JP2000026550A - Polyethylene-amino acrylate graft copolymer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resin and a resin composition which are excellent in film strength and impact resistance, have good heat sealability and high-speed moldability, and can obtain a film having high transparency. And a method for producing the film. SOLUTION: Ethylene (co) of requirements (a) to (b)
Polymer: (a) Density 0.86 to 0.97 g / cm
³ , (b) melt flow rate 0.01 to 100 g / 1
0 minutes, (c) a molecular weight distribution _{(M W / M N) 1.5~5} .
0 and (d) the composition distribution parameter (Cb) is 2.00
In the following 80 to 99.9 parts by weight, the general formula CH ₂ = CR ¹ C
OOC _n H _2n NR ² R ³ (R ¹ is hydrogen or a methyl group,
R ² and R ³ are hydrogen or an alkyl group having 1 to 4 carbon atoms,
n shows 1-4. ) In the range of 0.1 to 20
A method for producing a polyethylene-aminoacrylate-graft copolymer grafted by weight (total 100 weight parts), a resin composition containing the polymer, and a film.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polyethylene-aminoacrylate graft copolymer film having high strength, excellent transparency, and good heat sealability, and a method for producing the same.

[0002]

2. Description of the Related Art It is a copolymer of ethylene alone or a copolymer of ethylene and an α-olefin having a linear molecular structure.
An ethylene (co) polymer having a density of 86 to 0.97 g / cm ³ has excellent transparency, impact resistance, and creep resistance as compared with high density polyethylene (HDPE),
Further, it has excellent impact resistance and creep resistance as compared with high-pressure low-density polyethylene (LDPE), and is widely used in the field of packaging materials, especially films and laminations.

However, ethylene (co) polymer as a film material is inferior in fluidity at the time of melting as compared with high-density polyethylene and high-pressure low-density polyethylene,
There was a problem that molding workability was poor. That is, the ethylene (co) polymer has a very high Newtonian property at the time of flow, has a large shear stress in a high shear rate region, easily causes melt fracture at the time of molding, is inferior in high-speed moldability, and has a low flowability at the time of molding. There was a problem that the required energy was large. Further, the ethylene (co) polymer has a very low resistance to melt elongation deformation, that is, a melt tension (melt tension), and therefore, there has been a problem that bubbles cannot be stably expanded during inflation molding. To solve these problems,
A film is formed by blending 10 to 50% by weight of a high-pressure method density polyethylene with an ethylene (co) polymer. Although the melt tension is somewhat improved, there is a new problem that the excellent strength, transparency and heat sealability inherently possessed by the ethylene (co) polymer cannot be stably obtained.

[0004]

DISCLOSURE OF THE INVENTION The present invention relates to a resin and a resin which are excellent in film strength and impact resistance, have good heat sealability and high-speed moldability, and are capable of obtaining a film having high transparency. An object of the present invention is to develop a composition, a film using the composition, and a method for producing the composition.

[0005]

Means for Solving the Problems The above-mentioned problems have the following problems: [1] An ethylene (co) polymer satisfying the following requirements (a) to (b): (a) a density of 0.86 to 0.97 g / cm ³ , (B)
Melt flow rate 0.01 to 100 g / 10 minutes,
(Iii) a molecular weight distribution (M _W / M _N) is 1.5 to 5.0, and (d) composition distribution parameter (Cb) of 2.00 or less 8
0 to 99.9 parts by weight of the general formula (1) CH ₂ ＣＲCR ¹ COOC _n H _2n NR ² R ³ (1) (where R ¹ is hydrogen or a methyl group, R ² and R ³ represents hydrogen or an alkyl group having 1 to 4 carbon atoms, and n represents an integer of 1 to 4). Polyethylene-aminoacrylate-graft copolymer,

[2] An ethylene (co) polymer satisfying the following requirements (a) to (f): (a) a density of 0.86 to 0.97 g / cm ³ , (b)
Melt flow rate 0.01 to 100 g / 10 minutes,
(C) a molecular weight distribution (M _W / M _N) is 1.5 to 5.0,
(D) The composition distribution parameter (Cb) is 1.08 to 2.
(E) The presence of substantially a plurality of peaks in the elution temperature-elution amount curve by the continuous heating elution fractionation method (TREF). (F) orthodichlorobenzene (O) at 25 ° C.
DCB) The soluble content X (wt%), the density d and the melt flow rate (MFR) must satisfy the following relationships: a) d-0.008 log MFR ≧ 0.93, X <2.0 b) d When −0.008 log MFR <0.93, X <9.8 × 10 ³ × (0.9300−d ++ 0.000
8logMFR) ² +2.0 80 to 99.1 parts by weight of the general formula (1) CH ₂ ＣＲCR ¹ COOC _n H _2n NR ² R ³ (1) (where R ¹ is hydrogen or methyl A group, R ² and R ³ are hydrogen or an alkyl group having 1 to 4 carbon atoms, and n is an integer of 1 to 4). A total of 100 parts by weight) grafted polyethylene-aminoacrylate-graft copolymer,

[3] The polyethylene-aminoacrylate-graft copolymer 1 according to the above [1] or [2]
A polyethylene-aminoacrylate-graft copolymer resin composition comprising 00 parts by weight and less than 50 parts by weight of another polyolefin; [4] the polyethylene-aminoacrylate-graft copolymer according to the above [1] or [2], or A polyethylene-aminoacrylate-graft copolymer film comprising the polyethylene-aminoacrylate-graft copolymer according to claim 3 and having a haze value of less than 20%. [5] The polyethylene according to the above [1] or [2]. −
Consisting of 100 parts by weight of amino acrylate-graft copolymer and less than 50 parts by weight of another ethylene-based copolymer,
A polyethylene-aminoacrylate-graft copolymer film having a haze value of less than 20%,

[6] (A) to (1) described in the above [1]
To 100 parts by weight of the ethylene (co) polymer satisfying the requirement of (d) or the requirements of (a) to (f) described in [2],
General formula (1) CH ₂ ＣＲCR ¹ COOC _n H _2n NR ² R ³ (1) (where R ¹ is hydrogen or a methyl group, R ² and R ³ are hydrogen or a carbon number of 1 to 4) Wherein 0.1 to 20 parts by weight of the aminoalkyl acrylate compound represented by the formula (1) is graft-copolymerized in a film forming machine. [7] The method for producing a polyethylene-aminoacrylate-graft copolymer film according to [4], [7] the requirements (a) to (d), or claims, which have been previously kneaded or respectively kneaded. Item 100: 100 parts by weight of ethylene (co) polymer and less than 50 parts by weight of other ethylene-based copolymers satisfying the requirements of (a) to (f) described in Item 2 and the general formula (1) CH ₂ = CR ^{1 _{COOC n H 2n NR 2 R 3}} · (1) (wherein, R ¹ is hydrogen or a methyl group, R ² and R ³ are hydrogen or an alkyl group having 1 to 4 carbon atoms, n is an integer of any of 1 to 4.) At the indicated The graft copolymerization of 0.1 to 20 parts by weight of the aminoalkyl acrylate compound is carried out in a film forming machine.
The above object has been achieved by developing a method for producing a polyethylene-aminoacrylate-graft copolymer film described in (1).

[0009]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail.
Examples of the ethylene (co) polymer used for the polyethylene-aminoacrylate-graft copolymer of the present invention include:
Ethylene homopolymer or ethylene and α-olefin-
A copolymer of olefins, obtained by (co) polymerizing ethylene or ethylene with an α-olefin-olefin having 3 to 20 carbon atoms;
(D) requirements, that is, (a) g / cm ³ is 0.86 to 0.97 g / cm ³ ,
(B) Melt flow rate (hereinafter abbreviated as MFR)
0.01 to 100 g / 10 min, (c) molecular weight distribution (hereinafter abbreviated as Mw / Mn) 1.5 to 5.0, (d)
It is an ethylene (co) polymer satisfying a tissue distribution parameter (Cb) of 2.00 or less.

The ethylene (co) polymer is ethylene alone or a copolymer of ethylene and at least one selected from α-olefins having 3 to 20 carbon atoms. Here, the α-olefin having 3 to 20 carbon atoms is preferably an α-olefin having 3 to 12 carbon atoms, specifically, propylene, 1-butene, 4-methyl-1-pentene, 1-hexene, −
Octene, 1-decene, 1-dodecene, and the like. In addition, the content of these α-olefins is desirably selected in a total of usually 30 mol% or less, preferably 3 to 20 mol%.

(A) The density of the ethylene (co) polymer according to the present invention is 0.86 to 0.97 g / cm ³ , preferably 0.89 to 0.95 g / cm ³ , more preferably 0.1 to 0.95 g / cm ³ .
(B) MFR is 0.01 to 100 g / 10 min, preferably 0.1 to 50 g / 10 min, and more preferably 0.5 to 0.9 g / cm ^3.
The range is 40 g / 10 minutes. 0.86g / cm density
^If it is less than ³ , rigidity and heat resistance are poor, and the blocking properties of the film are poor. ^{On the other hand} , if it exceeds 0.97 g / cm ³ , it is too hard, and the tensile strength, impact strength and the like become low. MF
If R is less than 0.01 g / 10 minutes, the moldability is poor, and 1
If it exceeds 00 g / 10 minutes, the mechanical strength decreases.

(C) The molecular weight distribution (Mw / Mn) of the ethylene (co) polymer is in the range of 1.5 to 5.0, preferably 1.6 to 4.5, and more preferably 1.7. ４4.0. If the Mw / Mn is less than 1.5, the moldability is poor, and if it exceeds 5.0, the impact resistance is poor. Generally, molecular weight distribution (Mw / Mn) of ethylene (co) polymer
Is a gel permeation chromatography (GP
C), the weight average molecular weight (Mw) and the number average molecular weight (M
n) and their ratio (Mw / Mn) can be calculated.

(D) The ethylene (co) polymer of the present invention has a composition distribution parameter (Cb) of not more than 2.00. And the low molecular weight component or the high degree of branching component oozes out onto the resin surface, causing a problem in hygiene. The method of measuring the composition distribution parameter (Cb) is as follows. That is, orthodichlorobenzene to which an antioxidant is added (OD
A sample was added to CB) so that the concentration was 2.0% by weight, and 1
Heat and dissolve at 35 ° C. The solution is transferred to a column filled with diatomaceous earth (Celite 545), cooled to 25 ° C at a rate of 0.1 ° C / min, and the sample is deposited on the celite surface. Next, while flowing ODCB through the column at a constant flow rate, the temperature of the column is increased stepwise to 120 ° C. in steps of 5 ° C. to elute and separate the sample. Methanol is mixed with the eluate, the sample is reprecipitated, filtered and dried to obtain fraction samples at each elution temperature. The weight fraction of the eluted sample and the degree of branching (degree of branching per 1000 carbon atoms) at each temperature are measured by ¹³ C-NMR.

For each fraction from 30 ° C. to 90 ° C., the branching degree is corrected as follows. That is, the degree of branching measured with respect to the elution temperature is plotted, and the correlation is approximated to a straight line by the least squares method to create a calibration curve. The correlation coefficient of this approximation is large enough. The value obtained from this calibration curve is defined as the degree of branching of each fraction. The elution temperature is 95
For components above ° C, a linear relationship is not always established between the elution temperature and the degree of branching, so this correction is not performed and the measured value is used.

Next, the weight fraction w of each fraction
i is the degree of branching per 5 ° C. of elution temperature. _j Change amount (b_j −
b_j-1 ) Divided by the relative density c_i And for the degree of branching
The relative concentration is plotted to obtain a composition distribution curve. This composition
Divide the distribution curve by a certain width and calculate Cb from the following formula
You.

## EQU1 ## Cb = ( _{ c _j b _j ² / _{ c _j b _j )} ( _{ c _j b _j / Σ
c _j ) where c _j and b _j are the relative density and branching degree of the j-th section, respectively. Composition distribution polyester meter Cb
Is 1.0 when the composition of the sample is uniform, and the value increases as the composition distribution spreads.

Many methods have been proposed for describing the composition distribution of the ethylene-α-olefin copolymer. For example, in Japanese Patent Application Laid-Open No. 60-88016, numerical processing is performed on the assumption that the cumulative weight fraction has a specific distribution (log normal distribution) with respect to the number of branches of each separated sample obtained by solvent separation of the sample. , Weight average branching degree (Cw) and number average branching degree (C
n). The accuracy of this approximation calculation is reduced when the number of branches of the sample and the cumulative weight fraction deviate from the lognormal distribution, and the correlation obtained with commercially available LLDPE is considerably low, and the accuracy is not sufficient. The method of measuring Cw / Cn and the method of numerical processing are different from those of Cb of the present invention, but if the values are compared, the value of Cw / Cn becomes considerably larger than Cb.

The ethylene (co) polymer according to the present invention exhibits good performance by satisfying the above parameters (a) to (d), but more preferably the following (a) to (f) Requirements: (a) density 0.86 to 0.97 g / cm ³ , (b) melt flow rate 0.01 to 100 g / 10 min, (c) molecular weight distribution (Mw / Mn) 1.5 to 5 2.0, (d) the composition distribution parameter (Cb) is 1.08 to 2.00,
(E) that a plurality of peaks of an elution temperature-elution amount curve by a continuous heating elution fractionation method (TREF) are substantially present;
(F) Ortho dichlorobenzene (ODC) at 25 ° C
B) Soluble content X (wt%) is related to density (d) and melt flow rate (MFR) as follows: (a) When d-0.0081 log MFR ≧ 0.93, X <2.0; (B) d-0.0081 log MFR <
In the case of 0.93, X <9.8 × 10 ³ × (0.9300−d + 0.008
It is desirable to use an ethylene (co) polymer satisfying (1MFR) ² +2.0.

The composition distribution parameter (Cb) of the ethylene (co) polymer used in the present invention is 1.08 to 2.0.
0, but preferably 1.10 to 1.7.
0, more preferably 1.13 to 1.60, further preferably 1.10 to 1.50.

(E) The ethylene (co) polymer preferably has a plurality of peaks in an elution temperature-elution amount curve obtained by a continuous heating elution fractionation method (TREF). It is particularly preferred that the peak is between 85 ° C and 100 ° C. The presence of this peak increases the melting point, increases the crystallinity, and improves the heat resistance and rigidity of the molded body. The elution temperature-elution amount curve of the first copolymer of the present invention is as shown in FIG. 1, and the elution temperature-elution amount curve of the copolymer with the second metallocene catalyst of the present invention is shown in FIG. As shown, these copolymers are clearly different, but the resins that can be used in the present invention include these copolymers.

The measuring method of the continuous heating elution fractionation method (TREF) is as follows. That is, a heat-resistant stabilizer is added to the sample, and then the sample is heated and dissolved at 135 ° C. in ODCB so that the sample concentration becomes 0.05% by weight. 5 ml of this heated solution
Was injected into a column filled with glass beads.
Cool to 25 ° C. at a cooling rate of 1 ° C./min and deposit the sample on the surface of the glass beads. Next, the column temperature is raised at a constant rate of 50 ° C./hour while flowing ODCB through the column at a constant flow rate, and samples that can be dissolved in the solution at each temperature are sequentially eluted. At this time, as for the concentration of the sample in the solvent, the absorption of the asymmetric stretching vibration of methylene at a wavenumber of 2925 cm ^-1 is continuously detected by an infrared detector. From this concentration, an elution temperature-elution amount curve can be obtained. The continuous heating elution fractionation method (TREF) can analyze a change in the elution rate with respect to a temperature change continuously with a very small amount of a sample, so that relatively fine peaks that cannot be detected by the fractionation method can be detected.

(F) The ethylene (co) polymer 2 of the present invention
The relationship between the ODCB soluble content X weight% at 5 ° C. and the density (d) and MFR is such that the values of d and MFR are d−0.0.
When 08 log MFR ≧ 0.93, X is 2% by weight.
Less than 1% by weight, d-0.008
In the case of log MFR <0.93, X <9.8 × 10
³ x (0.9300-d + 0.008 log MFR) ²
+2.0, preferably X <7.4 × 10 ³ × (0.9
300−d + 0.008 log MFR) ² +1.0, more preferably X <5.6 × 10 ³ × (0.9300−
d + 0.008 log MFR) ² +0.5.

The ODCB-soluble matter at 25 ° C. is measured by the following method. 0.5 g of a sample is added to 20 ml
Heat at 135 ° C. for 2 hours with DCB to completely dissolve the sample and cool to 25 ° C. After leaving this solution at 25 ° C. overnight, the filtrate is collected by filtering through a Teflon filter. The asymmetric stretching vibration of methylene in the filtrate was measured at a wave number of 292.
The peak area around 5 cm ^-1 is determined, and the sample concentration is calculated from a calibration curve created in advance. From this value, the ODCB-soluble matter at 25 ° C. is determined.

The ODCB-soluble component at 25 ° C. is a high branching component and a low molecular weight component contained in the ethylene-α-olefin copolymer, and causes hygiene problems and blocking of the inner surface of the molded article. It is desirable that the content is small. The amount of ODCB solubles is affected by the comonomer content and molecular weight. Therefore, the fact that the density and the amounts of MFR and ODCB-soluble component, which are indicators, satisfy the above relationship indicates that the uneven distribution of α-olefin contained in the whole copolymer is small.

In the present invention, the ethylene (co) polymer to be used only has to satisfy the above-mentioned properties (a) to (d), and the production method thereof is not particularly limited, but the catalyst comprises the following C1 to C4. It is desirable to carry out the polymerization using That is, C1: a general formula Me ¹ (R ² ) _p (OR ³ ) _r (X ¹ ) _4-pqr (where Me ¹ represents zirconium, titanium, or hafnium, and R ¹ and R ³ each have 1 carbon atom) -24 represents a hydrocarbon group, R ² represents a 2,4-pentanedionato ligand or a derivative thereof, a benzoylmethanato ligand, a benzoylacetonate ligand or a derivative thereof, and X ¹ represents a halogen atom. And p, q and r are each 0 ≦ p <
4, an integer satisfying the ranges of 0 ≦ q ≦ 4, 0 ≦ r ≦ 4, and 0 ≦ p + q + r ≦ 4. ),

C2: General formula Me ² (R ⁴ ) _m (OR ⁵ ) _n (X ² ) _zmn (wherein Me ² is an element in Groups I to III of the periodic table;
⁴ and R ⁵ each represent a hydrocarbon group having 1 to 24 carbon atoms, and X ² represents a halogen atom or a hydrogen atom (however, X ²
Is a hydrogen atom, Me ² is limited to a group III element of the periodic table. ), Z represents the valence of Me ² , m and n are each an integer satisfying the range of 0 ≦ m <z, 0 ≦ n ≦ z, and 0 ≦ m + n ≦ z. C3: an organic cyclic compound having a conjugated double bond, and C4: a modified organic aluminum compound and / or a boron compound containing an A1-O-A1 bond obtained by reacting an organic aluminum compound with water. Catalyst.

The general formula Me of the catalyst component (C1)¹ R¹ _p
R^Two _q(OR^Three)_r(X¹)_4-pqr In the formula of the compound represented by,
Me¹ Represents zirconium, titanium and hafnium. This
The types of these transition metals are not limited,
Can be used, but a dimer having excellent weather resistance of the copolymer can be used.
Preferably, ruconium is included. R¹ And R ^Three 
Is a hydrocarbon group having 1 to 24 carbon atoms,
A prime number of 1 to 12, more preferably 1 to 8,
Includes methyl, ethyl, propyl, and isopropyl
Groups, alkyl groups such as butyl group; vinyl group, allyl group
Any alkenyl group; phenyl group, tolyl group, xylyl
Group, mesityl group, indenyl group, naphthyl group, etc.
Benzyl group, trityl group, phenethyl group, styrene
Ryl, benzhydryl, phenylbutyl, neof
And an aralkyl group such as an aryl group. They are
There may be branches. R^Two Is 2,4-pentanediona
Ligand or its derivative, benzoylmethanato coordination
Benzoylacetonate ligand or its derivative
You. X¹ Is halogen such as fluorine, iodine, chlorine and bromine
P, q and r are respectively 0 ≦ p ≦ 4, 0
≦ q ≦ 4, 0 ≦ r ≦ 4, 0 ≦ p + q + r ≦ 4
Is an integer to be filled.

Specific examples of the catalyst component (C1) represented by the general formula include tetramethyl zirconium, tetraethyl zirconium, tetrabenzyl zirconium, tetrapropoxy zirconium, tripropoxy monochlorodisilconium, tetrabutoxy zirconium,
Examples thereof include tetrabutoxytitanium, tetrabutoxyhafnium, and the like. In particular, Zr (OR ³ ) ₄ compounds such as tetrapropoxyzirconium and tetrabutoxyzirconium, and two or more kinds thereof may be used in combination. Specific examples of the 2,4-pentanedionato ligand or a derivative thereof, a benzoylmethanato ligand, a benzoylacetonato ligand or a derivative thereof include tetra (2,4-pentanedionato) zirconium, Tri (2,4-pentanedionato) chlorite zirconium, di (2,4-pentanedionato) dichlorite zirconium, (2,4-pentanedionato) trichloride zirconium, di (2,4-pentanedionato ) Diethoxide zirconium, di (2,4-pentanedionato) di-n-propoxide zirconium, di (2,4
-Pentanedionato) di-n-butoxide zirconium, di (2,4-pentanedionato) dibenzylzirconium, di (2,4-pentanedionato) dineofylzirconium, tetra (dibenzoylmethanato) zirconium , Di (dibenzoylmethanato) diethoxide zirconium, di (dibenzoylmethanato) di-n-propoxide zirconium, di (dibenzoylmethanato)
Di-n-butoxide zirconium, di (benzoylacetonato) diethoxide zirconium, di (benzoylacetonato) di-n-propoxide zirconium,
And di (benzoylacetonato) di-n-butoxide zirconium.

The general formula Me ² (R ⁴ ) of the catalyst component (C2)
_m (OR ⁵ ) _n (X ² ) In the formula of the compound represented by _zmn , Me ²
Represents a group I-III element of the periodic law, such as lithium, sodium, potassium, magnesium, calcium, zinc, boron, and aluminum. R ⁴ and R ⁵ are each a hydrocarbon group having 1 to 24 carbon atoms, preferably 1 to 24 carbon atoms.
12, more preferably 1 to 8 hydrocarbon groups, specifically, alkyl groups such as methyl group, ethyl group, propyl group, isopropyl group and butyl group; alkenyl groups such as vinyl group and allyl group; phenyl group And aryl groups such as tolyl group, xylyl group, mesityl group, indenyl group and naphthyl group; and aralkyl groups such as benzyl group, trityl group, phenethyl group, styryl group, benzhydryl group, phenylbutyl group and neophyl group. These may have branches. X ² represents a halogen atom or a hydrogen atom such as fluorine, iodine, chlorine and bromine. However, when X ² is a hydrogen atom, Me ² is limited to a group III element of the periodic table exemplified by boron, aluminum and the like. Z represents the valence of Me ² , m and n are integers satisfying the ranges of 0 ≦ m <z and 0 ≦ n ≦ z, respectively, and 0 ≦ m + n ≦ z.

Specific examples of the compound represented by the general formula of the catalyst component (C2) include organic lithium compounds such as methyllithium and ethyllithium; and organic magnesium compounds such as dimethylmagnesium, diethylmagnesium, methylmagnesium chloride and ethylmagnesium chloride. Compounds; organic zinc compounds such as dimethyl zinc and diethyl zinc; organic boron compounds such as trimethyl boron and triethyl boron; trimethyl aluminum, triethyl aluminum, triisobutyl aluminum, trihexyl aluminum, tridecyl aluminum, diethyl aluminum chloride, ethyl aluminum dichloride, Ethyl aluminum sesquichloride, diethyl aluminum ethoxide, diethyl aluminum hydride, etc. Derivatives such as aircraft aluminum compound.

The organic cyclic compound having a conjugated double bond of the catalyst component (C3) includes a cyclic ring having two or more, preferably 2 to 4, more preferably 2 to 3 conjugated double bonds. One or more than two, the total carbon number is 4 to 2
4, a cyclic hydrocarbon compound having preferably 4 to 12; the cyclic hydrocarbon compound is partially a hydrocarbon residue of 1 to 6 (typically, an alkyl group or an aralkyl group having 1 to 12 carbon atoms). A cyclic hydrocarbon compound having one or more rings having two or more, preferably 2 to 4, more preferably 2 to 3 conjugated double bonds, and having 4 to 24 carbon atoms in total. An organosilicon compound having a cyclic hydrocarbon group of preferably 5 to 12; said cyclic hydrocarbon group being partially substituted with 1 to 6 hydrocarbon residues or an alkali metal salt (sodium or lithium salt) Organosilicon compounds are included. Particularly, those having a cyclopentadiene structure in any of the molecules are preferable. Suitable compounds as described above include cyclopentadiene, indene, azulene or their alkyl, aryl, aralkyl, aralkyl or aryloxy derivatives. Further, these compounds are bonded (crosslinked) via alkylene (the number of carbon atoms of which is usually 2 to 8, preferably 2 to 3).
The compounds described above are also preferably used.

The organosilicon compound having a cyclic hydrocarbon group can be represented by the following general formula. (A) _L Si (R) _4-L wherein A represents a cyclic hydrogen group exemplified by a cyclopentadienyl group, a substituted cyclopentanedienyl group, an indenyl group, and a substituted indenyl group; R represents a methyl group; Alkyl groups such as ethyl group, propyl group, isopropyl group and butyl group; alkoxy groups such as methoxy group, ethoxy group, propoxy group and butoxy group; aryl groups such as phenyl group; aryloxy groups such as phenoxy group; Represents an aralkyl group of 1 to 24, preferably a hydrocarbon residue having 1 to 12 carbon atoms or hydrogen, and L represents 1 ≦
L ≦ 4, preferably 1 ≦ L ≦ 3.

Specific examples of the organic cyclic hydrocarbon compound of the component (C3) include cyclopentadiene, methylcyclopentadiene, ethylcyclopentadiene, 1,3-
Dimethylcyclopentadiene, indene, 4-methyl-
C5-C24 cyclopolyenes or substituted cyclopolyenes such as 1-indene, 4,7-dimethylindene, cycloheptatriene, methylcycloheptatriene, cyclooctatetraene, azulene, fluorene and methylfluorene, monocyclopentane Examples include dienyl silane, biscyclopentadienyl silane, triscyclopentadienyl silane, monoindenyl silane, bisindenyl silane, and trisindenyl silane.

Catalyst component (C4) The modified organoaluminum compound containing an A1-O-A1 bond obtained by reacting an organoaluminum compound with water is obtained by reacting an alkylaluminum compound with water. Modified organoaluminum, usually called aluminoxane, containing usually 1 to 100, preferably 1 to 50 A1-O-A1 bonds in the molecule. The modified organoaluminum compound may be linear or cyclic. The reaction between the organoaluminum and water is usually performed in an inert hydrocarbon. As the inert hydrocarbon, aliphatic, alicyclic, and aromatic hydrocarbons such as pentane, hexane, heptane, cyclohexane, benzene, toluene, and xylene are preferable. Reaction ratio of water and organoaluminum compound (water /
(A1 molar ratio) is generally 0.25 / 1 to 1.2 / 1, preferably 0.5 / 1 to 1/1.

As the boron compound, triethylaluminum tetra (pentafluorophenyl) borate (triethylammonium tetra (pentafluorophenyl)
Borate, dimethylanilinium tetra (pentafluorophenyl) borate (dimethylanilinium tetra (pentafluorophenyl) borate, butylammonium tetra (pentafluorophenyl) borate, N, N-
Dimethylanilinium tetra (pentafluorophenyl) borate, N, N-dimethylaniliniumtetra (3,5-difluorophenyl) borate and the like can be mentioned.

The above catalyst may be used by mixing and contacting C1 to C4, but it is preferable to use the catalyst by supporting it on an inorganic carrier and / or a particulate polymer carrier (C5). Examples of the inorganic carrier and / or the particulate polymer carrier include a carbonaceous material, a metal, a metal oxide, a metal chloride, a metal carbonate or a mixture thereof, a thermoplastic resin, and a thermosetting resin. Suitable metals that can be used for the inorganic carrier include iron, aluminum, nickel and the like. Specifically, SiO ₂ ,
Al ₂ O ₃ , MgO, ZrO ₂ , TiO ₂ , B ₂ O ₃ ,
CaO, ZnO, BaO, ThO ₂ and the like or mixtures _{thereof, SiO 2 -Al 2 O 3,} SiO 2 -V 2
O ₅ , SiO ₂ —TiO ₂ , SiO ₂ —MgO, Si
O ₂ —Cr ₂ O _{3 and the} like. Among them, Si
It is preferable that the main component be at least one component selected from the group consisting of O ₂ and Al ₂ O ₃ . Also,
As the particulate polymer carrier, any of a thermoplastic resin and a thermosetting resin can be used. Specifically, particulate polyolefin, polyester, polyamide, polyvinyl chloride, polymethyl (meth) acrylate, polystyrene, poly Examples include norbornene, various natural polymers, and mixtures thereof.

The above-mentioned inorganic carrier and / or particulate polymer carrier can be used as they are, but preferably, as a pretreatment, these carriers are treated with an organic aluminum compound or a modified organic aluminum oxy compound containing an A1-O-A1 bond. Component (C5) after contact treatment
Can also be used.

The process for producing the ethylene (co) polymer used in the present invention is carried out by a gas phase polymerization method substantially free of a solvent in the presence of the catalyst, a slurry polymerization method, a solution polymerization method, or the like. In a state where oxygen, water, etc. are substantially turned off, aliphatic hydrocarbons such as butane, pentane, hexane, and heptane; aromatic hydrocarbons such as benzene, toluene, and xylene; and alicyclic hydrocarbons such as cyclohexane and methylcyclohexane It is produced in the presence or absence of an inert hydrocarbon solvent exemplified as above. The polymerization conditions are not particularly limited, but the polymerization temperature is usually 15 to 350 ° C, preferably 20 to
To 200 ° C, more preferably 50 to 110 ° C.
The polymerization pressure is usually from normal pressure to 70 kg / cm ^{2 in} the case of the low and medium pressure method.
G, preferably normal pressure to 20 kg / cm ² G, the case of high pressure process typically 1500 kg / cm ² G or less.
The polymerization time is usually from 3 minutes to 10 hours, preferably from 5 minutes to 5 hours in the case of the low and medium pressure method. In the case of the high-pressure method, it is usually 1 minute to 30 minutes, preferably about 2 minutes to 20 minutes. Further, the polymerization is not particularly limited to a one-stage polymerization method, but also to a multi-stage polymerization method of two or more stages in which polymerization conditions such as hydrogen concentration, monomer concentration, polymerization pressure, polymerization temperature, catalyst and the like are different from each other.

In the present invention, the above (A1) and (A2)
Ethylene (co) polymer to another ethylene polymer (B)
95% by weight or less can be blended. Other Etch above
(B1) high-pressure radical polymerization as the lene polymer (B)
0.91-0.94 g / cm^Three Homopolymerization of
Copolymer or copolymer of ethylene and unsaturated monomer
(B2) low, medium, high pressure ion polymerization
Degree 0.94g / cm^Three Linear low density polyethylene, (B
3) Density 0.94 g / cm ^Three Above all, high density polyethylene
At least one ethylene-based heavy selected from the group of
Coalescence.

The low-density polyethylene (B1) produced by high-pressure radical polymerization has a density of 0.91 to 0.94 g / cm
³ , preferably 0.912 to 0.935 g / cm ³ , more preferably 0.912 to 0.930 g / cm ³ , and a melt flow rate (MFR) of 0.01 to
50 g / 10 min, preferably 0.1 to 30 g / 10 min,
Preferably it is 0.2 to 20 g / 10 minutes. Within this range, the melt tension of the composition is in an appropriate range, and film formation is easy. The melt tension is 1.5 to 25 g, preferably 3 to 20 g. Melt tension is an item of elasticity of the resin, and if it is in the above range, the film can be easily formed. Mw / Mn is 3.0 to 20, preferably 4.0 to 1
It is desirably in the range of 5.

The ethylene polymer (B1) obtained by another high-pressure radical polymerization method of the present invention includes a copolymer of ethylene and an unsaturated monomer. Examples of these copolymers include ethylene-vinyl ester copolymers and copolymers with ethylene-α, β-unsaturated carboxylic acids and derivatives thereof.

The ethylene-vinyl ester copolymer of the present invention refers to vinyl propionate containing ethylene as a main component,
It is a copolymer with vinyl ester monomers such as vinyl acetate, vinyl caproate, vinyl caprylate, vinyl laurate, vinyl stearate, and vinyl trifluoroacetate. Among them, particularly preferred is vinyl acetate (EVA). That is, ethylene 50 to 99.5% by weight, vinyl ester 0.5 to 5
0% by weight, other copolymerizable unsaturated monomers 0 to 49.5
Copolymers consisting of% by weight are preferred. Particularly, the vinyl ester content is 3 to 20% by weight, preferably 5 to 15% by weight.
Range. The MFR of these copolymers is 0.1 to 2
0 g / 10 min, preferably 0.3 to 10 g / 10 min, and the melt tension is 2.0 to 25 g, preferably 3 to 20 g.
It is.

Typical copolymers of the present invention with ethylene-α, β-unsaturated carboxylic acids or derivatives thereof include ethylene- (meth) acrylic acid or its alkyl ester copolymer. Examples of these comonomers include acrylic acid, methacrylic acid, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, propyl acrylate, propyl methacrylate, isopropyl acrylate, isopropyl methacrylate, and acrylic acid-n-. Butyl, n-butyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, lauryl acrylate, lauryl methacrylate, stearyl acrylate, stearyl methacrylate,
Glycidyl acrylate, glycidyl methacrylate and the like can be mentioned. Among them, particularly preferred are alkyl esters of (meth) acrylic acid such as methyl and ethyl (EEA). In particular, the content of the (meth) acrylate is in the range of 3 to 20% by weight, preferably 5 to 15% by weight. MFR of these copolymers
Is 0.1 to 20 g / 10 min, preferably 0.3 to 10 g
g / 10 minutes, and the melt tension is 2.0 to 25 g, preferably 3 to 20 g.

Other copolymers include ethylene and α, β unsaturated carboxylic acids such as copolymers of ethylene and maleic anhydride or derivatives thereof, ionomers and the like.

The linear low-density polyethylene (B) having a density of 0.94 g / cm ³ by the low, medium and high pressure ionic polymerization method of the present invention.
2) means ethylene-α having a density of less than 0.91 g / cm ³
-Olefin copolymer rubber, low crystalline ethylene-α-olefin copolymer, ultra-low density polyethylene, 0.91-
Linear low-density polyethylene of less than 0.94 g / cm ³ ; The MFR of these resins is 0.01 to 100 g
/ 10 minutes, preferably 0.1 to 50 g / 10 minutes, and more preferably 0.1 to 30 g / 10 minutes. M
If the FR is less than 0.01 g / 10 minutes, there is a possibility that the moldability is deteriorated. If the FR exceeds 100 g / 10 minutes, the impact resistance and the tensile strength may be reduced. Among the linear low-density polyethylene (B1), a density of 0.88 to 0.94 g
/ Cm ³ , molecular weight distribution (Mw / Mn) is 1.5 to
It is desirably in the range of 4.5, preferably in the range of 1.6 to 4.0, more preferably in the range of 1.8 to 3.5. If the molecular weight distribution is less than 1.5, the moldability will be poor, and if it exceeds 4.5, the impact resistance will be poor and the transparency will be insufficient.

The polyethylene-aminoacrylate graft copolymer according to the present invention is an ethylene (co) polymer 8
It is obtained by grafting 0.1 to 20 parts by weight of an aminoacrylate compound to 0.0 to 99.9 parts by weight. If the amount of the ethylene (co) polymer is less than 80.0 parts by weight, the tensile strength of the film is low, and if it exceeds 99.9 parts by weight, the heat sealability and impact strength are poor.

The aminoalkyl used in the present invention
Acrylate compounds have the general formulaA compound represented by the formula:¹ Is hydrogen or methyl
Yes, R^Two , R^Three Is hydrogen or methyl, ethyl, n-propyl
Carbon number such as ropyl, isopropyl, tertiary butyl
1 to 4 alkyl groups. Also, n is an integer from 1 to 4.
Indicates the number, C_n H _2nSpecific examples of methylene, ethyl
Len, trimethylene, tetramethylene, dimethylmethyl
, Methylethylmethylene, dimethylethylene, methyl
Trimethylene and the like.

Specific examples of the aminoalkyl acrylate compound represented by the above general formula include aminomethyl (meth) acrylate, aminoethyl (meth) acrylate, amino normal butyl (meth) acrylate, N
-Methylaminoethyl (meth) acrylate, N-ethylaminoethyl (meth) acrylate, N-isopropylaminoethyl (meth) acrylate, N-tert-butylethyl (meth) acrylate, Nn-butylaminoethyl (meth) Acrylate, N, N-dimethylaminomethyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylate, N, N-dimethylaminoisopropyl (meth) acrylate, N, N-dimethylamino-n-butyl (meth) ) Acrylate, N,
N-dimethylaminohexyl (meth) acrylate,
N, N-diethylaminoethyl (meth) acrylate,
N, N-di-n-propylaminoethyl (meth) acrylate, N, N-diisopropylaminoethyl (meth)
Acrylate, N-di-n-butylaminoethyl (meth) acrylate, N-methyl-N-ethylaminoethyl (meth) acrylate, N-methyl-NN-butylaminoethyl (meth) acrylate, N, N- Di-n-
Acrylic esters such as propylaminopropyl (meth) acrylate and methacrylic esters corresponding thereto can be mentioned. Of the methacrylates, N, N-diethylaminoethyl methacrylate and N, N-dimethylaminoethyl methacrylate are preferred.

The grafting reaction is not particularly limited, but in the polyethylene-aminoacrylate graft copolymer film of the present invention, the polyethylene and the aminoalkyl acrylate compound are formed into a film in the presence of an organic peroxide. It can be produced by simultaneously performing the graft reaction and the film forming in an extruder mounted on the machine, and this method is also excellent in economic efficiency. Also,
As another method, a polyethylene-aminoacrylate graft copolymer is produced by using a kneader such as an extruder or a kneader such as a Banbury mixer or a radiation irradiator, and then forming the film with a normal film forming machine. Is also good.

Examples of the reaction initiator used in the graft polymerization reaction include benzoyl peroxide, lauryl peroxide, azobisisobutyronitrile, dicumyl peroxide, t-butyl hydroperoxide,
α, α′-bis (t-butylperoxydiisopropyl) benzene, di-t-butyl peroxide, 2,5
-(T-butylperoxy) hexine and the like are preferably used.

0.005 to 2.0 parts by weight, preferably 0.01 to 2.0 parts by weight, based on 100 parts by weight of the total of the ethylene (co) polymer and the aminoalkyl acrylate compound.
Used in the range of 1 part by weight. If the addition amount of the reaction initiator is less than 0.005 parts by weight, substantially no modification effect is exhibited, and even if it exceeds 2.0 parts by weight, it is difficult to obtain an effect proportional to the addition amount. The decomposition or crosslinking of the polymer may cause a reaction or the like. The reaction initiator is decomposed by heating, and the amino acrylate is grafted on the polyethylene to obtain a graft copolymer (hereinafter sometimes simply referred to as a copolymer). In this case, it is considered that the reaction initiator is decomposed and a part of the initiator is taken out of the copolymer and a part thereof is taken into the copolymer, and it is difficult to accurately define the amount in the copolymer. The molding temperature at the time of performing the graft reaction to obtain a polyethylene-amino acrylate graft copolymer simultaneously with the above-mentioned film molding is appropriately selected in consideration of the deterioration of the resin, the decomposition temperature of the reaction initiator, and the like. Reaction temperatures in the range 〜250 ° C. are used.

To the polyethylene-aminoacrylate graft copolymer of the present invention, if necessary, stabilizers, antistatic agents, coloring agents such as pigments, and other additives are added as long as the objects of the present invention are not impaired. can do. This addition may be made at the time of film formation or at the time of producing the polyethylene-aminoacrylate graft copolymer.

The polyethylene-aminoacrylate graft copolymer film of the present invention can be formed by various well-known methods. For example, when the graft reaction is performed in an extruder, air-cooled inflation, water-cooled inflation, T-die method and the like are suitable, and air-cooled inflation is particularly preferable. The production of the air-cooled blown film can be performed by an air-cooled blown film production apparatus, for example, by mixing LLD, an aminoalkyl acrylate compound and a reaction initiator, and mixing 150-2.
The extruder is extruded at a temperature of 50 ° C. through a circular die, is contacted with air blown from an air-cooled air ring, is rapidly cooled, is solidified, is taken out with a pinch roll, and is wound around a frame. By this method, it is possible to simultaneously improve the transparency, strength and heat sealability of the air-cooled blown film, which has been difficult to solve at the same time. Of course, in addition to the air-cooled blown film, a water-cooled blown film and a T-die film can be produced, and a film having excellent transparency can be obtained.

The thickness of the polyethylene-aminoacrylate-graft copolymer film of the present invention is from 10 to 200 μm, more preferably from 30 to 200 μm, from the viewpoint of ease of use.
~ 100 microns. According to the production method as described above, a polyethylene-aminoacrylate-graft copolymer film having excellent transparency having a haze value of less than 20% can be obtained. Haze value is ASTM D10
03. Further, the haze value in the present invention is shown as a numerical value obtained by summing the external haze value and the internal haze value.

In the polyethylene-aminoacrylate-graft copolymer film of the present invention, the aggregate of crystalline lamella protruding irregularly on the film surface has a particle diameter (L = 60 to 120 °) of high-density polyethylene particles. It has the characteristic of being smaller than the diameter (L = 500-700 °), and can smoothen the film surface and reduce the external haze value of the film. Furthermore, the grain size of the microcrystals inside the film is also reduced, and the internal haze value of the film can be reduced. Further, by reducing the crystal grain size and increasing the molecular motion, the melting temperature is lowered and low-temperature heat sealability is exhibited. The LLD component is 80.0 to 99.9.
Because of the weight part, high strength, which is an excellent property of the linear low density polyethylene film, is maintained.

[0055]

Examples (Examples 1-2 and Comparative Examples 1-2) [Production of ethylene (co) polymer] (Preparation of solid catalyst) Catalyst preparation machine with electromagnetic induction stirrer under nitrogen atmosphere (No. 1) , Purified toluene was added thereto, and then dipropoxydichlorozirconium [Zr (OPr)
₂ Cl ₂ ] and 48 g of methylcyclopentadiene
Was added thereto, and 45 g of tridecylaluminum was added dropwise while maintaining the reaction system at 0 ° C. After completion of the addition, the reaction system was maintained at 50 ° C. and stirred for 16 hours. (This solution is referred to as solution A.) Then, under a nitrogen atmosphere, another catalyst-prepared machine (N
o. Add purified toluene to 2), add solution A above,
Then, a toluene solution of 6.4 mol of methylaluminoxane was added and reacted. (This is referred to as solution B.) Next, under a nitrogen atmosphere, the above-mentioned catalyst preparation machine with stirring (N
o. Add purified toluene to 1), then add 40
Silica (Grade # 952, manufactured by Fuji Devison, surface area: 300 m ² / g) 140 calcined at 0 ° C. for a predetermined time
After adding 0 g, the entire amount of the B solution was added, and the mixture was stirred at room temperature. Next, the solution was removed by nitrogen blowing to obtain a solid powder having good fluidity. (This is referred to as catalyst C.)

(Polymerization Reaction) Using a continuous fluidized bed gas phase polymerization apparatus, a polymerization temperature of 70 ° C. and a total pressure of 20 kgf / cm ² G
To copolymerize ethylene with 1-butene or 1-hexene. The polymerization was carried out by continuously supplying the catalyst C, and the polymerization was carried out while continuously supplying each gas in order to keep the gas composition in the system constant.

(Physical Properties of Polymer) (1) Ethylene-1-butene copolymer (I) Density: 0.910 g / cm ³ MFR: 0.5 g / 10 min Molecular weight distribution (Mw / Mn): 2.7 Composition distribution parameter (Cb): 1.24 d-0.008 log MFR: 0.912 ODCB soluble matter (%): 3.0 <9.8 × 10 ³ × (0.9300-d + 0.008 log MFR) ² +2. 0 TREF peak temperature: 70.3 ° C, 75.1 ° C, 95.1 ° C (3 points)

(2) Ethylene-1-hexene copolymer Density = 0.912 g / cm ³ MFR = 0.7 g / 10 min Molecular weight distribution (Mw / Mn) = 2.6 Composition distribution parameter Cb = 1.23 d −0.008 log MFR = 0.913 d−0.008 log MFR = 0.912 ODCB soluble matter (%) = 2.8 <9.8 × 10 ³ × (0.9300−d + 0.0008 l)
ogMFR) ² +2.0 TREF peak temperature = 2 points of 69.7 ° C. and 92.1 ° C.

(Graft Method and Production of Film) By air-cooled inflation molding, LLD was converted into ethylene (co) polymer in the presence of an organic peroxide directly in an extruder.
And an aminoalkyl acrylate compound,
At the same time, a film was formed. As organic peroxides,
Benzoyl peroxide was added in an amount of 0.1 to 100 parts by weight of the total amount of the LLD and the aminoalkyl acrylate compound.
One part by weight was used. LLD has a density of 0.950 g / c
m ³ , melt flow rate (MFR) 0.04 g / 1
The thing of 0 minute was used, and aminoethyl acrylate was used as the aminoalkyl acrylate compound. LLD
The compounding ratio of aminoethyl acrylate and aminoethyl acrylate was set to 95/5 in Example 1 and 90/10 in Example 2. In Comparative Examples 1 and 2, no aminoalkyl acrylate compound was used, and in Comparative Example 1, no organic peroxide was used. The resin composition having the above mixing ratio was formed into a film having a thickness of 30 μm by an air-cooled inflation molding machine. The molding conditions were a molding temperature of 200 ° C. and a blow ratio of 3.

(Measurement method of film physical properties) Haze value: ASTM D1003 Heat sealing property: Cut into a strip having a film width of 15 mm, and heat it by changing the temperature under the conditions of a sealing pressure of 2 kg / cm ² and a sealing time of 1 second. This sample was peeled at a rate of 300 mm / min, and the peel strength was examined. The seal temperature at which the peel strength was 1 kg was regarded as the heat sealability. Impact strength: ASTM D781

[0061]

[Table 1]

From the results shown in Table 1, it can be seen that the film using the resin of the first invention has excellent impact strength, and has well-balanced properties such as heat sealability and haze value. It could be confirmed.

[0063]

The polyethylene-aminoacrylate graft copolymer described above has flexibility when formed into a film, has an appropriate melting temperature, and has high strength.
It also has good impact strength, heat sealability, and high transparency. Therefore, it is a film that can be easily heat-sealed at a low temperature and that is not easily broken even when subjected to an impact. Such an excellent resin contains 0.1 to 20% by weight of an aminoalkyl acrylate compound based on polyethylene having specific physical property values [(a) to (d) or (a) to (f)]. The resin composition is obtained very easily by graft copolymerization using an extruder as described above, and is blended in an amount of less than 50 parts by weight with respect to 100 parts by weight of the obtained polyethylene-aminoacrylate graft copolymer. Gives a film having the same physical properties as that of the graft copolymer alone. This graft copolymer greatly improves the processability of linear low-density polyethylene, which has been regarded as having a problem in processability despite having many excellent performances. It is greatly expanded.

[Brief description of the drawings]

FIG. 1 is an example of a TREF curve of a copolymer of the present invention.

FIG. 2 is an example of a TREE curve of a metallocene copolymer.

 ────────────────────────────────────────────────── ─── Continuing on the front page (72) Shinichi Yagi 2-3-2 Yoko, Kawasaki-ku, Kawasaki-shi, Kanagawa F-term in Kawasaki Research Laboratory, Japan Polyolefin Co., Ltd. 4F071 AA15 AA15X AA19 AA21X AA33 AA77 AA81 AA82 AA88 AC08 AF05Y AF14 AF23 AF26 AF30 AF59 AH04 BA01 BB06 BB09 BC01 4J002 BB032 BB062 BB072 BB082 BB092 BB232 BN031 CD192 FD030 FD090 FD100 GG02 4J026 AA11 AA12 AA13 AA14 DB33 DA02 DA10

Claims (7)

[Claims] 1. An ethylene (co) polymer satisfying the following requirements (a) to (b): (a) a density of 0.86 to 0.97 g / cm ³ , and (b) a melt flow rate of 0.01 to 100g / 10
Min, (iii) a molecular weight distribution (M _W / M _N) is 1.5 to 5.0, and (d) a composition distribution parameter (Cb) of 2.00 or less 80 to 99.9 parts by weight, formula (1 _{^{) CH 2 = CR 1 COOC n}} H 2n NR 2 R 3 ····· (1) ( provided that, R ¹ is hydrogen or a methyl group, R ² and R ³ are hydrogen or an alkyl group having 1 to 4 carbon atoms, n represents an integer of any one of 1 to 4.) A polyethylene-aminoacrylate-graft copolymer obtained by grafting 0.1 to 20 parts by weight (total 100 parts by weight) of an aminoalkyl acrylate compound represented by the following formula: 2. 100 parts by weight of an ethylene (co) polymer satisfying the following requirements (a) to (f): (a) a density of 0.86 to 0.97 g / cm ³ , and (b) a melt flow. Rate 0.01-100g / 10
Min, (iii) a molecular weight distribution (M _W / M _N) is 1.5 to 5.0, the (d) composition distribution parameter (Cb) from 1.08 to 2.
(E) The presence of a plurality of peaks in the elution temperature-elution amount curve by the continuous heating elution fractionation method (TREF). (F) orthodichlorobenzene (ODC) at 25 ° C.
B) The soluble content X (wt%), the density d and the melt flow rate (MFR) satisfy the following relationship: a) d-0.008 log MFR ≧ 0.93, X <2.0 b) d When −0.008 log MFR <0.93, X <9.8 × 10 ³ × (0.9300−d ++ 0.000
8logMFR) ² +2.0 General formula (1) CH ₂ ＣＲCR ¹ COOC _n H _2n NR ² R ³ ... (1) (where R ¹ is hydrogen or a methyl group, and R ² and R ³ are hydrogen Or an alkyl group having 1 to 4 carbon atoms, and n represents an integer of 1 to 4), which is grafted with 0.1 to 20 parts by weight (total 100 parts by weight). Polyethylene-aminoacrylate-graft copolymer. 3. Polyethylene according to claim 1 or 2.
A polyethylene-aminoacrylate-graft copolymer resin composition comprising 100 parts by weight of an aminoacrylate-graft copolymer and less than 50 parts by weight of another polyolefin. 4. A polyethylene-amino comprising the polyethylene-aminoacrylate-graft copolymer according to claim 1 or 2 or the polyethylene-aminoacrylate-graft copolymer according to claim 3, wherein the haze value is less than 20%. Acrylate-graft copolymer film. 5. The polyethylene according to claim 1 or 2.
Consisting of 100 parts by weight of amino acrylate-graft copolymer and less than 50 parts by weight of another ethylene-based copolymer,
A polyethylene-aminoacrylate-graft copolymer film having a haze value of less than 20%. 6. 100 parts by weight of an ethylene (co) polymer satisfying the requirements (a) to (d) according to claim 1 or the requirements (a) to (f) according to claim 2 General formula (1) CH ₂ ＣＲCR ¹ COOC _n H _2n NR ² R ³ (1) (where R ¹ is hydrogen or a methyl group, R ² and R ³ are hydrogen or a carbon atom having 1 to 1 carbon atoms) Wherein the alkyl group of 4 and n is an integer of 1 to 4) are graft copolymerized in a film forming machine with 0.1 to 20 parts by weight of the aminoalkyl acrylate compound represented by the formula (1). Item 4
3. The method for producing a polyethylene-aminoacrylate-graft copolymer film according to item 1. 7. Ethylene which has been kneaded in advance or which satisfies the requirements (a) to (d) according to claim 1 or the requirements (a) to (f) according to claim 2 respectively. 100 parts by weight of the (co) polymer and other ethylene-based copolymers of less than 50 parts by weight and the general formula (1) CH ₂ = CR ¹ COOC _n H _2n NR ² R ³ (1) , R ¹ is hydrogen or a methyl group, R ² and R ³ are hydrogen or an alkyl group having 1 to 4 carbon atoms, and n is an integer of 1 to 4). 6. The graft copolymerization of 1 to 20 parts by weight in a film forming machine.
3. The method for producing a polyethylene-aminoacrylate-graft copolymer film according to item 1.