JPH03296510A - Ethylene-pentene-1 copolymer - Google Patents

Abstract

PURPOSE:To prepare the title copolymer which can be formed into a film excellent in the balance between impact strength and unsealability as well as in transparency and blocking resistance by copolymerizing ethylene with pentene-1 in such a manner that the resulting copolymer satisfies specific requirements. CONSTITUTION:Ethylene and pentene-1 are copolymerized in the presence of a specific catalyst in such a manner that the resulting copolymer satisfies the requirements that the melt flow rate is 0.01-100g/10min; that the density is 0.87-0.94g/cm<3>; that the structural units derived from pentene-accounts for 1-25wt.%; that in a 40mum - thick cast film obtd. by casting the copolymer, the ratio (RS) of impact strength to tear strength in the direction of taking out the film satisfies the formula (wherein MFR is the melt flow rate of the copolymer; and d is its density); and that the DSC melting peak pattern obtd. by elevating the temp. of a 0.5mm - thick sheet sample, which has been prepd. by melting the copolymer at 200 deg.C and then slowly cooling the melt to 50 deg.C at a temp. fall rate of 0.31 deg.C/min to allow the melt to crystallize, from 10 deg.C to 200 deg.C at a temp. rise rate of 10 deg.C/min using a DSC has has two melting peaks.

Description

[Detailed description of the invention]

[0001]

[Technical field of the invention]

The present invention relates to an ethylene/pentene-1 copolymer, and more specifically, by satisfying specific requirements, when formed into a film, it has an excellent balance between impact resistance and unsealability, and also has excellent transparency. This invention relates to a novel ethylene/pentene-1 copolymer that exhibits significantly less change in transparency before and after heat treatment and also has excellent blocking resistance between films. [0002]

[Technical background of the invention]

Linear low-density polyethylene (LLDPE), which is a copolymer of ethylene and α-olefin, can be formed into a film compared to high-pressure low-density polyethylene (LDPE) and has superior impact strength in some cases, so it is difficult to form into a film. It is widely used as a raw material. [0003] By the way, films obtained from ethylene-butene-1 copolymer have moderate tear strength and are easy to open, but have a problem in that their impact strength is somewhat inferior. [0004] On the other hand, a film obtained from a copolymer of ethylene and an α-olefin having 6 or more carbon atoms has high impact strength, but the tear strength is higher than required, so the film is easily There was a problem in that it did not tear, and therefore had poor opening properties. [0005]Therefore, there is a strong desire for an ethylene/α-olefin copolymer that can provide a film that has good impact strength and is also easy to open. In addition, attempts have been made to use α-olefins with a large number of carbon atoms as comonomers with the aim of further improving the impact strength of the film. However, in this case, the blocking resistance of the film deteriorates to some extent, and furthermore, the transparency of the film decreases significantly due to heat treatment. In particular, for lamination films, in order to increase the dimensional stability accuracy, after forming the film,
Generally, the aging operation is carried out at a temperature of around 0.degree. C., but in this case, the surface of the film sometimes becomes white and the transparency of the film decreases. [0006] The present inventors conducted extensive studies to solve the problems associated with the above-mentioned ethylene/α-olefin copolymer film, and found that ethylene and pentene-1 were combined in the presence of a specific catalyst. When an ethylene/pentene-1 copolymer that satisfies specific requirements is formed into a film by polymerization, the resulting film suffers from poor balance between impact resistance and unsealability, as well as blocking resistance. Furthermore, the present inventors have discovered that the reduction in transparency caused by heat treatment can be largely suppressed, leading to the completion of the present invention. [0007]

[Purpose of the invention]

The present invention has been made in view of the prior art as described above, and has an excellent balance between impact resistance and unsealability when formed into a film, and also has excellent balance between impact resistance and unsealability. The object of the present invention is to provide a novel ethylene/pentene-1 copolymer which exhibits significantly less change in the properties of the film and which also has excellent blocking resistance between films. [0008]

[Summary of the invention]

The ethylene/pentene-1 copolymer according to the present invention is a copolymer consisting of ethylene and pentene-1, and is characterized in that it satisfies the following requirements (A) to (E). (A) has a melt flow rate of 0.01 to 100 g/10 min as measured by ASTM D 1238E; (B) has a density of 0.87 to 0.94 g/cm as measured by ASTM D 1505; (C) The structural unit derived from pentene-1 is 1 to 25% by weight, and (D) The impact strength of a 40 μm thick film obtained by molding the copolymer into a cast film, and the The ratio (R5) to the tear strength satisfies the following formula, and R
S≧-201og M F R-1000d +968
(In the formula, MFR represents the melt flow rate of the copolymer, and d represents the density of the copolymer.) A crystallized sheet with a thickness of 0.5 mm was used as a sample, and the temperature was measured from 10°C to 10°C using DSC. The DSC melting peak pattern obtained when the temperature is raised to 200 °C at a temperature increase rate of °C/min has two melting peaks, a peak height Hh on the high temperature side and a peak height Hl on the low temperature side. The ratio Hh/Hl and the density of the copolymer satisfy the following formula. [0009] 0 < Hh/Hl < 60 d -52,0 (in the formula, H
h is the peak height on the high temperature side, Hl is the peak height on the low temperature side,
d represents the density of the copolymer. ) The ethylene/pentene-1 copolymer according to the present invention satisfies the above-mentioned characteristics, so when formed into a film, it has excellent impact resistance and transparency, and the change in transparency before and after heat treatment is remarkable. It also has excellent blocking resistance between films. [00103

[Detailed Description of the Invention] The ethylene/pentene-1 copolymer according to the present invention will be specifically described below. The ethylene/pentene-1 copolymer according to the present invention is a random copolymer obtained by copolymerizing ethylene and pentene-1 in the presence of a specific catalyst. In addition to ethylene and pentene-1, a small amount of other α-olefins or polyenes may be copolymerized in the ethylene/pentene-1 copolymer according to the present invention. Here other α
-Olefins include, for example, propylene, 2-methylpropylene, 1-butene, 1-hexene, 4-methyl-1-pentene, 3-methyl-1-pentene, 1-octennonene-1, decene-1, undecene-1 , dodecene-1, and the like. In addition, as the above polyene,
Examples include butadiene, isoprene, 1,4-hexadiene, dicyclopentadiene, 5-ethylidene-2-norbornene, and the like. [0011] The ethylene/pentene-1 copolymer according to the present invention has AS
The melt flow rate (MFR) measured by TMD 1238E is from 0.01 to 100 g/10 min, preferably from 0.05 to 50 g/10 min. This MFR
is 0. If O is less than 1 g/10 min, the moldability of the copolymer will decrease, and the transparency of the resulting film will tend to decrease, and the MFR will be less than 100 g/10 min.
If the temperature exceeds 10 minutes, the mechanical strength tends to decrease. [0012] The ethylene/pentene-1 copolymer according to the present invention has a density of 0.87 to 0.94 g/cm3, preferably 0.8
It is 8 to 0.93 g/cm3. Note that here the density is AS
This is a value measured by TMD 1505. [0013] In the ethylene/pentene-1 copolymer according to the present invention, the amount of structural units derived from pentene-1 is 1 to 25% by weight, preferably 4 to 23% by weight, particularly preferably 6 to 20% by weight. The structural unit derived from ethylene is 75
It is present in an amount of -99% by weight, preferably 77-96%, particularly preferably 80-94%. [0014] In this ethylene/pentene-1 copolymer, as mentioned above, the content of structural units derived from α-olefins other than ethylene and pentene-1 is 10% by weight or less, preferably 5% by weight or less, particularly preferably may be included in an amount of up to 3% by weight. [0015] As a sample, a sheet with a thickness of 0.5 mm obtained by heating the ethylene/pentene-1 copolymer of the present invention to 200° C. to melt it, and then cooling and crystallizing it at a cooling rate of 10° C./min. The DSC melting peak pattern obtained when the temperature was raised from 10°C to 200°C at a heating rate of 10°C/min using DSC shows three peaks (Figure 2). On the other hand, after heating the ethylene-pentene-1 copolymer according to the present invention to 200°C and melting it,
A 0.5 mm thick sheet obtained by super slow cooling and crystallization at a cooling rate of 1 ° C./min (hereinafter, the sample obtained in this way is referred to as "super slow cooling sample") was used as a sample. The DSC melting peak pattern obtained when the temperature is raised from 10 °C to 200 °C at a temperature increase rate of 10 °C/min using DSC has two melting peaks, and a high temperature side peak height Hh, Ratio to low temperature side peak height Hl Hh/
Hl and the density d of the copolymer satisfy the following formula (FIG. 1). [0016] 0<Hh/Hl<60d-52,0...[I] Preferably 0<Hh/Hl<40d-34,5...[■'1 Particularly preferably 0<Hh/Hl<1 ... [I"
] (In the formula, Hh represents the peak height on the high temperature side, Hl represents the peak height on the low temperature side, and d represents the density of the copolymer.) Here, the analysis of the DSC melting peak pattern of the super slowly cooled sample is as follows. For the high temperature side foot of the high temperature side melting peak, 3
A tangent line was drawn starting from a point on the melting curve at 0° C., and this was used as the baseline. A perpendicular line was drawn from the highest point of the peak to this baseline, and the distance between this intersection and the highest point of the peak was determined as the peak height. [0017] 40 obtained by molding the ethylene/pentene-1 copolymer according to the present invention having the above-mentioned properties into a cast film.
[II
], RS top -20logMFR-1000d+968
-[II] (In the formula, MFR represents the melt flow rate of the copolymer, and d represents the density of the copolymer.) Preferably, -201og on RS MFR-1000d +97
3 -...[II'], particularly preferably 200≧RS≧-201og MF R-1000d
+975 - [II"]. [0018] The ratio (RS) of this impact strength to tear strength is (-201o
g MF R-1000d +968), the film may have high impact strength but poor opening properties;
The film tends to have good unsealability but poor impact strength. Note that 40 μm used to measure the RS value
The thick raw film tyrene/pentene-1 copolymer was heated at a resin temperature of 220 to 240°C, a chill roll temperature of 30 to 40°C,
65 mm at a film forming speed of 20 to 30 m/min and a draft ratio (film thickness/lip opening degree) of 0.05 to 0.07.
This is a film created using a T-die film molding machine equipped with a φ extruder. [0019] Furthermore, the impact strength of a 40 μm thick cast film obtained by processing the copolymer according to the present invention as described above is usually 1.
000k100O/cm or more, preferably 1200kg
-Cm/cm or more. [0020] Furthermore, the tear strength (TM, ) of the film in the pulling direction,
The melt flow rate (MFR) of the ethylene/pentene-1 copolymer preferably satisfies the relationship represented by the following formula [III]. [0021] log TMD≦-0, 3'71og MF R-5,
1d+6.72 - [III] (where d represents the density of the copolymer) A more preferable relationship is log TMD≦-〇, 371og MF R-5,1
d +6.65 ・-[III'] A particularly preferable relationship is log TMD≦-0,371og MF R-5,1
d +6.59 − [III”]. [0022] In this way, the tear strength (TMD) in the take-off direction of the film as described above and the MFR have a relationship as shown in the above formula [III]. A film having excellent impact strength and unsealability can be obtained from the ethylene/pentene-1 copolymer satisfying the above-mentioned conditions.
Stress cracking resistance (ifSC property (ESCR), ASTM D1) of a 2 mm thick press sheet obtained by molding a copolymer in accordance with ASTM D 1928
Measured according to 692, Antalox 100%, 50
°C) is 10 hours or more, satisfies the relationship shown by the following equation [IV-a], and ESCR≧0.7X10 (log
880-1o MF R) (0,952-d)
=-[IV-a] (where 2.0≦VFR≦50, and d represents the density of the copolymer) Preferably, ESCR≧0.9X10 (log80-logMFR)
(0,952-d)...-[IV'-a] Particularly preferably, ESCR≧1. IXlo(log80-logMFR)
(0,952-d) = -[IV"-a] is satisfied. [0024] The ethylene/pentene-1 copolymer of the present invention can also be
2mm obtained by molding according to TM D 1928
Stress cracking resistance (S resistance) of thick press sheet
C property (ESCR), measured in accordance with ASTM D 1692, Antalox 10%, 50°C) is 20 hours or more and satisfies the relationship shown by the following formula [IV-b], and the ES
CR≧1.4X104 (log 440-1o MF
R)2(0,952-d)-[IV-b] (wherein 1.0≦MFR≦20, and d represents the density of the copolymer) Preferably, ESCR≧1.7X10 (log40 -logMFR)
(0,952-d) =-[IV'-b] Particularly preferably, ESCR≧2. OX104 (log40-logMFR
)2(0,952-d)...[IV"-b] is satisfied. [0025] Furthermore, the ethylene-pentene-1 copolymer of the present invention is
2m obtained by molding according to STM D 1928
The stress cracking resistance (SC resistance (ESCR), measured in accordance with ASTM D 1692, Antalox 10%, 60°C) of the m-thick press sheet is 50 hr or more, and the following formula [IV-c] satisfies the relationship shown by
ESCR≧0.50xlO (logloo-1og M
F R) (0,952-d) -[IV-c]
(wherein, 0.1≦MFR≦5, and d represents the density of the copolymer) Preferably, ESCR≧0.65X10 (1og100-1og
MFR) (0,952-d) ...-[IV'
-c] Particularly preferably, ESCR≧0.80X10 (logloo-1og
MF R) (0,952-d) −[IV”-c
] is satisfied. [0026] Further, the haze of the press sheet as described above
It is preferable that the melt flow rate (MFR) of the ethylene/pentene-1 copolymer satisfy the relationship represented by the following formula [V]. [0027] log HA Z E≦15d-0,451og MF
R-12,23・=[V] (in the formula, d represents the density of the copolymer) A more preferable relationship is 1og HAZE≦15d-0,451og MF R-
12,26・-[V'], and a particularly preferable relationship is 1og HAZE≦15 d-0,451og MF R
−12,30・−[V”]. [0028] 0, 1 m used to measure the above physical properties
The press sheet having a thickness of m was made from an ethylene/pentene-1 copolymer in accordance with ASTM D 1928. In addition, the HAZE value should be measured in accordance with ASTM D 1003. [0029] Next, the method for producing the ethylene/pentene-1 copolymer according to the present invention will be explained. The ethylene/pentene-1 copolymer according to the present invention can be produced by combining ethylene and pentene-1, for example, as shown below. It can be produced by copolymerizing in the presence of an olefin polymerization catalyst. [0030] The olefin polymerization catalyst used in producing the ethylene/pentene-1 copolymer according to the present invention includes, for example, [A] a liquid titanium catalyst component consisting of a halogen-containing magnesium compound, oleyl alcohol, and a titanium compound. , and [B] a halogen-containing organoaluminum compound. [0031] As the halogen-containing magnesium, magnesium chloride, magnesium bromide, magnesium iodide, and magnesium fluoride are used, and among these, magnesium chloride is particularly preferably used. [0032] As a titanium compound, Ti(OR)gX4-g (in the formula, R is a hydrocarbon group, X is a halogen, and g is O-
4) is used. [0033] Specifically, such titanium compounds include T i
Ti(OCH3)C13, Ti(OC2H5)C13, Ti(0-1C3H7)C13, Ti(〇-nC4H9)C13, T1(OC2H5) ) B r3, T 1 (0-1C3H7) B r3, Ti (Otc4
H9) Trihalogenated alkoxytitanium such as Br3;
Dihalogenated alkoxy titanium such as Ti(OCH3)2C12, Ti(OC2H5)2C12, Ti(0-1C3H7)2C12, Ti(0-nC4H9)2C12, Ti(OC2H5)2Br2; Ti(OCH3)3C11 Ti(OC2H5)3C1 , Ti(O-1C3H7)3C11 Ti(0-nC4H9)3C11 Ti(OC2H5)3Br; Ti(OCH3)4, Ti(O-nC3H7)4, Ti(0-1C3H7) 4, Ti(O-nC4H9)4,'ri(ocH) Ti(OC6H1,)4.61
34' Ti(OC8H1□)4, Ti[0CH(CH)CHC4H9]4, Ti(OC9
H19)4, Ti[0C6H3(CH3)2]4, Ti(OC18H3,)4, Ti(OCH3)2(OC4H9)2, Ti(OC3H
7) 3(QC4H9), Ti(OC2H5)2(OC4
H9)2, Ti(QCH) (0-1C3H7)2, T
i(OCH)(OC18H3,)3, Ti(OC2H5
)2(OC18H35)2・Ti(OC2H5)3(○
Examples include tetraalkoxytitanium such as Cl8H35). Among these, 1≦g≦4 is preferable, 2≦g≦4 is more preferable, and tetraalkoxytitanium is particularly preferably used. [0034] The liquid titanium catalyst component [A] used in producing the ethylene/pentene-1 copolymer according to the present invention is:
It is a substantially homogeneous solution consisting of halogen-containing magnesium as described above, oleyl alcohol, and titanium compound as described above. [0035] For such [A] titanium catalyst component in a liquid state, it is preferable to prepare a mixture of, for example, halogen-containing magnesium and oleyl alcohol, and then bring this mixture into contact with a titanium compound. Preferred methods include a method in which the mixture of halogen-containing magnesium and oleyl alcohol may be in a solution state or a suspension state. [0036] [A] When preparing a titanium catalyst component in a liquid state, 4
A mixture of halogen-containing magnesium and oleyl alcohol and a titanium compound are heated at 0°C or higher, preferably 40 to 200°C, and more preferably 50 to 150°C.
It is desirable to allow the reaction to occur for at least 15 minutes, preferably for 15 minutes to 24 hours, particularly preferably for 30 minutes to 15 hours. [A] The titanium catalyst component in a liquid state is a liquid state in which halogen-containing magnesium, oleyl alcohol, and a titanium compound are simultaneously mixed at a temperature of 40°C or higher, preferably 40 to 200°C, more preferably 50 to 150°C, for 1 minute or more, preferably 1
It can also be prepared by contacting and reacting for 5 minutes to 24 hours, particularly preferably 30 minutes to 15 hours. [0037] A hydrocarbon solvent can also be used when preparing a liquid titanium catalyst component consisting of halogen-containing magnesium, a titanium compound, and oleyl alcohol. [0038] That is, a halogen-containing magnesium compound and oleyl alcohol may be dissolved in a hydrocarbon solvent and then brought into contact with a titanium compound, or a halogen-containing magnesium compound, oleyl alcohol, and a titanium compound may be dissolved in a hydrocarbon solvent and brought into contact with each other. Good too. [0039] Examples of such hydrocarbon solvents include aliphatic hydrocarbons such as pentane, hexane, heptane, octanedecane, dodecane, tetradecane, and kerosene; cyclopentane, methylcyclopentane, cyclohexane, methylcyclohexane, cyclooctane, and cyclohexene. Alicyclic hydrocarbons such as benzene, toluene, xylene, ethylbenzene, cumene, cymene; Halogenated hydrocarbons such as dichloroethane, dichloropropane, trichloroethylene, carbon tetrachloride, chlorobenzene, etc. etc. are used. [0040] The halogen-containing magnesium, titanium compound, and osyl alcohol are preferably used in the following amounts. The molar ratio of oleyl alcohol/MgCl2 is usually 2 to 2.
4, preferably 2 to 3. [0041] The titanium compound/MgCl2 usually has a molar ratio of 0.04 to 0.04.
Preferably 0.30 o, 05 to 2 o, and 2 o. Oleyl alcohol/titanium compound has a molar ratio of 5 to 10
0, preferably 10 to 8o. [0042] The halogen-containing organic aluminum [B] used in producing the ethylene/pentene-1 copolymer according to the present invention includes dialkylaluminum halides such as diethylaluminum chloride, dibutylaluminum chloride, and diethylaluminum bromide; Alkylaluminum sesquihalides such as ethylaluminum sesquichloride, butylaluminum sesquichloride, ethylaluminum sesquipromide; partially halogenated alkyls such as alkylaluminum cybarides such as ethylaluminum dichloride, propylaluminum dichloride, butylaluminum dibromide Aluminum; mention may be made of partially alkoxylated and halogenated alkylaluminiums, such as ethylaluminum ethoxy chloride, butylaluminum butoxychloride, ethylaluminum ethoxybromide and the like. [0043] In addition to these halogen-containing organic AI compounds, halogen-free organic AI compounds can also be used, such as trialkylaluminum such as triethylaluminum and tributylaluminium; trialkenylaluminum such as triisoprenylaluminum; alkyl Aluminum alkoxide; Alkylaluminum sesquialkoxide such as ethylaluminum sesquiethoxide, butylaluminum sesquibutoxide, partially alkoxy 2,5 with an average composition represented by RAl (OR), etc.
0.5 dialkylaluminum hydrides such as diethylaluminum hydride, dibutylaluminum hydride; other partially hydrogenated alkylaluminums such as alkylaluminum dihydrides such as ethylaluminum dihydride, probylaluminum dihydride, etc. Further, examples of compounds similar to these include organoaluminum compounds in which two or more aluminum atoms are bonded via oxygen atoms or nitrogen atoms. Examples of such compounds include (CH)AlOAl(C2H5)2, (CH)AlOAl(C4H9)2, 2Hs methylaluminoxane, and the like. [0044] Furthermore, as a halogen-free organic Al compound, No.
Complexes of group metals and aluminum can also be used,
Such compounds include LiAl(CH), Li
Examples include Al(C7H15)4. Among these, it is particularly preferable to use trialkylaluminum or alkylaluminum in which two or more of the above-mentioned aluminum compounds are combined. These halogen-free organic aluminum compounds can also be used in combination with halogen-containing organic aluminum compounds in an amount of 70 mol% or less, preferably 40 mol% or less, particularly preferably 10 mol% or less. [0045] The ethylene/pentene-1 copolymer according to the present invention is obtained by carrying out a polymerization reaction in a hydrocarbon solvent using the catalyst component described above. Examples of hydrocarbon solvents include aliphatic hydrocarbons and their halogen derivatives such as pentane, hexane, heptane, octane, decane, dodecane, and kerosene; alicyclic hydrocarbons and their halogen derivatives such as cyclohexane, methylcyclopentane, and methylcyclohexane; Examples include aromatic hydrocarbons such as benzene, toluene, and xylene, and halogen derivatives such as chlorobenzene. Moreover, the olefin itself used for polymerization can also be used as a liquid medium. [0046] When carrying out the polymerization reaction, the amount of titanium atoms per 11 reaction volumes is 0.0005 to about 1 mmol, more preferably about o, ooi to about 0.5 mmol, and the organoaluminum compound is mixed with aluminum/titanium (atom ratio) is approximately 1~
It is preferable to use the number to be about 2,000, preferably about 5 to about 100. The polymerization temperature of the olefin is about 20 to about 300°C, preferably about 65 to about 250°C. In addition, the polymerization pressure is atmospheric pressure ~ 3000 kg/cm2-G
It is preferably about 2 to about 100 kg/cm2-G, particularly about 5 to about 50 kg/cm2-G. [0047] In olefin polymerization, hydrogen is preferably present in order to control the molecular weight. Polymerization can be carried out batchwise or continuously. It is also possible to carry out the process in two or more stages with different conditions. [0048] The ethylene/pentene-1 copolymer according to the present invention has excellent transparency, impact resistance, tear resistance, blocking resistance, low temperature heat sealability, heat resistance and stress crack resistance, and Because it has well-balanced properties, it is particularly suitable as a packaging film. However, it is not limited to use as a film, and can also be used to make containers and daily necessities by T-die molding, blown film molding, blow molding, injection molding, extrusion molding, etc. It can be processed into various molded products such as pipes, tubes, etc. It can also be made into various composite films by extrusion coating or coextrusion molding on other films, and can also be used for applications such as steel pipe coating materials, electric wire coating materials, and foam molded products. Alternatively, other thermoplastic resins such as high-density polyethylene, medium-density polyethylene, polypropylene, poly-1-butene, poly-4
-Methyl-1-pentene, a copolymer of low crystallinity or amorphous ethylene and propylene or 1-butene, and a polyolefin such as a propylene/1-butene copolymer can also be used in blends. [0049] The ethylene/pentene-1 copolymer obtained as above may be added with a heat stabilizer, a weather stabilizer, an antistatic agent, an antiblocking agent, a lubricant, a nucleating agent, a pigment, and a dye, as necessary. , inorganic or organic fillers can also be blended. [0050] [Effects of the Invention] The ethylene/pentene-1 copolymer according to the present invention satisfies the above-mentioned specific requirements, so when formed into a film, it has an excellent balance between impact resistance and unsealability. It also has excellent transparency, and there is very little change in transparency before and after heat treatment, and it also has excellent blocking resistance between films. It also has good SC resistance and haze, making it suitable for various uses. [00513

[Examples] The present invention will be explained below with reference to Examples, but the present invention is not limited to these Examples. [0052] [Example 1] [0053]

[Example 1] [Preparation of titanium catalyst component (A)] 476 g of commercially available anhydrous magnesium chloride was suspended in 101 g of n-decane under a nitrogen atmosphere, and 4.4 g of oleyl alcohol was added.
0 kg was added thereto, and the mixture was reacted at 135° C. for 5 hours with stirring. As a result, a colorless and transparent liquid was obtained. [0054] After cooling this solution to 110°C, Ti (OC2H5
) 4 was added, and the reaction was continued at 110° C. for 5 hours. The resulting solution was stored at room temperature. [Polymerization] Using a continuous polymerization reactor with an internal volume of 2001, dehydrated and purified hexane was used at 1001/Hr, ethylaluminum sesquichloride was 19.9 mmol/Hr, and the catalyst obtained above was converted into Ti atoms at 0. Copolymerization was carried out under the conditions that -G was continuously supplied at a rate of .50 mmol/Hr, the residence time was 1 hour, and the copolymer concentration with respect to the solvent hexane was 105 g/L. The catalyst activity corresponded to 19200 g-copolymer/mmol-Ti. Table 1 shows polymerization conditions and polymerization results.
Table 2 shows the film properties of the obtained copolymer.

[Example 2 and Comparative Examples 1 to 4] In Example 1, polymerization was carried out by changing some of the polymerization conditions as shown in Table 1. The polymerization conditions are shown in Table 1, and the film properties are shown in Table 2. [Granulation] Irganox manufactured by Ciba Geigy was added to the obtained copolymer.
1076 (0.20 wt.%) Calcium stearate (o.io wt.%) and silica (0.10 wt.%)
was added to perform granulation. [Film Preparation and Evaluation Method] A film with a width of 420 mm and a thickness of 0.04 mm was molded using a commercially available T-die film molding machine equipped with a 65 mmφ extruder. The resin temperature during molding was 235°C, the extruder screw rotation speed was 40 rpm, and the chill roll temperature was 3.
Molding was carried out at 5° C., at a film forming speed of 20 m/min, and at a draft ratio of 0.057. [Measurement method] The following method was used to measure the physical properties of the film. (1) Haze: According to ASTM D 1003. (2) Gloss: According to ASTM D 523. (3) Blocking: ASTM D 1893
Measurements were made on a film that had been left undisturbed for 7 days under a 10 kg load in a 50°C oven. (4) Tear strength: According to JIS Z 1702. (5) Impact strength: According to JIS P 8134. (6) Heat sealing: 100℃, 105℃, 110℃, 115℃, 120℃ using Toyo Seiki heat sealer
Sealing was performed at upper seal bar temperatures of , 125°C, and 130°C. Heat sealing was performed at each temperature with n=5, and the seal sample was peeled using an Instron universal testing machine with a chuck distance of 30 mm and a crosshead speed of 300 mm/min. The lowest temperature at which the peeling form was not stretch peeling but heat-sealed part breakage or raw fabric breakage at n=3 or higher out of n=5 was defined as the lowest complete heat-sealing temperature. The details of the heat sealing conditions are shown below. [0055] i, Seal pressure 2 kg/cm2 ii, Seal time = 1 second iii, Upper seal bar temperature: 100°C, 105°C, 110°C, 115°C, 120°C, 125°C, 130°C iv, Lower seal bar Temperature near 0℃ ■, Test piece: 120X15mm vi, Seal width: 10mm [0056]

[Table 1]

[Table 2]

[Brief explanation of the drawing]

FIG. 1 is a DSC melting peak pattern obtained by measuring an "ultra-slow-cooled sample" of the ethylene-pentene-1 copolymer according to the present invention under normal measurement conditions.

FIG. 2 is a DSC melting peak pattern obtained by measuring the ethylene/pentene-1 copolymer according to the present invention under normal measurement conditions.

[Document base]

[Figure 11 drawing [Figure 2]

Claims (2)

[Claims] 1. An ethylene/pentene-1 copolymer obtained by copolymerizing ethylene and pentene-1, which satisfies the following requirements (A) to (E): Pentene-1 copolymer; (A) has a melt flow rate of 0.01 to 100 g/10 min as measured by ASTM D 1238E; and (B) has a density of 0.87 to 0.0 g/10 min as determined by ASTM D 1505. 94 g/cm^3, (C) the structural unit derived from pentene-1 is 1 to 25% by weight, and (D) the impact strength of a 40 μm thick film obtained by molding the copolymer into a cast film. , the ratio (RS) to the tear strength in the pulling direction of the film satisfies the following formula, and RS
≧-20logMFR-1000d+968 (in the formula, M
FR represents the melt flow rate of the copolymer, and d represents the density of the copolymer. ) (E) After melting the copolymer at 200°C, the temperature decreasing rate is 0.
．． 0.5 which was slowly cooled to 50°C at 31°C/min and crystallized.
Using DSC as a sample of a sheet with a thickness of mm at 10℃
The DSC melting peak pattern obtained when the temperature is raised from 10°C to 200°C at a heating rate of 10°C/min has two melting peaks, a high-temperature side peak height Hh, and a low-temperature side peak height Hl. The ratio Hh/Hl and the density of the copolymer satisfy the following formula. 0<Hh/Hl<60d-52.0 (In the formula, Hh represents the peak height on the high temperature side, Hl represents the peak height on the low temperature side, and d represents the density of the copolymer.) 2. A film comprising the ethylene/pentene-1 copolymer according to claim 1.