JP2825704B2 - Ethylene copolymer film - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a composition distribution characteristic and a branching degree distribution characteristic.
, Random properties, measured by differential scanning calorimeter
Depends on melting point (hereinafter sometimes abbreviated as DSC melting point)
Crystallinity characteristics, crystallinity and molecular weight distribution by X-ray diffraction method
Novel ethylene α-olef in combining various properties such as
The present invention relates to a film comprising an in-copolymer. Further details
Has a density of 0.90 g / cm³Above is transparency, impact resistance
Resistance, tear resistance, blocking resistance, environmental stress crack resistance,
Excellent heat resistance and low temperature heat sealability
Ethylene-α-ole that has the properties of
A fin copolymer film is provided. Conventionally, ethylene polymers and copolymers have been used.
Various polymers and copolymers have been proposed and are known.
Among these ethylene polymers and copolymers, high pressure
Low density polyethylene (hereinafter abbreviated as HP-LDPE)
May be flexible and relatively transparent
Therefore, for example, films, hollow containers, hollow molded products, pies
Pipes, steel pipe coatings, wire coatings, foamed products, and other
Used in various applications. However, HP-
LDPE has impact resistance, tear resistance, environmental stress crack resistance (hereinafter referred to as
Below, sometimes abbreviated as ESCR)
Due to the difficulties, the fields of application where these performances are required
Was restricted in its use. [0003] On the other hand, ethylene and α-ole
Low-density polyethylene obtained by copolymerizing
Below, L-LDPE may be abbreviated) HP-L
Superior mechanical strength, ESCR and transparency compared to DPE
Is also good, so that HP-LD
It is attracting attention as a substitute for PE. Recently, bag making
Speed of packaging machines such as packaging machines,
The demand for thinner and higher strength is remarkable. However, L-LD
PE is one of those applications where the performance is strictly required.
In the field, mechanical strength, optical properties and heat sealing
Is not enough, and improvement of these performances is required.
And balance these properties with the other properties.
There has been a demand for the development of an ethylene copolymer which has both functions. The present applicant has responded to such a demand.
To develop a new ethylene copolymer, US Patent No. 4
No. 205021 (corresponding, JP-A-53-92987)
Report). However, specific proposals for this proposal
The ethylene copolymer shown has a broad composition distribution and low
Since it contains non-negligible amounts of crystalline composition components,
Depending on the purpose and application, there is no room for improvement in blocking resistance.
The land has come. On the other hand, attention has been paid to improvement in blocking resistance.
JP-A-57-105411 discloses an ethylene copolymer.
In the gazette, the melt flow rate is 0.1 to 100 g / 1.
0 min and a density of 0.91 to 0.94 g / cm³
Xylene absorption rate per unit amorphous (Y) and crystallization
The relationship with the degree (X) is [0006] (Equation 6) Ethylene copolymer having a single DSC melting point
Coalescence has been proposed. However, this ethylene copolymer
Also has a poor balance between heat resistance and low temperature heat sealability,
Heat resistance deteriorates when trying to improve heat sealability
On the other hand, when trying to improve heat resistance,
Has the disadvantage that the
Ethylene copolymer is sufficient for blocking resistance
Not something. Further, Japanese Patent Application Laid-Open No. 57-126809 discloses
Has a specific long-chain branching index and a specific short-chain branching distribution.
Ethylene-α-olefin copolymer having
I have. However, this ethylene copolymer has a wide composition distribution
Points, and properties such as transparency and impact resistance are not good.
What is a material that is satisfying and has various characteristics in a well-balanced manner
It is difficult to be. Further, Japanese Patent Publication No. 46-21212 is also disclosed.
Has a narrow molecular weight distribution using a vanadium-based catalyst
Method for Continuous Production of Uniform Random Partially Crystalline Copolymer
Has been proposed. The ethylene copolymer according to this proposal is
The molecular weight distribution is extremely narrow and the crystallinity is extremely low.
These ethylene copolymers for applications such as films and sheets
Even when used, balance heat resistance and low-temperature heat sealability
It is difficult to make it complex and anti-blocking
There is a drawback that the property is poor. The present inventors have developed mechanical properties, optical properties,
Blocking resistance, heat resistance, low temperature heat sealing, etc.
Properties and balance these excellent properties.
Dedicated to develop ethylene copolymers
Investigation revealed that ethylene-α-olefin copolymerization
Body composition distribution characteristics, branching degree characteristics, randomness
Set of properties, DSC melting point properties, crystallinity, molecular weight distribution, etc.
The copolymer specified by the combination is superior to the above properties.
And a balance of properties.
Furthermore, as a result of conducting research based on this new knowledge,
Ethylene / α-olefin that satisfies all of the following characteristic conditions
Copolymer can be easily produced and has a density of 0.90 g / cm
³Above, transparency, impact resistance, tear resistance, blockkin resistance
Resistance, environmental stress crack resistance, heat resistance and low temperature heat sealing
Good balance of these excellent properties
It becomes an ethylene copolymer that has not been described in the conventional literature,
The density is 0.90 g / cm³Less than, transparency, impact resistance
Excellent heat resistance and low-temperature heat sealability and use vanadium catalyst
A homogeneous random partially crystalline copolymer produced using
Wide molecular weight distribution, good moldability, and various thermoplastic
Impact resistance and low-temperature heat
With excellent performance as a modifier to improve
Found to be an ethylene copolymer not described in the literature
Was. Accordingly, an object of the present invention is to provide a new type of air conditioner.
It is an object of the present invention to provide a styrene copolymer film. That is, according to the present invention, ethylene and carbon atoms
Substantially consisting of α-olefin in the range of 4 to 20
Ethylene and α-olefin random having linear structure
It is a polymer film, and the following (A) to (K) Key
Cases, (A) Melt measured according to ASTM D1238E
Flow rate in the range of 0.01 to 200 g / 10 min
In, (B) a density of 0.850 to 0.930 g / cm³Range of
In the enclosure, (C) General formula [I] [0012] (Equation 7) U = (Cw / Cn-1) × 100 [I] [In the formula, Cw indicates a weight average branching degree, and Cn indicates a number average.
Indicates the degree of divergence. ] The composition distribution parameter represented by
(U)40That: (D) the degree of branching in 1000 carbon atoms is 2 or less
10% by weight of the composition component in the ethylene copolymer
% Or less, (E) The degree of branching in 1000 carbon atoms is 30 or more
The proportion of the composition component in the ethylene copolymer is 70
% Or less, (F) The average chain length ratio of methylene groups is 2.0 or less.
thing, (G) One or more melting points measured with a differential scanning calorimeter
Are plural (n, n ≧ 3), and (I) Melting point (T₁) Has the general formula [II] [0013] (Equation 8) [Where T₁If more than one melting point exists,
It shows the value of the high melting point (° C.), where d is the ethylene copolymer
Density (g / cm³). ] In the range represented by
And (Ii) When there are a plurality of (n, n ≧ 3) melting points
In this case, the highest melting point (T₁° C) and their multiple melting points
Is the difference from the lowest melting point (Tn ° C.) of the general formula [III] [0014] (Equation 9) In the range represented by (Iii) the maximum melting point (T₁℃) and those multiple
The second highest melting point (T₂℃)
General formula [IV] [0015] (Equation 10) In the range represented by (H) A plurality (n, where n ≧ 3) of DSC melting points
The highest melting point (T₁(° C)
(H₁) And the total crystal fusion heat (H_T) And the general formula
[V] [0016] [Equation 11] 0 <H₁/ H_T≦ 0.40 [V] In the range represented by (I) The crystallinity measured by X-ray diffraction is 15 to 7
0% range, (J) Measured by gel permeation chromatography
Determined molecular weight distribution (Mw / Mn) of 2.5 to 10
Being in range,(K) The heat sealing start temperature is 95 to 125 ° C.
thing, Characterized byRueFrom a Tylene copolymer
Film is the gist of the invention. [0017] The above objects of the present invention and even many other objects.
Targets and advantages will become more apparent from the following description.
There will be. The ethylene copolymer film of the present invention is
It is specified by the characteristics of (A) to (J). Below, each feature
The nature is described in detail. Ethylene copolymer forming the film of the present invention
Coalescence is in the range of 4 to 20 carbon atoms with ethylene
Etch having a substantially linear structure consisting of α-olefin
It is a len-α-olefin random copolymer. here
The α-olefin component unit has 4 to 20 carbon atoms.
Α-olefin, preferably 4 to 18 α-olefins
And particularly preferably 4 to 12 α-olefins,
Even one or more of these components may be mixed.
not useable. As such an α-olefin component unit
Specifically, 1-butene, 1-pentene, 1-hexene
4-methyl-1-pentene, 1-heptene, 1-
Octene, 1-decene, 1-tetradecene, 1-octade
Sen can be exemplified. The ethylene copolymer of the present invention
The content of the α-olefin component unit constituting the polymer,
Compositions specified by (C), (D) and (E)
It is optional within a range that satisfies the distribution.
5 to 40 mol%, preferably 0.5 to 30 mol%, especially
Preferably it is in the range of 1.5 to 20 mol%. Ethylene copolymer forming the film of the present invention
The union has a substantially linear structure. Where virtually
Has a branch based on the α-olefin.
Having a long-chain branched and cross-linked structure.
Means that This means that the ethylene copolymer
By completely dissolving in an n-decane solvent at 130 ° C.
Is confirmed. The ethylene copolymer of the present invention comprises (A)
Flow rate (hereinafter may be abbreviated as MFR)
Is 0.01 to 200 g / 10 min, preferably 0.0
It is in the range of 5 to 150 g / 10 min. The MFR is 2
If it exceeds 00g / 10min, the moldability and machine
The mechanical strength became inferior, less than 0.01g / 10min
Even if the size is too small, the moldability will be reduced
It is. Well, here (A) MFR is ASTM D 1
It is a value measured by 238E. The ethylene copolymer of the present invention has a (B) density
Is 0.850 to 0.930 g / cm³, Preferably 0.
880-0.930 g / cm³It is. The density is 0.9
30g / cm³Transparency and tear resistance if too large
0.85
0 g / cm³If it is too small, the blocking resistance will be remarkable.
With inferior inconvenience. In the present invention, (B)
The degree is a value measured according to ASTM D 1505. The ethylene copolymer of the present invention comprises (C)
Formula [I] [0024] (Equation 12) [Wherein, Cw represents the weight average branching degree, and Cn represents several flats.
The composition distribution parameter represented by], indicating the degree of uniform branching.
(U) is 50 or less, for example, 0 <U ≦ 50, preferably 4
0 or less, more preferably 30 or less. The U is a composition of the copolymer irrespective of the molecular weight.
A parameter that indicates the distribution of components.
(D), (E), (F), (G) and closely related
Thus, one of the important properties for specifying the structure of the copolymer of the present invention
It is. And if the U is too large exceeding 50, the composition
Distribution is too wide, transparency, tear resistance, impact resistance, blow resistance
Inferior in sticking property and low-temperature heat sealing property,
Excellent properties and excellent performance of the copolymer of the present invention
Lance is difficult to exhibit its combined properties. In the present invention,
In the above equation (1) for calculating U, Cw and Cn are
It is a value measured and determined by the following method. In order to fractionate the composition of the ethylene copolymer
Mixing the copolymer with p-xylene and butyl cellosolve
In a solvent (volume ratio: 80/20), heat-resistant stabilizer 2,5-di
-Tert-butyl-4-methylphenol in the presence of
Then, after dissolving, diatomaceous earth (trade name Celite 560 Jiyong Man)
Bill (made in the United States)
And a solvent of the same composition as the mixed solvent in the column
Column temperature from 30 ° C to 5
Gradually increase to 120 ° C in steps of ° C,
The ethylene copolymer was separated and reprecipitated in methanol after fractionation.
Separation is obtained by filtration and drying. Then the carbon number of each fraction
The number of branches C per 1000 is 13C, which is the same as the following item (D).
-The number of branches C and the cumulative weight of each classification
The quantity fraction I (w) is calculated by the following equation (2) according to a lognormal distribution.
Cw and Cn are obtained by the least square method. [0027] (Equation 13)Where β²Is [0029] [Equation 14] And Co²Is [0030] (Equation 15) Is represented by The ethylene copolymer of the present invention comprises (D) a branched
Degree 2 / 1000C or less (copolymer main chain carbon 1000
Ethylene component of the composition component whose number of branches per unit is 2 or less)
10% by weight or less, for example, 10-0 weight
%, Preferably 5% by weight or less, more preferably 3% by weight
% Or less. The condition for the degree of branching in the above (D) is that the copolymer main chain
Having a main chain structure with too small degree of branching bonded to
Is a parameter that means a small amount.
Closely related to the composition distribution parameter of the above (C),
Together with the composition distribution parameter (U), the ethylene
It is one of the important properties to specify the structure of the polymer. Soshi
And the composition component having a degree of branching of 2 / 1000C or less is 10
The copolymer contained excessively in excess of the amount of
Inferior in tearability, impact resistance and low-temperature heat sealability, the present invention
Excellent properties of copolymer and balance of its excellent properties
It is difficult to exhibit well-combined properties. In the present invention,
The degree of branching means the number of branches per 1000 carbon atoms in the main chain of the copolymer.
And is a value measured by the following method. sand
That is, G. J. Ray, P .; E. FIG. Johnson an
d J. R. Knox. Macromolecule
s, 10, 773 (1977).
And carbon-13 nuclear magnetic resonance (¹³C-NMR) spectrum
Using the signal of the methylene carbon observed by
This is a value obtained from the area intensity. Further, the ethylene copolymer of the present invention comprises
(E) Etch of a component having a branching degree of 30 / 1000C or more
70% by weight or less, for example,
0 to 0% by weight, preferably 20% by weight or less, more preferably
Or less than 5% by weight. The condition for the degree of branching in (E) is that the copolymer main chain
A component with a main chain structure with too many branches bonded to
A parameter meaning a small amount,
The composition distribution parameter of (C) and the degree of branching of (D)
Closely related to the conditions, the composition distribution parameter
(U) and the degree of branching condition (C).
It is one of the important properties to specify the structure of the polymer. Soshi
And (E) a composition component having a branching degree of 30 / 1000C or more.
Is excessively contained in excess of 70% by weight.
Blocking properties are extremely deteriorated and contaminated
This is inconvenient because of the The measurement of the degree of branching is as follows:
It can be performed in the same manner as the method described in the above (D).
You. The ethylene copolymer of the present invention is heated at 23 ° C.
N-decane-soluble matter is usually 0 to 60% by weight, preferably
Is in the range of 0 to 5% by weight, more preferably 0 to 2% by weight.
is there. In the present invention, the n-decane soluble matter is 130
10 g of ethylene copolymer in 1 liter of n-decane at ℃
Stabilizer 2,5-tert. Butyl-4-methyl-pheno
Dissolved in the co-presence of a gel and kept at 130 ° C for 1 hour.
° C / min. Precipitates when cooled to 23 ° C at
The weight of the ethylene copolymer was determined, and this value was used for a 10 g sample.
Of the weight subtracted from 10% of the sample (weight
%). Further, the ethylene copolymer of the present invention comprises:
(F) The average chain length ratio of methylene groups is 2.0 or less, preferably
It is preferably 1.7 or less, more preferably 1.5 or less. The average chain length ratio of (F) is determined according to the copolymer of the present invention.
Structure of Ethylene and α-Olefin in Body Chain
And a parameter indicating the above (C) to (E).
The ethylene copolymer of the present invention
It is one of the important characteristics that determine the structure of the body. And
The average chain length ratio of the (F) methylene group exceeds 2.0 and is large.
Copolymers that are too high will have poor transparency, tear resistance, impact resistance,
Poor rocking properties and low-temperature heat sealing properties
Excellent properties of coalescence and their excellent properties in a well-balanced manner
It is difficult to exhibit the combined properties. In the present invention, (F)
The average chain length ratio of methylene groups is¹³Using C-NMR
Methylene average chain length calculated from the measured degree of branching,
The number of methylenes between branches (between two adjacent branches) is 6 or more
Block methylene mean run calculated excluding the following cases
Ratio of chain length, ie, average block length of block methylene / methyl
It is a value determined by the average chain length of the len. Further, the ethylene copolymer of the present invention comprises
(G) one or more DSC melting points (n, n ≧ 3)
And satisfies the following conditions. (I) Melting point (T₁) Has the general formula [II] [0040] (Equation 16) Preferably, [0041] [Equation 17] [Where T₁Is used when there are multiple melting peaks.
Indicates the value of the highest melting point (° C.), where d is the ethylene copolymer weight.
Combined density (g / cm³). Range represented by]
It is in. (Ii) A plurality of (n, n ≧ 3) DSs
If a C melting point is present, the highest melting point (T₁℃)
Difference from the lowest melting point (Tn ° C) of the plurality of melting points
Has the general formula [III] [0043] (Equation 18) Preferably, [0044] [Equation 19] More preferably, [0045] (Equation 20) In the range represented by (Iii) The maximum melting point (T₁℃) and it
The second highest melting point (T
₂° C) is different from the general formula [IV] [0047] (Equation 21) Preferably, [0048] (Equation 22) More preferably, [0049] (Equation 23) In the range represented by One or more of these (n, n ≧
The DSC melting points of 3) and their interrelationships are described below.
(H) The ethylene copolymer of the present invention together with the heat of crystal fusion
A parameter related to the crystallinity characteristics due to the DSC melting point.
In addition, the same
Important characteristics for specifying the structure of the ethylene copolymer of the present invention
It is one of gender. And in the (G) DSC melting point characteristic,
And T₁Is (175 × d-46) ° C. [d is as described above.
Below], heat resistance is inferior if too low, and T₁Is 125 ° C
If it is too high, transparency and low-temperature heat sealability will be poor,
Also, T₁-Tn is too high above 65 ° C or T₁−
T₂If the temperature exceeds 20 ° C and is too high, tear resistance, impact resistance
And the low-temperature heat-sealing property deteriorated
The balance of the excellent properties of the body and its excellent properties
It is difficult to exhibit the properties provided. In the present invention,
In (G), the DSC melting point and the following (H)
Heat of crystal fusion (H₁) And the total crystal fusion heat (H_T)
Means a value measured and determined by the following method. Immediately
Using a differential scanning calorimeter, sample 3 mg at 200 ° C.
After melting for 5 minutes, the temperature was lowered at a rate of 10 ° C./min. Down to 20 ℃
After heating and holding at this temperature for 1 minute, the temperature was raised at a rate of 10 ° C.
/ Min. DSC endotherm by heating up to 150 ° C
Get the curve. In the endothermic peak in the DSC endothermic curve,
Appears as the hottest peak or shoulder
T in attached figure 1₁Or T in FIG.₁(High temperature side of the shoulder
Inflection point P of₁And the inflection point P on the low temperature side₂Pulled in
Intersection of tangents) Maximum melting point (T₁). 1 and 2
As shown, for a plurality of DSC melting points,
T to the low temperature side₁, T₂,... Tn, and T₂But
The second highest melting point, Tn, is the lowest melting point. On the other hand, as shown in FIG. 1 and FIG.
A straight line connecting the points at 60 ° C and 130 ° C in the SC endothermic curve (Figure
, Surrounded by the baseline A-A ′) and the endothermic curve therebetween.
The amount of heat in the filled part is the total crystal fusion heat (H_T).
Also, as shown in FIG.₁) As peak
If it appears, T₁Minimum point B of the curve on the low temperature side
More perpendicular to temperature coordinate axis C₃And the perpendicular C₃And ba
Sline AA '(C in the figure)₂Part) and endothermic curve (Figure
Medium, curve part C between AB₁)
Heat of the maximum melting point (T₁) Of heat of crystal fusion (H₁)When
Then, as shown in FIG.₁) With a shoulder
Appears at the inflection point immediately below the shoulder
P₂And T₂Inflection point P on the high temperature side of₃Pull in each with
From the intersection B 'of the tangent to the temperature coordinate axis C₃Lower
The perpendicular C₃And the baseline A-A '(C in the figure)₂Part)
And endothermic curve (C in the figure)₃B ″ and A at the intersection of the extension and curve of
Curve part C between₁The amount of heat in the shaded area surrounded by)
With the highest melting point (T₁) Crystal melting heat (T₁). The ethylene copolymer of the present invention comprises (H)
Among the plural (n, where n ≧ 3) DSC melting points,
High melting point (T₁) Of crystal melting heat (H₁) [Defined above]
And the total crystal fusion heat (H_T) Ratio to [defined above]
General formula [V] [0053] (Equation 24) Preferably, [0054] (Equation 25) It is. The heat of crystal fusion H of (H)₁/ H
_TIs the ethylene copolymer of the present invention together with the characteristics of the above (G).
Is related to the crystallinity characteristics due to the DSC melting point. This H₁/
H_TIf the ratio exceeds 0.40 and is too large, tear resistance and impact resistance will occur.
Deteriorates impact resistance, low-temperature heat sealability, etc.
Under the binding parameter conditions, the copolymer of the present invention is excellent
Properties that combine the various properties and their excellent properties in a well-balanced manner
It helps to demonstrate quality. (I) Crystallization of the ethylene copolymer of the present invention
The degree is 15-70%, preferably 30-70%, more preferably
Or in the range of 40 to 65%. The crystallinity is 70%
If it is too large, tear resistance, impact resistance, low temperature heat
Decreases sealability, crystallinity is less than 15% and is too low
In this case, blocking resistance and heat resistance will be remarkably inferior.
Therefore, it is necessary to be within the above range. In addition, the Echile
The crystallinity of the copolymer is determined by X-ray diffraction.
is there. The measurement method connects the diffraction angles of 7 ° to 31.5 °
The straight line is used as the background, and the others are
I went according to the method described. S. L. Aggrwal a
nd G. P. Tilley, J .; Polym. Sc
i. ,18, 17 (1955). The (J) molecular weight distribution (M) of the copolymer of the present invention
w / Mn) is 2.5 to 10, preferably 2.5 to 7, and
More preferably, it is in the range of 2.5 to 5. The ethylene copolymer
If the molecular weight distribution of the coalesce exceeds 10
, Environmental stress cracking resistance is significantly reduced,
If it is less than 2.5, the moldability will decrease.
The molecular weight distribution of the ethylene copolymer was determined by gel permeation.
The value measured by Chromatography
You. The ethylene copolymer of the present invention is, for example,
It can be manufactured by such a method. For example,
Ratio table containing tan, magnesium and halogen as essential components
Area is 50m²/ G or more of the highly active solid component (a)
Titanium contact obtained by treating with coal (b)
Medium component (A), organoaluminum compound catalyst component (B)
And catalyst formed from halogen compound catalyst component (C)
Using ethylene and α-olefin to obtain a predetermined density.
The copolymer is copolymerized. At this time, the organic aluminum compound
Part or all of the catalyst component (B) is a halogen compound
In this case, the use of the halogen compound catalyst component (C) is omitted.
can do. The highly active solid component (a) itself has a high content.
It can be an active titanium catalyst component.
Widely known. Basically, with magnesium compounds
Titanium compounds with or without auxiliary reagents
Reaction to obtain a solid component with a large specific surface area.
Let The solid component (a) has a specific surface area of about 50 m²/ G
Above, for example, about 50 to about 100 m²/ G, preferably
About 80 to 900m²/ G, and its composition is generally
Tan content of about 0.2 to about 18% by weight, preferably 0.1%
3 to about 15% by weight, halogen / titanium (atomic ratio) of about 4
From about 300, preferably from about 5 to about 200, magnesium
/ Titanium (atomic ratio) is about 1.8 to about 200, preferably
From about 2 to about 120. In addition to each of these ingredients,
Elements, metals, functional groups, electron donors, etc.
You may. For example, other elements and metals are aluminum
And silicon, and alkoxy and aryloxy as functional groups.
It may contain a thio group or the like. Also, as an electron donor
Is, for example, ethers, carboxylic acids, esters
And ketones. Preferred of the solid component
As an example of the production method, magnesium halide and aluminum
The complex with coal is treated with an organometallic compound, and the treated product is treated.
A method of reacting with a titanium compound can be exemplified.
You. The details of this method are described in, for example, Japanese Patent Publication No. 50-27070.
No., published in Japanese Unexamined Patent Publication No. Used for treating the highly active solid component (a)
As the alcohol (b), aliphatic, alicyclic or aromatic
Aromatic alcohols, such as alcohol
It may have a substituent such as an xy group. Yo
More specifically, methanol, ethanol, n-propano
, Iso-propanol, tert-butanol,
n-hexanol, n-octanol, 2-ethylhexyl
Sanol, n-decanol, oleyl alcohol, shiku
Lopentanol, cyclohexanol, benzyl alcohol
, Isopropylbenzyl alcohol, cumyl alcohol
And methoxyethanol. these
In particular, aliphatic alcohols having 1 to 18 carbon atoms
It is preferable to use For alcohol treatment, use hexane, heptane, etc.
It is preferably carried out in an inert hydrocarbon, for example,
0.005 to 0.2 mol / l of solid component (a), especially
Suspended to be 0.01 to 0.1 mol / l,
Cole from 1 to 80 per atom of titanium in solid component (a)
Moles, especially 2 to 50 moles.
preferable. Reaction conditions differ depending on the type of alcohol.
For example, about -20 ° C to about + 100 ° C, preferably about
At a temperature of -10 ° C to about + 100 ° C, several minutes to about 10 hours
About 10 minutes to about 5 hours.
Is good. By alcohol treatment, alcohol (b) becomes
In the form of alcohol and / or alkoxy groups in the solid component
It is incorporated in an amount of 3 to 10 per atom of titanium.
0 mol, especially 5 to 80 mol, especially 5 to 80 mol
Preferably, the treatment is performed as follows. Then triethyl
Treat with aluminum. This reaction causes part of titanium
May be desorbed from the solid components.
When there is a soluble component, after the reaction is completed,
Wash the catalyst component well with an inert solvent before subjecting it to polymerization.
Is good. The thus obtained titanium catalyst component (A) and
Organoaluminum compound catalyst component (B) used together
Is typically represented by the general formula RnAlX_3-n(R is hydrocarbon
For example, C₁~ C_FifteenAn alkyl group of C₂~ C₈of
X represents a halogen such as an alkenyl group, and 0 <n ≦ 3)
Compound, specifically, triethylaluminum
Trialkyl such as aluminum and triisobutylaluminum
Aluminum; diethylaluminum chloride, dii
Dialkyl alkyls such as sodium butyl aluminum chloride
Minium halide; ethyl aluminum sesquichlori
Alkyls such as ethyl aluminum sesquibromide
Aluminum sesquihalide; ethyl aluminum di
Alkylaluminum dichloride such as chloride;
Or a mixture thereof. rear
When the halogen compound catalyst component (C) described above is not used
Has an average composition in the above general formula, preferably
1.5 ≦ n2.0, more preferably 1.5 ≦ n ≦ 1.8
It is preferable to use the component (B) so that The halogen compound catalyst component (C) is ethyl
Halogenated carbon such as chloride and isopropyl chloride
Halogenating agent of (B) such as hydrogen or silicon tetrachloride
And the like that can act as Halogenated hydrocarbon
When used, about 2 to 5 mol per 1 mol of the component (B)
It can be used at a rate of degrees. Also like silicon tetrachloride
When a halogenating agent is used, the components (B) and (C)
Of halogen in the component (B)
0.5 to 2 atoms, especially 1 to 1.5 atoms,
It is preferable to use such a ratio. The copolymerization of ethylene depends on the presence of an inert diluent.
Under or in the absence, for example at a temperature of 0 to about 300 ° C
The reaction can be performed in a liquid phase or a gas phase. Especially
Ethylene copolymer dissolves in the presence of inert hydrocarbon
Under conditions of about 120 ° -300 ° C., preferably 13 ° C.
When copolymerization is performed at a temperature of about 0 ° to 250 ° C.,
The desired ethylene copolymer can be easily obtained. Chita
The amount of the catalyst component (A) used is, for example, in terms of titanium atoms.
About 0.0005 to about 1 mmol / 1, preferably about
0.001 to about 0.1 mol / l and organic aluminum
The catalyst component (B) is an amount that maintains the polymerization activity.
Al / Ti (atomic ratio) of about 1 to about 2000, preferably
Or about 10 to about 500
No. The polymerization pressure is generally from atmospheric pressure to about 100 kg / cm²,When
About 2 to about 500 kg / cm²Preferably
No. The ethylene copolymer of the present invention has a density of
0.90 g / cm³The above ethylene copolymer is HP-L
Not only DPE but also transparency compared to conventional L-LDPE
Brightness, impact resistance, tear resistance, blocking resistance, low temperature
Excellent heat sealability, heat resistance and ESCR.
It has excellent properties in a well-balanced manner.
It is suitable as a wearing film, but is not limited to this application.
-Die molding, inflation film molding, hollow molding
Films, containers, days, etc. by shape, injection molding, extrusion molding, etc.
Processing into various molded products such as supplies, pipes, tubes, etc.
Can be. Extrusion coating or co-extrusion on other films
Various composite films can be formed by molding
Rust, steel pipe covering, electric wire covering, foamed product, etc.
Also used for applications. Or other thermoplastics, eg
For example, HP-LDPE, medium density polyethylene, high density poly
Ethylene, polypropylene, poly 1-butene, poly 4-
Methyl-1-pentene, low crystalline or amorphous ethyl
Copolymers of ethylene and propylene or 1-butene,
Polyolefins such as propylene / 1-butene copolymer
It can be used by rendering. Or petroleum resin,
Wax, heat stabilizer, weather stabilizer, antistatic agent,
Chiblocking agent, lubricant, nucleating agent, pigment, dye, inorganic
Or organic filler, synthetic rubber or natural rubber
It can also be used. In the ethylene copolymer of the present invention,
Density 0.90g / cm³Ethylene copolymers less than
Excellent transparency, impact resistance and low-temperature heat sealability
The density is 0.90 g / cm³Above ethylene
Can be used for similar applications as coalescence, but various
By blending with thermoplastic resin, these thermoplastics
Impact resistance of resin, low temperature impact resistance or low temperature heat sealability
Can be significantly improved, the thermoplastic resin
It can be used as an excellent modifier. The ethylene
When blending a copolymer as a modifier with the thermoplastic resin
Can be used as is, or
It can also be used as a modified product of a tylene copolymer.
Examples of the modified ethylene copolymer include the ethylene copolymer.
Styrene, α-methylstyrene, vinyl toluene
Grafting of aromatic unsaturated hydrocarbons such as indene and indene
Copolymerized modified ethylene copolymer, ethylene copolymer
Acrylic acid, methacrylic acid, maleic acid, fumaral
Acid, citraconic acid, itaconic acid, endocis-5,6-
Dicarboxy-2-norbornene, methyl-endosis
-5,6-dicarboxy-2-norbornene, anhydrous male
Inic acid, citraconic anhydride, itaconic anhydride,
Su-2-norbornene-5,6-dicarboxylic anhydride,
Methyl acrylate, methyl methacrylate, maleate di
Methyl, dimethyl fumarate, dimethyl citraconic acid,
Dimethyl itaconate, endocis-2-norbornene-
Unsaturated carboxylic acids such as dimethyl 5,6-dicarboxylate
Graft copolymerizing an acid, an acid anhydride or an ester thereof
And modified ethylene copolymers.
The content of the modified component in the modified ethylene copolymer is
Usually 0.01 to 100 parts by weight of the ethylene copolymer
100 parts by weight, preferably in the range of 0.1 to 50 parts by weight
is there. Of the ethylene copolymer or the modified ethylene copolymer
The mixing ratio is 100 parts by weight of the thermoplastic ethylene copolymer.
0.1 to 100 parts by weight, preferably 0.2 to 100 parts by weight
It is in the range of 50 parts by weight. Examples of the thermoplastic resin include the above-mentioned polyolefins.
Olefins, polystyrene, poly α-methylstyrene
, Acrylonitrile-styrene copolymer, acrylonitrile
Styrene such as tolyl-butadiene-styrene copolymer
Polymer, polyethylene terephthalate, polybutylene
Polyester polymers such as terephthalate, polycap
Lolactate, polyhexamethylene adipamide, poly
Hexamethylene sebasamide, polydecamethylene adipami
Polyamide polymers such as
Polyarylene oxide such as enylene oxide, poly
Various thermoplastics such as oxymethylene and polycarbonate
Specific examples of the conductive resin can be given. The ethylene
Modified by blending of polymer or modified ethylene copolymer
The thermoplastic resin composition, if necessary, a heat stabilizer,
Weathering stabilizer, antistatic agent, antiblocking agent, lubricant
Agents, nucleating agents, pigments, dyes, inorganic or organic fillers, etc.
It can also be blended. Next, the present invention will be described specifically with reference to examples.
I do. The ethylene copolymer obtained according to the present invention
Was evaluated according to the following method. That is, the copolymer was prepared using commercially available high-pressure polyethylene.
Film forming machine (for modern machinery)
The film was 350 mm wide and 30 μm thick. Success
Mold condition: resin temperature 180 ° C, screw rotation speed 100r
pm, die diameter 100mm, daslit width 0.7mm
is there. Next, the film was evaluated by the following method. F
Is (%): ASTM D 1003 impact strength (kg-
cm / cm): Film impact tester manufactured by Toyo Seiki
It measured using. The impact head sphere was 1 ″ φ. [0070] Elmendorf tear strength (kg / cm): ASTM D 1922 Blocking value (g): The peel bar is made of glass according to ASTM D 1893.
Then, the peeling speed was set to 20 cm / min. Heat seal start temperature (° C.): Use a heat sealer made by Toyo Tester and pressurize at the specified temperature.
2kg / cm²And heat seal for 1 second
Was. Specimen width is 15mm, peel test speed 300mm
/ Min. The heat sealing start temperature is
In this case, the method of breaking the test piece does not depend on the peeling of the sealing surface,original
The temperature at which the breakage of the opposite part began to occur. [0072] 【Example】Example 1 <Catalyst preparation> Remove 1 mol of commercially available anhydrous magnesium chloride in a nitrogen atmosphere
Suspend in water-purified hexane 21 and add ethanol while stirring.
After dropping 6 mol of phenol over 1 hour, the mixture was reacted at room temperature for 1 hour.
I responded. This is followed by 2.6 moles of diethylaluminum chloride.
The lid was added dropwise at room temperature and stirring was continued for 2 hours. Next, four salt
After adding 6 moles of titanium oxide, raise the temperature of the system to 80 ° C and
The reaction was performed while stirring for a while. Separate the solid part after the reaction
And washed repeatedly with purified hexane. The solid (A
The composition of -1) was as follows. Next, it was converted to Ti of A-1 suspended in purified hexane.
500 mmol ethanol for 50 mmol
The mixture was added at room temperature, heated to 80 ° C., and reacted for 1 hour. reaction
Then, the temperature was lowered to room temperature, and 150 mmol of triethyl alcohol was added.
The reaction was carried out while adding minium and stirring for 1 hour. Anti
The reacted solid was washed repeatedly with purified hexane. This
The composition of the catalyst (B-1) obtained as follows is as follows:
Atsuta.*) The resulting solid is H₂After decomposition and extraction with O-acetone, gasket
It was quantified as ethanol in (b). <Polymerization> It was dehydrated and purified using a continuous polymerization reactor having an internal volume of 200 l.
Hexane 100 l / hr, ethyl aluminum sesqui
Chloride 15 mmol / hr, catalyst obtained above
(B-1) converted to Ti and divided by 1.0 mmol / hr
And feed continuously, and simultaneously
13 kg / hr, 13 kg of 4-methyl-1-pentene
/ Hr, hydrogen is continuously supplied at a rate of 30 l / hr,
Polymerization temperature 165 ° C, total pressure 30kg / cm², Residence time 1
Time, the copolymer concentration with respect to the solvent hexane was 130 g /
The copolymerization was carried out under the condition of 1. The catalytic activity is 13.0
It corresponded to 00 g-copolymer / mmol-Ti. The results of the copolymerization obtained and the evaluation of the film
The results are shown in Tables 2 and 3. [0075]Examples 2 to 6 Using the same polymerization reactor and catalyst component (B-1) as in Example 1,
Change the type of organic Al component and α-olefin
Thus, continuous copolymerization was performed. Table 1 shows the polymerization conditions.
The evaluation results of properties and films are shown in Tables 2 and 3. [0076]Comparative Example 1 In Example 1, (B-1) was used as the Ti catalyst component.
Instead, (A-1) before reacting with ethanol
A continuous copolymerization was carried out in the same manner as in Example 1 except for the use. catalyst
The activity is 19,100 g copolymer / mmol-Ti.
Was. Table 3 shows the physical properties. The polymer obtained here has the composition
Somewhat broad distribution, high crystalline and low crystalline
Therefore, the blocking resistance is insufficient. [0077]Comparative Example 2 In the same polymerization as in Example 1, the organic Al compound component
And triethylaluminum 20 mmol / hr, Ti
Reacted with ethanol instead of (B-1) as a catalyst component
(A-1) before being converted to Ti atoms is 0.42 mm
ol / hr, ethylene 13 kg / hr, hydrogen 40 l / h
r, 4-methyl-1-pentene at a rate of 30 kg / hr
Feeding was continued and polymerization was carried out. The catalytic activity is 31,0
It corresponded to 00 g copolymer / mmol-Ti. Table 3 shows the physical properties. The polymer obtained here has a considerably broad composition distribution.
And high crystallinity and low crystallinity.
Inferior in lightness, blocking resistance and low-temperature heat sealability
Was.Comparative Example 3 The solvent dehydrated and purified in an autoclave having an internal volume of 2 liters.
0.8 l of sun and 0.2 l of 4-methyl-1-pentene
And purge the system thoroughly with nitrogen.
2.0 mmol, comparative example2The Ti catalyst used in
Add 0.02 mmol in terms of atoms, and then add hydrogen
0.6kg / cm²And 2.5 kg /
cm²And keep the polymerization temperature at 70 ° C for 2 hours.
We went together. 295 g of the copolymer was obtained. The catalytic activity was 14,800 g copolymer / mm
ol-Ti. Table 3 shows the physical properties of the obtained copolymer.
Was. The polymer obtained here has a very broad composition distribution.
And has a single melting point at 124.5 ° C.
Properties were poor. [0083] [Table 1][0084] [Table 2][0085] [Table 3][0086]

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 shows an example of an endothermic curve by DSC of an ethylene copolymer forming a film of the present invention. FIG. 2 shows an example of an endothermic curve by DSC of an ethylene copolymer forming a film of the present invention.

Continuation of front page (58) Field surveyed (Int.Cl. ⁶ , DB name) C08F 210/00-210/18 C08J 5/18

Claims (1)

(57) [Claims] Ethylene and α- having from 4 to 20 carbon atoms
A film of an ethylene-α-olefin random copolymer having a substantially linear structure consisting of olefin and
And the following (A) ~ (K) requirements associated Yotsute characterized to satisfy the Rue styrene copolymer film of. (A) the melt flow rate measured by ASTM D1238E is in the range of 0.01 to 200 g / 10 min; (B) the density is in the range of 0.850 to 0.930 g / cm ³ ; (C) General formula [I] ## EQU1 ## U = (Cw / Cn-1) × 100 [I] [wherein, Cw indicates a weight average branching degree, and Cn indicates a number average branching degree. ] Is represented by the composition distribution parameter (U)
Is 40 or less, (D) 1000 pieces of that percentage of ethylene copolymers in the degree of branching of two following composition components in the carbon atoms is 10% by weight or less, (E) 1000 carbons (F) the average chain length ratio of methylene groups is 2.0 or less, and the proportion of the constituent components having a degree of branching in atoms of 30 or more in the ethylene copolymer is 70% by weight or less; G) One or more melting points (n, n ≧ 3) measured by a differential scanning calorimeter exist, and (i) the melting point (T ₁ ) is represented by the general formula [II]. 175 × d-46) ° C. to 125 ° C. [II] [where T ₁ represents the maximum melting point (° C.) when a plurality of melting points are present. The density (g / cm ³ ) is shown. (Ii) when there are a plurality of melting points (n, n ≧ 3), the highest melting point (T ₁ ° C) and the lowest melting point among the plurality of melting points. (Tn ° C.) in the range represented by the general formula [III] 18 <T ₁ −Tn ≦ 65 [III], and (iii) the maximum melting point (T ₁ ° C.) and their The difference from the _second highest melting point (T ₂ ° C) among the plurality of melting points is in the range represented by the general formula [IV] 0 <T ₁ −T ₂ ≦ 20 [IV], (H) The ratio between the heat of crystal fusion (H ₁ ) and the total heat of crystal fusion (H _T ) at the highest melting point (T ₁ ° C.) of a plurality (n, where n ≧ 3) of the DSC melting points is represented by the general formula [V] [Equation 5] _{0 <H 1 / H T ≦} 0.40 in a range represented by [V], (I) X-ray diffraction method It is 15 not measured the degree of crystallinity 7
In the range of 0%, (J) and this in the range of from 10 gel permeation Chillon chromatograph molecular weight distribution measured by E (w / n) is 2.5, the (K) heat seal initiation temperature 95 125 ° C
thing.