produced in the n+1 stage
shows. ), 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_1 is absent or represents sulfur or an alkylidene group having 1 to 4 carbon atoms, and R_2 and R_3 are each hydrogen or the same or different type having 1 to 8 carbon atoms. , M represents a monovalent to trivalent metal atom, and n represents an integer of 1 to 3.) (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_1 is a methylene group,
The high-rigidity, high-melt viscoelastic ethylene according to claim 1 or 2, wherein the alkyl groups represented by R_2 and R_3 are t-butyl groups.
Propylene block copolymer composition. (4) Claims (1) or (2) in which sodium-2,2'-methylene-bis-(4,6-di-t-butylphenyl) phosphate is blended as compound A. The highly rigid and highly melt viscoelastic ethylene-propylene block copolymer composition according to any one of Items 1 to 9. (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. A highly rigid and highly melt viscoelastic ethylene-propylene block copolymer composition.