Specification
DESCRIPTION FILM OR LAMINATE COMPRISING ETHYLENE-BASED RESIN OR ETHYLENE-BASED RESIN COMPOSITION
TECHNICAL FIELD
[0001] The present invention relates to a film including, in at least a part thereof, a layer comprising an ethylene-based resin or an ethylene-based resin composition containing the resin, and a laminate having a layer comprising an ethylene-based resin or an ethylene-based resin composition containing the resin and a layer other than a layer comprising an olefin-based resin.
BACKGROUND ART
[0002] Ethylene-based resins have been molded by various molding processes and applied to various uses. Depending upon these molding processes and uses, properties required for the ethylene-based resins vary. For example, in the case of production of a cast film by T-die molding, there occurs neck-in that the edge of a film shrinks in the central direction. In order to reduce the neck-in to the minimum, an ethylene-based resin having a high melt tension for its molecular weight must be selected. In order to prevent sag or break in blow molding or in order to prevent vibration or
break of a bubble in an inflation film, the same properties as above are necessary.
[0003] Further, it is known that in the case of production of a cast film by T-die molding, regular variation in thickness, which is called "take-off surge" (sometimes called "draw resonance") and occurs in the take-off direction of a film, is brought about.
[0004] In order to solve such problems, a composition of an ethylene-based polymer obtained by the use of a metallocene catalyst and high-pressure low-density polyethylene (patent documents 1 and 2), and an ethylene-based polymer prepared by the use of a specific catalyst
(patent documents 3 to 6) have been proposed, but it is difficult to efficiently obtain ethylene-based resins excellent not only in molding properties, such as stability of a bubble in the inflating molding and neck-in/take-off surge or low extrusion load in the T-die molding, but also in mechanical strength.
[0005] The present inventors have earnestly studied under such circumstances as mentioned above, and as a result, they have found that an ethylene-based resin having specific molecular structure and specific melt properties and an ethylene-based resin composition containing the resin are excellent in molding properties, such as stability of a
bubble in the inflating molding and neck-in/take-off surge or low extrusion load in the T-die molding. The present inventors have also found that such an ethylene-based resin and such an ethylene-based resin composition containing the resin are excellent in sealing property and adhesion property to other resins, metals, papers, etc., and that a film obtained therefrom is excellent in mechanical strength and has properties such as low odor property and easy tear property. Thus, the present inventors have achieved the present invention.
Patent document 1: Japanese Patent Laid-Open Publication No. 65443/1994
Patent document 2: Japanese Patent Laid-Open Publication No. 26079/1995
Patent document 3: Japanese Patent Laid-Open Publication No. 276807/1990
Patent document 4: Japanese Patent Laid-Open Publication No. 213309/1992
Patent document 5: pamphlet of International Patent Publication No. 93/08221
Patent document 6: Japanese Patent Laid-Open Publication No. 311260/1996
DISCLOSURE OF THE INVENTION PROBLEM TO BE SOLVED BY THE INVENTION
[0006] It is an object of the present invention to provide a single-layer or multilayer film excellent in any one of sealing property, adhesion property to other ethylene-based resins, mechanical strength, low odor property and easy tear property.
[0007] It is another object of the present invention to provide a laminate excellent in any one of sealing property and adhesion property to other resins, metals, papers and the like.
MEANS TO SOLVE THE PROBLEMS [0008] The film according to the present invention includes, in at least a part thereof, a layer comprising an ethylene-based resin (R), which is a copolymer of ethylene and an α-olefin of 4 to 10 carbon atoms and satisfies the following requirements (1) to (5) at the same time or an ethylene-based resin composition (R') containing the resin (R) ;
(1) the melt flow rate (MFR) at 190°C under a load of 2.16 kg is in the range of 0.1 to 50 g/10 min,
(2) the density (d) is in the range of 875 to 970 kg/m3,
(3) the ratio [MT/n*(g/P)] of a melt tension [MT(g)] at 190°C to a shear viscosity [n*(P)l at 200°C and at an angular velocity of 1.0 rad/sec is in the range of l.OOxlO-4 to 9.00xl0-4,
(4) the sum [(M+E) (/1000C)] of the number of methyl branches [M(/1000C)] and the number of ethyl branches
[E(/1000C)], each number being based on 1000 carbon atoms and measured by 13C-NMR, is not more than 1.8, and
(5) the zero shear viscosity [n0(P)] at 200°C and the
weight-average molecular weight (Mw) as measured by a GPC-
viscosity detector method (GPC-VISCO) satisfy the following
relational formula (Eq-1):
0.01xlO~13*Mw3-4 ^ r]o ^ 4.5xl0-13xMw3-4 (Eq-1) The film of the invention is, for example, a film wherein on one surface of the layer comprising the ethylene-based resin (R) or the resin composition (R') is laminated an ethylene-based resin (P1) that is different from the ethylene-based resin (R) or the resin composition (R'), or a film wherein on one surface of the layer comprising the ethylene-based resin (R) or the resin composition (R') is laminated an ethylene-based resin (P1) that is different from the ethylene-based resin (R) or the resin composition (R'), and on the other surface is laminated an ethylene-based resin (P2) that is different from the ethylene-based resin (R) or
the resin composition (R') ((P1) and (P2) may be the same or different).
[0009] As uses of the film of the invention, there are a film for a sealant, a surface protective film, a low-odor film for food packaging, an easy-tear film, a thick film for heavy-duty packaging or agriculture use having a thickness of
not less than 60 µm, a film wherein the layer comprising the ethylene-based resin (R) or the resin composition (R') is an adhesive layer for a surface protective film, etc. [0010] The laminate according to the present invention is a laminate obtained by laminating a layer selected from a paper in the form of a sheet, an engineering plastic layer and an aluminum layer on one surface of a layer comprising the ethylene-based resin (R) or the resin composition (R') through an anchor coating agent, and if necessary, laminating a layer of an ethylene-based resin (P3) that is different from the ethylene-based resin (R) or the resin composition (R') on the other surface, or a laminate obtained by laminating a layer selected from a paper in the form of a sheet, an engineering plastic layer and an aluminum layer on one surface of an ethylene-based resin (P3) that is different from the ethylene-based resin (R) or the resin composition (R') through an anchor coating agent and laminating a layer
comprising the ethylene-based resin (R) or the resin
composition (R') on the other surface.
[0011] In the present invention, the laminate means a
laminate including a layer comprising an ethylene-based resin
or a resin composition and a layer comprising other than an
olefin-based resin.
[0012] As uses of the laminate of the invention, there are
a liquid packaging material, a packaging material for viscous
substance, a laminated paper, an adhesive tape, etc.
EFFECT OF THE INVENTION
[0013] For example, the film of the present invention is, excellent in heat-sealing strength as use for a sealant film; excellent in mechanical strength, and there is no fear of exerting an evil influence on the taste of the contained food as a use for a low-odor film for food packaging; excellent in balance of tear strengths in the MD direction and the TD direction as a use for an easy-tear film; and excellent in mechanical strength as a use for heavy-duty packing or agriculture.
[0014] For example, the laminate of the present invention is excellent in bag breaking strength and sealing strength as a use for packaging material for liquid/viscous substance; and is excellent in adhesion between the layer comprising the
ethylene-based resin (R) or the ethylene-based resin composition (R') and the paper base as a use for a laminated paper.
BRIEF DESCRIPTION OF THE DRAWING
[0015] Fig. 1 is a figure in which the weight-average
molecular weights (Mw) and the zero shear strengths (0) of the ethylene-based resins disclosed in Preparation Examples 1 to 32 and all the comparative preparation examples are plotted. In the figure, white squares indicate preparation examples, and black squares indicate comparative preparation examples. Number symbols in the figure indicate preparation example numbers or comparative preparation examples numbers. Two straight lines in the figure are borderlines indicating the upper and the lower limits of the parametric formula.
BEST MODE FOR CARRYING OUT THE INVENTION
[0016] The film and the laminate according to the present invention are described in detail hereinafter. [0017] The film and the laminate of the invention include, in at least a part thereof, a layer comprising the following ethylene-based resin (R) or the ethylene-based resin composition (R') containing the resin (R).
[0018] Ethylene-based resin (R)
First, the ethylene-based resin (R) for use in the invention is described in detail.
[0019] Although the ethylene-based resin (R) may be composed of only one kind of an ethylene-based polymer or may be composed of two or more kinds of ethylene-based polymers, this resin is characterized by necessarily satisfying all of the following requirements (1) to (5). When the ethylene-based resin (R) is composed of only one kind of an ethylene-based polymer, the ethylene-based polymer (Rl) is efficiently prepared by the later-described polymerization process. When the ethylene-based resin (R) is composed of two or more kinds of ethylene-based polymers, the ethylene-based polymer (Rl) and an ethylene-based polymer (R2) other than the polymer (Rl) are preferably contained, and the ethylene-based polymer (R2) is, for example, a copolymer of ethylene and an α-olefin having 4 to 10 carbon atoms obtained by the use of a metallocene catalyst or a Ziegler catalyst or high-pressure-processed low-density polyethylene prepared by a high-pressure radical polymerization process. When the ethylene-based resin is composed of two or more kinds of ethylene-based polymers, the compositional ratio between the ethylene-based polymer (Rl) and the ethylene-based polymer (R2) and the type of the ethylene-based polymer (R2) are not specifically restricted so long as blending of (Rl) with (R2)
is feasible and the blended resin satisfies the requirements (1) to (5) at the same time. Whether blending is carried out or not is a matter properly determined by a person skilled in the art according to the use to which the ethylene-based resin (R) or the ethylene-based resin composition (R') of the invention is applied. In usual, the ethylene-based resin (R) is composed of only the ethylene-based polymer (Rl) from the viewpoint that a step of blending or the like can be omitted. However, it is a matter arbitrarily determined according to the use application that high-pressure-processed low-density polyethylene is blended as the ethylene-based polymer (R2) in order to emphasize an effect of, for example, the requirement (3) of the requirements which the ethylene-based polymer (Rl) should satisfy, or that a specific ethylene-based polymer (R2) is used in combination to form a blend in the case where novel property that is not inherent in the ethylene-based polymer (Rl) is desired to be imparted. When the ethylene-based polymer (R2) is blended, the compositional ratio of the ethylene-based polymer (Rl) in the ethylene-based resin (R) is set to be usually not more than 99% by weight, preferably not more than 70% by weight, more preferably not more than 30% by weight.
[0020] The ethylene-based resin (R) is characterized by satisfying the aforesaid requirements (1) to (5) at the same
time. These requirements (1) to (5) are described below in
detail.
[0021] Requirement (1)
The melt flow rate (MFR) of the ethylene-based resin (R) at 190°C under a load of 2.16 kg is in the range of 0.1 to 50 g/10 min, preferably 1.0 to 50 g/10 min, more preferably 3.0 to 30. When the MFR is not less than 0.1 g/10 min, shear viscosity of the ethylene-based resin (R) is not too high, so that the resin is excellent in molding properties, and when the resin is molded into, for example, a film, its appearance is excellent. When the MFR is not more than 50 g/10 min, tensile strength and heat-sealing strength of the ethylene-based resin (R) are excellent. The MFR is a value measured under the conditions of a temperature of 190°C and a load of 2.16 kg in accordance with ASTM D1238-89.
[0022] In general, MFR strongly depends upon the molecular weight. That is to say, as the MFR is decreased, the molecular weight is increased, and as the MFR is increased, the molecular weight is decreased. It is known that the molecular weight of the ethylene-based resin (R) is determined by a compositional ratio of hydrogen to ethylene (hydrogen/ethylene) in the polymerization system for preparing an ethylene-based polymer constituting the ethylene-based resin (e.g., Kazuo Soga, KODANSHA "CATALYTIC
OLEFIN POLYMERIZATION", P. 376 (1990)). On this account, by increasing or decreasing the hydrogen/ethylene ratio, it becomes possible to prepare the ethylene-based resin (R) having MFR of the above range.
[0023] Requirement (2)
The density (d) of the ethylene-based resin (R) is in the range of 875 to 970 kg/m3, preferably 877 to 965 kg/m3, more preferably 880 to 960 kg/m3. The density (d) is a value of a test sample that is measured by a density gradient tube after the sample is heat-treated at 120°C for 1 hour and then linearly slowly cooled down to room temperature over a period of 1 hour.
[0024] When the density (d) is not less than 875 kg/m3, heat resistance of the ethylene-based resin (R) is excellent, and a film formed from the ethylene-based resin (R) has low surface stickiness. On the other hand, when the density (d) is not more than 970 kg/m3, low-temperature heat-sealing property of the ethylene-based resin (R) is excellent.
[0025] In general, density depends upon the α-olefin content in the ethylene-based polymer. As the α-olefin content is decreased, the density becomes higher, and as the α-olefin content is increased, the density becomes lower. It is known that the α-olefin content in the ethylene-based polymer is determined by a compositional ratio of an α-olefin
to ethylene (a-olefin/ethylene) in the polymerization system
(e.g., Walter Kaminsky, Makromol. Chem. 193, P. 606 (1992)). On this account, by increasing or decreasing the α-olefin/ethylene ratio in the preparation of an ethylene-based polymer constituting the ethylene-based resin (R), it becomes possible to control the density of the polymer, and by the use of such a control method, it becomes possible to prepare the ethylene-based resin (R) having a density of the above range.
[0026] Requirement (3)
The ratio [MT/n*(g/P) of a melt tension [MT(g)] of the ethylene-based resin (R) at 190°C to a shear viscosity
[n*(P)] thereof at 200°C and at an angular velocity of 1.0 rad/sec is in the range of 1.00x10-4 to 9.00x10-4, preferably 2.00xl0-4 to 7.00xl0-4, more preferably 2.60xl0-4 to 5.00xl0-4. The ethylene-based resin having MT/n* of not less than 1.00x10-4 is excellent in neck-in.
[0027] By the preparation under the conditions described in the later-described Preparation Example 31, an ethylene-based polymer having MT/n* in the vicinity of the lower limit of the above range can be obtained, and by the preparation under the conditions described in Preparation Example 19, an ethylene-based polymer having MT/n* in the vicinity of the upper limit of the above range can be obtained.
[0028] In the present invention, the melt tension (MT) was determined by measuring a stress given when a molten polymer is extended at a given rate. In the measurement, an MT measuring machine manufactured by Toyo Seiki Seisaku-sho, Ltd. was used. The measurement was carried out under the measuring conditions of a resin temperature of 190°C, a melting time of 6 minutes, a barrel diameter of 9.55 mm, an extrusion rate of 15 mm/min, a take-up rate of 24 m/min (when a molten filament is broken, the take-up rate is decreased by 5 m/min each time), a nozzle diameter of 2.095 mm and a nozzle length of 8 mm.
[0029] The shear viscosity (n*) at 200°C and at an angular velocity of 1.0 rad/sec was determined by measuring an angular velocity [ (rad/sec) ] variance of a shear viscosity (n*) in the range of 0.02512≤≤100 at a measuring temperature of 200°C. In the measurement, a dynamic stress rheometer SR-5000 manufactured by Rheometric Scientific, Inc. was used. As a sample holder, a parallel plate having a diameter of 25 mm was used, and the thickness of the sample was set to about 2.0 mm. As the points of measurements, 5 points were set based on one figure of . The strain was properly selected from the range of 3 to 10% so that the torque in the measuring range would be detectable and torque-over should not be brought about. The sample used in the shear viscosity
measurement was prepared by press molding a test sample to a thickness of 2 mm by the use of a press molding machine manufactured by Shinto Metal Industries Corporation under the conditions of a preheating temperature of 190°C, a preheating time of 5 minutes, a heating temperature of 190°C, a heating time of 2 minutes, a heating pressure of 100 kg/cm2, a cooling temperature of 20°C, a cooling time of 5 minutes and a cooling pressure of 100 gk/cm2.
[0030] Requirement (4)
The sum [(M+E) (/1000C)] of the number of methyl branches
[M(/1000C)] and the number of ethyl branches [E(/1000C)] of the ethylene-based resin (R), each number being measured by 13C-NMR, is not more than 1.8, preferably not more than 1.3, more preferably not more than 0.8, particularly preferably not more than 0.5. In the present invention, the number of methyl branches and the number of ethyl branches are each defined as a number based on 1000 carbon atoms, as described later.
[0031] It is known that if short-chain branches such as methyl branches and ethyl branches are present in an ethylene-based resin, the short-chain branches are incorporated into a crystal to widen lattice spacing of the crystal, and therefore, mechanical strength of the resin is lowered (e.g., Zenjiro Osawa, et al., "Kobunshi no jumyo
yosoku to chojuka gijutsu" (Estimation of Polymer Life and Technique for Life Extension), p. 481, N.T.S. (2002)). On that account, when the sum (M+E) of the number of methyl branches and the number of ethyl branches is not more than 1.8, mechanical strength of the resulting ethylene-based resin becomes excellent.
[0032] The number of methyl branches and the number of ethyl branches in the ethylene-based resin strongly depend upon the polymerization process for preparing an ethylene-based polymer constituting the ethylene-based resin, and the number of methyl branches and the number of ethyl branches in an ethylene-based polymer obtained by high-pressure radical polymerization are larger than those in an ethylene-based polymer obtained by coordination polymerization using a Ziegler catalyst system. In the case of coordination polymerization, the number of methyl branches and the number of ethyl branches in the ethylene-based polymer strongly depend upon a compositional ratio of propylene or 1-butene to ethylene (propylene/ethylene, 1-butene/ethylene). On this account, by increasing or decreasing the 1-butene/ethylene ratio, it becomes possible to prepare the ethylene-based resin having the sum (M+E) of the number of methyl branches and the number of ethyl branches in the above range.
[0033] The number of methyl branches and the number of ethyl branches measured by 13C-NMR are determined in the following manner. In the measurement, an ECP500 model nuclear magnetic resonance apparatus (1H, 500 MHz) manufactured by JEOL Ltd. was used, and the number of integration times was 10,000 to 30,000. As a chemical shift reference, a main chain methylene peak (29.97 ppm) was used. The measurement was carried out by introducing 250 to 400 mg of a sample and 3 ml of a mixed liquid of special grade o-dichlorobenzene available from Wako Pure Chemical Industries, Ltd. and benzene-d6 available from ISOTEC Co., Ltd. (o-dichlorobenzene:benzene-d6 =5:1, by volume) into a commercially available NMR measuring quartz glass tube having a diameter of 10 mm, then heating them at 120°C and homogeneously dispersing them. Assignment of each absorption in the NMR spectrum was carried out in accordance with "Kagaku Ryoiki Zokan No. 141, NMR-Sosetsu to jikken gaido [I]
(Chemical Region Extra Issue No. 141, NMR-Review and Experimental Guide [I]), pp. 132-133". The number of methyl branches based on 1,000 carbon atoms was calculated from a ratio of the integrated intensity of absorption (19.9 ppm) of methyl group derived from methyl branch to the integral sum total of absorptions appearing in the range of 5 to 45 ppm. The number of ethyl branches based on 1,000 carbon atoms was
calculated from a ratio of the integrated intensity of absorption (10.8 ppm) of ethyl group derived from ethyl branch to the integral sum total of absorptions appearing in the range of 5 to 45 ppm. [0034] Requirement (5)
The zero shear viscosity [n0(P)] of the ethylene-based resin (R) at 200°C and the weight-average molecular weight (Mw) thereof as measured by a GPC-viscosity detector method (GPC-VISCO) satisfy the following relational formula (Eq-1). (Formula Removed)
Preferably, they satisfy the following relational formula (Eq-2).
(Formula Removed)
More preferably, they satisfy the following relational formula (Eq-3).
(Formula Removed)
Particularly preferably, they satisfy the following relational formula (Eq-4).
(Formula Removed)
It is known that when the zero shear viscosity [n0(P)] is log-log plotted against the weight-average molecular weight (Mw), a resin whose elongation viscosity does not show strain curability, such as a linear ethylene-based polymer having no long-chain branch, conforms to a power rule with a
slope of 3.4, while a resin whose elongation viscosity shows strain rate curability, such as high-pressure-processed low-density polyethylene, exhibits a zero shear viscosity [n0(P)] that is lower than the rule(C. Gabriel, H. Munstedt, J. Rheol., 47(3), 619 (2003)). When the zero shear viscosity
[(P)] at 200°C is not more than 4. 5xl0-13xMw3-4, the elongation viscosity of the resulting ethylene-based polymer shows strain rate hardening, and therefore, take-off surge does not occur.
[0039] That the ethylene-based resin (R) satisfies the above relational formula (Eq-1) and that when 0 and Mw of the ethylene-based resin (R) are log-log plotted, log (o) and logMw are present in the region defined by the following relational formula (Eq-1') have the same meanings as each other.
[0040] 3.4Log(Mw)-15.000 ≤ Log(0) ≤ 3.4Log(Mw)-12.3468 (Eq-1')
Fig. 1 is a figure in which log(0) and logMw of all the ethylene-based resins described in the later-described preparation examples are plotted. By the preparation under the conditions described in the later-described Preparation Example 2, an ethylene-based resin wherein the relationship between the zero shear viscosity [no(P)] and the weight-average molecular weight (Mw) defined by the above parametric
inequality (Eq-1) is close to the borderline defined by the following formula (Eq-1") of the parametric inequalities (Eq-1' ) can be obtained. On the other hand, by the preparation under the conditions described in the Preparation Example 29, an ethylene-based resin wherein the relationship therebetween is close to the borderline defined by the following formula
(Eq-1'") of the parametric inequalities (Eq-1') can be obtained.
[0041] Log(o) = 3.4Log(Mw)-15.0000 (Eq-1") Log(o) = 3 . 4Log (Mw)-12 . 3468 (Eq-1'") The zero shear viscosity [o(P)] at 200°C was determined in the following manner. An angular velocity ( (rad/sec) ) variance of a shear viscosity (n*) at a measuring temperature of 200°C was measured in the range of 0.025122, mean particle diameter: 55 um) having been dried at 250°C for 10 hours was suspended in 77 liters of toluene in a nitrogen atmosphere, and then the suspension was cooled down to 0 to 5°C. To this suspension, 39.5 liters of a toluene solution of methylalumoxane (1.79 mmol/ml in terms of Al atom) were added dropwise over a period of 1 hour. During the addition, the temperature in the system was maintained at 0 to 5°C.
Successively, the reaction was carried out at 0 to 5°C for 30 minutes, then the temperature was raised up to 95 to 100°C over a period of 1.5 hours, and the reaction was consecutively carried out at this temperature for 4 hours. Thereafter, the temperature was lowered down to 55 to 60°C, and the supernatant liquid was removed by decantation. The solid component thus obtained was washed with toluene four times, and then toluene was added to give a total amount of 166.3 liters. Thus, a toluene slurry of the solid component (S-4) was prepared. A part of the resulting solid component (S-4) was withdrawn, and the concentration was examined. As a result, the slurry concentration was 84.6 g/liter, and the Al concentration was 0.422 mol/liter. [0243] Preparation of solid catalyst component (X-18)
In a reactor having an internal volume of 114 liters and equipped with a stirrer, 22.6 liters of toluene and 8.2 liters (695 g in terms of solid component) of the toluene slurry of the solid component (S-4) prepared above were placed in a nitrogen atmosphere. Further, 4.0 liters of a toluene solution of the metallocene compound (a-2) and a metallocene compound (B-3) (4.4 mmol in terms of Zr atom) were further introduced ((a-2)/(B-3) molar ratio = 20/80). The reaction was carried out at an internal temperature of 20 to 25°C for 1 hour. Thereafter, the supernatant liquid was
removed by decantation. The solid catalyst component thus obtained was washed with hexane four times, and then hexane was added to give a total amount of 45 liters. Thus, a hexane slurry of the solid catalyst component (X-18) was prepared. [0244]
(Formula Removed)
[0245] Preparation of prepolymerized catalyst (XP-18)
Successively, the hexane slurry of the solid catalyst component (X-18) obtained above was cooled down to 10°C, and then ethylene was continuously fed to the system for several minutes at atmospheric pressure. During the feeding, the temperature in the system was maintained at 10 to 15°C. Thereafter, 1.4 mol of diisobutylaluminum hydride (DiBAl-H) and 45 ml of 1-hexene were added. After the addition of 1-hexene, ethylene was fed again at 0.5 to 1.0 kg/hr to initiate prepolymerization. After 100 minutes from the initiation of prepolymerization, the temperature in the system rose up to 30°C, and thereafter, the temperature in the system was maintained at 30 to 35°C. After 40 minutes from the initiation of prepolymerization, 23.0 ml of 1-hexene
was added, and also after 110 minutes, 23.0 ml of 1-hexene was added.
[0246] After 140 minutes from the initiation of prepolymerization, feed of ethylene was stopped, and the system was replaced with nitrogen to terminate prepolymerization. Thereafter, the supernatant liquid was removed by decantation. The prepolymerized catalyst thus obtained was washed with hexane three times to obtain a prepolymerized catalyst (XP-18) in which 3.00 g of a polymer was produced based on 1 g of the solid catalyst component. A part of the resulting prepolymerized catalyst component was dried, and the composition was examined. As a result, 0.47 mg of Zr atom was contained based of 1 g of the solid catalyst component.
[0247] Polymerization
Using a continuous fluidized bed gas phase polymerization apparatus, copolymerization of ethylene and 1-hexene was carried out under the conditions of a total pressure of 2.0 MPα-G, a polymerization temperature of 75°C and a gas linear velocity of 0.8 m/sec. The prepolymerized catalyst (XP -18) prepared above was dried and continuously fed at 3 g/hr. In order to maintain the gas composition constant during the polymerization, ethylene, 1-hexene, hydrogen and nitrogen were continuously fed (gas composition:
l-hexene/ethylene=0.008 m.r., ethylene concentration=56.2%). The yield of the resulting ethylene-based polymer was 2.8 kg/hr.
[0248] To the resulting ethylene-based polymer, 0.1% by weight of Irganox 1076 (product of Ciba Specialty Chemicals Inc.) and 0.1% by weight of Irgafos 168 (product of Ciba Specialty Chemicals Inc.) were added as heat stabilizers, and the mixture was melt kneaded by the use of a single screw extruder having a screw diameter of 65 mm (manufactured by Placo Co., Ltd.) under the conditions of a preset temperature of 180°C and a screw rotational speed of 50 rpm. Thereafter, the resulting kneaded mixture was extruded into strands, and the strands were cut with a cutter to give pellets as test samples. The samples were subjected to physical property measurements and extrusion lamination molding. The results are set forth in the table. [0249] Preparation Example 34 Preparation of solid catalyst component (X-19)
In a reactor having an internal volume of 114 liters and equipped with a stirrer, 28.9 liters of toluene and 4.1 liters (350 g in terms of solid component) of the toluene slurry of the solid component (S-4) prepared above were placed in a nitrogen atmosphere. Further, 2.0 liters of a toluene solution of the metallocene compound (a-2) and the
metallocene compound (B-3) (0.004 mmol in terms of Zr atom) were further introduced ((A-2)/(B-3) molar ratio = 27/73). The reaction was carried out at an internal temperature of 20 to 25°C for 1 hour. Thereafter, the supernatant liquid was removed by decantation. The solid catalyst component thus obtained was washed with hexane four times, and then hexane was added to give a total amount of 37 liters. Thus, a hexane slurry of the solid catalyst component (X-19) was prepared. [0250] Preparation of prepolymerized catalyst (XP-19)
Successively, the hexane slurry of the solid catalyst component (X-19) obtained above was cooled down to 10°C, and then ethylene was continuously fed to the system for several minutes at atmospheric pressure. During the feeding, the temperature in the system was maintained at 10 to 15°C. Thereafter, 0.9 mol of diisobutylaluminum hydride (DiBAl-H) and 22 ml of 1-hexene were added. After the addition of 1-hexene, ethylene was fed again at 0.5 kg/hr to initiate prepolymerization. After 30 minutes from the initiation of prepolymerization, the temperature in the system rose up to 16°C, and thereafter, the temperature in the system was maintained at 16 to 20°C. After 40 minutes from the initiation of prepolymerization, 12.0 ml of 1-hexene was
added, and also after 90 minutes, 12.0 ml of 1-hexene was added.
[0251] After 140 minutes from the initiation of prepolymerization, feed of ethylene was stopped, and the system was replaced with nitrogen to terminate prepolymerization. Thereafter, the supernatant liquid was removed by decantation. The prepolymerized catalyst thus obtained was washed with hexane three times to obtain a prepolymerized catalyst (XP-19) in which 3.00 g of a polymer was produced based on 1 g of the solid catalyst component. A part of the resulting prepolymerized catalyst component was dried, and the composition was examined. As a result, 0.53 mg of Zr atom was contained based of 1 g of the solid catalyst component.
[0252] Polymerization
An ethylene-based polymer was obtained in the same manner as in Preparation Example 33, except that the prepolymerized catalyst (XP-19) was used and the ethylene/1-hexene copolymerization conditions were changed to the conditions shown in Table 13. Using the resulting ethylene-based polymer, test samples were prepared in the same manner as in Preparation Example 33. The samples were subjected to physical property measurements and extrusion lamination molding. The results are set forth in Table 13.
[0253] Preparation Examples 35 and 36 Polymerization
An ethylene-based polymer was obtained in the same manner as in Preparation Example 34, except that the ethylene/1-hexene copolymerization conditions were changed to the conditions shown in Table 13. Using the resulting ethylene-based polymer, test samples were prepared in the same manner as in Preparation Example 33. The samples were subjected to physical property measurements and extrusion lamination molding. The results are set forth in Table 13. [0254] Preparation Example 37 Polymerization
An ethylene-based polymer was obtained in the same manner as in Preparation Example 34, except that the ethylene/1-hexene copolymerization conditions were changed to the conditions shown in Table 13. Using the resulting ethylene-based polymer, test samples were prepared in the same manner as in Preparation Example 33. The samples were subjected to physical property measurements and extrusion lamination molding. The results are set forth in Table 13. [0255]
Table 13
(Table Removed)
[0256] Example 1
Preparation of solid component (S-5)
In a reactor having an internal volume of 260 liters and equipped with a stirrer, 10 kg of silica (Si02, mean particle diameter: 65 (im) having been dried at 250°C for 10 hours was suspended in 88.5 liters of toluene in a nitrogen atmosphere, and then the suspension was cooled down to 0 to 5°C. To this suspension, 78.2 liters of a toluene solution of methylalumoxane (3.0 mmol/ml in terms of Al atom) were added dropwise over a period of 60 minutes. During the addition, the temperature in the system was maintained at 0 to 5°C. Successively, the reaction was carried out at 0 to 5°C for 30 minutes, then the temperature was raised up to 95 to 100°C over a period of about 1.5 hours, and the reaction was consecutively carried out at 95 to 100°C for 4 hours. Thereafter, the temperature was lowered down to 60°C, and the supernatant liquid was removed by decantation. The solid component thus obtained was washed with toluene four times, and then toluene was added to give a total amount of 130 liters. Thus, a toluene slurry of a solid component (S-5) was prepared. A part of the resulting solid component was withdrawn, and the concentration was examined. As a result, the slurry concentration was 138.5 g/liter, and the Al concentration was 1.0 mol/liter.
Preparation of solid catalyst component (X-20)
In a reactor having an internal volume of 114 liters and equipped with a stirrer, 21.0 liters of toluene and 16.2 liters (1865 g in terms of solid component) of the toluene slurry of the solid component (S-5) prepared above were placed in a nitrogen atmosphere. On the other hand, in a reactor having an internal volume of 100 liters and equipped with a stirrer, 36.1 liters of toluene were placed in a nitrogen atmosphere, then with stirring, 5.5 liters of a toluene solution of the metallocene compound (a-l) (7.40 mmol/liter in terms of Zr atom) were introduced, and subsequently, 5.0 liters of a toluene solution of the metallocene compound (B-l) (3.20 mmol/liter in terms of Zr atom) were further introduced, followed by mixing for several minutes ((a-l)/(B-l) molar ratio = 70/30). Subsequently, the mixed solution thus prepared was forcedly fed to the aforesaid reactor being filled with the toluene slurry of the solid component (S-5) in advance. After the forced feeding, the reaction was carried out at an internal temperature of 20 to 25°C for 1 hour. Thereafter, the supernatant liquid was removed by decantation. The solid catalyst component thus obtained was washed with hexane three times, and then hexane was added to give a total amount of 47 liters. Thus, a
hexane slurry of the solid catalyst component (X-20) was
prepared.
Preparation of prepolymerized catalyst (XP-20)
Successively, the hexane slurry of the solid catalyst component (X-20) obtained above was cooled down to 10°C, and then ethylene was continuously fed to the system for several minutes at atmospheric pressure. During the feeding, the temperature in the system was maintained at 10 to 15°C. Thereafter, 2.5 mol of triisobutylaluminum (TIBAL) and 123 ml of 1-hexene were added. After the addition of 1-hexene, ethylene was fed again at 1.8 kg/hr to initiate prepolymerization. After 35 minutes from the initiation of prepolymerization, the temperature in the system rose up to 23°C, and thereafter, the temperature in the system was maintained at 24 to 26°C. After 87 minutes from the initiation of prepolymerization, 61.0 ml of 1-hexene was added, and also after 150 minutes, 61.0 ml of 1-hexene was added.
[0257] After 212 minutes from the initiation of prepolymerization, feed of ethylene was stopped, and the system was replaced with nitrogen to terminate prepolymerization. Thereafter, the supernatant liquid was removed by decantation. The prepolymerized catalyst thus obtained was washed with hexane six times to obtain a
prepolymerized catalyst (XP-20) in which 3.03 g of a polymer was produced based on 1 g of the solid catalyst component. A part of the resulting prepolymerized catalyst component was dried, and the composition was examined. As a result, 0.60 mg of Zr atom was contained based of 1 g of the solid catalyst component.
[0258] Into an evaporation dryer having an internal volume of 43 liters and equipped with a starrier, 25 liters (3330 g in terms of solid prepolymerized catalyst) of the hexane slurry of the prepolymerized catalyst (XP-20) was transferred in a nitrogen atmosphere. After the transferring, the pressure in the dryer was reduced to -65 KPaG over a period of about 3.5 hours, and when the pressure reached -65 KPaG, vacuum drying was carried out for about 4.0 hours to remove hexane and a volatile component of the prepolymerized catalyst. The pressure was further reduced to -100 KPaG, and when the pressure reached -100 KPaG, vacuum drying was carried out for 6 hours. The total volatile content of the resulting prepolymerized catalyst (XP-20) was 0.3% by weight. Polymerization
To a fluidized bed gas phase polymerization reactor having an internal volume of 1.7 m3, the prepolymerized catalyst component (XP-20) obtained above was fed at 0.06 mmol/hr in terms of Zr atom. Then, nitrogen, ethylene and 1-
hexene were fed so that the ethylene partial pressure would become 1.5 MPa*A, the gas phase 1-hexene/ethylene ratio would become 0.014 m.r., and the gas linear velocity in the reactor would become 0.7 m/sec. With continuously drawing the polymer out of the polymerization reactor so that the amount of the polymer in the polymerization reactor would become constant, polymerization was carried out under the conditions of a total pressure of 2.0 MPaG, a polymerization temperature of 80°C and a residence time of 7.3 hours. From the polymer continuously drawn out of the polymerization reactor, unreacted ethylene was substantially removed by a flush hopper. Thereafter, the polymer was dried by a drying device, and an ethylene-based polymer was obtained at 3.3 kg/hr. [0259] Preparation of laminate
The resulting ethylene-based polymer [A] was extrusion laminated on a base material by the use of a laminator, manufactured by Sumitomo Heavy Industries, Ltd., having an extruder of 65 mm diameter and a T-die of 500 mm die width under the conditions of an air gap of 130 mm, an under-die resin temperature of 295°C and a take-off rate of 80 m/min so that the film thickness would become 25 urn. As the base material, a laminate obtained by coating one surface of a biaxially stretched nylon film (trade name: Emblem ONM, product of Unitika Ltd.) of 15 urn thickness with a urethane-
based anchor coating agent and then extrusion laminating an ethylene-based mixed resin obtained by blending 50 parts by weight of linear low-density polyethylene obtained by the use of a Ziegler catalyst with 50 parts by weight of high-pressure-processed low density polyethylene in a thickness of 25 jam was used. The above extrusion lamination of the ethylene-based polymer was carried out on the side of the ethylene-based mixed resin layer of the above laminate.
[0260] Heat-sealing strength between the ethylene-based polymer layers of the extrusion laminated film and bag breaking strength of a bag prepared from the extrusion laminated film were measured and evaluated in accordance with the aforesaid methods. Examples 2 to 5
Heat-sealing strength and bag breaking strength were measured and evaluated in the same manner as in Example 1, except that each of the ethylene-based polymers prepared in Preparation Examples 34 to 37 was used instead of the ethylene-based polymer used in Preparation Example 1. Comparative Example 1
Heat-sealing strength and bag breaking strength were measured and evaluated in the same manner as in Example 1, except that high-pressure-processed low-density polyethylene
(trade name: Mirason IIP, product of Prime Polymer Co., Ltd.)
was used instead of the ethylene-based polymer used in Preparation Example 1. Comparative Example 2
Heat-sealing strength and bag breaking strength were measured and evaluated in the same manner as in Example 1, except that low-density polyethylene (trade name: Ultozex 20100J, product of Prime Polymer Co., Ltd.) was used instead of the ethylene-based polymer used in Preparation Example 1.
Comparative Example 3
Heat-sealing strength was measured and evaluated in the same manner as in Example 1, except that the ethylene-based polymer of Comparative Preparation Example 3 was used.
[0261] The results are set forth in Table 14.
[0262]
Table 14
(Table Removed)
Example 6
[0263] Extrusion lamination
An ethylene-based polymer obtained in the same manner as in Example 1 was extrusion laminated on a craft paper of 50 g/m2, which was a base material, by the use of a laminator, manufactured by Sumitomo Heavy Industries, Ltd., having an extruder of 65 mm diameter and a T-die of 500 mm die width under the following conditions.
Air gap: 130 mm
Under-die resin temperature: 325°C
Take-off rate: 200 m/min, 250 m/min, 300 m/min
Film thickness: 10 um
The resulting laminated paper was evaluated on paper adhesion. Comparative Example 4
A laminated paper was prepared in the same manner as in Example 6, except that high-pressure-processed low-density polyethylene (trade name: Mirason IIP, product of Prime Polymer Co., Ltd.) was used instead of the ethylene-based polymer used in Preparation Example 6. The resulting laminated paper was evaluated on paper adhesion. Comparative Example 5
A laminated paper was prepared in the same manner as in Example 6, except that low-density polyethylene (trade name:
Ultozex 20100J, product of Prime Polymer Co., Ltd.) was used instead of the ethylene-based polymer used in Preparation Example 6. The resulting laminated paper was evaluated on paper adhesion. Comparative Example 6
A laminated paper was prepared in the same manner as in Example 6, except that the ethylene-based polymer of Comparative Preparation Example 3 was used. The resulting laminated paper was evaluated on paper adhesion.
[0264] The results are set forth in Table 15.
[0265]
Table 15
(Table Removed)
Example 7
[0266] Preparation of external layer
A biaxially stretched nylon film (trade name: Emblem ONM, product of Unitika Ltd., abbreviated to "ONy") of 15um thickness was coated with a urethane-based anchor coating agent as an external layer, and the solvent was evaporated. Thereafter, with extrusion laminating high-pressure-processed low-density polyethylene (Mirason IIP, product of Prime Polymer Co., Ltd.), a 9-um aluminum foil, product of Showa Aluminum K.K., was bonded to prepare a multilayer film. This multilayer film was used as an external layer. The above extrusion lamination was carried out by the use of a laminator (manufactured by Sumitomo Heavy Industries, Ltd.) having an extruder of 65 mm diameter and a T-die of 500 mm width under the conditions of a take-off rate of 80 m/min, an under-die resin temperature of 325°C and an air gap of 190 mm.
[0267] Preparation of laminate
With extrusion laminating an ethylene-based polymer [A] obtained in the same manner as in Example 1 in a thickness of 25 (irn on the aluminum surface of the above external layer film, a 25-jim film, TUX-FCS available from Tohcello Co., Ltd., was bonded as an internal layer to obtain a laminate. The above extrusion lamination was carried out by the use of a laminator (manufactured by Sumitomo Heavy Industries, Ltd.)
having an extruder of 65 mm diameter and a T-die of 500 mm width under the conditions of a take-off rate of 50, 100, 150, 200 and 250 m/min, an under-die resin temperature of 325°C and an air gap of 190 mm. [0268] Aluminum adhesion strength measurement
Adhesion strength between the aluminum surface of the external layer and the resin layer obtained by extrusion lamination molding in the laminate obtained above was measured as aluminum adhesion strength.
Width of test specimen: 15 mm
Peel angle: 180 degrees
Peel rate: 300 mm/min Examples 8 to 11
Aluminum adhesion strength was measured in the same manner as in Example 7, except that each of the ethylene-based polymers prepared in Preparation Examples 34 to 37 was used instead of the ethylene-based polymer used in Example 7. Comparative Example 7
A laminate was prepared in the same manner as in Example 7, except that the ethylene/1-hexene copolymer was replaced with high-pressure-processed low-density polyethylene (Mirason IIP, product of Prime Polymer Co., Ltd.). Then, adhesion strength between the aluminum surface of the external layer and the resin layer obtained by extrusion
lamination molding in the resulting laminate was measured in the same manner as in Example 7. Comparative Example 8
A laminate was prepared in the same manner as in Example 7, except that the ethylene/1-hexene copolymer was replaced with low-density polyethylene (Ultozex 20100J, product of Prime Polymer Co., Ltd.). Then, adhesion strength between the aluminum surface of the external layer and the resin layer obtained by extrusion lamination molding in the resulting laminate was measured in the same manner as in Example 7. Comparative Example 9
A laminate was prepared in the same manner as in Example 7, except that the ethylene-based polymer of Comparative Preparation Example 3 was used. Then, adhesion strength between the aluminum surface of the external layer and the resin layer obtained by extrusion lamination molding in the resulting laminate was measured in the same manner as in Example 7.
[0269] The results are set forth in Table 16.
Table 16
(Table Removed)
Example 12
[0271] Process for preparing ethylene-based polymer
Preparation of an ethylene-based polymer was carried out by the process described in Preparation Example 8. [0272] Preparation of resin composition
The resulting ethylene-based polymer and product pellets of GD1588, which are product of Prime Polymer Co., Ltd., were blended in a weight ratio of 15:85. To the blend, 0.1% by weight of Irganox 1076 (product of Ciba Specialty Chemicals Inc.) and 0.1% by weight of Irgafos 168 (product of Ciba Specialty Chemicals Inc.) were further added as heat stabilizers, and the mixture was melt kneaded by the use of a single screw extruder having a screw diameter of 65 mm, manufactured by Placo Co., Ltd., under the conditions of a preset temperature of 180°C and a screw rotational speed of 50 rpm. Thereafter, the resulting kneaded mixture was extruded into strands, and the strands were cut with a cutter to give pellets as test samples. [0273] Inflation molding (single layer)
Using the resulting pellets, air-cooling inflation molding was carried out under the following molding conditions to prepare a film having a thickness of 40 um and a width of 320 mm, and molding properties (motor load, bubble stability, etc.) were evaluated.
Film molding conditions
Molding machine: inflation molding machine of 50 mm diameter manufactured by Modern Machinery Co., Ltd.
Screw: barrier type screw
Die: 100 mm (diameter), 2.0 mm (lip width)
Air ring: 2-gap type
Molding temperature: 190°C or 170°C
Extrusion rate: 28.8 kg/hr
Take-off rate: 20 m/min
Transparency and tear strength of the film obtained as above were measured. Comparative Example 10
Pellets were prepared in the same manner as in Example 12, except that product pellets of UZ5010, which is a product of Prime Polymer Co., ltd., were used instead of the ethylene-based polymer. Using these pellets, air-cooling inflation molding was carried out in the same manner as in Example 12 to prepare a film, and transparency and tear strength of the film were measured. [0274]
Table 17
(Table Removed)
[0275] Preparation Example 1
To an ethylene-based polymer obtained by the process described in Preparation Example 8, Irganox 1076 (product of Ciba Specialty Chemicals Inc.) and Irgafos 168 (product of Ciba Specialty Chemicals Inc.) were added as heat stabilizers so that the amounts thereof would become 0.1% by weight and 0.1% by weight, respectively, and the mixture was melt kneaded by the use of a single screw extruder having a screw diameter of 65 mm (manufactured by Placo Co., Ltd.) under the conditions of a preset temperature of 180°C and a screw rotational speed of 50 rpm. Thereafter, the resulting kneaded mixture was extruded into strands, and the strands were cut with a cutter to give pellets as test samples.
Example 13
[0276] Preparation of film
Using the ethylene-based resin composition obtained in Preparation Example 1, air-cooling inflation molding (single layer) was carried out under the following molding conditions to prepare a film having a thickness of 40 um and a width of 320 mm. [0277] Film molding conditions
Molding machine: inflation molding machine of 50 mm diameter manufactured by Modern Machinery Co., Ltd.
Screw: barrier type screw
Die: 100 mm (diameter), 2.0 mm (lip width)
Air ring: 2-gap type
Molding temperature: 130°C
Extrusion rate: 28.8 kg/hr
Take-off rate: 20 m/min
Film thickness: 40 um
The resulting ethylene-based resin composition and the resulting film were subjected to physical property measurements and molding evaluation. The results are set forth in Table 18. Comparative Example 11
Using product pellets of UZ5019F, which is a product of Prime Polymer Co., Ltd., as test samples, a film was prepared
in the same manner as in Example 13, and physical property measurements and molding evaluation were carried out. The results are set forth in Table 18. Since the resin pressure increased at 130°C, inflation molding was impossible.
[0278] Table 18
(Table Removed)
Example 14
[0279] Preparation of film
Using the ethylene-based resin composition obtained in
Preparation Example 1, air-cooling inflation molding (single
layer) was carried out under the following molding conditions
to prepare a film having a thickness of 40 um and a width of
320 mm.
[0280] Film molding conditions
Molding machine: inflation molding machine of 50 mm diameter manufactured by Modern Machinery Co., Ltd.
Screw: barrier type screw
Die: 100 mm (diameter), 2.0 mm (lip width)
Air ring: 2-gap type
Molding temperature: 190°C
Extrusion rate: 28.8 kg/hr
Take-off rate: 20 m/min
Film thickness: 40 urn
The resulting ethylene-based resin composition and the resulting film were subjected to physical property measurements and molding evaluation. The results are set forth in Table 19. Comparative Example 12
Using product pellets of UZ5019F, which is a product of Prime Polymer Co., Ltd., as test samples, a film was prepared in the same manner as in Example 14, and physical property measurements and molding evaluation were carried out. The results are set forth in Table 19. [0281]
Table 19
WE CLAIMS
1. A film including, in at least a part thereof, a layer comprising an ethylene-based resin (R) which is a copolymer of ethylene and an α-olefin of 4 to 10 carbon atoms and satisfies the following requirements (1) to (5) at the same time or an ethylene-based resin composition (R') containing the resin (R);
(1) the melt flow rate (MFR) at 190°C under a load of 2.16 kg is in the range of 0.1 to 50 g/10 min,
(2) the density (d) is in the range of 875 to 970 kg/m3,
(3) the ratio [MT/n*(g/P)] of a melt tension [MT(g)] at 190°C to a shear viscosity [n*(P)] at 200°C and at an angular velocity of 1.0 rad/sec is in the range of 1.00x10-4 to 9.00xl0-4,
(4) the sum [(M+E)(/1000C)] of the number of methyl branches [M(/1000C)] and the number of ethyl branches
[E(/1000C)] as measured by 13C-NMR, each number being based on 1000 carbon atoms, is not more than 1.8, and
(5) the zero shear viscosity [n0(P)] at 200CC and the
weight-average molecular weight (Mw) as measured by a GPC-
viscosity detector method (GPC-VISCO) satisfy the following
relational formula (Eq-1):
(Equation Removed)
2. The film as claimed in claim 1, wherein on one surface of the layer comprising the ethylene-based resin (R) or the resin composition (R') is laminated an ethylene-based resin (P1) that is different from the ethylene-based resin (R) or the resin composition (R' ).
3. The film as claimed in claim 1 or 2, wherein on one surface of the layer comprising the ethylene-based resin (R) or the resin composition (R') is laminated an ethylene-based resin (P1) that is different from the ethylene-based resin
(R) or the resin composition (R'), and on the other surface is laminated an ethylene-based resin (P2) that is different from the ethylene-based resin (R) or the resin composition
(R') ((P1) and (P2) may be the same or different).
4. The film as claimed in any one of claims 1 to 3, which is a film for a sealant.
5. The film as claimed in any one of claims 1 to 3, which is a surface protective film.
6. The film as claimed in any one of claims 1 to 3, wherein the layer comprising the ethylene-based resin (R) or
the resin composition (R') is an adhesive layer for a surface protective film.
7. The film as claimed in any one of claims 1 to 3, which is a low-odor film for food packaging.
8. The film as claimed in any one of claims 1 to 3, which is an easy-tear film.
9. The film as claimed in any one of claims 1 to 3, which is a thick film for heavy-duty packaging or agriculture having a thickness of not less than 60 urn.
10. A laminate obtained by laminating a layer selected from a paper in the form of a sheet, an engineering plastic layer and an aluminum layer on one surface of a layer comprising the ethylene-based resin (R) or the resin composition (R' ) through an anchor coating agent, and as needed, laminating a layer of an ethylene-based resin (P3) that is different from the ethylene-based resin (R) or the resin composition (R') on the other surface.
11. A laminate obtained by laminating a layer selected from a paper in the form of a sheet, an engineering plastic
layer and an aluminum layer on one surface of an ethylene-based resin (P3) that is different from the ethylene-based resin (R) or the resin composition (R') through an anchor coating agent and laminating a layer comprising the ethylene-based resin (R) or the resin composition (R') on the other surface.
12. The laminate as claimed in claim 10 or 11, which is a liquid packaging material or a viscous substance packaging material.
13. The laminate as claimed in claim 10 or 11, which is a laminated paper.
14. The laminate as claimed in claim 10 or 11, which is an adhesive tape.