JPS5871910A - Olefinic block copolymer - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

Detailed Description of the Invention [1') Background Technical Field of the Invention The present invention relates to a soft thermoplastic olefin block copolymer with excellent heat resistance, impact resistance, surface tackiness, and scratch resistance. Regarding merging.

In recent years, heat resistance (
tp! j, shape retention against external forces at high temperatures)
In addition, impact resistance, especially electrical resistance at similar temperatures, is becoming increasingly important for soft thermoplastic Tlj. Soft materials include voricarbonated vinyl containing plasticizer,
There are ethylene-vinyl acetate copolymers, ethylene-(X-olefin copolymers (medium to low-density polyethylene), etc., but although these are deceptive in their impact resistance at low temperatures,
Inferior in heat deformation resistance. Random copolymers of zolopyrene and other olefins are generally less resistant to heat deformation than those materials, but their flexibility is unmatched and their impact resistance at room temperature is poor. It is weak against impact at low temperatures. Therefore, materials that simultaneously satisfy these properties are, for example, polypropylene and ethylene.
Propylene rubber etc'f J4 is made by mechanical blending. However, the cost associated with the BlenP process makes it a less appealing material. In addition, as described later, the present inventors proposed a new flexible polyolefin system based on a block co-di-coupling method, but achieved extremely excellent heat resistance, flexibility, and impact resistance of 1%. Although it was a material that had been improved, there was still room for improvement in terms of surface properties such as surface viscosity and scratch resistance.

In addition, in the section -G and in the present invention (details will be described later), the soft material refers to Olzen bending stiffness (+(1'
M) to 5,000kg/CIn2 or less, narrower +n
4,000k? A: less than m2, 3
, 500 kg/btr+2 or less. There is no particular restriction on the lower limit, but when considerations other than flexibility (particularly heat resistance) are taken into consideration, it is difficult to set the lower limit below 5001X9A71L2.

PRIOR ART Many attempts have been made to improve the impact resistance using propylene polymers. (fl Haruba, Random copolymer of propylene and ethylene (Special Publication No. 42-22052
No. 46-42988, etc.), and block copolymers (Japanese Patent Publication No. 38-14834, No. 38-21)
No. 494, No. 39-1836, No. 42-22688, U.S. Patent No. 3,624,1.84, British Patent No. 889°230, No. 957, No. 777, No. 1"
, 134. ．． No. 660, A411, etc.), Random-Jl-polymer of propylene and butene-1 (U.S. Pat.
, No. 918, 457, No. 3, 278.

504, 3,332,921, JP-A-50-38787, JP-A-53-79984, etc.), random copolymers of propylene and hexene-1 (
JP-A No. 49-53'983, etc.), propylene and 4
-Random copolymer with methyl ester-1 (JP-A-5
3-104686, etc.) are representative. The prior art of Jl et al. has been successful in producing a propylene-based polymer Jeonju point that has improved the impact resistance to some extent, but all of them are hard or semi-hard materials, or even if they are soft, they cannot be used at low temperatures. The impact resistance was not sufficiently improved, the heat resistance was poor, and the various requirements aimed at by the present invention were not all satisfied.

Additionally, the present inventors had previously proposed a block copolymer consisting of propylene and a C5-12 linear α-olefin as a propylene-based soft thermoplastic resin material with excellent heat resistance and transparency. (Refer to Japanese Patent Publication No. 1982-68532), although it was confirmed that this product had a considerable improvement effect in terms of impact resistance, it still could not fully meet the demand for high vinegar 1 impact resistance. According to another proposal by the present inventors (see JP-A-56-43314 and JP-A-56-4.3315), a random copolymer of propylene and a C5-12 linear α-olefin block (crystalline and soft heat-resistant 8 required purple) and ethylene homopolymer block, binary random copolymer block of ethylene and C5-12 linear α-olefin,
Or a ternary random copolymer block consisting of ethylene, C5-12 linear α-olefin, and propylene (
A block copolymer consisting of both resistant elements) is
It is a unique material with excellent heat resistance and impact resistance, but it also has improved surface properties (surface tackiness, J, scratch resistance).

(n) Summary of the Invention Contrary to the above findings, one of the blocks (A) or A block copolymer containing a binary or tertiary random copolymer of ethylene (and propylene) and a C5-12 linear α-olefin is a copolymer? The present inventors have discovered that by selecting one-piece collation properties, Hamura can be made with an ambiguous balance of heat resistance, corrosion resistance (particularly impact resistance at low temperatures), surface properties, and flexibility. was discovered by. In other words, such a copolymer exhibits a low temperature of −′ at room temperature or higher.
; Not only does it have impact resistance sufficient to withstand use at low temperatures of A1°C and even below -40°C, and has high heat resistance above 120°C, especially above 130°C, but also has extremely low surface tackiness. It was found that it has excellent surface properties such as being resistant to scratches.

Therefore, the olefinic block copolymer according to the present invention is determined by the following (1) and (2);
2. This is a special mission.

(1) MFR (ASTM-D-1238(L)) is o, 01-2o.

(g/Io minutes).

(2) Selected from a propylene homopolymer block and a binary random copolymer block of propylene and ethylene or zotene-1, and having a propylene content of 1
At least one of the blocks fA) that is
y part, a binary or ternary copolymer of ethylene, a C4-12 α-olefin, and optionally propylene, and has an ethylene content of 30 ffi! % Koshime>+5@
At least one of the blocks (B) below the seam is 50~
Contains 10 parts.

The block copolymers according to the invention are comprised of flocs (A) selected from homopolymer blocks of propylene and binary random copolymers of propylene and ethylene or butene-1 and having a propylene content of 60 gw. Joroku Z35 is a binary or ternary copolymer of one or more ethylene, C4~, 2 α-olefins, and optionally propylene, with an ethylene content of 3 ()
Contains one or two of the following blocks (B).

The block copolymer according to the present invention does not contain one block each of (A) and (B), but
There are cases where either one or both of them are printed 11M times.

Furthermore, there are no restrictions on how each block is arranged.

Block (refers to a portion formed by polymerization of Al and zolopylene alone or under conditions where propylene and ethylene or zothene-1 are present in the same group. Block (R) is a portion formed by polymerization of ethylene and C5-12 (A) and (B) may be formed first. (A) and (B) may be formed first. or) (B) If the block contains several collars,
The individual (A) blocks or B) blocks do not necessarily have to have the same composition or molecular composition. However, usually one block each of fA) and CB) is (A) - (
B).

Such a block copolymer is one in which a random copolymer block with the same composition and a random copolymer block with a different composition coexist in one polymer molecular chain. It may be either a mixture or a mixture of these.

The block copolymer of the present invention comprises one or more blocks, preferably 50 to 90 parts by weight, preferably 50 to 90 parts by weight, preferably 70 parts by weight, and one or two or more blocks (B)'k 50 to 10 parts by weight, preferably 50 to 202 parts, more preferably 50 to 30 parts by weight
Heavy spirit department sinks. Block (A) is a part that has the characteristics of thermoplastic #4 resin with crystals, and block (B) is a part that has rubber-like properties of amorphous or low crystallinity.
If the content of A) is below the above range, heat resistance and adhesion properties will not be exhibited. If the content of opposite Vc (A) exceeds the above range, flexibility and impact resistance will be insufficient.

Block (A) is a homopolymer of propylene or a random copolymer of propylene and ethylene or butene-1 (ethylene is more preferred), but the block is a copolymer with ethylene. The content of propylene in (A) is (at least 30% by weight, preferably 1 to 10% by weight of ethylene, preferably 3 to 8.5 weights, more preferably 4 to 7 weights) The content of butene-1 in the case of a copolymer with butene-1 is 5
~30 vehicle volume, preferably 10 to 25 vehicle volume, more preferably 15 to 25 vehicle volume, or more. Block fA
) must be a component of a crystalline thermoplastic monopolymer, so unless the ethylene or butene content exceeds the above range and the crystallinity is not too low, it should be a propylene homopolymer. It may be a random copolymer of propylene and ethylene or butene-1, but if the flexibility of the final copolymer is desired, the lower limit of the master key of ethylene or butene-1 is It must be as described above. In other words, the above range 1? The flexibility of the underlying block (A) is lost and it is necessary to increase the time of the block (B) (human factors) to maintain the flexibility of the final block copolymer at a predetermined level. This results in deterioration of the heat resistance and surface properties of the block copolymer, which is contrary to the purpose of the present invention.

Block (B) is a binary or ternary random comonomer of ethylene (and propylene) and C4-12 α-olefin, but in any case, block (
The ethylene content in block B) is more than 30 f% and less than 5%, preferably 35 to 75N, preferably 40 to 10%.Block (B) is Since it is necessary to have elastomeric properties of poor quality or extremely low crystallinity, if the ethylene content exceeds the above range, the crystallinity will become too high, which is undesirable.On the contrary, if the ethylene content falls below the above range, The following problems arise depending on the type of α-olefin used in combination as a comonomer.Although the comonomer or butene-1,4-methylpentene-1 itself can form a crystalline polymer, In some cases, if the ethylene content falls below the above range, the crystallinity of block (B) becomes too high.

In addition, if the comonomer is one such as hexene-1, which itself forms a liquid phase at room temperature, block (B
) becomes too low. For the same reason, the ethylene content in the final copolymer is 3 to 47.5%,
Preferably, the length is 7 to 40 M [longitudinal stripes, preferably more than 15 to 38 threads].

Specific examples of C4-12 α-olefins used as comonomers include butene-1, pentene-1, hexene-1, heptene-1, octene-1, nonene-1,
Straight chain α-olefins such as decene-1, undecene-1 and dodecene-1, and 3-methylbutene-1,3
-Methylpentene-1,3-ethylpentene-1,3-
Methylhexene-1,4-methylpentene-1,4,4
-dimethylpentene-1,4-methylhexene-1,5
-Methylhexene-1,5,5-,)methylhexene-
1,3,5-dimethylhexene-1,3゜5.5-)
Branched α-olefins such as dimethylhexene-1 are applicable. Among these α-olefins, 1-butene and 1-hexene are preferred. Particularly preferred is butene-1.

The comonomer constituting block (B) is usually selected from the C4 to C12 α-olefins mentioned above, but if necessary, some of these α-olefins may be replaced with propylene for the purpose of reducing costs. It is possible.

As the comonomer to be combined with ethylene in block (B), C4-15 α-olefin is preferable to propylene because it maintains a better balance between strength and flexibility, but it is also preferable to use C4-15 α-olefin in view of maintaining a better balance between strength and flexibility. When considering various lances, a portion of the α-olefins of 04 to 12, usually about half an age on a heavy weight basis, can be replaced with propylene.

2) Molecular weight The molecular weight of the block copolymerization method is MFR (ASTM-D-
1238(L)) is 0.01~200(g/10
It is necessary to enter a range equivalent to over minutes. If the molecular weight exceeds the above range, the molecular weight will be too low and the mechanical strength of the comonomer will not reach a practical level, or molding itself will become impossible.

If the MFR falls below the above range, the molecular weight will be too high and the viscoelastic properties in the melted state will deteriorate, making it impossible to mold.

3) Fractionation of copolymer The copolymer of the present invention contains a block (A) and a block (B), and the block (A) is composed of a crystalline polymer,
The blocks (B) each consist of a rubbery monomer, but in reality, as described above, and as a manifestation of the polymolecular nature that the polymer compound inherently has, it is a mixture.

Therefore, the block copolymer of the present invention can also be defined as having a specific thermal medium fractionation noq-turn.

(1) Solvent fractionation Solvent fractionation is carried out using cold xylene as follows. That is, 300 ml of p-xylene and approximately 0.0
7g of polymer (Ag) and fK: heated at the boiling point of p-xylene for 15 minutes (using oil/water bath) to make it easy to understand, let it cool down naturally while immersed in an oil path, and then leave it in a groove for a while. to precipitate 2-limer.

The precipitated polymer is suction filtered using a furnace cloth to obtain a solid polymer (dry@Bg) and a solution (Cg after concentration and drying).

Cold xylene available (uncorrected) and the same year (uncorrected)
are fixed as cxs' and CXl5', respectively, as follows.

cxs'=danX 100 (, tJX, #q6)CXl
5' = ÷
5 are each ionized as follows.

(2) Analysis of fractionation results The cold xylene soluble fraction (CXS) is mainly a rubbery polymer (block CB) produced in the second stage polymerization (details will be described later). In CXS, generally no decomposition peak is observed by DSC (differential scanning calorimetry). CXS means 10 inches or more, preferably 15 inches or more, and more preferably 20 inches or more.

On the other hand, the cold xylene insoluble matter (CXIS) is a crystalline polymer (block (A)) mainly produced in the first stage polymerization (details in aJ later). CXl8 generally has one or more resolution peaks of 11M measured by DSC, and the temperature of the highest peak among them is at least 120°C,
Preferably at least 130°C, more preferably at least 140°C.

The content of CXl5 is 4Xl or less, preferably 85% or less, more preferably ff11% or less.

2. Manufacture of block copolymer 1) Ammonium sulfur The block copolymer of the present invention is produced by (a) a homopolymer block of propylene or a binary block of propylene and ethylene or butene-1 in the presence of a stereoregular polymerization catalyst. 50 to 90 parts by weight, preferably 50 parts by weight of the original random copolymer block
~) D) A step of producing a polymeric part, more preferably a polymeric part, and middle) a binary or tertiary random copolymer of ethylene (and propylene) and a C4-12 α-olefin. Seki~lO heavy liquid part, preferably shi)~20
It can be manufactured by combining with the step of producing a superimposed part, more preferably a superposition part.

Although steps (a) and (b) may be carried out first, they are usually carried out in the order of (a) to (b). (stomach)
, Although other polymerization steps (for example, zoropyrene homopolymerization step) may be included before, during, or after (b), the amount of polymer produced therein will be the same as that produced in each step of (a) and (b). It needs to be in a small proportion compared to the amount of polymer. especially,(
When producing a binary random copolymer block of propylene and ethylene or butene-1 in step (a), step (a)
After producing a propylene homopolymerized portion of about 30 M parts or less prior to the step, by carrying out steps (a) and (b), the heat resistance and red softness of the final copolymer can be further improved. I can do it.

2) Catalyst Suitable stereoregular polymerization catalysts for use in the present invention are, for example, those mainly containing a titanium component and an organoaluminum compound. Titanium components include α, β, r
Alternatively, a titanium compound supported on a field body such as δ-type titanium trichloride or magnesium chloride may be used. Among titanium trichlorides, titanium trichloride is particularly obtained by replacing titanium tetrachloride with organic aluminum (the main component is thought to be a eutectic composite of titanium trichloride and aluminum chloride).
Therefore, when titanium trichloride obtained by extracting and removing aluminum chloride using a complexing agent and activated by an appropriate method is used as the titanium component of the catalyst, compared to when using other titanium trichlorides. Block (B) can be made more Zam-like.

If you want to obtain a high catalyst yield of block copolymer,
It is preferable to use titanium trichloride or titanium tetrachloride supported on magnesium chloride or the like.

The organoaluminum compound has the general formula AIRaY3
It is preferable to use a compound represented by -a.

a is O (any number of a≦3, Y is a halogen atom, R is 0
It has about 1 to 18 hydrocarbon residues, preferably an alkyl group or an aryl group. Specifically, triethylaluminum and diethylaluminum chloride are preferred.

The catalyst consisting of this combination of two essential components may also be combined with a small amount of an electron donor as a third component. As the electron donor, organic beak esters, ethers, amines, alcohols, ketones, aldehydes, phenols, etc. are used.

3) Polymerization condition 1 can be carried out by either a continuous method or a patch method. When carried out in a continuous manner, one or more polymerization tanks are used for each of the steps (a) and (b), and each tank is allowed to carry out the reaction under steady conditions. In the Nototsuchi method, the next step is carried out after a predetermined amount of monomer in each step has completed the entire or scheduled reaction, but once the predetermined amount of monomer has reacted, part or all of the unreacted monomer is removed from the tank. After taking it outside, the next process will be carried out.

The method of the present invention is usually carried out at a polymerization temperature of 0 to 200 DEG C., a polymerization pressure of 0 to 100 ky/c, i2 (gauge J)E). A slight self-pressure (gauge ff') is allowed. Hydrogen can be used to control the molecular weight of the co-conjugate. It is also permissible to vary the degree of hydrogen conductivity between each step to cause a difference in the molecular weight of the co-TJ+7 combined blocks produced therein.

Usually, the polymerization is carried out in an inert hydrocarbon such as n-hebutane or n-hexane by the turbid polymerization method (6) or by the bath liquid polymerization method.

3. Experimental Examples In the following Examples and Yield Examples, unless otherwise specified, the test methods used to evaluate each product are as follows.

(11MFR (230℃, 2.16 kq)
Cg /lo minutes] ASTM-D-1238 (L) (2) Olsen bending stiffness 1st grade (10° angle) (yu/
2] ASTM-D-747 (Sample: Pressed sheet with thickness 21i1111) (3) Tensile strength [kg/1121JIS-6301 Test ring 8: No. 3 type (Sample: Injection molded sheet with 2111+li) ( 4)
Tensile elongation [related] JIS-ni-6
301 Trial piece: Type 3 (5) Deformation rate under heat and pressure [H] A sample (1-IFIX IC
A press sheet (1n x 2inn thick) was attached, and after 1 hour of 1 ft was removed at a temperature of 130° C. and a load of 3-2, the load was removed and the deformation rate of the wall thickness was obtained after 10 minutes.

(6) Surface adhesion Two strip-shaped specimens of Mo2 and 26 inches in width are cut out from a silk press sheet with a thickness of 1. Sandwich a piece of kraft paper with a thickness of 70 g/m2, and then sandwich the kraft paper and a glass plate from the outside of this double-sided test piece, and add 50 g// from both sides of the glass plate.
Pressure treatment is performed at 23° C. for 24 hours while applying a pressure of □2.

Then, the pressure is released and the glass plate and kraft paper are removed. The two primary test pieces are obtained in a state where they are glued together due to surface tackiness, except for the part where the original kraft paper was sandwiched (secondary test piece).

Holding the non-bonded end of the secondary test piece, the bonded portion was slowly φ1114 across a width of 1 (:m), and then the non-bonded end was placed in the chuck of a shock-and-thread type tensile testing machine.

The testing machine was operated at a tensile speed of 200 tu+ for 7 minutes to perform T-shaped peeling across the secondary test piece Kanayama 5-, read the maximum load (g/2 (:m width)) during peeling, and then peel the test piece. Strong opposition.

- Measure the peel strength at 6 points on the sample and find the arithmetic mean value.

(7) Scratch resistance Layer 500 g of "bleached kraft paper" whose surface is not sized on a press sheet with a thickness of 1-IIIll.
An iron block of 1 is placed as load 1, and the kraft paper is rubbed against the press sheet at a speed of 500 + 1117 minutes, and the degree of scratches is judged by 21%.

The evaluation will be displayed as follows.

Towards = almost no scratches.

O = Slight scratches.

Δ - Some scratches are observed.

× = Scratches are noticeable.

Example 1 10 liter stainless steel with horizontal stirring
After the inside of the reactor was sufficiently replaced with propylene gas, 3.5 liters of heptane was added as a polymerization solvent. Maintain the temperature inside the vessel at a high temperature and use diethylaluminum chloride (DEAC) as a catalyst.2. Og and titanium trichloride (1'-Tl-15J manufactured by Marubeni Tsurupei Chemical Co., Ltd.) 0.40 g
assisted. Next, propylene and hydrogen are each added to 36
Supply was started at a rate of 0 g/hour and 3.9 liters (STP replacement culm) at a rate of 7:00, and at the same time, the temperature of hot water in the vessel was rapidly raised to 05°C. When the total amount of propylene supplied reached 390 gK, both supplies were completely stopped and the pressure inside the vessel decreased to 2.0 kp/
The progylene remaining in the vessel was allowed to react until the pressure decreased to ci2 (gauge pressure).

Here, the unreacted gas in the vessel was released until the pressure in the vessel reached 0.4 kg/Bo2 (gauge pressure) (Block A
(prosolene independent Togo)). However, in the following experimental examples, the pressure inside the vessel was 2 kg at the end of monomer supply, and As
(gauge pressure), at that point the pressure in the chamber immediately increases to 0.4 kg/? ``Unreacted gas was released until the pressure reached 2 (gauge pressure).

Next, the temperature inside the vessel was set at 55°C, and 40 g/hour and 80 g of ethylene, zoropyrene, and butene-1 were added respectively.
/hour and Ii4 g was fed over a period of 3 hours and 15 minutes at a rate of 7 hours. During this time, the temperature inside the reactor was maintained at 55° C. and hydrogen was not supplied (mP (ethylene/propylene/butene-1 copolymerization) of block B above).

The obtained block co-11 aggregate was purified with alcohol to obtain a dry product.

Table 1 shows the proportion, composition, and physical properties of each block of the obtained copolymer. However, since it is difficult to calculate the production ratio and composition of each block from this experiment alone, we separately carried out the actual reaction up to the mid-polymerization stage under the same conditions as in this example, and then immediately decomposed the catalyst and performed the same procedure as in this example. It was indirectly calculated by measuring the mold needle and composition of the polymer obtained by purification and drying under the specified conditions, and assuming that these also apply to each polymerization step in this example.

Further, the composition was determined by carbon-13 NMH.

Example 2 Same as Example 1 except that the supply rates of ethylene, propylene and butene-1 during block B production were all g/hr, 36 g/hr and 192 g/hr, respectively, and the feeding time was 3 hours. A block copolymer was produced under the following conditions.

The results are shown in Table 1.

Example 3 Without supplying propylene during the production of block B, the supply rate of ethylene and butene-1 was increased to +x+ g, respectively.
A block copolymer was produced under the same conditions as in Example 1, except that the feed rate was 7 hours and 384 g/hour, and the feeding time was 3 hours.

The results are shown in Table 1.

Example 4 The polymerization temperature during the production of block A was set at 55°C, and not only propylene but also ethylene was supplied at the same time, and the feeding rate of the latter was
elRg/hour, and the supply times of ethylene, propylene, and butene-1 during block Bg production were 50 g/hour, 50 g/hour, and 120 g/hour, respectively.
A block copolymer was produced under the same conditions as in Example 1 except that the supply time was 3 hours.

The results are shown in Table 1.

Example 5 Without feeding propylene during block B production, the feeding rates of ethylene and butene-1 were
A block copolymer was produced under the same conditions as in Example 4 except that the amount was 384 g/hour.

The results are shown in Table 1.

Example 6 During the production of Block A, the supply of ethylene was started 15 minutes after the start of supply of propylene, and the supply rate of ethylene was 22 g.
A block copolymer was produced under the same conditions as in Example 5, except that the heating time was set to /min.

The results are shown in Table 1.

Example 7 t? of 1 combined solvent (hezothane)? 2.6 liters, the W mixing temperature during crushing of block B was 65°C, hexene-1 was supplied instead of butene-1, and the supply rates of ethylene and hexene-1 were 70 g/hour and 680 g/hour, respectively.
The block copolymer was produced under the same conditions as in Example 4, except that the time was 7 o'clock, the supply of hexene-1 was stopped after 1 hour, and the supply of ethylene was continued for 1 hour and 45 minutes. Manufactured.

The results are shown in Table 1.

Example 8 The temperature during block A-iJ production was 55°C, and not only propylene but also ethylene was supplied. However, ethylene was started 15 minutes after the start of propylene supply, and the supply rate was 2.
2 g/min, and when producing block B, ethylene, propylene, and hexene-1 were supplied as monomers, and their feeding rates were 50 g/hr and 50 g/hr, respectively.
A block copolymer was produced under the same conditions as in Example 7, except that the supply of uchihexene-1 was stopped at 1 hour and the other supplies were continued for an additional 1 hour and 45 minutes.

The results are shown in Table 1.

Comparative Example 1 Total propylene supply time during block A production: 2 hours 15
The conditions were the same as in Example 3, except that the hydrogen supply rate was 1.2 liters (STP equivalent) and 7 hours, and the monomer supply time during block B production was 0.75 hours. A block copolymer was produced.

The results are shown in Table 1.

Example 2 Hydrogen was supplied during the production of Block B, and the supply rate of ethylene, butene-1 and hydrogen was 75g each.
/hour, 15g/hour and 0.61Jttle (STP m
tt) A block copolymer was produced under the same conditions as in Example 3 except that the time was 7 o'clock.

The results are shown in Table 1.

Comparative Example 3 A block copolymer was produced under the same conditions as in Example 3, except that the supply rate of ethylene and butene-1 during block Be production was f 15 g 7 hours and 450 g/hour.

The results are shown in Table 1.

Comparative Example 4 Adding propylene supply time during block A production, hydrogen supply rate 'ii 5.0 liters (STP, +1
Example 8 except that the time was set at 7:00 p.m.) and the monomer supply time during block B production was set at 5.0 hours.
A block copolymer was produced under the same conditions.

The results are shown in Table 1.

Claims (1)

[Scope of Claims] An olefin block copolymer characterized by the following (1) and (2). (1) MFR (ASTM-D-1238(L))
is 0.01~2o. (g/l, 0 minutes). (2) The $99j polymer block of propylene and the binary random copolymer block of propylene and ethylene or butene-1 are made and the propylene gold wire is imprinted. At least one block (A) i that is greater than or equal to
50-: 40 parts by weight, ethylene and C4~, α of 2
- A binary or ternary copolymer of an olefin and zolopyrene with an ethylene content of 30% by weight
f: Contain at least one of the following blocks (B) in the amount of 1 part by weight (1 part by weight).