JP2004277744A - Film and sealant - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a film excellent in clarity, impact strength, heat sealing property at a low temperature, heat seal strength and the like and effective itself or as a sealant. <P>SOLUTION: This film contains, as the essential component, an ethylene-α-olefin copolymer which satisfies following (1) to (6): (1) the density is 0.86-0.96 g/cm<SP>3</SP>, (2) the melt flow rate (MFR) is 0.01-200 g/10min, (3) the molecular weight distribution (Mw/Mn) is 1.5-4.5, (4) the composition distribution parameter Cb is 1.08-2.00, (5) the o-dichlorobenzene (ODCB) soluble part X (wt.%), the density d and the MFR satisfy followings; (a) X<2.00 when d-0.008logMFR≥0.93, and (b) X<9.8×10<SP>3</SP>×(0.9300-d+0.008logMFR)<SP>2</SP>+2.0 when density d and MFR satisfy d-0.008logMFR<0.93 and (6) a plurality of peaks are in the elution temperature-elution amount curve obtained by a continuous temperature rising elution fractionation method. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention is a film having excellent heat sealing properties such as transparency, impact strength, low-temperature heat sealing property, heat sealing strength, and excellent anti-blocking properties, and a material having gas barrier properties and strong stiffness. Another object of the present invention is to provide a sealant film used for a part of a laminate having the above characteristics. The film is used for a packaging material or a packaging bag. In addition, the film obtained by laminating a material having gas barrier properties and strong stiffness using the film as a sealant is, for example, various packaging materials such as pickles, dairy products, retort foods or frozen foods, foods such as confectionery, clothing, etc. It is used for medicines and infusion containers, packaging materials for transporting various liquids, bolts, containers and the like.

  A linear low-density polyethylene polymer (LLDPE) is widely used as various packaging materials because of its excellent moldability, transparency, strength, and heat sealing strength (for example, Patent Documents 1 and 2). However, recently, higher transparency and film strength are required. Further, higher speed is required for a film using an automatic bag making machine or the like, and a film having further excellent low-temperature heat sealing properties is required.

  When heat sealing is performed at a high speed, heat sealing is performed in a short time, so that welding is insufficient and strength is likely to be insufficient. As one method of improving this, there is a method of increasing the temperature of the heat seal bar. However, this method causes a problem such as curling of the laminated resin. Another method is to lower the melting point of the resin by lowering the density of the resin. However, in the conventional LLDPE, when the density is lowered, the high-branching low-molecular weight component increases and elutes on the surface, and the film becomes sticky and the mouth opening property is deteriorated, or they are disadvantageously transferred to the contents. .

The LLDPE film is laminated with a resin having excellent gas barrier properties such as polyamide, polyester, and saponified ethylene-vinyl acetate, or a resin having high rigidity such as high-density polyethylene or polypropylene, so that the gas barrier properties or rigidity are strong. A laminate having good heat-sealing properties having such properties as above has a wider application as a packaging material suitable for high-speed bag making, for example, a packaging material for foods, a packaging bag, a food container, a drug container and the like. The LLDPE film is widely used also as a film (sealant film) for a heat seal layer of these laminates. These laminates are laminated on a substrate by an extrusion lamination method, a dry lamination method, a sand lamination method, a coextrusion T-die method, a coextrusion inflation method, or the like. Above all, in the dry lamination method etc., lamination is performed using a polyether-based adhesive, polyurethane-based adhesive, vinyl acetate-based adhesive, isocyanate-based adhesive, polyethyleneimine-based adhesive, etc. Then, heat treatment is performed to cure the adhesive. At this time, the lubricant added to the film is transferred to the adhesive layer, and the opening property and the lubricity of the laminated surface are deteriorated, which causes problems in the bag making and filling steps.
JP-A-52-135386 JP-A-61-284439

  An object of the present invention is to eliminate these drawbacks of the prior art, and more specifically, a novel ethylene / α-olefin copolymer having excellent strength, heat resistance and moldability that is not found in conventional LLDPE. Providing a film with high transparency, high impact strength, low elution of low molecular weight resin component and excellent low temperature heat sealing property by polymer, and strong adhesive strength with laminate material, anti-blocking property and lubricity It is an object of the present invention to provide a laminate sealant that is well-balanced, has excellent low-temperature heat sealing properties, and is excellent in gas barrier properties, high-speed bag making properties, and the like.

  First, the present invention is different from a commercially available ethylene / α-olefin copolymer polymerized with a metallocene catalyst, which is a novel ethylene / α-olefin copolymer having a narrow molecular weight distribution and a moderately wide composition distribution. By using a polymer, a film having higher strength than conventional ones, excellent low-temperature heat sealability and transparency, and having less sticky film surface is provided.

  Secondly, the present invention is characterized in that by adding a specific lubricant to the ethylene / α-olefin copolymer, a low-temperature heat-sealing property, excellent strength, a good balance of anti-blocking property and lubricity, and high-speed bag making are provided. An object of the present invention is to provide a sealant for a laminate, which has excellent properties and does not decrease the adhesive strength to a laminate material.

That is, the first of the present invention is:
(A) A film comprising an ethylene / α-olefin copolymer satisfying the following (A) to (F).
(A) Density of 0.86 to 0.96 g / cm ³
(A) Melt flow rate (MFR) is 0.01 to 200 g / 10 min.
(C) Molecular weight distribution (Mw / Mn) is 1.5 to 4.5.
(D) The composition distribution parameter Cb is 1.08 to 2.00.
(E) Orthodichlorobenzene (ODCB) soluble content at 25 ° C. X (wt%) and density d and MFR satisfy the following relationship: a) Density d and MFR values are d−0.008 log MFR ≧ 0. In the case of 93, X <2.0
b) When the values of the density d and the MFR are d−0.008 log MFR <0.93, X <9.8 × 10 ³ × (0.9300−d + 0.008 log MFR) ² +2.0
(F) There are a plurality of peaks in an elution temperature-elution amount curve by a continuous heating elution fractionation method (TREF).

A second aspect of the present invention is that the ethylene / α-olefin copolymer satisfying the following (A) to (A) is not less than 20% by weight and the density is 0.86 to 0.96 g / cm ^3.
(A) Melt flow rate (MFR) is 0.01 to 200 g / 10 min.
(C) Molecular weight distribution (Mw / Mn) is 1.5 to 4.5.
(D) The composition distribution parameter Cb is 1.08 to 2.00.
(E) Orthodichlorobenzene (ODCB) soluble content at 25 ° C. X (wt%) and density d and MFR satisfy the following relationship: a) Density d and MFR values are d−0.008 log MFR ≧ 0. In the case of 93, X <2.0
b) When the values of the density d and the MFR are d−0.008 log MFR <0.93, X <9.8 × 10 ³ × (0.9300−d + 0.008 log MFR) ² +2.0
(F) a composition comprising a plurality of peaks of an elution temperature-elution amount curve by continuous temperature-elution elution fractionation (TREF), and (B) a composition containing 80% by weight or less of another ethylene polymer. Film.

A third aspect of the present invention is that the density of 100 parts by weight of the ethylene / α-olefin copolymer (A) satisfying the following (A) to (F) is 0.86 to 0.96 g / cm ^3.
(A) Melt flow rate (MFR) is 0.01 to 200 g / 10 min.
(C) Molecular weight distribution (Mw / Mn) is 1.5 to 4.5.
(D) The composition distribution parameter Cb is 1.08 to 2.00.
(E) Orthodichlorobenzene (ODCB) soluble content at 25 ° C. X (wt%) and density d and MFR satisfy the following relationship: a) Density d and MFR values are d−0.008 log MFR ≧ 0. In the case of 93, X <2.0
b) When the values of the density d and the MFR are d−0.008 log MFR <0.93, X <9.8 × 10 ³ × (0.9300−d + 0.008 log MFR) ² +2.0
(F) a composition comprising 0.03 to 0.25 parts by weight of an aliphatic amide having a plurality of peaks of an elution temperature-elution amount curve by a continuous heating elution fractionation method (TREF) It is a sealant.

A fourth aspect of the present invention is that the ethylene / α-olefin copolymer satisfying the following (A) to (F) is not less than 20% by weight (A) and the density is 0.86 to 0.96 g / cm ^3.
(A) Melt flow rate (MFR) is 0.01 to 200 g / 10 min.
(C) Molecular weight distribution (Mw / Mn) is 1.5 to 4.5.
(D) The composition distribution parameter Cb is 1.08 to 2.00.
(E) Orthodichlorobenzene (ODCB) soluble content at 25 ° C. X (wt%) and density d and MFR satisfy the following relationship: a) Density d and MFR values are d−0.008 log MFR ≧ 0. In the case of 93, X <2.0
b) When the values of the density d and the MFR are d−0.008 log MFR <0.93, X <9.8 × 10 ³ × (0.9300−d + 0.008 log MFR) ² +2.0
(F) a plurality of peaks of an elution temperature-elution amount curve by a continuous heating elution fractionation method (TREF) and (B) a resin component consisting of 80% by weight or less of another ethylene-based polymer (C) A sealant comprising a composition containing 0.03 to 0.25 parts by weight of an aliphatic amide.

  The film of the present invention is a film having high impact strength, little elution of resin components, and excellent in transparency, anti-blocking property, and low-temperature heat sealing property. In addition, the sealant of the present invention has the above-mentioned properties, does not decrease the adhesive strength with the laminated substrate, has a good balance of anti-blocking properties and lubricity, and is excellent in low-temperature heat sealing properties and high-speed bag making properties, and has gas barrier properties. It is suitable for providing a laminate having the same.

Hereinafter, the present invention will be described in detail.
The ethylene / α-olefin copolymer (A) of the present invention is a novel ethylene / α-olefin copolymer different from an ethylene / α-olefin copolymer polymerized with a so-called general metallocene-based catalyst. And a copolymer of at least one selected from α-olefins having 3 to 20 carbon atoms. 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, 1-octene, Examples thereof include 1-decene and 1-dodecene. It is desirable that the content of these α-olefins is generally selected in a range of usually 30 mol% or less, preferably 20 mol% or less.

(A) The density of (a) the ethylene / α-olefin copolymer is 0.86 to 0.96 g / cm ³ , preferably 0.88 to 0.935 / cm ³ , and more preferably 0.90 to 0. 0.925 g / cm ³ . If the density is less than 0.86 g / cm ³ , rigidity and heat resistance are poor, and if it is 0.96 g / cm ³ or more, impact resistance is not sufficient.

  The (A) MFR of the ethylene / α-olefin copolymer (A) is in the range of 0.01 to 200 g / 10 min, preferably 0.1 to 100 g / 10 min, and more preferably 0.2 to 50 g / min. Is preferred. When the MFR is less than 0.01 g / 10 min, the moldability is poor, and when the MFR is 200 g / 10 min or more, the strength is reduced.

  The (A) method for calculating the molecular weight distribution (Mw / Mn) of the ethylene / α-olefin copolymer is determined by gel permeation chromatography (GPC) using a weight average molecular weight (Mw) and a number average molecular weight (Mn). And the ratio Mw / Mn is determined. These Mw / Mn are 1.5 to 4.5, preferably 1.6 to 4.0, and more preferably 1.8 to 3.5. If Mw / Mn is less than 1.5, the moldability is poor, and if it is 4.5 or more, the impact resistance is poor.

  The (A) ethylene / α-olefin copolymer (d) has a composition distribution parameter Cb of 1.08 to 2.00, preferably 1.10 to 1.80, more preferably 1.12 to 1.80. It is preferably in the range of 70. If it is less than 1.08, the rigidity is inferior to the density, and if it is 2.00 or more, the transparency and the low-temperature heat sealability deteriorate.

  The method for measuring the composition distribution parameter Cb of (A) the ethylene / α-olefin copolymer is as follows.

  That is, an antioxidant is added to the sample, and the sample is heated and dissolved at 135 ° C. in ODCB so that the sample concentration becomes 0.2% by weight. The heated solution is transferred to a column filled with diatomaceous earth (Celite 545), cooled to 25 ° C. at a cooling rate of 0.1 ° C./min, and the sample is deposited on the celite surface. Next, while flowing the ODCB at a constant flow rate and gradually increasing the column temperature to 120 ° C. in steps of 5 ° C., the sample is eluted and the sample is separated and collected at each temperature. This solution is reprecipitated by adding methanol, which is a precipitant for the sample, followed by filtration and drying to obtain samples at each elution temperature. The weight fraction and the degree of branching (the number of branches per 1000 carbon atoms) of each sample are determined by 13C-NMR.

  For the fraction collected at an elution temperature of 30 ° C. to 90 ° C., the degree of branching 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 corrected by this calibration curve is defined as the degree of branching of each fraction. If the elution temperature is 95 ° C. or higher, this correction is not performed because a linear relationship is not always established between the elution temperature and the degree of branching.

Then the weight fraction wi of each fraction to obtain the relative concentration c _i divided by the amount of change in the degree of branching b _i per the elution temperature _{5 ℃ (b i -b i-} 1), relative with respect to the degree of branching The concentration is plotted to obtain a composition distribution curve. This composition distribution curve is divided by a constant radiation, and a composition distribution parameter Cb is calculated from the following equation.

Here, c _j and b _j are the relative density and branching degree of the j-th section, respectively. The composition distribution parameter Cb is 1.0 when the composition of the sample is uniform, and the value increases as the composition distribution spreads.

Many proposals have been made for a method of 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. The ratio between the weight average branching degree (Cw) and the number average branching degree (Cn) is determined. The approximation calculation accuracy is lowered when the number of branches and cumulative weight fraction of the sample deviate from the logarithmic normal distribution, correlation coefficient R ² to perform measurements on commercially available LLDPE is fairly low, the accuracy of the values is not sufficient. This Cw / Cn and Cb of the present invention have different definitions and measurement methods.

The (A) ethylene / α-olefin copolymer of the present invention has (d) the relationship between the amount X (wt%) of the ODCB-soluble component at 25 ° C. and the densities d and MFR. When 008 log MFR ≧ 0.93 is satisfied,
X is less than 2% by weight, preferably less than 1% by weight, and more preferably less than 0.5% by weight. When d-0.008 log MFR <0.93, X <9.8 × 10 ³ × (0.9300-d + 0 .008 log MFR) ² +2.0
Preferably X <7.4 × 10 ³ × (0.9300−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
Must be met.

The ODCB-soluble component (X important%) at 25 ° C. of the ethylene / α-olefin copolymer (A) of the present invention is measured by the following method.
0.5 g of the sample is added to 20 ml of ODCB and heated at 135 ° C. for 2 hours to completely dissolve the sample and then cooled to 25 ° C. After leaving this solution at 25 ° C. overnight, it is filtered through a Teflon filter to collect the filtrate. The absorption peak area near the wave number 2925 cm ⁻¹ of the asymmetric stretching vibration of methylene is determined in the sample solution, and the sample concentration in the filtrate is calculated from a calibration curve created in advance. From this value, the ODCB-soluble content at 25 ° C. is determined.

  The soluble component is a component having a high degree of branching and a low molecular weight component contained in the ethylene / α-olefin copolymer, and causes a decrease in heat resistance and causes stickiness on the surface of a molded product. Is desirable. The amount of ODCB solubles is affected by the comonomer content and molecular weight of the copolymer. Therefore, the fact that the index and the amounts of MFR and ODCB-soluble component, which are the indexes, satisfy the above-mentioned relationship indicates that the proportion of α-olefin locally copolymerized at a high concentration is small.

  The (A) ethylene / α-olefin copolymer of the present invention must have a plurality of peaks in the elution temperature-elution amount curve obtained by (f) continuous temperature elution fractionation (TREF). It is particularly preferred that the peak on the high temperature side exists between 85 ° C and 100 ° C. The presence of this peak increases the melting point and the crystallinity, thereby improving the heat resistance and rigidity of the molded body. FIG. 1 is an elution temperature-elution amount curve of the copolymer of the present invention. FIG. 2 is an elution temperature-elution amount curve of a copolymer using a general metallocene catalyst, and both are remarkably different.

The measuring method of the continuous heating elution fractionation method (TREF) according to the present invention is as follows. An antioxidant is added to the sample, and the sample is heated and dissolved in ODCB at 135 ° C. so as to have a sample concentration of 0.05% by weight. 5 ml of the heated sample solution is injected into a column filled with glass beads, cooled to 25 ° C. at a cooling rate of 0.1 ° C./min, and the sample is deposited on the surface of the glass beads. Next, the column temperature is raised at a constant rate of 50 ° C./hr while flowing ODCB through the column at a constant flow rate, and the samples are sequentially eluted. At this time, the concentration of the sample eluted in the solvent is continuously detected by the infrared detector using the wave number of asymmetric stretching vibration of methylene of 2925 cm ⁻¹ . From this value, the relationship between the concentration of the ethylene / α-olefin copolymer contained in the solution and the elution temperature is determined. In the TREF analysis, a change in the elution rate with respect to a temperature change can be continuously analyzed with a very small amount of sample, so that relatively fine peaks that cannot be detected by the fractionation method can be detected.

  The specific ethylene / α-olefin copolymer (A) of the present invention has a narrow molecular weight distribution and a moderately wide composition distribution, and unlike the conventional Ziegler catalyst, has low-temperature heat sealability, strength, and transparency. It is excellent.

The method for producing the specific (A) ethylene / α-olefin copolymer of the present invention is not particularly limited as long as a copolymer satisfying the above properties (A) to (F) is produced. It is desirable to polymerize with a catalyst consisting of E5.
That is, E1: a compound represented by the general formula Me ¹ R ¹ _p (OR ² ) _q X ¹⁴ _-pq (wherein Me ¹ represents Zr, Ti, Hf, and R ¹ and R ² each represent carbon A hydrocarbon group of the formulas 1 to 24, X ¹ represents a halogen atom, p and q are integers satisfying the ranges of 0 ≦ p ≦ 4 and 0 ≦ p + q ≦ 4, respectively; E2: general formula Me ² R ³ _m (OR ⁴ ) _n X ² _z-m-n (Me ² is a group I to III element in the periodic table, R ³ and R ⁴ are each a hydrocarbon group having 1 to 24 carbon atoms. , X ² represents a halogen atom or a hydrogen atom (however, when X ² is a hydrogen atom, Me ² is limited to a group III element of the periodic table), z represents a valence of Me ² , and m and n is an integer satisfying the range of 0 ≦ m ≦ z, 0 ≦ n ≦ z, and 0 ≦ m + n ≦ z , E3: an organic cyclic compound having a conjugated double bond, E4: a modified organic aluminum compound containing an Al—O—Al bond obtained by reacting an organic aluminum compound with water, E5: an inorganic carrier and / or a particulate polymer A catalyst obtained by alternately contacting a support.

In the formula of the compound represented by the general formula Me ¹ R ¹ _p (OR ² ) _q X ¹⁴ _-p-q of the catalyst component (E1), zirconium, titanium and hafnium are shown as described above for Me ¹ . The type of these transition metals is not limited, and a plurality of transition metals can be used. However, it is particularly preferable that zirconium having excellent weather resistance of the copolymer is contained. R ¹ and R ² are each a hydrocarbon group having 1 to 24 carbon atoms, preferably 1 to 12 carbon atoms, and more preferably 1 to 8 carbon atoms, and specifically, methyl, propyl, isopropyl, and butyl groups. Alkyl groups such as vinyl group and allyl group; aryl groups such as phenyl group, tolyl group, xylyl group, mesityl group, indenyl group and naphthyl group; benzyl group, trityl group, phenethyl group, styryl group and benzhydryl. And aralkyl groups such as phenylbutyl group and neophyl group. These may have branches. X ¹ represents a halogen atom such as fluorine, iodine, chlorine and bromine, and p and q each satisfy the range of 0 ≦ p <4, 0 ≦ q <4, 0 ≦ p + q ≦ 4, and preferably 0 ≦ p + q ≦ 4 range.

  Examples of the compound represented by the above-mentioned catalyst component (E1) represented by the general formula include tetramethylzirconium, tetraethylzirconium, tetrabenzylzirconium, tetrapropoxyzirconium, tripropoxymonochlorodiconium, dipropoxydichlorozirconium, tetrabutoxyzirconium, tribubutoxymonochlorosiliconium. , Dibutoxydichlorozirconium, tetrabutoxytitanium, tetrabutoxyhafnium and the like, and two or more of these may be used in combination.

The general formula ^{_{Me 2 R 3 m (OR 4}} ) of the catalyst component (E2) ⁿ _{X 2} wherein Me ² in the compound represented by the _z-m-n represents the periodic table I~III group element, lithium , Sodium, potassium, magnesium, calcium, zinc, boron, aluminum and the like. R ³ and R ⁴ are each a hydrocarbon group having 1 to 24 carbon atoms, preferably 1 to 12 carbon atoms, more preferably 1 to 8 carbon atoms, and specifically, methyl, ethyl, propyl, isopropyl, Alkyl groups such as butyl group; alkenyl groups such as vinyl group and allyl group; aryl groups such as phenyl group, tolyl group, xylyl group, mesityl group, indenyl group and naphthyl group; benzyl group, trityl group, phenethyl group and styryl group And aralkyl groups such as a benzhydryl group, a phenylbutyl group and a neophyl group. These may have a branch, and 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 0 ≦ m ≦ z, 0 ≦ n ≦ z, respectively, and 0 ≦ m + n ≦ z.

  Examples of the compound represented by the general formula of the catalyst component (E2) include organic lithium compounds such as methyl lithium and ethyl lithium; organic magnesium compounds such as dimethyl magnesium, dimethyl magnesium, methyl magnesium chloride, and ethyl magnesium chloride; dimethyl zinc Organic boron compounds such as trimethylboron and triethylboron; trimethylaluminum, triethylaluminum, triisobutylaluminum, trihexylaluminum, tridecylaluminum, diethylaluminum chloride, ethylaluminum dichloride, ethylaluminum sesquichloride Aluminum, such as diethyl aluminum ethoxide, diethyl aluminum hydride Derivatives such compounds can be mentioned.

  The organic cyclic compound having a conjugated double bond of the catalyst component (E3) refers to one or more rings having two or more, preferably 2 to 4, more preferably 2 to 3, conjugated double bonds. A cyclic hydrocarbon compound having 2 or more and having a total carbon number of 4 to 24, preferably 4 to 12; wherein the cyclic hydrocarbon compound is partially a hydrocarbon residue of 1 to 6 (typically, carbon A cyclic hydrocarbon compound substituted with an alkyl group or an aralkyl group of the formulas 1 to 12; one or more rings having two or more conjugated double bonds, preferably two to four, more preferably two to three. An organosilicon compound having a cyclic hydrocarbon group having 2 or more and having a total carbon number of 4 to 24, preferably 4 to 12; a hydrocarbon residue or an alkali metal in which the cyclic hydrocarbon is partially 1 to 6 With salt (sodium or lithium salt) It includes organic silicon compounds conversion. Particularly preferably, those having a cyclopentadiene structure in any of the molecules are desirable.

  Examples of suitable compounds include cyclopentadiene, indene, azulene, and alkyl, aryl, aralkyl, alkoxy or aryloxy derivatives thereof. Further, a compound obtained by bonding (crosslinking) these compounds via an alkylene group (the number of carbon atoms of which is usually 2 to 8, preferably 2 to 3) is also preferably used.

  The organosilicon compound having a cyclic hydrocarbon group can be represented by the following general formula.

A _L SiR _4-L

  Here, A represents the cyclic hydrogen group exemplified by a cyclopentadienyl group, a substituted cyclopentadienyl group, an indenyl group, and a substituted indenyl group, and R represents a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group. An alkyl group such as a methoxy group, an ethoxy group, a propoxy group, a butoxy group; an aryl group such as a phenyl group; an aryloxy group such as a phenoxy group; an aralkyl group such as a benzyl group; Represents from 24 to 24, preferably from 1 to 12, hydrocarbon residues or hydrogen, and L is 1 ≦ L ≦ 4, preferably 1 ≦ L ≦ 3.

  Specific examples of the organic cyclic hydrocarbon compound of the component (E3) include cyclopentadiene, methylcyclopentadiene, ethylenecyclopentadiene, 1,3-dimethylcyclopentadiene, indene, 4-methyl-1-indene, and 4,7-dimethyl. C7-C24 cyclopolyene or substituted cyclopolyene such as indene, cycloheptatriene, methylcycloheptatriene, cyclooctatetraene, azulene, fluorene, methylfluorene, monocyclopentadienylsilane, biscyclopentadienyl Examples include silane, triscyclopentadienylsilane, monoindenylsilane, bisindenylsilane, and trisindenylsilane.

  Catalyst component (E4) A modified organoaluminum compound containing an Al-0-Al bond obtained by reacting an organoaluminum compound with water is obtained by reacting an alkylaluminum compound with water to form a modified so-called aluminoxane. An organoaluminum is obtained, which usually contains 1 to 100, preferably 1 to 50 Al-O-Al 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.
The reaction ratio (water / Al molar ratio) between water and the organoaluminum compound is usually from 0.25 / 1 to 1.2 / 1, preferably from 0.5 / 1 to 1/1.

Examples of the catalyst component (E5) inorganic carrier and / or particulate polymer carrier include carbonaceous materials, metals, metal oxides, metal chlorides, metal carbonates or mixtures thereof, thermoplastic resins, thermosetting resins, and the like. . Suitable metals that can be used for the inorganic carrier include iron, aluminum, nickel and the like.
Specific examples include SiO ₂ , Al ₂ O ₃ , MgO, ZrO ₂ , TiO ₂ , B ₂ O ₃ , CaO, ZnO, BaO, ThO _{2 and the} like, or a mixture thereof. Examples include SiO ₂ —Al ₂ O ₃ , SiO ₂ —V ₂ O ₅ , SiO ₂ —TiO ₂ , SiO ₂ —V ₂ O ₅ , SiO ₂ —MgO, and SiO ₂ —Cr ₂ O ₃ . Among them, those mainly containing at least one component selected from the group consisting of SiO ₂ and Al ₂ O ₃ are preferable.
Further, as the particulate polymer carrier, any of a thermoplastic resin and a thermosetting resin can be used. Specifically, particulate polyolefin, polyester, polyamide, polyvinyl chloride, poly (methyl methacrylate), Examples include polystyrene, polynorbornene, 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 preliminary treatment, these simple substances are contact-treated with an organoaluminum compound or a modified organoaluminum compound containing an Al-O-Al bond. After that, it can be used as the component (E5).

  The (A) ethylene / α-olefin copolymer of the present invention is produced by a gas phase method, a slurry method, a solution method, or the like, and is not particularly limited, such as a one-stage polymerization method or a multi-stage polymerization method, but it has physical properties and economy. It is desirable to manufacture by a gas phase method from the balance of the properties and the like.

The other ethylene polymer (B) of the present invention is an ethylene / α-olefin copolymer, an ethylene polymer obtained by high-pressure radical polymerization, or an ethylene copolymer. The first (B1) of these preferable ones is that the density of the ethylene / Ziegler type catalyst or the Phillips catalyst (collectively referred to as Ziegler type catalyst) obtained by the conventional ionic polymer is 0.86 to 0.96 g / cm ³ . An α-olefin copolymer, specifically, high-density ethylene (HDPE), medium-density polyethylene (MDPE), linear low-density polypropylene (LLDPE), very low-density polyethylene (VLDPE), and the like.

The high / medium / low density polyethylene (HDPE, MDPE, LLDPE) by the Ziegler type catalyst of the present invention has a density of 0.91 to 0.96 g / cm ³ , preferably 0.91 to 0.94 / cm ³ ( LLDPE), and the MFR is selected in the range of 0.1 to 20 g / 10 min, preferably 0.5 to 15 g / min, and more preferably 0.7 to 10 g / 10 min. Mw / Mn is 2.5 to 7, preferably 3 to 5.5.

The very low density polyethylene (VLDPE) by the Ziegler type catalyst of the present invention is a density of 0.86 to less than 0.91 g / cm ³ , preferably 0.88 to 0.91 g / cm ³ , and an MFR of 0.1 to less. It is selected in the range of 20 g / 10 min, preferably 0.5 to 15 g / 10 min.
The ultra-low-density polyethylene (VLDPE) has a polyethylene exhibiting properties intermediate between linear low-density polyethylene (LLDPE) and ethylene / α-olefin copolymer rubber (EPR, EPDM), and is preferably A property having a density of 0.86 to 0.91 g / cm ³ , a maximum peak temperature (Tm) by differential scanning calorimetry (DSC) of 60 ° C. or more, and preferably a boiling n-hexane insoluble content of 10% by weight or more. Is a specific ethylene / α-olefin copolymer having a high crystallinity represented by a linear low-density polyethylene, which is polymerized using a catalyst comprising a solid catalyst component containing at least titanium and / or vanadium and an organoaluminum compound. A resin that has both a part and an amorphous part represented by an ethylene / α-olefin copolymer rubber. Strength, and heat resistance, rubber elasticity, and low-temperature impact resistance coexist well-balanced of the latter features.

The α-olefin of the ethylene / α-olefin copolymer with the Ziegler-type catalyst has a carbon number of 3 to 12, preferably 3 to 10, and specifically includes propylene, butene-1, 4-methylpentene. -1, hexene-1, octene-1, decene-1, dodecene-1 and the like.
The content of these α-olefins is preferably selected within a range of 40 mol% or less.

  The second (B2) of other preferred ethylene polymers of the present invention is a copolymer of low-density polyethylene, ethylene-vinyl ester copolymer, ethylene α, β-unsaturated carboxylic acid or a derivative thereof by high-pressure radical polymerization. It is a polymer.

The low-density polyethylene (LDPE) has an MFR of 0.1 to 20 g / min, preferably 0.2 to 15 g / 10 min. Within this range, the melt tension of the composition is in an appropriate range, and film formation is easy. The density is less than 0.91~0.94g / cm ^3, preferably 0.912~0.935cm ^3, more preferably from 0.912~0.930g / cm ³ melt tension 1.5~25g is , 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.
Moreover, Mw / Mn is 3.0 to 10, preferably 4.0 to 8.0.

With the ethylene-vinyl ester copolymer of the present invention, ethylene-based vinyl propionate produced by a high-pressure radical polymerization method, vinyl acetate, vinyl caproate, vinyl caprylate, vinyl uralylate, vinyl stearate, It is a copolymer with a vinyl ester monomer such as vinyl trifluoroacetate. Among them, particularly preferred is vinyl acetate (EVA). That is, a copolymer comprising 50 to 99.5% by weight of ethylene, 0.5 to 50% by weight of a vinyl ester, and 0 to 49.5% by weight of another copolymerizable unsaturated monomer is preferable. In particular, the vinyl ester content is in the range of 3 to 20% by weight, preferably 5 to 15% by weight.
The MFR of these copolymers is 0.1 to 20 g / min, preferably 0.3 to 10 g / min, and the melt tension is 2.0 to 25 g, preferably 3 to 20 g.

Representative copolymers of the ethylene and α, β-unsaturated carboxylic acids or derivatives thereof of the present invention include ethylene- (meth) acrylic acid or its alkyl ester copolymers. As monomers of acrylic acid, methacrylic acid, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, propyl acrylate, propyl methacrylate, isopropyl acrylate, isopropyl methacrylate, isopropyl methacrylate, n-butyl acrylate, Examples thereof include n-butyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, lauryl acrylate, lauryl methacrylate, stearyl acrylate, stearyl methacrylate, glycidyl acrylate, glycidyl methacrylate, and the like. 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.
The MFR of these copolymers is 0.1 to 20 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.

  When the main purpose of the film of the present invention is to improve transparency, low-temperature heat sealability, strength, anti-blocking property, low elution property, etc., the above-mentioned specific ethylene / α-olefin copolymer (A) It is preferable to use the composition alone or to form a composition containing these as a main component. In addition, when these characteristics are maintained to some extent, and the workability and economy are taken into account, it is desirable that the component (B) is appropriately blended. When the component (B) is blended with the component (A), the component (A) can be blended in an amount of 20% by weight or more and the component (B) can be blended in an amount of 80% by weight or less. In the case of maintaining transparency and obtaining a film having a good balance of the processability, the component (A) is 95 to 50% by weight, the component (B) is 5 to 50% by weight, and the component (A) is preferably 90 to 50% by weight. 60% by weight and the component (B) are selected in the range of 10 to 40% by weight. If the compounding amount of the component (A) is less than 20% by weight and the compounding amount of the component (B) is 80% by weight or more, there is a possibility that properties such as low-temperature heat sealing properties and anti-blocking properties are not exhibited.

  The first film of the present invention is obtained by molding the component (A) and / or (B) by an inflation molding method, a T-die molding method, or the like, and has lubricity, anti-blocking property, low-temperature heat sealing property, and transparency. It has high mechanical strength and excellent low migration of resin components to package contents.It is used alone in various packaging materials, packaging bags, containers, etc., and is suitable for heat sealing applications utilizing its excellent heat sealing properties. ing. The thickness varies depending on the purpose, application and the like, but is 3 to 500 μm.

  As described above, the film may be used as a single-layer film by an inflation molding method or a T-die molding method, or may be used as a multi-layer film utilizing the characteristics of the film of the present invention. For example, the film of the present invention as a surface layer, a strong multilayer film having excellent heat sealing properties with a medium-low density polyethylene as an inner layer, or a heat sealing property with a film of the present invention as a surface layer and recycled polyethylene as an inner layer. An excellent inexpensive multilayer film, a multilayer film combining these, or the like is conceivable.

The aliphatic amide (C) of the present invention is added to improve the lubricity of the film, and can provide a laminating film that does not cause deterioration in the opening property and lubricity due to heat treatment.
When these fatty acid amides are used as the second sealant of the present invention, care must be taken because they may adversely affect the adhesion of the laminate to the laminated substrate. That is, among the fatty acid amides, (C1) an unsaturated fatty acid bisamide and (C2) an unsaturated fatty acid amide having a melting point of 65 to 90 ° C. are used in an amount of 0.01 to 0.2 part by weight, respectively, and both (C1) ) And (C2) are blended so that the total amount is 0.03 to 0.25 parts by weight, since it becomes possible to improve the lubricity of the film without impairing the adhesion to the laminated base material. It is preferably used to provide a sealant suitable for dry lamination.

  Examples of the unsaturated fatty acid bisamide (C1) include ethylene bisoleic acid amide, ethylene bis erucic acid amide, hexamethylene bis oleic acid amide, N, N'-dioleyl adipamide, N, N'-dioleyl sebacic acid amide Etc. are exemplified. These are added in an amount of 0.01 to 0.2 parts by weight based on 100 parts by weight of the resin component. If the amount is less than 0.01, the lubricity and anti-blocking properties will be poor, and if it exceeds 0.2 parts by weight, the adhesion to the laminated material described below may be poor.

  The melting point of the unsaturated fatty acid amide (C2) having a melting point of 65 to 90 ° C. is measured at a temperature of 10 ° C./min by a differential scanning calorimeter (DSC). Those having a melting point of less than 65 ° C. may have poor anti-blocking properties, and those having a melting point of more than 90 ° C. may have insufficient lubricity. The addition amount is 0.01 to 0.2 parts by weight based on 100 parts by weight of the resin component, and the total addition amount of the component (C1) and the component (C2) is in the range of 0.03 to 0.25 part by weight. Need to be added. If the amount of the component (C2) is less than 0.01 part by weight, the lubricity becomes insufficient. If the amount exceeds 0.25 part by weight, the adhesion to the laminated material becomes insufficient. If the total of the components (C1) and (C2) is less than 0.03 parts by weight, the lubricity and anti-blocking properties will be insufficient, and if it exceeds 0.25 parts by weight, the adhesion to the laminated material will be insufficient.

The sealant is obtained by laminating the above-mentioned single-layer or multilayer film with another material and using it as a heat seal layer.
The material to be attached at this time varies depending on the required application. For applications requiring gas barrier properties such as food packaging, for example, polyamide resins such as 6 nylon and 6,6 nylon, polyethylene terephthalate, polybutylene Examples include polyester resin such as terephthalate, saponified ethylene / vinyl acetate copolymer, vinylidene chloride resin, polyvinyl alcohol resin, polycarbonate resin, or those obtained by subjecting aluminum to vapor deposition, and metal foil such as aluminum and copper. Further, for the purpose of strengthening the stiffness for the purpose of self-contained containers and high-speed bag making, high-density polyethylene, polypropylene, polybutene-1 and the like can be mentioned. In some cases, these may be used in appropriate combination and laminated.

  When used as a laminate, the lamination method may be an appropriate lamination method such as an extrusion lamination method, a dry lamination method, a sand lamination method, a co-extrusion T-die method, and a co-extrusion inflation method. In particular, it is effective to laminate by a dry lamination method. In the case of the co-extrusion T-die method, co-extrusion inflation method, or the like, an intermediate layer for adhesion is made of LLDPE graft-modified with a monomer having a polar group such as maleic anhydride, an ionomer resin, or a mixture of both. Can be

  The sealant is a film used as a heat seal layer of a single layer or a laminated film as described above, and is required to have excellent low-temperature heat sealability and strength after heat seal. The thickness when used as a laminated film varies depending on the purpose and application, but is 3 to 250 μm, preferably 5 to 200 μm, more preferably 10 to 180 μm. Alternatively, a plurality of films having the same thickness may be attached to each other.

  In the film or sealant of the present invention, an antistatic agent, an antioxidant, a lubricant, an anti-blocking agent, an anti-fogging agent, an organic or inorganic pigment, and an ultraviolet ray inhibitor, as long as the object of the present invention is not impaired. Known additives such as a dispersant and the like can be added.

  Examples: Next, the present invention will be described in more detail by way of examples, but the present invention is not limited to these examples. The test methods performed are shown below.

(Physical property test method)
Density: Based on JIS K6760.
Melt flow rate: Based on JIS K6760.
Tensile impact test: Based on ASTM D1822.

(T-die film forming conditions)
Apparatus: Extruder screw diameter: 30 mmφ, manufactured by Union Plastics Co., Ltd.
T die: Surface length 300mm
Screw rotation speed: 50r. p. m
Extrusion amount: 4.8 kg / hr
Die lip gap: 1.2mm
Transaction speed: 6.1-6.3 m / min
Molding resin temperature: 210-240 ° C
Film thickness: 50 μm
Chill roll temperature: 40 ° C
Screw mesh: 80 mesh / 120 mesh / 80 mesh Corona treatment: about 45 dyne / cm

(Dry lamination processing conditions)
Base material: biaxially stretched nylon film (15 μm thickness)
Lami machine: Lab Co., Ltd. test coater MGC-180
Anchor coat agent: Toyo Morton Co., Ltd. polyether 308A / B (compounding ratio = 1: 1)
Pasting surface: Corona treated surface Aging: 40 ° C after lamination, 2 days

(T-die film evaluation method)
Low-temperature heat-sealing property: Heat-sealing was performed using a sheet sealer manufactured by Tester Sangyo Co., Ltd. at several appropriately selected temperatures at a pressure of 2 kg / cm ² and a sealing time of 1 second. The film was subjected to a peeling test at a peeling test speed of 300 mm / min with a test piece width of 15 mm. The temperature at which the peel rate of the test piece at this time was 500 g was represented by a value obtained by interpolation. The lower the temperature, the better the low-temperature heat sealability.
Haze: Direct reading haze computer HGH-2DP manufactured by Suga Test Instruments Co., Ltd. conformed to JIS K7105.
Blocking strength: A sample obtained by stacking two films face-to-face and applying a load of 5 kg / 10 cm ² and adjusting the state at 50 ° C. for 2 hours at 23 ° C. and 50 RH, manufactured by Toyo Seiki Co., Ltd. Using a tensile test, the force required for shearing peeling when pulled at a pulling speed of 500 mm / min was measured.

(Laminated film evaluation method)
Blocking strength: Toyo Seiki Co., Ltd., at 23 ° C. and 50 RH, for a sample obtained by stacking the sealant surfaces of the laminated films face-to-face and applying a load of 10 kg / 25 cm ² for condition control at 40 ° C. for 5 days. Using a tensile test, the force required for shearing peeling when pulled at a pulling speed of 100 mm / min was measured.
Slippery: Using a static friction coefficient measuring device manufactured by Shinto Kagaku Co., Ltd., the slip angle θ was measured at a slope rising speed of 1.7 ° / sec for the sealant surfaces under the conditions of a width of 35 mm, a length of 75 mm and a load of 200 gr. And tan θ. A smaller value indicates better lubricity.
Adhesiveness: The sealants of the laminated films were heat-sealed with silver having a width of 5 mm at 140 ° C., a pressure of 2 kg / cm ² and a sealing time of 1 second using a heat sealer manufactured by Tester Sangyo Co., Ltd. This film was used as a test piece having a width of 15 mm, the tensile breaking strength was set to 300 mm / min, and the tensile breaking speed was measured. Since the tensile breaking strength of the biaxially stretched nylon film is much higher than that of the polyethylene single film, the tensile strength of the heat-sealed portion of the laminated film is large if the adhesion is good, reflecting the tensile properties of nylon. If the adhesion is insufficient, only the strength of polyethylene is exhibited, so that the tensile strength of the heat-sealed portion of the laminated film decreases. When the tensile strength of the heat-sealed portion of the laminated film was 4.5 kg / 15 mm width or more, the adhesiveness was good (○). When the tensile strength was less than 4.5 kg / 15 mm width, the adhesiveness was insoluble (×).

Among the resins used, A1 to A5 were polymerized by the following method.
(Adjustment of solid catalyst)
Purified toluene was added to the catalyst preparation device (No. 1) using an electromagnetic induction stirrer under nitrogen, and then 28 g of dipropoxydichlorozirconium (Zr (OPr) ₂ Cl ₂ ) and 48 g of methylcyclopentadiene were added. While maintaining the temperature, 45 g of tridecylaluminum was added dropwise. 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. Next, purified toluene was added to another catalyst-prepared device with a stirrer (No. 2) under nitrogen, and the above solution A and then a 6.4 mol solution of methylaluminoxane in toluene were added and reacted. This is called liquid B.
Next, purified nitrogen was added to a preparation device with a stirrer (No. 1) under nitrogen, and 1400 g of silica (Fuji Devison, grade # 952, surface area 300 m ² / g) previously calcined at 400 ° C. for a predetermined time was added. After the addition, the entire amount of the B solution was added, and the mixture was stirred at room temperature. Then, the solvent was removed by nitrogen blowing to obtain a solid catalyst powder having good fluidity. This is designated as catalyst C.

(In the case of sample A1)
Ethylene and 1-butene were copolymerized at a polymerization temperature of 70 ° C. and a total pressure of 20 kgf / cm ² G using a continuous fluidized bed gas phase polymerization apparatus. 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.
The physical properties of the produced copolymer are shown in Table 1.

(Polymerization of Samples A2 to A4)
The polymerization was carried out in the same manner as in (A1) except that the molar ratio of 1-butene / ethylene was changed. The physical properties of the copolymer are shown in Tables 1 and 2 together with the experimental results.

(In case of sample A5)
(A5) was polymerized by performing the same operation as (Al) except that the monomer was 1-hexene. The physical properties of the copolymer are shown in Table 1 together with the experimental results.

(Other resins)
B1: Polymerization by slurry polymerization using linear low-density polyethylene tetrachloride, triethylaluminum catalyst, and butene-1 as a comonomer using Ziegler catalyst (density = 0.921 g / cm ³ , MFR = 1.9 g / min)
B2: Low-density polyethylene by high-pressure radical polymerization (density = 0.925 g / cm ³ , MFR = 3.2 g / 10 min, manufactured by Nippon Petrochemical Co., Ltd.)

(Lubricant)
EA: erucamide (trade name: Neutron S, manufactured by Nippon Seika Co., Ltd.)
EBOA: Ethylene bisoleic acid amide (trade name: Slipax O, manufactured by Nippon Kasei Co., Ltd.)
SA: stearic acid amide (trade name: Neutron 2, manufactured by Nippon Seika Co., Ltd.)
EBSA: Ethylene bisthrea phosphoric acid amide (trade name: Slipax E, manufactured by Nippon Kasei Co., Ltd.)

[Experimental example 1]
Table 1 shows the results of the evaluation on the T-die film.
In Experimental Example 1, 0.24 parts by weight of Irganox 1076 (manufactured by Ciba-Geigy), 0.12 parts by weight of Irgafos 168 (manufactured by Ciba-Geigy) and 100 parts by weight of erucamide (based on 100 parts by weight of the resin component (A1)) EA) 0.07 part by weight, ethylene bisoleic acid amide (EBOA) 0.04 part by weight, calcium stearate (manufactured by NOF Corporation) 0.1 part by weight, and natural silica as an anti-blocking agent (trade name Celite Super) Fros, manufactured by John Manville Co., Ltd.), uniformly mixed with a Henschel mixer for about 30 seconds, pelletized, formed into a sheet having a thickness of 0.5 mm by a press, and subjected to a tensile impact test (TIS). T-die molding was performed under the above conditions to obtain a 50 μm film (base paper), and the low-temperature heat sealability, haze, and blocking strength were measured. . The results are shown in Table 1.

[Experimental Examples 2 to 8]
Evaluation as a T-die film was performed in the same manner as in Experimental Example 1. The same operation as in Experimental Example 1 was performed using the resin components shown in Table 1. The results are also shown in Table 1.

[Experimental example 9]
Evaluation as a T-die film was performed in the same manner as in Experimental Example 1. As shown in Table 1, (B1) was used as a resin component, and 0.5 parts by weight of an anti-blocking agent was added. Table 1 also shows the results.
TIS and low-temperature heat sealability are poor, and haze and anti-blocking properties are also slightly poor.

[Experimental example 10]
Evaluation as a T-die film was performed in the same manner as in Experimental Example 1. As shown in Table 1, the same operation as in Experimental Example 1 was performed except that (B2) was used as the resin component. Table 1 also shows the results.
TIS is inferior, and haze is slightly inferior.

[Experimental example 11]
Tables 2 and 3 show the evaluation results of the laminated films.
In Experimental Example 11, the T-die film formed under the above conditions was dry-laminated with a nylon film under the above conditions, and the adhesiveness, lubricity, and blocking strength with the obtained laminated film were measured. The results are shown in Table 2.

[Experimental Examples 12 to 18]
Using the resin components shown in Table 2, the same operation as in Experimental Example 11 was performed. The results are also shown in Table 2.

[Experimental example 19]
As shown in Table 3, the same operation as in Experimental Example 13 was performed without adding a lubricant. The results are also shown in Table 3.
Poor lubrication and anti-blocking properties.

[Experimental example 20]
As shown in Table 3, only EBOA was added as a lubricant, and the other operations were the same as in Experimental Example 13. The results are also shown in Table 3.
Anti-blocking properties and lubricity are relatively insufficient.

[Experimental example 21]
As shown in Table 3, only EA was added as a lubricant, and the other operations were the same as those in Experimental Example 13. The results are also shown in Table 3.
Anti-blocking properties and lubricity are relatively insufficient.

[Experimental example 22]
As shown in Table 3, 0.26 parts by weight of EA and EBOA were added in total as lubricants, and the other operations were the same as in Experimental Example 13. The results are also shown in Table 3.
The adhesive of the laminated film is defective.

[Experimental example 23]
As shown in Table 3, 0.07 parts by weight of EA and 0.22 parts by weight of EBOA were added as lubricants, and the other operations were the same as in Example 13. The results are also shown in Table 3.
The adhesion of the laminate film is poor.

[Experimental example 24]
As shown in Table 3, 0.22 parts by weight of EA and 0.04 parts by weight of EBOA were added as lubricants, and the other operations were the same as in Example 13. The results are also shown in Table 3.
The adhesion of the laminate film is poor.

[Experimental example 25]
As shown in Table 3, SA and EBSA were added as lubricants, and the other operations were the same as in Experimental Example 13. The results are also shown in Table 3.
Lubricity and anti-blocking properties are relatively insufficient.

3 shows an elution temperature-elution amount curve of the copolymer of the present invention. 3 shows an elution temperature-elution amount curve of a copolymer with a typical metallocene catalyst.

Claims (5)

(A) A film comprising an ethylene / α-olefin copolymer satisfying the following (A) to (F).
(A) Density of 0.86 to 0.96 g / cm ³
(A) Melt flow rate (MFR) is 0.01 to 200 g / 10 min.
(C) Molecular weight distribution (Mw / Mn) is 1.5 to 4.5.
(D) The composition distribution parameter Cb is 1.08 to 2.00.
(E) Orthodichlorobenzene (ODCB) soluble content at 25 ° C. X (wt%) and density d and MFR satisfy the following relationship: a) Density d and MFR values are d−0.008 log MFR ≧ 0. In the case of 93, X <2.0
b) When the values of the density d and the MFR are d−0.008 log MFR <0.93, X <9.8 × 10 ³ × (0.9300−d + 0.008 log MFR) ² +2.0
(F) There are a plurality of peaks in an elution temperature-elution amount curve by a continuous heating elution fractionation method (TREF). (A) 20% by weight or more of ethylene / α-olefin copolymer satisfying the following (A) to (F): (A) Density is 0.86 to 0.96 g / cm ³
(A) Melt flow rate (MFR) is 0.01 to 200 g / 10 min.
(C) Molecular weight distribution (Mw / Mn) is 1.5 to 4.5.
(D) The composition distribution parameter Cb is 1.08 to 2.00.
(E) Orthodichlorobenzene (ODCB) soluble content at 25 ° C. X (wt%) and density d and MFR satisfy the following relationship: a) Density d and MFR values are d−0.008 log MFR ≧ 0. In the case of 93, X <2.0
b) When the values of the density d and the MFR are d−0.008 log MFR <0.93, X <9.8 × 10 ³ × (0.9300−d + 0.008 log MFR) ² +2.0
(F) a plurality of peaks of an elution temperature-elution amount curve by a continuous heating elution fractionation method (TREF); and (B) a composition containing 80% by weight or less of another ethylene copolymer. Film. (A) Ethylene / α-olefin copolymer 100 weight satisfying the following (A) to (F): (A) Density is 0.86 to 0.96 g / cm ³
(A) Melt flow rate (MFR) is 0.01 to 200 g / 10 min.
(C) Molecular weight distribution (Mw / Mn) is 1.5 to 4.5.
(D) The composition distribution parameter Cb is 1.08 to 2.00.
(E) Orthodichlorobenzene (ODCB) soluble content at 25 ° C. X (wt%) and density d and MFR satisfy the following relationship: a) Density d and MFR values are d−0.008 log MFR ≧ 0. In the case of 93, X <2.0
b) When the values of the density d and the MFR are d−0.008 log MFR <0.93, X <9.8 × 10 ³ × (0.9300−d + 0.008 log MFR) ² +2.0
(F) a composition comprising 0.03 to 0.25 parts by weight of an aliphatic amide having a plurality of peaks of an elution temperature-elution amount curve by a continuous heating elution fractionation method (TREF) And sealant. (A) 20% by weight or more of ethylene / α-olefin copolymer satisfying the following (A) to (F): (A) Density is 0.86 to 0.96 g / cm ³
(A) Melt flow rate (MFR) is 0.01 to 200 g / 10 min.
(C) Molecular weight distribution (Mw / Mn) is 1.5 to 4.5.
(D) The composition distribution parameter Cb is 1.08 to 2.00.
(E) Orthodichlorobenzene (ODCB) soluble content at 25 ° C. X (wt%) and density d and MFR satisfy the following relationship: a) Density d and MFR values are d−0.008 log MFR ≧ 0. In the case of 93, X <2.0
b) When the values of the density d and the MFR are d−0.008 log MFR <0.93, X <9.8 × 10 ³ × (0.9300−d + 0.008 log MFR) ² +2.0
(F) There are a plurality of peaks in an elution temperature-elution amount curve by a continuous temperature eluted fractionation method (TREF) and (B) 100 parts by weight of a resin component of 80% by weight or less of another ethylene-based polymer and (C) A sealant comprising a composition containing 0.03 to 0.25 parts by weight of an aliphatic amide.   The (C) fatty acid amide (C1) comprises an unsaturated fatty acid bisamide and (C2) an unsaturated fatty acid amide having a melting point of 65 to 90 ° C., and the amount thereof is 0.01 to 0 with respect to 100 parts by weight of the resin component. 5. The sealant according to claim 3, wherein the total amount of the two components (C1) and (C2) is 0.03 to 0.25 parts by weight. 6.

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