JPH0670161B2 - High rigidity and high melt viscoelasticity ethylene-propylene block copolymer composition - Google Patents

Description

TECHNICAL FIELD The present invention relates to a high-rigidity and high-melting viscoelasticity ethylene-propylene block copolymer composition. More specifically, the present invention relates to a high-rigidity and high-melting viscoelasticity ethylene-propylene block copolymer composition having extremely excellent rigidity and heat resistance.

[Conventional technology]

In general, propylene-based polymers have excellent processability, chemical resistance,
Since it has electrical and mechanical properties, it is processed into injection-molded products, blow-molded products, films, sheets, fibers and the like and used for various purposes. However, the sheet obtained by using the propylene-based polymer has a fast sag during the hot forming for the secondary processing, has a narrow range of processing conditions, is inferior in molding efficiency, and has a large sag in the wide sheet. There are various problems such that the thickness of the secondary processed product is likely to be uneven and overlapping wrinkles are likely to occur. Therefore, at present, 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, the blow molding method can be applied only to small products. If a high-molecular-weight propylene-based polymer is used to prevent the above-mentioned sagging, poor fluidity, large load during molding, large energy loss, risk of causing mechanical troubles, and rough skin of the molded product, resulting in loss of commercial value, etc. There is a problem.

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 propylene-based polymer may be subjected to mechanical impact or used at low temperature. There is a problem that it is difficult to use for molded products. Generally, there is an incompatible relationship between the impact resistance and the rigidity surface such as the rigidity and heat resistance of the plastic material.
It is often extremely difficult to improve and improve the former and the latter at the same time. For specific applications of the propylene-based polymer and further for expansion of demand, it is required to further improve not only the above-mentioned impact resistance but also the rigidity. By improving these physical properties, it becomes possible to use the propylene-based polymer in the application field where other general-purpose resins such as high-impact polystyrene (HIPS) resin or ABS resin are used. Several proposals have been made for improving the impact resistance of propylene-based polymers.
In particular, the method of copolymerizing propylene with ethylene is well known. The obtained ethylene-propylene block copolymer has a significantly improved low-temperature impact resistance as compared with the propylene homopolymer, but has a problem that the rigidity is lowered.

Therefore, for the purpose of improving the secondary processability, blow moldability, and rigidity of the above-mentioned sheet related to the propylene-based polymer, it is specified in Japanese Patent Application No. 60-283728 filed by the same applicant as the present application. An ethylene-propylene block copolymer having a specific molecular weight distribution obtained by polymerization in the presence of the above catalyst has been proposed. In addition, it is often practiced to blend an organic nucleating agent such as pt-butyl aluminum benzoate or 1,3,2,4-dibenzylidene sorbitol with a propylene-based polymer for the purpose of improving rigidity. There is.

[Problems to be solved by the invention]

However, the secondary processability and blow moldability of a sheet using an ethylene-propylene block copolymer having a specific molecular weight distribution obtained by polymerization in the presence of a specific catalyst proposed in Japanese Patent Application No. 60-283728. Is sufficiently satisfactory for practical use, on the other hand, although it is considerably improved in terms of rigidity, it is not yet sufficiently satisfactory. Further, an ethylene-propylene block copolymer having a specific molecular weight distribution obtained by polymerization in the presence of the specific catalyst described above has a p-t-
The ethylene-propylene block copolymer composition prepared by blending aluminum butylbenzoate or 1,3,2,4-dibenzylidene sorbitol has a high rigidity and a high heat resistance, although the effect of improving the rigidity is considerably recognized. It is not yet fully satisfactory for use in the required applications.

The present inventors have conducted extensive studies to solve the above-mentioned problems associated with the propylene-based polymer composition containing the above-mentioned various nucleating agents. As a result, an ethylene-propylene block copolymer having a specific molecular weight distribution and a specific isotactic pentad fraction (P) was added to the following general formula [I].
It was found that a composition obtained by blending a phosphate compound (hereinafter, referred to as compound A) represented by can solve the above-mentioned problems of the propylene polymer composition, and the present invention is based on this finding. completed.

(However, in the formula, R ₁ is absent, sulfur or an alkylidene group having 1 to 4 carbon atoms, R ₂ and R ₃ are each hydrogen or an alkyl group having 1 to 8 carbon atoms which is the same or different, and M is a monovalent group. ~ Trivalent metal atom, and n is an integer of 1 to 3.) As is clear from the above description, the object of the present invention is to make a sheet into a secondary processability and a blow moldability, and It is an object of the present invention to provide an ethylene-propylene block copolymer composition having excellent rigidity and heat resistance.

[Means for solving 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 step is 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, MFRn; MFR of the polymer formed in the nth stage; MFRn + 1; indicates the MFR of the polymer formed in the n + 1th stage) are satisfied, and the polymer formed in the polymerization step (I). The relationship between the isotactic pentad fraction (P) and the melt flow rate (MFR) of (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 mixed with 100 parts by weight of a crystalline ethylene-propylene block copolymer of FR + 0.955. A highly rigid and highly melt viscoelastic ethylene-propylene block copolymer composition.

(However, in the formula, R ₁ is absent, sulfur or an alkylidene group having 1 to 4 carbon atoms, R ₂ and R ₃ are each hydrogen or an alkyl group having 1 to 8 carbon atoms which is the same or different, and M is a monovalent group. Is a trivalent metal atom, and n is an integer of 1 to 3.) The ethylene-propylene block copolymer used in the present invention contains propylene having an ethylene content of 0 to 1% by weight, or propylene and ethylene. The polymer (A) produced in the polymerization step (I) mainly composed of propylene, which is polymerized in the above steps, is 60 to 95% by weight of the total amount of the polymer, and then the ethylene content is 10 to 100% by weight. Polymer (B) produced in the polymerization step (II) mainly composed of ethylene or ethylene obtained by polymerizing ethylene and propylene in one or more steps is 40 to 5% by weight of the total amount of the polymer, and contains ethylene. Amount of total polymer Crystalline ethylene is 20% - shall apply propylene blow stick copolymer, formula molecular weight of each polymer produced in each stage of the polymerization process (I) is a melt flow rate (MFR) (1) (However, MFRn; MFR of the polymer produced in the nth stage; MFRn + 1; MFR of the polymer produced in the n + 1th stage) are satisfied, and the polymer (A) produced in the polymerization step (I) is satisfied. The relationship between the isotactic pentad fraction (P) and the melt flow rate (MFR) is 1.00 ≧ P ≧ 0.015logM
It is a crystalline ethylene-propylene block copolymer with FR + 0.955. Such an ethylene-propylene block copolymer is produced by the production method described in Japanese Patent Application No. 60-283728, which is related to the application of the same applicant as the present application. That is, an organoaluminum compound (I) such as triethylaluminum, diethylaluminum monochloride or the like, or a reaction product (VI) of an organoaluminum compound (I) with an electron donor (A) such as diisoamyl ether is converted into titanium tetrachloride (C). With a solid product (II) obtained by reacting an electron donor (A) and an electron acceptor (B) such as titanium tetrachloride with an organoaluminum compound (II). IV) In combination with, for example, triethylaluminum, diethylaluminum monochloride, etc. and an aromatic carboxylic acid ester (V), for example methyl p-toluate, a molar ratio V of said aromatic carboxylic acid ester (V) and said solid product (III) / I
Produced in a 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 II = 0.1 to 10.0. The polymer (A) is polymerized so as to be 60 to 95% by weight of 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 ethylene-based polymerization step (II) 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. It can be obtained by copolymerization. 1 in this case
By stage is meant one segment of continuous or temporal feeding 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, in addition to 1% by weight or less of ethylene, putene-1,4-methyl. Pentene-1, styrene or non-conjugated dienes can be used in combination. However, in order to maintain the rigidity and heat resistance of the ethylene-propylene block copolymer of the present invention at a high level, homopolymerization of propylene is desirable and easy to carry out. 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 ethylene-propylene block copolymer which is the final product. Is. 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%, based on the 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 or the like can be used in combination 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, in the polymerization step (I), only propylene was used in an amount of 70
When the polymer is polymerized by weight, the amount of ethylene copolymerized in the polymerization step (II) is limited to 20% by weight or less. In that case, the remaining 10 to 27% by weight can be propylene or propylene. Other .alpha.-olefins, except ethylene in a certain range, must be block copolymerized. However, when 80% by weight of propylene is polymerized in the polymerization step (I), only 20% by weight of ethylene can be polymerized in the polymerization step (II). As described above, within the limits of the stage in which ethylene can be polymerized and the limit of the ethylene content in the total amount of polymer, ethylene alone or mixed with propylene or other α-olefin is used. The block copolymerization of the present invention can be carried out in one step or 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 100 g / 10 minutes, but especially for sheet molding and blow molding, the MFR value is Is 0.0
5 to 10 g / 10 min, preferably 0.10 to 5.0 g / 10 min is 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 not found to be 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, the isotactic pentad fraction (P) means Macromolecules, Volume 6, No. 6, November to December, pages 925 to 926 (1973 version) [Macromolecules, Vo
l.6, No.6, November-December, 925-926 (1973)], that is, at the pentad unit in the propylene-based polymer molecular chain measured using ¹³ C-NMR. This is the isotactic fraction. In other words, the fraction is
It means the fraction of propylene monomer units in which five propylene monomer units are continuously and isotactically bonded.
The method for determining the attribution of the spectrum peak in the measurement using ¹³ C-NMR described above is described in Macromolecules, Volume 8, 5
Issue, September-October, pages 687-689 (1975 edition) [Macromolec
ules, Vol.8, No.5, September-October, 687-689 (197
5)] based on. Incidentally, ¹³ C-in the examples described later
For measurement by NMR, an FT-NMR 270 MHz device was used,
The signal detection limit was improved to 0.001 in terms of isotactic pentad fraction by performing integrated measurement of 00 times. Generally, the requirement for the relational expression between the isotactic pentad fraction (P) and the melt flow rate (MFR) is MFR.
Since the propylene-based polymer having a low ratio has a lower fraction P, the propylene-based polymer to be used has the constitutional requirement of limiting the lower limit of P corresponding to its MFR. Since P is a fraction, 1.00 is the upper limit. Crystalline ethylene whose relationship between the isotactic pentad fraction (P) and the melt flow rate (MFR) of the polymer (A) produced in the polymerization step (I) does not satisfy 1.00 ≧ P ≧ 0.015 logMFR + 0.955 In the propylene block copolymer, the effect of improving rigidity and heat resistance is not sufficiently exerted. The above-mentioned MFR complies with JIS K 7210, 2
Measure at 30 ℃ and 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 reaction ratio of ethylene / propylene was prepared in advance, and using this as a standard sample, a calibration curve was prepared by the infrared absorption spectrum method, and the polymerization step (I
The reaction amount ratio of ethylene / propylene of I) is obtained, and further calculated from the ethylene content of all copolymers. In order to obtain the value of the relational expression of the above-mentioned formula (1), the polymerization step (I)
The MFR of each polymer produced in each polymerization step is as follows, taking the case where the polymerization step (I) is composed of three-step polymerization as an example.

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} ; MFR MFR _{1 + 2 + 3 of} all polymers produced in the first and second stages; MFR W ₁ ; of all polymers produced in first, second and third stages Ratio of the polymer produced in the first step to the total polymer produced in the polymerization step (I) (* 2) W ₂ ; to the total polymer produced in the polymerization step (I) of the polymer produced in the second step Ratio (* 2) W ₃ ; Ratio of the polymer formed in the third step to the total polymer formed in the polymerization step (I) (* 2) W ₁ + W ₂ + W ₃ = 1.0 * 1; sampled and measured.

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

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

The ethylene-propylene block copolymer used in the present invention is a usual propylene-based polymer, that is, a homopolymer of propylene, propylene and ethylene, butene-1, pentene-1, 4, as long as the effect of the present invention is not impaired. -Crystalline random copolymer or crystalline block copolymer with one or more α-olefins such as methyl-pentene-1, hexene-1, and octene-1, propylene and vinyl acetate, acrylate Or a saponified product of the copolymer, 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 propylene-based polymer. A modified propylene-based polymer modified with an unsaturated carboxylic acid or its derivative can be mixed and used in the combined product. , Various synthetic rubbers (e.g. ethylene -
Propylene copolymer rubber, ethylene-propylene-non-conjugated diene copolymer rubber, polybutadiene, polyisoprene, chlorinated polyethylene, chlorinated polypropylene, styrene-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 (eg polyethylene, polybutene, poly-
Polyolefin except polystyrene such as 4-methylpentene-1, polystyrene, styrene-acrylonitrile copolymer, acrylonitrile-butadiene-styrene copolymer, polyamide, polyethylene terephthalate, polybutylene terephthalate, polyvinyl chloride, etc.) It can also be used. At this time, the mixture satisfies the above formula (1) and the above 1.00 ≧ P ≧ 0.
Anything satisfying 015logMFR + 0.955 will do.

The compound A used in the present invention is sodium-2,
2'-methylene-bis- (4,6-di-t-butylphenyl) phosphonate, sodium-2,2'-ethylidene-bis- (4,6-di-t-butylphenyl) phosphonate, lithium-2,2 ' -Methylene-bis- (4,6-di-
t-butylphenyl) phosphonate, lithium-2,
2'-ethylidene-bis- (4,6-di-t-butylphenyl) phosphonate, sodium-2,2'-ethylidene-bis- (4-i-propyl-6-t-butylphenyl) phosphate, lithium-2, 2'-methylene-bis- (4-methyl-6-t-butylphenyl) phosphonate, lithium-2,2'-methylene-bis- (4-ethyl-6-t-butylphenyl) phosphonate, calcium-bis- [2 , 2'-thiobis- (4-methyl-6
-T-butylphenyl) phosphonate], calcium-bis- [2,2'-thiobis- (4-ethyl-6-t-
Butylphenyl) phosphonate], calcium-bis- [2,2'-thiobis- (4,6-di-t-butylphenyl) phosphonate], magnesium-bis- [2,2 ']
-Thiobis- (4,6-di-t-butylphenyl) phosphonate], magnesium-bis- [2,2'-thiobis- (4-t-octylphenyl) phosphonate], sodium-2,2'-butylidene- Bis- (4,6-di-methylphenyl) phosphonate, sodium-2,2'-butylidene-bis- (4,6-di-t-butylphenyl) phosphonate, sodium-2,2'-t-octylmethylene-bis -(4,6-di-methylphenyl) phosphonate, sodium-2,2'-t-octylmethylene-bis- (4,6-di-t-butylphenyl) phosphonate, calcium-bis- [2,2'-methylene -Bis-
(4,6-di-t-butylphenyl) phosphonate],
Magnesium-bis- [2,2'-methylene-bis- (4,6
-Di-t-butylphenyl) phosphonate], barium-bis- [2,2'-methylene-bis- (4,6-di-t-
Butylphenyl) phosphonate], sodium-2,
2'-methylenebis- (4-methyl-6-t-butylphenyl) phosphonate, sodium-2,2'-methylene-bis- (4-ethyl-6-t-butylphenyl) phosphonate, sodium (4,4'-dimethyl) −6,6′−
Di-t-butyl-2,2'-bisphenyl) phosphonate, calcium-bis-[(4,4'-dimethyl-6,6'-
Di-t-butyl-2,2'-biphenyl) phosphonate], sodium-2,2'-ethylidene-bis- (4-
s-Butyl-6-t-butylphenyl) phosphonate, sodium-2,2'-methylene-bis- (4,6-di-
Methylphenyl) phosphonate, sodium-2,2 '
-Methylene-bis- (4,6-di-ethylphenyl) phosphonate, potassium-2,2'-ethylidene-bis-
(4,6-di-t-butylphenyl) phosphonate, calcium-bis- [2,2'-ethylidene-bis- (4,6-
Di-t-butylphenyl) phosphonate], magnesium-bis- [2,2'-ethylidene-bis- (4,6-di-
t-butylphenyl) phosphonate], barium-bis- [2,2′-ethylidene-bis- (4,6-di-t-butylphenyl) phosphonate], aluminum-tris- [2,2′-methylene-bis- ( 4,6-di-t-butylphenyl) phosphonate], aluminum-tris-
[2,2'-Ethylidene-bis- (4,6-di-t-butylphenyl) phosphonate] or a mixture of two or more thereof can be exemplified. Particularly preferred is sodium-2,2'-methylene-bis- (4,6-di-t-butylphenyl) phosphonate. The compounding ratio of the compound A is 0.01 to 1 part by weight, preferably 0.05 to 0.5 part by weight, relative to 100 parts by weight of the above 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 effect cannot be expected and it is not practical. It is also uneconomical.

In the composition of the present invention, various additives usually added to the propylene polymer, for example, 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 for metal soaps, etc. Alternatively, neutralizing agents, 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 fibers, etc.) or coupling agents (for example, silane-based, titanate-based, boron-based,
For the purpose of the present invention, the inorganic filler or organic filler (for example, wood flour, pulp, waste paper, synthetic fiber, natural fiber, etc.) surface-treated with a surface treating agent such as aluminate, zircoaluminate, etc. It can be used in combination as long as it does not deteriorate. In particular, when an inorganic filler is used in combination, the rigidity and the heat resistance rigidity are further improved, and therefore it is preferable to use the filler together.

The composition of the present invention is prepared by adding a predetermined amount of the above-mentioned compound A and the above-mentioned various additives usually added to a propylene-based polymer to the ethylene-propylene block copolymer according to the present invention, which is usually mixed with a conventional mixing device. Mix using a Henschel mixer (trade name), super mixer, ribbon blender, Banbury mixer, etc., and melt kneading temperature 170 ℃ -300 ℃ with a normal single screw extruder, twin screw extruder, Brabender or roll. , Preferably at 200 ° C. to 250 ° C. by melt-kneading and pelletizing. The obtained composition is used for producing a desired molded article by various molding methods such as an injection molding method, an extrusion molding method and a blow molding method. Especially when the composition of the present invention is used for the production of a sheet for secondary processing and a blow molded product, the effect of the present invention becomes remarkable, which is preferable.

[Action]

It is generally known that the phosphate compound represented by the compound A in the present invention acts as a nucleating agent to improve rigidity and heat resistance as disclosed in JP-A-58-1736. However, by blending the compound A with an ethylene-propylene block copolymer having a specific molecular weight distribution and a specific isotactic pentad fraction (P) according to the present invention, a conventionally known nucleating agent is blended. From the above, a surprising synergistic effect which cannot be predicted at all is exhibited, and a composition having extremely excellent rigidity and heat resistance is obtained.

〔effect〕

The composition of the present invention is (1) significantly superior in rigidity and heat resistance as compared with the conventionally known composition of ethylene-propylene block copolymer composition containing various nucleating agents. (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.

〔Example〕

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.

I) Secondary workability of sheet (heating vacuum forming property): Using the pellet obtained, a sheet having a width of 60 cm and a thickness of 0.4 mm was prepared by an extrusion forming method, and the heating vacuum forming property of the sheet was evaluated as a model. Cut the sheet into 40 cm x 40 cm,
Fix it tightly in a cm x 40 cm frame and put it in a constant temperature room 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, when it starts to hang down again, it behaves steadily. At this time, (a) measure the amount of sag immediately before the sheet starts to return as the maximum amount of sag (mm).

(B) Measure the amount of deformation (mm) that the sheet drooped to the maximum from the point where it drooped to the original position, and then return the maximum amount of deformation / maximum drooping amount x 100 to the maximum amount of return (%). ).

(C) Measure the time (seconds) for the sheet to hang down 10 mm again from the point where the sheet has returned to the maximum, and use this as the holding time.

The material having good secondary workability (vacuum formability) of the sheet by the above evaluation method means a material having minimum sag, maximum return, and long holding time.

II) Rigidity: width 60 cm, thickness 0.4 m using the obtained pellet
A sheet of m is prepared by an extrusion molding method, a predetermined test piece is prepared using the sheet, and Young's modulus is measured (ASTM D
882) and tensile yield strength measurements (ASTM D 882)
The rigidity was evaluated by carrying out (according to). A material having high rigidity means a material having a large Young's modulus 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 strength were used using the test pieces. Was measured and shown as the average value.

III) Heat resistance rigidity: length of 130mm using the pellet obtained,
A test piece with a width of 13 mm and a thickness of 6.5 mm was prepared by injection molding, and the heat distortion temperature was measured using the test piece (JIS K 720
According to 7, the heat resistance and rigidity were evaluated by applying a load of 4.6 kgf / cm ² ). A material having high heat resistance and rigidity means a material having a high heat distortion temperature.

IV) Impact resistance: width 60 cm, thickness using the pellet obtained
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
The impact resistance was evaluated by carrying out TM D 781). A material having excellent impact resistance means a material having high punching impact strength.

Production Examples 1 to 5 (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 25
Reaction mixture (VI) (diisoamyl ether / DEAC molar ratio 2.4) by mixing at ℃ for 5 minutes and reacting at the same temperature for 5 minutes.
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 (VI) was added dropwise thereto over 3 hours. Warm and react for another hour, cool to room temperature (20 ° C), remove the supernatant, add 30 ml of n-hexane and remove the supernatant by decantation. (II) Obtained 1.9 kg. The total amount of this solid product (II) is n
-While suspended in hexane 30, 1.6 kg of diisoamyl ether and 3.5 kg of titanium tetrachloride at room temperature are used for about 5 minutes at room temperature.
The mixture was added in minutes, and the mixture was reacted at 65 ° C 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, the mixture was stirred for 15 minutes, and allowed to stand to remove the supernatant, which was repeated 5 times. Then, it was 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, diethyl aluminum monochloride 850 g, and the solid product (III) 360
g, 3.8 g of methyl p-toluate were charged, and then propylene gas was supplied at 180 g / H for 2 hours while maintaining stirring at 30 ° C. for pretreatment.

(3) Polymerization method A polymerization slurry of n-hexane 26 / H in the polymerization vessel 1 and pretreated catalyst slurry was 240 ml / H in Production Example 1 and 240 in Production Example 2.
ml / H, Production Example 3 is 120 ml / H, Production Example 4 is 240 ml / H
And 240 g / H as Preparation Example 5 and 1 g per 1 g of the solid product (III) in the catalyst slurry with methyl p-toluate.
Was continuously supplied. The temperature of the polymerization vessel 1 is 70 ° C. in Production Examples 1 to 5, the temperature of the polymerization vessel 2 is 70 ° C. in Production Example 1, 60 ° C. in Production Example 2 and Production Examples 3 to 5
Is 70 ° C., the temperature of the polymerization vessel 3 is 70 ° C. in Production Example 1, 50 ° C. in Production Example 2 and 70 ° C. in Production Examples 3 to 5, and the pressure of the polymerization vessel 1 is 6 kg / cm ² G in Production Example 1. 4 kg / cm ² G as Production Example 2 and 6 kg / cm ² G as Production Examples 3 to 5,
The pressure of the polymerization vessel 2 was 8 kg / cm ² G in each of Production Examples 1 to 5, and the polymerization vessel 3 was used.
Pressure of 10kg / cm ² G for Production Example 1 and 12k for Production Example 2
Propylene was supplied to each polymerization vessel so as to be g / cm ² G and 10 kg / cm ² G in Production Examples 3 to 5, respectively. When the hydrogen concentrations in the gas phase parts of the polymerization vessels 1 to 3 of Production Examples 1, 4 and 5 were supplied so that only the polymerization vessel 1 had a hydrogen concentration of 5.9 mol%, the polymerization reactors 2 and 3 had 0.65 mol% and 0.069 mol% respectively. Atsuta When the hydrogen concentrations in the gas phase portions of Polymerization Units 1 to 3 of Production Example 2 were supplied so that only Polymerization Unit 1 had a hydrogen concentration of 14.5 mol%, Polymerization Units 2 and 3 had 1.0 mol% and 0.10 mol%, respectively.
Further, when the hydrogen concentrations in the gas phase portions of the polymerization vessels 1 to 3 of Production Example 3 were supplied so that only the polymerization vessel 1 had a concentration of 2.1 mol%, the polymerization vessels 2 and 3 had 0.41 mol% and 0.046 mol% respectively.
The analysis values of the polymerization ratio and melt flow rate of each polymerization vessel are as shown in Table 1. The polymerization vessel 1
The liquid level of ~ 3 was withdrawn by a control valve so that it became 80%.

Then, the slurry containing the polymer particles extracted from the polymerization vessel 3 was degassed in a pressure drop tank at 60 ° C. and 0.5 kg / cm ² G and transferred to the polymerization vessel 4 by a pump. The hydrogen concentration in the gas phase of the polymerizer 4
10 mol%, a temperature of 60 ° C., ethylene was supplied at 600 g / H, and the gas phase gas composition was ethylene / (ethylene + propylene) = 0.40 in Production Examples 1 to 3, ethylene / (ethylene + propylene) in Production Example 4. Polymerization reaction was continued by supplying propylene and hydrogen so as to be 0.07, and as Production Example 5, only hydrogen was supplied so that ethylene / (ethylene + propylene) = 1.00. The slurry exiting the polymerization vessel 4 is passed through a degassing tank, further deactivated the catalyst with methanol, and then neutralized with a 20 wt% sodium hydroxide aqueous solution.
Approximately white copolymer powder is obtained through each process of washing with water, separation, and drying.
It was obtained at 6.5 kg / H. The results of analysis of the copolymer are shown in Table 1.

In Table 1, the first step, the second step, the third step and the polymerization step (II) of the polymerization step (I) are the polymerization vessel 1, the polymerization vessel 2, the polymerization vessel 3 and the polymerization vessel described above, respectively. Bowl 4
Corresponds to the polymerization in. All of the polymerization vessels 1 to 4 had an inner volume of 150.

The results are shown in Table 1.

Production Example 6 The same procedure as in Production Example 1 was repeated except that methyl p-toluate was not used. The results are shown in Table 1.

Examples 1-3, Comparative Examples 1-6 Melt flow rates (MFR), isotactic pentad fractions (P) and ethylene contents 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
Sodium-2,2'-methylene-bis-as compound A
Predetermined amounts of (4,6-di-t-butylphenyl) phosphate and other additives were placed in a Hensell mixer (trade name) at the compounding ratios shown in Table 2 below, and the mixture was stirred and mixed for 3 minutes, and then the diameter was adjusted. A 40 mm single screw extruder was melt-kneaded at 200 ° C. to form a pellet. Also, powdery crystalline ethylene having each melt flow rate, each isotactic pentad fraction (P) and ethylene content produced in Production Examples 1 to 3 shown in Table 2 below as Comparative Examples 1 to 6 Examples 1 to 3 were prepared by adding 100 parts by weight of a propylene block copolymer to each of predetermined amounts of the additives shown in Table 2 below.
A melt-kneading process was carried out in accordance with to obtain pellets.

A sheet used for secondary workability, rigidity and impact resistance test of the sheet was prepared by extrusion molding the obtained pellet at a resin temperature of 250 ° C. In addition, the test piece used for the heat resistance rigidity test was performed by using the pellet obtained at a resin temperature of 250 ° C and a mold temperature of 50 ° C.
Was prepared by injection molding.

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 7 to 12 Melt flow rates (MFR) produced in Production Examples 1 to 3 shown in Table 3 below, respective isotactic pentad fractions (P) and ethylene contents. To 100 parts by weight of a powdery crystalline ethylene-propylene block copolymer having
Sodium-2,2'-methylene-bis-as compound A
(4,6-di-t-butylphenyl) phosphate, fine particles of talc having an average particle size of 2 to 3 μm as an inorganic filler, and other additives in predetermined amounts respectively in a blending ratio shown in Table 3 below. (Product name), and the mixture was 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 a pellet. Further, powdery crystalline ethylene having each melt flow rate, each isotactic pentad fraction (P) and ethylene content produced in Production Examples 1 to 3 shown in Table 3 below as Comparative Examples 7 to 12. A predetermined amount of each of the additives shown in Table 3 below was added to 100 parts by weight of the propylene block copolymer, and melt-kneaded according to Examples 4 to 6 to obtain pellets.

A sheet used for secondary workability, rigidity and impact resistance test of the sheet was prepared by extrusion molding the obtained pellet at a resin temperature of 250 ° C. In addition, the test piece used for the heat resistance rigidity test was performed by using the pellet obtained at a resin temperature of 250 ° C and a mold temperature of 50 ° C.
Was prepared by injection molding.

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.

Examples 7 to 8 and Comparative Examples 13 to 14 Each melt flow rate (MFR), each isotactic pentad fraction (P) and ethylene content produced in Production Examples 4 to 5 shown in Table 4 below. To 100 parts by weight of a powdery crystalline ethylene-propylene block copolymer having
Sodium-2,2'-methylene-bis-as compound A
Predetermined amounts of (4,6-di-t-butylphenyl) phosphate and other additives were placed in a Henschel mixer (trade name) at the compounding ratios shown in Table 4 below, and mixed by stirring for 3 minutes. Then, the mixture was melt-kneaded at 200 ° C. with a single screw extruder having a diameter of 40 mm to form pellets. Also, as Comparative Examples 13 to 14, a powdery crystalline ethylene-propylene block copolymer 100 having a melt flow rate, an isotactic pentad fraction and an ethylene content produced in Production Example 6 shown in Table 4 below. Predetermined amounts of the additives shown in Table 4 below were mixed in parts by weight, and melt kneading was performed according to Examples 7 to 8 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 ° C.
Was prepared by injection molding.

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 4.

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

Compound A; sodium-2,2'-methylene-bis- (4,6-
Di-t-butylphenyl) phosphate [manufactured by Adeka Argus Chemical Co., Ltd .; MARK NA-11] Nucleating agent 1; p-t-butylaluminum benzoate nucleating agent 2; 1,3,2,4-dibenzylidene Sorbitol Nucleating agent 3; Sodium-bis- (4-t-butylphenyl) phosphonate Phenoic antioxidant 1; 2,6-di-t-butyl-p-
Cresol phenolic antioxidant 2; tetrakis [methylene-3-
(3 ', 5'-di-t-butyl-4'-hydroxyphenyl) propionate] methane phosphorus 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 to 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 blending the compound A with a crystalline ethylene-propylene block copolymer having a molecular weight distribution and isotactic pentad fraction within the scope of the present invention. Yes, Examples 1-3 and Comparative Examples 1-3
Compared with (a crystalline ethylene-propylene block copolymer having a molecular weight distribution and isotactic pentad fraction within the scope of the present invention, which does not use an organic nucleating agent), 3 and Comparative Examples 1 to 3 have the same secondary workability of the sheet, but Comparative Examples 1 to 1
No. 3 is still insufficient in the effect of improving rigidity and heat resistance rigidity. Further, crystalline ethylene-having a molecular weight distribution and isotactic pentad fraction within the scope of the present invention in order to improve the rigidity and heat resistance of Comparative Examples 1-3.
Comparative Examples 4 to 6 and Examples 1 to 3 using an organic nucleating agent composed of a compound other than Compound A in the propylene block copolymer.
In comparison with Comparative Examples 4 to 6, although the effect of improving rigidity and heat resistance is considerably recognized, it is still not sufficient, and Examples 1 to 3 are remarkably excellent in rigidity and heat resistance,
It can be seen that a remarkable synergistic effect is observed by using the compound A. That is, the rigidity and the heat resistance obtained in the present invention are the values when the compound A is used in the crystalline ethylene-propylene block copolymer having the isotactic pentad fraction within the range limited in the present invention. It can be said that this is a unique effect. In addition, in Examples 1 to 3 which are compositions of the present invention, the use of the compound A did not cause a decrease in impact resistance although the rigidity was improved, and Comparative Examples 1 to 6 It was confirmed that the impact resistance was no better than that of the other.

Table 3 shows the propylene-based polymer used in Table 2,
Furthermore, it is a combination of talc as an inorganic filler,
Regarding this, the same effect as described above was confirmed.

The examples and comparative examples shown in Table 4 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 4, Examples 7-8 are compounded with Compound A in a crystalline ethylene-propylene block copolymer having a molecular weight distribution and isotactic pentad fraction within the scope of the present invention. Examples 7 to 8 and Comparative Example 13 (with a crystalline ethylene-propylene block copolymer having a molecular weight distribution within the scope of the present invention and an isotactic pentad fraction outside the scope of the present invention, organic Compared with those in which a nucleating agent is not added), the secondary workability of the sheets is similar in Examples 7 to 8 and Comparative Example 13, but the rigidity and heat resistance of Comparative Example 13 are significantly inferior. I understand. Comparing Comparative Example 14 in which the compound A was added to the composition of Comparative Example 13 and Examples 7 to 8, both sheets had similar secondary workability, but the effect of improving the rigidity and heat resistance rigidity of Comparative Example 14 was high. Is considerably higher than that of Comparative Example 13, but still not sufficient, and it is understood that Examples 7 to 8 are remarkably excellent in rigidity and heat resistance rigidity. In addition, when the compound A is blended in Examples 7 to 8 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 13 to 14. It was confirmed that there was no difference.

Therefore, 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, which is related to the application of the same applicant as the present application. It was confirmed that the composition of the present invention was significantly superior to the composition obtained by blending the nucleating agent with the copolymer in terms of the secondary processability of the sheet and the rigidity and heat resistance. Was done.

Claims (6)

[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 at each stage of the polymerization step (I) is the melt flow rate. Rate (MFR; load at 230 ℃ 2.1
The following formula (1) is used as the value of the molten resin discharge amount for 10 minutes when 6 kg is added. (However, MFRn; MFR of the polymer produced in the nth stage; MFRn + 1; MFR of the polymer produced in the n + 1th stage) are satisfied, and the polymer (A) produced in the polymerization step (I) is satisfied. The relationship between the isotactic pentad fraction (P) and the melt flow rate (MFR) 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 mixed with 100 parts by weight of a crystalline ethylene-propylene block copolymer of FR + 0.955. A highly rigid and highly melt viscoelastic ethylene-propylene block copolymer composition. (However, in the formula, R ₁ is absent, sulfur or an alkylidene group having 1 to 4 carbon atoms, R ₂ and R ₃ are each hydrogen or an alkyl group having 1 to 8 carbon atoms which is the same or different, and M is a monovalent group. A trivalent metal atom, and n represents an integer of 1 to 3.) 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 ₁ is a methylene group,
The high-rigidity and high-melting viscoelasticity ethylene-propylene block according to any one of claims (1) and (2), wherein the alkyl group represented by R ₂ and R ₃ is a t-butyl group. Copolymer composition. 4. A compound A comprising sodium-2,2'-methylene-bis- (4,6-di-t-butylphenyl) phosphate as a compound, and the compound is contained in the compound (1) or (2). The high-rigidity, high-melting viscoelasticity ethylene-propylene block copolymer composition according to any one of items. 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. object. 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. High rigidity and high rigidity according to claim (5), wherein one or more selected from barium, calcium silicate, glass fiber, carbon fiber, carbon black, potassium titanate and metal fiber is used. Melt viscoelastic ethylene-propylene block copolymer composition.