JPH01131210A - Ethylene copolymer film and molded article - Google Patents

Abstract

PURPOSE:To provide the title film composed of a copolymer of ethylene and a specific alpha-olefin, having a specific physical property, remarkably high weight- average molecular weight at the same intrinsic viscosity and excellent transparency, impact resistance and tear resistance and useful for packaging. CONSTITUTION:The objective film is composed of a random copolymer of ethylene and 1-30wt.% of a 5-18C alpha-olefin (preferably 4-methyl-1-pentene), having a density of 0.900-0.940g/cm<3>, an intrinsic viscosity [eta] of 0.8-4.0 (measured in decalin at 135 deg.C), a maximum melting point of 115-130 deg.C measured by differential thermal analysis and a viscosity ratio [eta]/[eta]l of 0.05-0.78 wherein [eta]l is intrinsic viscosity of a straight-chain polyethylene exhibiting the same weight-average molecular weight (measured by light-scattering). The average spherulite radius of the objective film is preferably <=6mum measured by laser-beam small-angle scattering. The film preferably exhibits plural melting points measured by differential thermal analysis.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an ethylene copolymer film and molded product having excellent transparency, impact resistance, and tear resistance.

High-pressure polyethylene is known as a resin with relatively good transparency, and is used for applications such as films and hollow containers. Regarding film applications, high-pressure polyethylene has low tear strength and impact strength, so it cannot be used in thin forms, and its fields of use are also restricted. Furthermore, since it is difficult to obtain a film with particularly excellent transparency by molding using the inflation method, there has been a desire to develop a latent resin with further improved transparency.

A copolymer of ethylene produced using a Ziegler type catalyst and an α-olefin having 3 or more carbon atoms is known as a resin having excellent mechanical strength and a density comparable to that of high-pressure polyethylene. Generally, Ziegler type catalysts manufactured using vanadium catalysts have a low melting point and therefore have problems in heat resistance. -10,000, titanium thread contact ts''ft: The drawback is that the copolymer obtained using this method generally has poor transparency. In this case, the transparency can be improved by appropriately selecting the conditions and catalyst. Although this was possible, the methods proposed so far (for example, in Japanese Patent Publication No. 49-55545) could only yield a copolymer with transparency comparable to that of high-pressure polyethylene.

In view of these lumps, the inventors have determined that the tear strength of the film is better than that of high-pressure polyethylene, as well as the impact strength.
As a result of our efforts to develop ethylene polymers with excellent transparency, we have discovered that it is possible to produce such copolymers by combining the requirements of camphor, and that such copolymers have been previously proposed. It was discovered that the structure, etc., is also different from that of the copolymer. It has been found that these copolymers can be produced by combining very limited requirements using the techniques described in, for example, Japanese Patent Publication No. 50-32270 and Japanese Patent Application Laid-open No. 50-95382. Therefore, the present invention
This invention relates to a selection invention of the inventions described in the above two publications.

The copolymer of the present invention has a significantly larger weight average molecular weight <M> than a conventional copolymer even if it has the same limiting viscosity.
w (by light scattering method) is shown. To express this in another way, the intrinsic viscosity of the copolymer of the present invention is [η)(135”
C, measured in decalin), and the weight average molecular weight at that time is <M>□, and the intrinsic viscosity of linear polyethylene having a molecular weight of (M> is [η]e, η), = 5.29X10 <M>W Calculated by
is in the range 0.051 η to 0.78, preferably 005 to 0.50.

As mentioned above, the fact that g'' is considerably smaller than 1 is due to short chain branching caused by a-olefin, which is a copolymerization component with ethylene (for example, in the case of 4-methyl-1-pentene, isobutyl In addition to (branching), the presence of many long chain branches is also indicated, indicating the difference from conventional ethylene copolymers which have only short chain branches.
For ethylene copolymers that are equivalent to or inferior to high-pressure polyethylene, the gl value is usually between 0.80 and 1.
Indicates a value between 0.

The copolymer of the present invention generally has a significantly smaller average spherulite radius R than a normal copolymer having the same copolymer composition. Here, the average spherulite radius R is after heating the copolymer to 220°C,
7, water-cooled and pressed under a pressure of 100 k (1/ω2-G)
It is determined by the small angle laser light scattering method using a 0μ press sheet. That is, using a laser beam small-angle scattering device, the incident light is all vertical light, and the scattered light is determined by the following formula from the scattering angle θm that gives the maximum value of the scattering intensity distribution of the so-called Hv scattering image obtained through a horizontally polarized analyzer. Find the radius R.

When R determined by this formula is defined as the average spherulite radius R, R is usually 6.0μ or less, preferably 40μ or less.

The copolymer of the present invention is usually analyzed by differential thermal analysis (nSc).
There are multiple melting points (points showing a sharp peak), often 2 to 6, preferably 3, determined from the endothermic curve. And its highest melting point is usually 115 to 130
'C% is often in the range 115 to 125°C.

For example, in Figure 1, g = 0.13, [η) = 1.42
, shows the DSO endothermic curve of an ethylene/4-methyl-1-pentene copolymer with a density of 0.926. 108″C, 1
Melting points are at 19°C and 122'C. This clearly indicates that several crystal forms exist. For comparison, Fig. 2 shows g, , = 0.83, (η) = 1.53,
1 shows a DSO endothermic curve of an ethylene-based 4-methyl-1-pentene copolymer having a density α927. It exhibits a unique melting point at 123'C.

The copolymers of the present invention also typically exhibit very narrow overall compositional distributions. Using the standard deviation σ expressed by the following formula as a measure of the spread of the composition distribution, the copolymer σ of the present invention is:
Usually less than 3.0%, often 1.0 to 2.5%
within the range of

xl is the ethylene composition of each section, r is the average value of xl, x=ΣX ω, and ω1 is the weight fraction.

Incidentally, σ of the copolymer shown in FIG. 1 is 1.35 mol%, and that of FIG. 2 is 3.72 mol%.

The composition was divided into five sections according to the Soxhlet extraction method, and the number of short chain branches based on a-olefin was determined by infrared m-yield spectroscopy. There are five classification categories as follows.

(1) p-xylene soluble part at room temperature (2) boiling n-hexane extraction part (3) boiling benzene extraction part (4) boiling n-hebutane extraction part (5) boiling p-xylene extraction part In order to have good transparency, the density of the polymer is 3.940 g/white 3 or less, preferably 0.9
Must be less than 35g/cIN. On the other hand, in order to have excellent mechanical properties and no stickiness, the density should be 0.900 g/3 or more, preferably 0.900 g/3 or more.
Must be at least 910g/cm.

On the other hand, the intrinsic viscosity [η] of the copolymer is 0.8 to 4.
0, preferably 1.0 to 3.0, and 1.0 to 3.0 is particularly suitable for film applications.

The copolymerization component a-olefin is an a-olefin having 5 to 18 carbon atoms, and specifically includes 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1
-decene, 1-dodecene, 1-tetradecene, 1-octadecene, or a mixture thereof, and α-olefins having 6 to 12 carbon atoms, especially 4-methylpentene, are preferred. Copolymerization-1 of the above components differs slightly depending on the copolymerization components, but in order to obtain a copolymer with the above density, it is usually 1.0 to 30% by weight, preferably 6.0 to 20% by weight. be. Note that when a /J-olefin having 4 or less carbon atoms is selected as a copolymerization component, a copolymer with excellent mechanical strength and/or transparency cannot be obtained.

In producing the copolymer of the present invention, selection of the melting medium and polymerization conditions is important. As a catalyst, a catalyst consisting of at least a titanium-based solid catalyst and an organoaluminum compound is used.As the titanium-based solid catalyst, a titanium catalyst supported on a compound containing magnesium halide, particularly magnesium chloride, is used. C4/T1 (weight ratio) is preferably in the range of 5 to 1501, and T: (molar ratio) is preferably in the range of about 90 to 90, and the surface area is 70 m2/g or more, preferably more than 153 m2/gtt,
Among these, it is particularly preferable to use the catalysts described in Japanese Patent Publication No. 50-52270 and Japanese Patent Application Laid-open No. 50-95382. In the method of Japanese Patent Publication No. 50-32270, in order to synthesize a catalyst having a surface area within the above range, 4 to about 7 moles of a lower alcohol, such as ethanol, are added to 1 mole of magnesium chloride, and this is reacted with the alcohol. by reacting with sufficient organoaluminum to give a oxidation effect, and then with titanium tetrachloride or an inert hydrocarbon solution of titanium tetrachloride.

In the method of JP-A-50-95582, the catalyst obtained by the method of JP-A-50-32270 is further reacted with a small amount of titanium tetrachloride and an organic phosphorium compound, thereby producing a catalyst suitable for the present invention. is obtained.

The catalyst obtained by these two methods is a combination of titanium, magnesium, chlorine, and aluminum, and has a surface area of 70 m2.
/g or more, preferably more than 150 m2/g and 500 m2
/g or less.

In order to obtain the copolymer of the present invention, it is important to select the organoaluminum compound that can be used together with the titanium catalyst. As an organoaluminum compound, the empirical formula RnAl0#3-n (
However, B is a hydrocarbon group such as an alkyl group, I S n
S2.5 An organoaluminum chloride having the empirical formula preferably 1.5<n<2.0, particularly preferably 1.5≦n≦1.8) is used as a cocatalyst. A mixture of two or more may be used as long as the average composition satisfies these empirical formulas. Preferred are alkyl aluminum sesquichlorides and/or dialkyl aluminum halides, particularly preferred are alkyl aluminum sesquihalides and mixtures thereof with dialkyl aluminum halides.

1 [If a trialkylaluminum coconut hydride, dialkylaluminum alkoxide, or alkylaluminum alkoxy hydride, which is used for ethylene polymerization as a fluminiram compound, is used as a cocatalyst, g) is usually 0.8
0 or more, σ is 3. (1 or more, the average spherulite radius B is larger than 7μ, and only a copolymer with one or two melting points can be obtained). Selection of conditions is also important. Polymerization is preferably carried out in the coexistence of a hydrocarbon solvent or under conditions where the monomer itself is dissolved at a temperature above the melting point of the copolymer, and the solvent and copolymer form a homogeneous phase. It is necessary to carry out the polymerization under the following conditions.It is preferable to carry out continuous polymerization while keeping the total monomer concentration constant.The range in which the solvent and copolymer form a uniform phase depends on the type of solvent, the monomers and hydrogen in the solution, etc. Since it varies depending on the concentration (pressure), polymerization temperature, molecular weight (intrinsic viscosity) of the copolymer, etc., the range must be determined in advance through preliminary experiments.

For example, (y7) = 1.42, density 0.926 g/
an3.4-Methyl-1-pentene containing 2.9 moles of ethylene/4-methyl-1-pentene copolymer with m point (IO8"C, 119°C, 122"C) in hexane solvent. (6) The precipitation point Tt is shown in Figure 5. The horizontal axis in Figure 3 shows the total pressure (the gas phase is the total pressure of hexane, ethylene, and in some cases 4-methyl-1-pentene), and the vertical axis shows the temperature at which the heterogeneous phase becomes (Hokudon temperature). show. line (1)
is hexane/4-methyl-1-pentene (85/15)
All precipitation points at a copolymer concentration of 150 g/l in a mixed system are shown, li! (2) is the same system with a copolymer concentration of 10og7'
Line (3) is the precipitation point of copolymer concentration 50 g/e.
The precipitation point of each is shown. Line (4) indicates the precipitation point at a copolymer concentration of 50 g/g in hexane. At temperatures higher than the precipitation point, it becomes a heterogeneous phase.

As is clear from the figure, the copolymer concentration is between 50 and 15
0g//! In the range of , it can be seen that the higher the copolymer concentration and the higher the pressure, the wider the temperature range in which polymerization can occur in a homogeneous phase. It is also clear that the operable temperature range differs depending on the amount of monomer dissolved.

FIG. 3 is a model, and for actual polymerization systems, it is necessary to determine the homogeneous phase region in advance.

If the copolymer concentration is too low, it is not economical and the operable temperature range is also narrow. Also, if the copolymer concentration is too high, the viscosity of the solution will increase too much. V polymerization reaction is inhibited.

Therefore, it is usually preferable to adjust the copolymer concentration to 50 to 200 g per 14 parts of gold and solvent.

Hydrocarbon solvents include n-hexane, n-hebutane,
Aliphatic hydrocarbons such as isohexane, n-pentane, octane, decane, kerosene, fatty hydrocarbons such as cyclohexane, methylcyclohexane, aromatic hydrocarbons such as benzene, toluene, xylene can be used.

The amount of the catalyst used is 1,0005 to 1.0 mmol of the solid catalyst component in terms of titanium atoms per 11 of the solvent.
Preferably 0.001 to 34m! rial, and also the organic 7/L/minium compound with aluminum-exchanged W.
01 to 10mm01, preferably 0.05 to 1
．． It is preferable to use it at a ratio of 0 mmol and adjust the Al/Ti (molar ratio) so that it is sharper than 1.

The feed ratio of the α-olefin having 5 to 18 carbon atoms, which is a copolymerization component, varies depending on the type of α-olefin, polymerization temperature, ethylene partial pressure in the polymerization vessel, etc., but is 0.05 to 1 mole of ethylene. from 20 mol, preferably 0.
It is about 10 to 5 moles.

The polymerization is preferably carried out under pressure, for example 2 to 100 kq/Z, preferably 15 to 70 kq/
It is better to use mouth 2. In order to adjust the molecular weight, it is preferable to coexist hydrogen.

The copolymer of the present invention has better transparency, tear resistance, and impact resistance than high-pressure polyethylene, and is suitable for use as a film. In particular, the fact that the film has excellent heat sealability and the above-mentioned properties indicates that it is suitable as a packaging film. In film,
Not only those obtained by the T-die method but also those obtained by the inflation method are highly transparent. The copolymer of the present invention can also be used to produce various molded products by blow molding, injection molding, extrusion molding, etc. Alternatively, another film may be extrusion coated to form a subsequent layer film.

Alternatively, other thermoplastic resins such as polyethylene, polypropylene, poly-1-butene, poly-4-methyl-
It can also be used in a blend with polyolefins such as 1-pentene, ethylene/propylene copolymer, ethylene/1-butene copolymer, propylene/1-butene copolymer, and the like. Alternatively, petroleum resins, waxes, stabilizers, antistatic agents, ultraviolet absorbers, synthetic or natural rubbers, lubricants, inorganic fillers, and the like may be blended and used.

Example 1 Catalyst Preparation> 10 mol of commercially available anhydrous magnesium chloride was dehydrated and purified in a nitrogen stream to produce 50% hexane! 60 mol of ethanol was added dropwise over 1 hour while stirring, and then 1 hour was added at room temperature.
Time reacted. To this was added dropwise 27 mol of diethylaluminium chloride at room temperature, and the mixture was stirred for 1 hour. Subsequently, 100 mol of titanium tetrachloride was added, and the temperature of the system was raised to 70°C, and the reaction was carried out with stirring for 3 hours. The generated solid portion is separated by decantation, washed repeatedly with purified hexane, and then made into a hexane suspension. The concentration of titanium was determined by titration.

Polymerization> Using a 200E continuous polymerization reactor, the dehydrated and purified solvent hexane was used at 80//hr, ethylaluminum sesquichloride was used at 32 mmo:L/hr, and the supported catalyst was converted into titanium at 1.2 mwol/hr. hr is continuously supplied, and ethylene 151q/hr- is simultaneously supplied in the polymerization vessel.
14-methyl-1-pentene15. Qkq/hr, water!
+004? /hr, and the polymerization temperature was 145
``O-, σ7 atr' a at total pressure 50, residence time 1 hour, concentration of copolymer in solvent hexane 112 g/A
? The copolymer was produced under the following conditions. The density of the obtained copolymer was 0.922 g/3, M = 2.
24, molecular weight MW=2.56 million, and 132 isobutyl groups per 1000 carbon atoms were detected. Matari=009
．． Spherulite radius R of 70μ quenched press sheet = 1.5μ
Met. A film having a width of 350 mm and a thickness of 3 Q/l was obtained from this copolymer using a commercially available high-pressure polyethylene tubular film forming IIA (manufactured by Modern Machinery). Molding conditions: Greasy temperature 180” C1 screw rotation speed 10
0 rotation, diameter 100mmφ, die slit cap 0.7m
It is m.

The molding results are shown in Table 1. Table 2 shows the results of molding commercially available low density polyethylene in the same manner.

Example 2 Using a continuous polymerization reactor of 200 mm, dehydrated and purified sitahexane was added at 80 d/hr, ethylaluminum sesquichloride 16 mmol/hr, diethylaluminum chloride 8 mmol/hr, and the catalyst described in Example 1 was added to titanium. Convert to 0.70mm○l/hr
is supplied to Wa, and at the same time in the polymerization vessel ethylene 13
．． 5 kQ/hr %4-methyl-1-pentene 14
．． 4kq/hr, hydrogen was continuously supplied at a rate of 7°1/br, polymerization temperature 145"c1 total pressure 30kg/crtt'G
The copolymer was produced under conditions such that the copolymer had a residence time of 1 hour and a compatibility of the copolymer with respect to hexane as a solvent of 119 g, 'g. The density of the obtained copolymer is 0.923 g/C
m3, M engineering = 4.05, molecular weight M w = 365,000,
17.0 isobutyl groups were detected per 1000 carbon atoms. g7 again? =0.35.70μ, and the spherulite radius R of the quenched press sea F was 1.7μ. Table 1 shows the results of film forming of this copolymer.

Example 3 <Catalyst Preparation> 10 mol of commercially available anhydrous magnesium chloride was suspended in dehydrated and purified hexane 501 in a nitrogen solution, 60 mol of ethanol was added dropwise over 1 hour with stirring, and the mixture was reacted for 1 hour at room temperature. did. To this was added dropwise 28 mol of diethylaluminium chloride at room temperature, and the mixture was stirred for 1 hour. Subsequently, 7 moles of titanium tetrachloride and 7 moles of triethylaluminum were added and a reduction reaction was carried out while stirring at room temperature for 4 hours, resulting in the solid portion changing color to brownish brown characteristic of trivalent titanium.

The titanium concentration of the obtained hexane suspension was determined by titration.

<Polymerization> Using the same continuous polymerization reactor as in Example 1, the dehydrated purified solvent hexane was 801/hr, ethylaluminum sesquichloride was 32 mmol/hr, and the supported catalyst was 1.2 mmol/hr in terms of titanium. hr is continuously supplied, and 12.5 hr of ethylene is simultaneously supplied in the polymerization vessel.
kQ/hr, 4-methyl-1-pentene 1 tct
g/hr, hydrogen was continuously supplied at a rate of 110 g/hr, polymerization temperature was 145" C1, total pressure was 7 at? a, residence time was 1 hour, and the concentration of copolymer with respect to solvent hexane was 11
The copolymer was produced under conditions of 0 g/β. The density of the obtained copolymer was 0.926g1α3, M engineering = 45
8. Molecular weight 1,370,000, carbon atoms 1000 (13.9 isobutyl groups were detected per flit. Mana g" = 0
．． 13, η 70 μ The spherulite radius R of the warehouse-cooled press sheet was 1.2 μ. Table 1 shows the results of molding this copolymer using the same molding method as in Example 1.

Example 4 80g/hr of hexane dehydrated and purified using a 200e continuous polymerization reactor, 20g/hr of diethylaluminum chloride
mmol/hr, the catalyst described in Example 3 was continuously supplied at 0.4 mmol/hr in terms of titanium,
Ethylene 15.5kQ/br simultaneously in the polymerization vessel,
Continuously supplied 4-methyl-1-pentene at a rate of 16.0 & 9/hr and hydrogen at a rate of 50 j/hr, polymerization temperature 145°C,
The copolymer was produced under conditions such that the total pressure was 501 g/att2G, the residence time was 1 hour, and the concentration of the copolymer with respect to the solvent hexane was 118 g/l. The density of the obtained copolymer was 0.924 g/Cm3, M = 4.68, and molecular weight y.
t, = 415,000, 15.2 isobutyl groups were detected per 1000 carbon atoms. Also, g”=0.30.
The spherulite radius R of the 70μ quench press plate η-t was 1.8μ. This copolymer was formed into a film under the same conditions as in Example 1, and the results are shown in Table 1.

Comparative Example 1 Solvent hexane dehydrated and purified using the same equipment used in Example 1 (80 l/hr r%) ethylaluminum 20 mmol/hr, catalyst described in Example 1 converted to titanium 0.28 mmol/hr hr is continuously supplied, and ethylene 14.hr is simultaneously supplied in the polymerization vessel. O, kq
/hr, 4-methyl-1-pentene 18-0kQ/b
r-, hydrogen, 40J? Polymerization temperature was 145°C, total pressure was 30k (t/cm2G, residence time was 1hr, copolymer concentration was 128g with respect to solvent hexane).
The copolymer was produced under conditions such that /(l).The density of the resulting molded composite was 0.920e, M = 4.65, molecular weight M = 98,000, per 1000 carbon atoms. 20.1 isobutyl groups were detected.g''=0.85.70
The spherulite radius R of the μ quenched press sheet η was 6.1 μ. This copolymer was formed into a film under the same conditions as in Example 1, and the results are shown in Table 1.

Comparative Example 2 Solvent hexane 801/hr,) ethylaluminum 1 dehydrated and purified using the same equipment used in Example 1
AgEt3-n(OEt)n obtained by reacting 0.5 mol of ethyl alcohol with m01 was 20 mmol/
hr, the catalyst used in Example 1 was converted into titanium and was 0.
Continuously supply 32 mmc+1/hr, and simultaneously feed ethylene 13.5 & 97 hr, 4 in the polymerization vessel.
- Methyl-1-pentene was continuously supplied at a rate of 16.0 & 9/hr and hydrogen at a rate of 50/hr, polymerization temperature was 145°C,
The copolymer was produced under the following conditions: total pressure 30 kq/α2o1 residence time 1 hr, copolymer concentration with respect to solvent hexane*15 g/(l).The density of the obtained copolymer was 0.
926g/α3, MI=5.22, molecule fiMw=7.
70,000, and the isobutyl group per 1000 carbon atoms is 13.
Eight were detected. Further, the spherulite radius R of the rapidly cooled pressed sheet with gη =0.95.70μ was 6.6μ. This copolymer was formed into a film under the same conditions as in Example 1, and the results are shown in Table 1.

Comparative Example 3 Using the same equipment used in Example 1, the dehydrated and purified solvent hexane 801/hr, diethylaluminum hydride 24 mraol/hr, and the catalyst described in Example 1 was converted into titanium to yield 0.4 mmol/hr. Continuously supplying ethylene 13.5
Aq, 4-methyl-1-pentene 16.5 to 9, hydrogen 5071? /hr, and the polymerization temperature was 145
°C, total pressure 30 ka/at' G, open for 1 hr during residence,
The copolymer was produced under conditions such that the copolymer concentration was 115 g to 7 g with respect to the solvent hexane. The resulting copolymer had a density of 0.925 g/Q13, M engineering = 4.30, molecule 11 Mw = 84,000, and isobutyl groups F per 1000 carbon atoms! 14.5 were detected. Also, gy7”=0.
Spherulite radius R of quenched press sheet of 92.701 = 6.2
It was μ. This copolymer was formed into a film under the same conditions as in Example 1, and the results are shown in Table 1.

Comparative Example] 4 Solvent hexane dehydrated and purified using the same equipment used in Example 1: 80 C/hr diisobutylaluminum: 24 mmol/hr; Catalyst described in Example 3: 0.32 mmol/hr in terms of titanium hr is continuously supplied, and 15.5 ko of ethylene is simultaneously supplied in the polymerization vessel.
, 4-methyl-1-pentene 15.0A (h hydrogen 5Ql
/hr, polymerization temperature 145℃, total pressure 3
The copolymer was produced under the following conditions: 0 ka/1v2G, residence time 1 hr, and copolymer concentration 105 g/l with respect to hexane solvent. The density of the obtained copolymer is 0
．． 924 g/Cryt', M engineering=443, molecular weight M
w=92,000, and 16.1 isobutyl groups were detected per 1000 carbon atoms. Also, gη'=0.85.70
The spherulite radius R of the quenched press sheet with μ was 7.3 μ. This copolymer was formed into a film under the same conditions as in Example 1, and the results are shown in Table 1.

Comparative Example 5 The same equipment used in Example 1 was used to dehydrate and purify the solvent, hexane 801/hr, diisobutylaluminum hydride 24 mmol/hr, and the catalyst described in Example 3, converted to titanium: 0.4 mmol/h
Continuously supplying r, ethylene 13.0&q%'-methyl-1-pentene 16.0k simultaneously in the polymerization vessel
Q.

Water 601! /hr, and the polymerization temperature was 145
°C, total pressure 3 chq/cM2a, residence time 1 hr,
Copolymer concentration 108 g/l relative to solvent hexane
The copolymer was produced under the following conditions. The density of the obtained copolymer was 0.924 g/α3, M engineering = 4.32,
Molecular weight Mw=85,000, and 15.8 isobutyl groups per 1000 carbon atoms were detected. Also g”=0.89
．． The spherulite radius R of the 70μ quenched press sheet was 6.3μ. This copolymer was formed into a film under the same conditions as in Example 1, and the results are shown in Table 1.

[Brief explanation of the drawing]

Attached FIG. 1 is a DSC endothermic curve for an example of the copolymer of the present invention. Further, FIG. 3 is a graph showing the relationship between total pressure and precipitation point (°C) in several types of solvents for several examples of the copolymers of the present invention. Patent applicant Mitsui Petrochemical Industries, Ltd. Figure 1 Figure 2 Procedural amendment (voluntary) August 8, 1988 Patent application No. 170015 of 1988 2 Title of invention Ethylene copolymer film and molded body 3 , Relationship with the case of the person making the amendment Patent applicant name (588) Mitsui Petrochemical Industries Co., Ltd. Telephone: 58
5-2256 5. Date of amendment order None 6. "Claims" column and "Detailed description of the invention" column of the specification to be amended (1) "Claims" of the specification of the present application The description in the column is corrected as shown in the attached sheet. (2) "Linear chain poly---11111---calculation)" from the third line to the last line from the bottom of page 4 of the present specification is corrected as follows. "Using linear polyethylene [standard linear polyethylene (linear polymethylene obtained by polymerization of diazomethane) 1], its intrinsic viscosity (measured at 135°C in decalin) and (
M) The intrinsic viscosity of the linear polyethylene that can be calculated using the following formula % formula % measured and determined regarding the relationship of w is [v
] (as a +) (3) "Suggested" in line 8 of page 5 is corrected to "it is presumed to imply." (4) "It is presumed to imply, j.""Composition" should be corrected as follows. "This means that the ethylene copolymer of the present invention is a random copolymer with good randomness, and its composition" (5 ) "l-Pentene, ---1-------α-olefin" in the 11th to last line of page 8 is corrected as follows: "l-pentene, l-hexene, ■-octene, ■ -decene, l-dodecene, l-tetradecene, l-octadecene, 3-methyl-1-butene, 3-methyl-1-pentene, 4-methyl-1-pentene, 3-methyl-1-hexene, 4-methyl -1-hexene, 5-methyl-1-
hexene, 3-methyl-1-heptene, 5-methyl-1
-heptene or a mixture thereof, in particular l-hexene, which is an α-olefin having 6 to 12 carbon atoms;
-octene, l-decene, 3-methyl-1-pentene,
4-Methyl-1-pentene, 5-methyl-1-hexene, 5-methyl-1-heptene" (6) Ibid., p. 26, No. 6
Correct "Water 60a" in the row to "Hydrogen 60a". (7) Add the following after Table 2 on page 28. "Example 5 Dehydration and purification using a 200Q continuous polymerization reactor I; Hexane 80ff/hr, diethyl aluminum chloride 2
5 mmol/hrx The catalyst described in Example 3 was continuously supplied at 0.5 mmol/hr in terms of titanium, and 14.0 kg/hr of ethylene was simultaneously supplied in the polymerization vessel.
Mixed α-olefin of hr, l-hexene, l-octene, and l-7” ene (manufactured by Mitsubishi Kasei Corporation, Guialene 61
0,1-hexene 35.9%, l-octene 33.3%
, a mixture of 30.8% l-decene
, Okg/hr, hydrogen was continuously supplied at a rate of 6012/hr, polymerization temperature was 145°C, and total pressure was 30 kg/cm.
The copolymer was produced under the following conditions: G, residence time: 1 hr, and the concentration of the copolymer in hexane as a solvent: 1259/12. The density of the obtained copolymer is 0.9229
7cm”, Ml-3,15, molecular weight MW-136,000,
The proportion of ethylene in the copolymer was 97.8 mo1%. Also gv-0, 70, 70
The spherulite radius of the quenched press sheet of μ is R-1,6 μ and I
;. Table 3 shows the results of forming a film using this copolymer under the same conditions as in Example 1. Example 6 Hexane 8012/hr, diethylaluminum chloride 40 dehydrated and purified using a 200Q continuous polymerization reactor
0.8 mmol/hr of the catalyst described in Example 3 in terms of titanium was continuously supplied, and 13.5 kg/hr of ethylene was simultaneously supplied in the polymerization vessel.
Mixed α-olefin of r, l-dodecene and l-tetradecene (manufactured by Mitsubishi Kasei Corporation, Dialene 124, a mixture of 56.6% l-dodecene and 43.4% l-tetradecene)
olefin) at 15.0 kg/hr, hydrogen at 60 kg/hr (2/hr
continuous supply at a rate of r, polymerization temperature 145°C, total pressure 30k
g/c+++"G, residence time 1 hr. The copolymer was produced under conditions such that the concentration of the copolymer with respect to the solvent hexane was 117 I/Q. The density of the obtained copolymer was 0.92527 cm", M I -3,91
The molecular weight was Mv-14.7, and the ethylene ratio in the copolymer was 98.6mol%. Also, the spherulite radius of the rapidly cooled press sheet with *gv=0.63.70μ was R-1.7μ. Table 3 shows the results of forming a film using this copolymer under the same conditions as in Example 1. Table 3 Example 7 80ff/hr of hexane dehydrated and purified using a 200Q continuous polymerization reactor, 20% of diethylaluminum chloride
mmol/hr1 The catalyst described in Example 3 was continuously supplied at 0.4 mmol/hr in terms of titanium, and at the same time 13.0 kg/hr of ethylene was supplied in the polymerization vessel.
r, 4-methyl-1-pentene 12.0 kg/hr, l
-hexene 1. okFi/hr, hydrogen was continuously supplied at a rate of 5112/hr, polymerization temperature 145°C, total pressure 30kg/hr.
The copolymer was produced under the following conditions: cm"G, residence time 1 hr, and the concentration of the copolymer relative to the solvent hexane was 12227Q.The density of the obtained copolymer was 0°924jJ.
7 cm3, Ml-'4.10, molecular weight My-26,30,000 The proportion of ethylene in the copolymer was 96.7 mo1%. Moreover, the spherulite radius R of the rapidly cooled press sheets of gv-0, 40, and 70μ was 1.6. Table 4 shows the results of forming a film using this copolymer under the same conditions as in Example 1. Example 8 Hexane 80α/h dehydrated and purified using a 200111 continuous polymerization reactor, diethyl aluminum chloride 2
0 mmol/hr, the catalyst described in Example 3 was continuously supplied at 0.35 mmol/hr in terms of titanium, and at the same time 13.0 mmol/hr of ethylene was added in the polymerization vessel. Okg
/hr, 4-methyl-1-pentene 9.0kg/hr. l-hexene4. 0 kg/hr, hydrogen was continuously supplied at a rate of 60 Q/hr, the polymerization temperature was 145°C, and the total pressure was 30 kg/hr.
The copolymer was produced under conditions such that the cm'G % residence time was 1 hr and the concentration of the copolymer to the solvent hexane was 116:j/12. The density of the obtained copolymer is 0.9
202/am”, Ml-3,6L molecular weight M vi −
22,90,000, and the ethylene ratio in the copolymer was 96.2 mo1%. Moreover, the spherulite radius R of the rapidly cooled press sheets of gη-0, 45, and 70μ was 1.7. Table 4 shows the results of forming a film using this copolymer under the same conditions as in Example 1. Table 4 "Claim (1) Density 0.900 to 0.940 g/cm'
, intrinsic viscosity [vl (measured at 135°C in decalin)
0.8 to 4.0, the highest melting point by differential thermal analysis is 11
Intrinsic viscosity of linear polyethylene showing the same weight average molecular weight (by light scattering method) from 5 to 130'O [vl Ratio of [vl to Q [vl / [vl a''g is 0
．． A random copolymer film of ethiwalene in the range of 0.05 to 0.78 and 1 to 30% by weight of an α-olefin having 5 to 18 carbon atoms. (2) The copolymer film according to claim (1), which has an average spherulite radius of 6 microns or less obtained by small-angle laser light scattering. (3) The copolymer film according to claim (1) or (2), which has a plurality of melting points based on differential thermal analysis. (4) The copolymer film according to any one of claims (1) to 3) Δyzf, wherein the standard deviation of the composition distribution is 3.0 mol% or less. (5) The copolymer film according to any one of claims (1) to 4), wherein the number of 8 fibers is 0.05 to 0.50. (6) The copolymer film according to any one of claims (1) to 5), wherein the α-olefin has 6 to 12 carbon atoms. (7) The copolymer film according to any one of claims (1) to 6), wherein the a-olefin is 4-methyl-1-pentene. (8) The copolymer film according to any one of claims (1) to 7), which has a density of 0.91 to 0.935 g/cm. (9) The copolymer film has a limiting viscosity of 1. The copolymer film according to any one of claims (1) to 8), which has a density of 0 to 3.0. (10) Density of 0.900 to 0.940 g/cm
linear chain exhibiting an intrinsic viscosity [vl (measured at 135°C, in decalin) of 0.8 to 4.0, a maximum melting point of 115 to 130°C by differential thermal analysis, and the same weight average molecular weight (by light scattering method). Intrinsic viscosity of polyethylene [vl12
Ratio of [11 [w] / [vl (random combination of ethylne with 1 to 8 atoms in the range of 0.05 to 0.78 and 1 to 30% by weight of a”-olefin having 5 to 18 carbon atoms) Molded polymer. (ll) Molded copolymer according to claim (10), which has an average spherulite radius of 6 μ or less obtained by small-angle laser light scattering. (12) Based on differential thermal analysis. A molded copolymer according to claim 10 or 11, which has a plurality of melting points. A copolymer skin according to any one of claims (10) to (12). 13) The copolymer molded article according to any one of claims 10 to 14, 9, wherein the ex-olefin has 6 to 12 carbon atoms. Copolymer molded product. (16) The copolymer molded product according to any one of claims (10) to (15), wherein the α-olefin is 4-methyl-1-pentene. (17) ) The molded copolymer according to any one of claims (10) to (16), which has a density of 0.91 to 0.935 kg/cm'. (108) The molded copolymer has a limiting viscosity of 1. 0 to 3.0, the copolymer molded product according to any one of claims (10) to (17).

Claims (18)

[Claims] (1) Density 0.900 to 0.940g/cm^3,
Intrinsic viscosity [η] of linear polyethylene having an intrinsic viscosity [η] of 0.8 to 4.0, a maximum melting point of 115 to 130°C as determined by differential thermal analysis, and the same weight average molecular weight (as determined by light scattering method) [η] ] ratio [η]/[η]l=^*
A copolymer film of ethylene having gη in the range of 0.05 to 0.78 and a small proportion of α-olefin having 5 to 18 carbon atoms. (2) The copolymer film according to claim (1), which has an average spherulite radius of 6 microns or less obtained by small-angle laser light scattering. (3) The copolymer film according to claim 1 or 2, which has a plurality of melting points based on differential thermal analysis. (4) The copolymer film according to claims (1) to (3), wherein the standard deviation of the composition distribution is 3.0 mol% or less. (5) The copolymer film according to claims (1) to (4), wherein g^*η is 0.05 to 0.50. (6) The copolymer film according to claims (1) to (5), wherein the α-olefin has 6 to 12 carbon atoms. (7) The copolymer film according to claims (1) to (6), wherein the α-olefin is 4-methyl-1-pentene. (8) The copolymer film according to claims (1) to (7), which has a density of 0.91 to 0.935 g/cm^3. (9) The copolymer film according to claims (1) to (8), which has an intrinsic viscosity of 1.0 to 3.0. (10) Density 0.900 to 0.940g/cm^3
, an intrinsic viscosity [η] of 0.8 to 4.0, a maximum melting point of 115 to 130°C by differential thermal analysis, and the same weight average molecular weight (by light scattering method) as compared to the intrinsic viscosity [η] of linear polyethylene [ η] ratio [η]/[η]l=g
A molded copolymer of ethylene and a small proportion of α-olefin having 5 to 18 carbon atoms, with η in the range of 0.05 to 0.78. (11) The molded copolymer according to claim (10), which has an average spherulite radius of 6 μm or less obtained by small-angle laser light scattering. (12) The copolymer molded article according to claim (10) or (11), which has a plurality of melting points based on differential thermal analysis. (13) The copolymer molded article according to claims (10) to (12), wherein the standard deviation of the composition distribution is 3.0 mol% or less. (14) The copolymer molded article according to claims (10) to (13), wherein g^*η is 0.05 to 0.50. (15) The copolymer molded product according to claims (10) to (14), wherein the α-olefin has 6 to 12 carbon atoms. (16) The copolymer molded article according to claims (10) to (15), wherein the α-olefin is 4-methyl-1-pentene. (17) Density is 0.91 to 0.935g/cm^3
A copolymer molded article according to claims (10) to (16). (18) The molded copolymer according to claims (10) to (17), which has an intrinsic viscosity of 1.0 to 3.0.