JP2000355359A - Film for melting bag, and melting bag made therefrom - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a film which is excellent in a characteristic of dart impact strength and moldability and also to obtain a melting bag made threrefrom by a method wherein the film is formed out of an ethylene-.α-olefine copolymer comprising specified ethylene and α-olefine, and relations regarding various conditions required at forming of the film are specified. SOLUTION: An ethylene.α-olefine copolymer comprising an ethylene and an α-olefine in which a melting tensity at 190 deg.C [MT (g)] and a melt flow rate [MFR (g/10 min.)] are in a relation satisfying a formula defined as MT<=2.2×MFR-0.84 is used. Then, a film is formed so that a resin pressure P (kg/cm2), a resin temperature T ( deg.C) and a resin extrusion output K (kg/hours) at film forming, a lip cross sectional area A (cm2) of a film molding machine and a melt flow rate [MFR (g/10 min.)] of the resin are in a relation satisfying a formula defined as 200×[K/(MFR1.5)/(T-120)/A0.2]0.2<=P<=450×[K /(MFR1.5)/(T-120)A0.2]0.2.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a film for a melting bag containing traffic paint and the like and a melting bag for the film.

[0002]

BACKGROUND OF THE INVENTION Melt bags are used for the packaging of products to be melt processed and used, for example, traffic paints. The melting bag is a packaging bag that can be melted together with the product during processing or use of the product and uniformly mixed with the product. As a material used for such a melting bag, an ethylene-acrylate copolymer (E
EA), an ethylene / methacrylic acid ester copolymer, an ethylene / vinyl acetate copolymer (EVA), or a resin in which a small amount of polyethylene is blended with them.

[0003] However, a conventional molten bag made of the above-mentioned material sometimes has a dart impact strength that is not always sufficient, and thus may be broken during handling in transportation or the like.

[0004] Therefore, there is a demand for the appearance of a film for a melting bag and a melting bag having excellent dart impact strength characteristics and moldability.

[0005]

SUMMARY OF THE INVENTION An object of the present invention is to solve the problems associated with the prior art as described above, and to provide a film for a molten bag excellent in dart impact strength characteristics and moldability and a molten bag thereof. The purpose is.

[0006]

SUMMARY OF THE INVENTION The film for a melting bag according to the present invention comprises:
The melt tension at 0 ° C. (MT (g)) and the melt flow rate (MFR (g / 10 minutes)) satisfy the relationship of MT ≦ 2.2 × MFR− ^0.84 , and ethylene and carbon atoms of 3 to 2
And a resin pressure P (kg / cm ² ) and a resin temperature T (° C.) at the time of forming a film comprising an ethylene / α-olefin copolymer (A1) comprising α-olefin of 0.
The resin extrusion rate K (kg / hour), the lip cross-sectional area A (cm ² ) of the film forming machine, and the melt flow rate (MFR (g / 10 minutes)) of the resin are 200 × [K ^{/ (MFR 1.5) / (T} -120) / A 0.2]
^0.2 ≦ P ≦ 450 × [K / (MFR ^1.5 ) / (T−120)
/ A ^0.2] is shaped with a relationship indicated by ^0.2, and wherein the dart impact strength of the film is not less than 1000g at a thickness of 200 [mu] m.

Further, another film for a melting bag according to the present invention is characterized in that (i) the melt tension at 190 ° C. (MT (g)) and the melt flow rate (MFR (g / 10 minutes)) are: MT> 2 2 × MFR ^-0.84 , and (ii) n-decane soluble component content ratio (W (% by weight)) and density (d (g / c) at room temperature.
m ³ )), when MFR ≦ 10 g / 10 min: W <80 × exp (−100 (d−0.88)) + 0.1 When MFR> 10 g / 10 min: W <80 × (MFR −9) ^0.26 × exp (−100 (d−
0.88)) + 0.1, and (iii) a differential scanning calorimeter (D
SC), the temperature (Tm (° C.)) and the density (d (g / cm ³ )) at the maximum peak position of the endothermic curve satisfy the relationship of Tm <400 × d-248, and ethylene and carbon 3 to 2 atoms
And a resin temperature P (kg / cm ² ) and a resin temperature T (° C.) of an ethylene / α-olefin copolymer (A2) comprising α-olefin of 0.
The resin extrusion rate K (kg / hour), the lip cross-sectional area A (cm ² ) of the film forming machine, and the melt flow rate (MFR (g / 10 minutes)) of the resin are 200 × [K ^{/ (MFR 1.5) / (T} -120) / A 0.2]
^0.2 ≦ P ≦ 450 × [K / (MFR ^1.5 ) / (T−120)
/ A ^0.2] is shaped with a relationship indicated by ^0.2, and wherein the dart impact strength of the film is not less than 1000g at a thickness of 200 [mu] m.

As the ethylene / α-olefin copolymer (A2), the following copolymers are preferred. (1) Ethylene which satisfies the above-mentioned relationships (i), (ii) and (iii) and (iv) has at least two peaks in an endothermic curve measured by a differential scanning calorimeter (DSC) -Α-olefin copolymer (A2). (2) The above-mentioned relationships (i), (ii) and (iii) are satisfied, and (v) 1
An ethylene / α-olefin copolymer (A2) in which a component that does not elute below 00 ° C. is present and the component is present in an amount of 10% or less of the whole. (3) The relationship of (i), (ii) and (iii) is satisfied, and (vi) the number of long-chain branches having 6 or more carbon atoms measured by NMR is 3 per 1000 carbon atoms. Ethylene-α-olefin copolymer (A2), which satisfies the above relationships (i), (ii) and (iii), and (vii) the α-olefin copolymerized with ethylene has 7 carbon atoms In the case where the number is more than 3, an ethylene / α-olefin copolymer (A2) in which the number of long-chain branches having 6 or more carbon atoms measured by NMR exceeds 3 per 1000 carbon atoms. (4) When the above-mentioned relations (i), (ii) and (iii) are satisfied and (viii) the number of carbon atoms of the α-olefin to be copolymerized with ethylene is 7 or less, the number of carbon atoms measured by NMR When the number of long chain branches of 6 or more is 100 carbon atoms
No more than 3 ethylene / α-olefin copolymers per 0 (A2).

In the ethylene / α-olefin copolymer (A) (including (A1) and (A2)), if necessary, a high-pressure low-density polyethylene (B) is blended in an amount of 50% by weight or less. May be.

[0010] The melting bag according to the present invention is characterized by being formed from the film for a melting bag according to the present invention.

[0011]

DETAILED DESCRIPTION OF THE INVENTION Hereinafter, the film for a molten bag and the molten bag according to the present invention will be described in detail.

Melt bag film The melt bag film according to the present invention is formed from the ethylene / α-olefin copolymer (A1) or (A2) under specific film conditions.

[Ethylene / α-olefin copolymer (A
1) and (A2)] Ethylene α used in the present invention
-The olefin copolymers (A1) and (A2) are linear (low-density) polyethylenes and are composed of ethylene and an α-olefin having 3 to 20 carbon atoms.

The ethylene / α-olefin copolymers (A1) and (A2) have a structural unit content (ethylene content) derived from ethylene of usually 65 to 99% by weight, preferably 70 to 98% by weight, more preferably Is from 75 to 96% by weight, and the content of structural units derived from α-olefins having 3 to 20 carbon atoms (α-olefin content) is usually from 1 to 1.
It is 35% by weight, preferably 2 to 30% by weight, more preferably 4 to 25% by weight.

The composition of the ethylene / α-olefin copolymer is usually determined by measuring the ¹³ C-NMR spectrum of a sample obtained by uniformly dissolving about 200 mg of the copolymer in 1 ml of hexachlorobutadiene in a 10 mmφ sample tube. 120
° C, measurement frequency 25.05 MHz, spectrum width 150
0 Hz, pulse repetition time 4.2 sec., Pulse width 6 μse
It is determined by measuring under the conditions of c.

Examples of the α-olefin having 3 to 20 carbon atoms include propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene,
Examples thereof include 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, and 1-eicosene.

The ethylene / α-olefin copolymers (A1) and (A2) have a density (d; ASTM D 1
505) is 0.895~0.930g / cm ^3, it is desirable to preferably 0.895~0.925g / cm ^3, more preferably in the range of 0.900~0.915g / cm ^3, also the melt Flow rate (MFR; ASTM D)
1238, 190 ° C, load 2.16kg) is 0.5-10g / 10
Min, preferably in the range of 1.0 to 7.0 g / 10 min, more preferably in the range of 1.0 to 5.0 g / 10 min.

The ethylene / α-olefin copolymer (A1) used in the present invention has a melt tension (MT (g)) at 190 ° C. and a melt flow rate (MFR (g / 10 g)).
Min)) satisfies the relationship expressed by MT ≦ 2.2 × MFR− ^0.84 .

Further, the ethylene.α-
The olefin copolymer (A2) has (i) a melt tension (MT (g)) at 190 ° C. and a melt flow rate (MFR).
(g / 10 minutes): MT> 2.2 × MFR ^-0.84, preferably 5.5 × MFR ^-0.65 >MT> 2.
The relationship ^represented by 2 × MFR ^-0.84 is satisfied.

Ethylene which satisfies such a relationship
The α-olefin copolymer (A2) has a high melt tension for its molecular weight and good moldability. The melt tension (MT) of the ethylene / α-olefin copolymer (A2) is measured as a stress when a molten sample is stretched at a constant speed. In the present invention, specifically, a molten sample (ethylene · α
-Olefin copolymer) was measured for resin temperature 190 ° C and extrusion speed 1
It is measured as a stress when stretched under the conditions of 5 mm / min, a winding speed of 10 to 20 m / min, a nozzle diameter of 2.09 mmφ, and a nozzle length of 8 mm.

The ethylene / α-olefin copolymer (A2) has (ii) an n-decane-soluble component content ratio (W (% by weight)) at room temperature (23 ° C.) and a density (d (g / C
m ³ )), when MFR ≦ 10 g / 10 min: W <80 × exp (−100 (d−0.88)) + 0.1, preferably W <60 × exp (−100 (d−0.0.
88)) + 0.1, more preferably W <40 × exp (−100 (d−0.0.
88)) + 0.1 MFR> 10 g / 10 min: W <80 × (MFR-9) ^0.26 × exp (−100 (d−
0.88)) + 0.1.

Ethylene which satisfies such a relationship
It can be said that the α-olefin copolymer (A2) has a narrow composition distribution. The measurement of the content (W) of the n-decane-soluble component of the ethylene / α-olefin copolymer (A2)
Approximately 3 g of an olefin copolymer is added to 450 ml of n-decane, dissolved at 145 ° C., cooled to room temperature, filtered to remove the n-decane insoluble portion, and recovering the n-decane soluble portion from the filtrate. It is. The smaller the n-decane soluble component content ratio (W), the narrower the composition distribution.

Further, the ethylene / α-olefin copolymer (A2) is obtained by (iii) a differential scanning calorimeter (DSC).
(Tm) at the maximum peak position of the endothermic curve measured by
(° C.)) and density (d (g / cm ³ )) satisfy the relationship represented by Tm <400 × d-248, preferably Tm <450 × d-296.

Ethylene which satisfies such a relationship
Since the α-olefin copolymer (A2) has a lower Tm than the density, the α-olefin copolymer (A2) is excellent in heat sealability as compared with an ethylene / α-olefin copolymer having the same density.

The relationship between the temperature (Tm) and the density (d) at the maximum peak position of the endothermic curve measured by the differential scanning calorimeter (DSC), and the fraction (W) and the density (n) of the n-decane soluble component. It can be said that the ethylene / α-olefin copolymer (A2) having the above-mentioned relationship with d) has a narrow composition distribution.

The ethylene / α-olefin copolymer (A
The Tm of 2) is as follows.
The temperature is raised to 200 ° C./min, held at 200 ° C. for 5 minutes, cooled to room temperature at 10 ° C./min, and then determined from an endothermic curve when the temperature is raised at 10 ° C./min. For the measurement, a DSC-7 type device manufactured by PerkinElmer Co., Ltd. is used.

As the ethylene / α-olefin copolymer (A2) used in the present invention, the following copolymers are preferred. (1) Ethylene which satisfies the above (i), (ii) and (iii), and (iv) has at least two peaks in an endothermic curve measured by a differential scanning calorimeter (DSC) -Α-olefin copolymer (A2). (2) The above-mentioned relationships (i), (ii) and (iii) are satisfied, and (v) 1
An ethylene / α-olefin copolymer (A2) in which a component that does not elute below 00 ° C. is present and the component is present in an amount of 10% or less of the whole. (3) The relationship of the above (i), (ii) and (iii) is satisfied, and (vi) the number of long-chain branches having 6 or more carbon atoms measured by NMR is 3 per 1000 carbon atoms. More than one ethylene / α-olefin copolymer (A2). Above all, when the relationship of the above (i), (ii) and (iii) is satisfied, and (vii) the α-olefin to be copolymerized with ethylene has more than 7 carbon atoms, the number of carbon atoms measured by NMR The number of long chain branches of 6 or more is 10 carbon atoms.
More than 3 ethylene / α-olefin copolymers per 00 (A2). (4) an ethylene / α-olefin copolymer obtained by copolymerizing ethylene and an α-olefin having 3 to 20 carbon atoms, which satisfies the above-mentioned relationships (i), (ii) and (iii); (Viii) When the number of carbon atoms of the α-olefin to be copolymerized with ethylene is 7 or less, the number of long chain branches having 6 or more carbon atoms measured by NMR is 100 carbon atoms.
No more than 3 ethylene / α-olefin copolymers per 0 (A2).

The temperature rise dissolution test (TREF) is performed in the following manner. After the sample solution is introduced into the column at 140 ° C, it is cooled at a rate of 10 ° C / hour to 25 ° C, and then continuously eluted at a constant flow rate of 1.0 ml while heating at a rate of 15 ° C / hour. Components to be detected online. The column used was a 2.14 cmφ × 15 cm column, the filler used was 100 μmφ glass beads, the solvent was orthodichlorobenzene, and the sample concentration was 200 mg / 4.
0 ml (ortho-dichlorobenzene), injection volume 7.5 m
l.

The number of branches in the ethylene / α-olefin copolymer was determined by ¹³ C-NMR. That is, 10
Approximately 250 mg of film was transferred to a 2.5 mm
l of orthodichlorobenzene / deuterated benzene (4 /
1 (volume ratio)) ¹³ C-NMR of a sample uniformly dissolved
At the observation frequency 1 by the proton complete decoupling method.
25.8 MHz, observation area 33,900 Hz, pulse width 45 °, pulse repetition time 5.5 seconds, measurement temperature 120
Measured under the conditions of ° C and 10,000 times of integration, "JMS-
REV.Macromol.Chem.Phys. "(C29 (2 & 3), 201-317 (1989))
Was determined according to the method described in the literature.

Carbon in ethylene / α-olefin copolymer
The number of long-chain branches having 6 or more elementary atoms is ¹³By C-NMR
Were determined. That is, about 250 mm in a 10 mmφ sample tube.
mg of film in 2.5 ml of orthodichlorobenzene
/ Uniformly dissolved in deuterated benzene (4/1 (volume ratio))
Of the sample¹³C-NMR by proton complete decoupling
Observation frequency 125.8 MHz, observation area 3
3,900 Hz, pulse width 45 °, pulse repetition time
5.5 seconds, measurement temperature 120 ° C, integration 10,000 times
Measured under the conditions of `` JMS-REV.Macromol.Chem.Phys. ''
(C29 (2 & 3), 201-317 (1989))
A genus was performed.

The number of long-chain branches having 6 or more carbon atoms is as follows:
From the total number of branches calculated from the total number of methine carbon atoms, methyl based on each branch other than a long-chain branch having 6 or more carbon atoms,
It was defined as the remainder obtained by subtracting the calculated number of branches from the methylene carbon atom.

[Ethylene / α-olefin copolymer (A
Preparation of 1)] The ethylene / α-olefin copolymer (A1) as described above contains a metallocene catalyst component described in, for example, JP-A-9-183816, JP-A-8-283377, and the like. It can be produced by copolymerizing ethylene and an α-olefin having 3 to 20 carbon atoms in the presence of a so-called metallocene olefin polymerization catalyst.

Such a metallocene-based olefin polymerization catalyst is usually a metallocene catalyst component comprising a transition metal compound of Group IVB of the Periodic Table having at least one ligand having a cyclopentadienyl skeleton; It is formed from a compound catalyst component, a carrier, and, if necessary, an organoaluminum compound catalyst component.

The details of the metallocene-based olefin polymerization catalyst and the method for producing the ethylene / α-olefin copolymer (A2) are described in JP-A-9-183816, JP-A-8-283377 and the like. I have.

[Ethylene / α-olefin copolymer (A
2) Preparation of the above-mentioned ethylene / α-olefin copolymer (A2) is described in, for example, JP-A-4-213309, JP-A-6-9724, and JP-A-6-2069.
No. 39, Japanese Patent Application Laid-Open No. 9-23512, Japanese Patent Application Laid-Open
0-251334, JP-A-10-251335, JP-A-2-276807, WO93 / 08
No. 22, Japanese Patent Application No. 10-370575, etc., containing ethylene and an α-olefin having 3 to 20 carbon atoms in the presence of a so-called metallocene-based olefin polymerization catalyst containing a metallocene catalyst component. Can be produced by copolymerizing

Such a metallocene olefin polymerization catalyst is usually a metallocene catalyst component comprising a transition metal compound of Group IVB of the Periodic Table having at least one ligand having a cyclopentadienyl skeleton; It is formed from a compound catalyst component and, if necessary, a carrier, an organoaluminum compound catalyst component, and an ionized ionic compound catalyst component.

Details of the metallocene olefin polymerization catalyst and the method for producing the ethylene / α-olefin copolymer (A2) are described in JP-A-4-213309, JP-A-6-9724, and JP-A-6-206939. JP, JP-A-9-235313, JP-A-10-25
No. 1334, JP-A-10-251335, JP-A-2-276807, WO93 / 0822, and Japanese Patent Application No. 10-370575.

[ Formation of Film for Melt Bag] The film for a melt bag according to the present invention is prepared by subjecting the ethylene / α-olefin copolymer (A1) or (A2) to an inflation method.
It can be manufactured under the following conditions by employing a normal film forming method such as a T-die method.

That is, from the ethylene / α-olefin copolymer (A1) or (A2), a resin pressure P (kg / cm ² ) for forming a film, a resin temperature T (° C.)
The resin extrusion rate K (kg / hour), the lip cross-sectional area A (cm ² ) of the film forming machine, and the melt flow rate (MFR (g / 10 minutes)) of the resin are 200 × [K / ( MFR ^1.5 ) / (T-120) / A ^0.2 ]
^0.2 ≦ P ≦ 450 × [K / (MFR ^1.5 ) / (T−120)
/ A ^0.2 ] is formed with a relationship represented by ^0.2 .

In the ethylene / α-olefin copolymer (A1) or (A2), if necessary, the high-pressure low-density polyethylene (B) is 50% by weight or less, preferably 5 to 40% by weight, Preferably, it can be blended in an amount of 5 to 30% by weight.

The high-pressure low-density polyethylene (B) is
Polyethylene produced from ethylene under high pressure in the presence of a radical polymerization catalyst, and a small amount of another vinyl monomer may be copolymerized if necessary.

The high-pressure low-density polyethylene (B) used in the present invention has a density (ASTM D 1505) of usually 0.917 to 0.917.
0.930 g / cm ³ , preferably 0.917 to 0.9
It is in the range of 25 g / cm ³ . The high-pressure low-density polyethylene (B) having a density in the above range is excellent in blown film moldability. The density was measured at a melt flow rate (MF) at 190 ° C. under a load of 2.16 kg.
R) The extruded strand obtained at the time of measurement is heat-treated at 100 ° C. for 1 hour, gradually cooled to room temperature over 1 hour, and measured with a density gradient tube.

Further, the melt flow rate (MFR; ASTM D 1238, 1) of this high pressure method low density polyethylene (B)
90 ° C, load 2.16 kg) is in the range of 0.1 to 3 g / 10 min, preferably 0.1 to 1.0 g / 10 min. The high-pressure low-density polyethylene (B) having a melt flow rate in the above range is excellent in blown film moldability.

In the present invention, if necessary, a pigment (for example, carbon black, carbon black, Additives such as titanium oxide), an antioxidant, a weather stabilizer, an antistatic agent, a slip agent, an anti-blocking agent and the like can be blended within a range that does not impair the object of the present invention.

The thickness of the film for a molten bag obtained as described above is arbitrary and varies depending on the amount of the product to be filled in the bag, but is practically about 80 to 150 μm. The melt bag film according to the present invention has a dart impact strength of 1000 g or more at a thickness of 200 μm and is excellent in impact resistance.

Melt bag The melt bag according to the present invention can be obtained by making a bag from such a film for a melt bag by a conventionally known method. This melting bag has excellent dart impact strength characteristics,
It can be put to practical use.

[0047]

According to the present invention, a film for a melting bag excellent in dart impact strength characteristics and moldability, and a melting bag thereof can be provided.

[0048]

EXAMPLES Hereinafter, the present invention will be described with reference to examples, but the present invention is not limited to these examples. (1) Granulation of ethylene copolymer 0.05 parts by weight of tri (2,4-di-t-butylphenyl) phosphate as a secondary antioxidant is added to 100 parts by weight of the ethylene copolymer. Parts, 0.1 part by weight of n-octadecyl-3- (4'-hydroxy-3 ', 5'-di-t-butylphenyl) propinate as a heat stabilizer, and 0.1 part of calcium stearate as a hydrochloric acid absorbent. Add 05 parts by weight. Thereafter, using a usual extruder, the mixture is melt-extruded at a set temperature of 180 ° C. to prepare granulated pellets. (2) Density (d) The strand obtained at the time of measuring the melt flow rate at 190 ° C. under a load of 2.16 kg is heat-treated at 120 ° C. for 1 hour, gradually cooled to room temperature over 1 hour, and measured with a density gradient tube. . (3) Composition of copolymer Determined by ¹³ C-NMR. That is, ¹³ C of a sample in which about 200 mg of a copolymer powder was uniformly dissolved in 1 ml of hexachlorobutadiene in a 10 mmφ sample tube.
Determined by measuring the NMRR spectrum under the conditions of a measurement temperature of 120 ° C., a measurement frequency of 25.05 MHz, a spectrum width of 1500 Hz, a pulse repetition time of 4.2 sec, and a pulse width of 6 μsec. (4) Melt flow rate (MFR) ASTM D12 was prepared using granulated pellets of the copolymer.
It is measured under the conditions of 190 ° C. and a load of 2.16 kg according to 38-65T. (5) DSC maximum peak temperature (Tm) This was performed using a DSC-7 type device manufactured by PerkinElmer. Temperature at maximum peak position in endothermic curve (Tm)
Is to pack about 5 mg of the sample into an aluminum pan at 10 ° C / min.
After the temperature was raised to 0 ° C and kept at 200 ° C for 5 minutes,
It is determined from an endothermic curve when the temperature is lowered to room temperature at a rate of 10 ° C./minute and then at a rate of 10 ° C./minute. (6) n-decane-soluble component amount ratio (W) The amount of n-decane-soluble component in the copolymer is measured by adding about 3 g of the copolymer to 450 ml of n-decane and dissolving at 145 ° C to 23 ° C. It cools, removes the n-decane insoluble part by filtration, and collect | recovers n-decane soluble part from a filtrate. The n-decane-soluble component amount ratio is defined as W = [weight of n-decane-soluble portion / weight of n-decane-insoluble portion and soluble portion] × 100 (%). The smaller the amount of the soluble component, the narrower the composition distribution. (7) Melt tension (MT) It is determined by measuring the stress when the melted polymer is stretched at a constant speed. In other words, granulated pellets of the copolymer were used as measurement samples, and were manufactured by Toyo Seiki Seisaku-sho, Ltd.
Using an MT measuring machine, resin temperature 190 ° C, extrusion speed 1
The operation is performed under the conditions of 5 mm / min, a winding speed of 10 to 20 m / min, a nozzle diameter of 2.09 mmφ, and a nozzle length of 8 mm. (8) Quantification of long-chain branching (LCB) Quantification of long-chain branching (LCB) was performed by NMR. (9) Temperature rise elution test (TREF) After the sample solution was introduced into the column at 140 ° C, the temperature was lowered at a rate of 1
It is cooled to 25 ° C. at 0 ° C./hour.
The components eluted continuously at a constant flow rate of 1.0 ml were detected online while increasing the temperature at a rate of ° C./hour.

The column used was a 2.14 cmφ × 15 cm column, the filler used was 100 μmφ glass beads, the solvent was orthodichlorobenzene, and the sample concentration was 20 μm.
0 mg / 40 ml (orthodichlorobenzene), and the injection amount was 7.5 ml.

[0050]

[Production Example 1] [Ethylene / 1-hexene copolymer [ML]
Production of LDPE (1)] [Preparation of catalyst] Silica dried at 250 ° C. for 10 hours 7.
After suspending 9 kg with 121 liters of toluene,
Cooled to 0 ° C. Thereafter, 41 l of a toluene solution of methylaluminoxane (Al = 1.47 mol / l) was added dropwise over 1 hour. At this time, the temperature in the system was set to 0 ° C
Kept. Subsequently, the reaction was carried out at 0 ° C. for 30 minutes.
The temperature was raised to 95 ° C. over 5 hours, and the reaction was performed at that temperature for 4 hours. Thereafter, the temperature was lowered to 60 ° C., and the supernatant was removed by a decantation method. The solid component thus obtained was washed twice with toluene and then resuspended in 125 liters of toluene. 20 liters of a toluene solution of bis (1,3-dimethylcyclopentadienyl) zirconium dichloride (Zr = 28.4 mmol / l) was dropped into the system at 30 ° C. for 30 minutes, and further cooled at 30 ° C. for 2 minutes. Allowed to react for hours. Thereafter, the supernatant was removed and the mixture was diluted with hexane for 2 hours.
By washing twice, a solid catalyst containing 4.6 mg of zirconium per gram was obtained.

[Preparation of Preliminary Polymerization Catalyst] To 160 liters of hexane containing 16 mol of triisobutylaluminum, 4.3 kg of the above solid catalyst was added.
Preliminary polymerization of ethylene was performed for 5 hours to obtain a prepolymerized catalyst in which 3 g of polyethylene was prepolymerized per 1 g of the solid catalyst. The intrinsic viscosity [η] of the ethylene polymer measured in decalin at 135 ° C. was 1.27 dl / g.

[Polymerization] Using a continuous fluidized-bed gas-phase polymerization apparatus, ethylene and 1-hexene were copolymerized at a total pressure of 20 kg / cm ² -G and a polymerization temperature of 80 ° C. 0.075 mmol / h of the above prepolymerized catalyst in terms of zirconium atoms
r, 10 mmol / hr of triisobutylaluminum
And ethylene, 1-hexene, hydrogen and nitrogen were continuously supplied to maintain a constant gas composition during the polymerization (gas composition; 1-hexene / ethylene = 0.
055, hydrogen / ethylene = 1.4 × 10 ⁻³ , ethylene concentration = 25%).

The yield of the obtained ethylene / 1-hexene copolymer [M-LLDPE (1)] was 6.0 kg / hr.
And the density (d) is 0.905 g / cm ³ ,
The FR was 2.0 g / 10 min, the MT was 2.2 g, and the maximum peak (Tm) of the melting point in DSC was 92.10 g.
0 ° C., the n-decane soluble component content ratio (W) at 23 ° C. was 1.4% by weight, and the ethylene content was 84.4%.
% By weight. Table 1 shows the physical properties of this copolymer [metallocene-based linear low-density polyethylene; M-LLDPE (1)].

This ethylene / 1-hexene copolymer [M-
LLDPE (1)] was pelletized by melt-kneading.

[0055]

[Production Example 2] [Ethylene / 1-hexene copolymer [ML]
Production of LDPE (2)] In Production Example 1, the density, MF
The gas composition was changed so that R was an ethylene / 1-hexene copolymer [M-LLDPE (2)] having the values shown in Table 1, the ethylene concentration was changed to 25%, and the polymerization temperature was changed to 70%.
Except that the temperature was changed to ° C., an ethylene / 1-hexene copolymer [M-LLDPE (2)] having an ethylene content of 85.9% by weight was obtained in the same manner as in Production Example 1.

The obtained ethylene / 1-hexene copolymer [metallocene linear low density polyethylene; M-LLD]
Table 1 shows the physical properties of PE (2)].

[0057]

[Production Example 3] [Ethylene / 1-hexene copolymer [ML]
Production of LDPE (3)] In the preparation of the catalyst component in Production Example 1, a toluene solution of bis (1,3-dimethylcyclopentadienyl) zirconium dichloride (Zr = 2
8.4 mmol / l) 13.2 l of a toluene solution of bis (1,3-n-butylmethylcyclopentadienyl) zirconium dichloride (Zr = 34.0 mmol / l) and bis ( 1,3-Dimethylcyclopentadienyl) zirconium dichloride in toluene solution (Zr = 28.4 mmol / L)
A catalyst was prepared in the same manner as in Production Example 1 except that 4.0 liters were used, and using this catalyst, an ethylene / 1-hexene copolymer having the density and MFR shown in Table 1 was used. M-LLDPE (3)], except that the gas composition was changed so that the ethylene content was 8
7.4% by weight of ethylene / 1-hexene copolymer [ML
LDPE (3)].

The obtained ethylene / 1-hexene copolymer [metallocene linear low density polyethylene; M-LLD
Table 1 shows the physical properties of [PE (3)].

[0059]

[Production Example 4] [Ethylene / 1-hexene copolymer [ML]
Production of LDPE (4)] In the preparation of the catalyst component in Production Example 1, a toluene solution of bis (1,3-dimethylcyclopentadienyl) zirconium dichloride (Zr = 2
Instead of 20 liters (8.4 mmol / l), 16.7 liters of a toluene solution of bis (1,3-n-butylmethylcyclopentadienyl) zirconium dichloride (Zr = 34.0 mmol / l) was used. Except for the above, a catalyst was prepared in the same manner as in Production Example 1, and the density and MFR were adjusted to the values of ethylene / 1-
Except that the gas composition was changed to become a hexene copolymer [M-LLDPE (4)], the same as in Production Example 1,
An ethylene / 1-hexene copolymer [M-LLDPE (4)] having an ethylene content of 87.9% by weight was obtained.

The obtained ethylene / 1-hexene copolymer [metallocene linear low-density polyethylene; M-LLD
Table 1 shows the physical properties of PE (4)].

[0061]

Example 1 Ethylene / 1-hexene copolymer obtained in Production Example 1 [M-LLDPE (1); ethylene content = 8
4.4% by weight, density (ASTM D 1505) = 0.905 g / c
m ³ , MFR (ASTM D 1238, 190 ° C, load 2.16 kg) =
2.0 g / 10 min, MT = 2.2 g, Tm = 92.0
85 ° C., W = 1.4% by weight] and 85 parts by weight of a high-pressure low-density polyethylene [density (ASTM D 1505) = 0.922 g / cm]
³ , MFR (ASTM D 1238, 190 ° C, load 2.16 kg) = 0.6
g / 10 min] of 15 parts by weight and 30 parts by weight of finely divided calcium carbonate [trade name: Whiten H, manufactured by Shiraishi Kogyo Co., Ltd.] using the following molding conditions and extrusion conditions shown in Table 1. 200 thickness by inflation molding method
A μm film was formed. [Inflation molding conditions] Inflation film molding machine 90 mmφ extruder manufactured by Modern Machinery Co., Ltd. Screw: L / D = 28 Compression ratio: 1.3 Die diameter: 200 mmφ Lip width: 2.5 mm Film thickness: 200 μm Extruder setting Temperature: cylinder 180 ° C, dice 19
0 ° C Swelling ratio: 1.4 Take-off speed: 7 m / min The dart impact strength of the obtained film was measured according to the following test method. Table 1 shows the results. [Test Method for Dart Impact Strength] ASTM D 17
The value obtained by dividing the value measured according to Method A of 09 by the thickness of the film was defined as the dirt impact strength.

Next, 3.65 g of the film obtained as described above was placed in a 500 ml beaker, and an aliphatic hydrocarbon resin [trade name: Hiretz ^™ R-500X; C5 anhydrous maleic] manufactured by Mitsui Chemicals, Inc. Acid-modified hydrocarbon resin, softening point (ring and ball method; JIS K 2207) = 98
100 ° C., hue (melting method; JIS K 5400) = 5 Gardner, acid value = 4.8 mg KOH / g], and the beaker was placed in a constant temperature oil bath adjusted to 200 ° C. and heated. When the temperature of this hydrocarbon resin reached 200 ° C., coarse calcium carbonate [trade name cold water sand # 30,
230 g, fine powdered calcium carbonate [trade name: Whiten H, manufactured by Shiraishi Industry Co., Ltd.] 230 g, acid value titanium powder [average particle size = 0.148 μm, anatase type acid value titanium, trade name: Taipek A-220, manufactured by Ishihara Sangyo Co., Ltd.] 30 g, plasticizer [trade name Arachid 251,
Arakawa Chemical Industries, Ltd.] 17g, Mitsui Hi-wax ^TM 110P
[Trade name; low molecular weight polyethylene manufactured by Mitsui Chemicals, Inc.]
7.3 g, 0.3 g of Mitsui High Wax ^™ 4202E [trade name; low molecular weight polyethylene manufactured by Mitsui Chemicals, Inc.], and 118 g of glass beads [trade name: GB-153T, manufactured by Toshiba Palo Tea Co.] are added and stirred. A hot melt type traffic paint containing a polyethylene bag was manufactured.

The flowability, melt viscosity, thixotropy, compressive strength, softening point and aggregate sedimentability of the hot melt type traffic paint obtained as described above were measured or evaluated according to the following methods. Table 2 shows the results. (1) Liquidity Zahn Visco City Cup No. 8 at 200 ° C. In addition, the Zahn Visco City Cup N used
o. 8 has an upper diameter of 33 mm and a height of 60 mm,
An outlet having a diameter of 8 mm is provided below the cup. (2) Melt Viscosity The viscosity at 6 and 60 rotations was measured at 200 ° C. using a Brookfield-type rotational viscometer. (3) Thixotropy (Thixotropic) The evaluation was made by dividing the melt viscosity at 6 rotations by the melt viscosity at 60 rotations. (4) Compressive strength Measured according to the method of JIS K5655. (5) Softening point Measured according to the method of JIS K5665. (6) Aggregate sedimentability The non-melted material was filled in a 50 ml beaker,
After standing at 2 ° C. for 2 hours, the mixture was cooled and cured, and the sedimentation rate of the filler on the vertical cut surface of the solidified product was measured.

[0064]

Example 2 In Example 1, the ethylene / 1-hexene copolymer [M-LLDPE (1)] obtained in Production Example 1 was used.
In place of the ethylene / 1-hexene copolymer obtained in Production Example 2 [M-LLDPE (2); ethylene content = 8
5.9% by weight, density (ASTM D 1505) = 0.908 g / c
m ³ , MFR (ASTM D 1238, 190 ° C, load 2.16 kg) =
1.7 g / 10 min, MT = 2.4 g, Tm = 104.0
° C, W = 1.0 wt%], and a 200 µm-thick film was formed in the same manner as in Example 1 except that the extrusion conditions shown in Table 1 were changed.

The dirt impact strength of the obtained film was measured in the same manner as in Example 1. Table 1 shows the results. Thereafter, using the obtained film, a hot melt type traffic paint containing a polyethylene bag was produced in the same manner as in Example 1.

The obtained hot melt type traffic paint was measured or evaluated for melt viscosity, thixotropy, compressive strength, softening point and aggregate sedimentability according to the following methods. Table 2 shows the results.

[0067]

Example 3 In Example 1, the metallocene linear low-density polyethylene [M-LLDPE] obtained in Production Example 1 was used.
(1)] in place of the ethylene 1-
Hexene copolymer [M-LLDPE (3); ethylene content = 87.4% by weight, density (ASTM D 1505) = 0.910
g / cm ³ , MFR (ASTM D 1238, 190 ° C, load 2.16k
g) = 2.1 g / 10 min, MT = 2.4 g, Tm = 10
9.2 ° C., W = 0.7% by weight, the number of long-chain branches (per 1000 carbon atoms) <1], and the extrusion conditions shown in Table 1 were changed. Similarly, a film having a thickness of 200 μm was formed.

The dirt impact strength of the obtained film was measured in the same manner as in Example 1. Table 1 shows the results. Thereafter, a hot melt type traffic paint containing a polyethylene bag was produced in the same manner as in Example 1 using the obtained film.

The resulting hot-melt traffic paint was measured or evaluated for melt viscosity, thixotropy, compressive strength, softening point, and aggregate sedimentability according to the following methods. Table 2 shows the results.

[0070]

Comparative Example 1 In Example 1, the ethylene / 1-hexene copolymer [M-LLDPE (1)] obtained in Production Example 1
Instead of the ethylene / 1-hexene copolymer obtained in Production Example 4 [M-LLDPE (4); ethylene content = 8
7.9% by weight, density (ASTM D 1505) = 0.910 g / c
m ³ , MFR (ASTM D 1238, 190 ° C, load 2.16 kg) =
2.0 g / 10 min, MT = 0.9 g, Tm = 108.8
° C, W = 0.5% by weight, number of long-chain branches (100 carbon atoms)
<1] and the extrusion conditions shown in Table 1 were changed, except that the thickness was 2
A 00 μm film was formed.

The dirt impact strength of the obtained film was measured in the same manner as in Example 1. Table 1 shows the results. Thereafter, using the obtained film, a hot melt type traffic paint containing a polyethylene bag was produced in the same manner as in Example 1.

The resulting hot-melt traffic paint was measured or evaluated for melt viscosity, thixotropy, compressive strength, softening point and aggregate sedimentability according to the following methods. Table 2 shows the results.

[0073]

Comparative Example 2 In Example 1, the ethylene / 1-hexene copolymer [M-LLDPE (1)] obtained in Production Example 1
And an ethylene-vinyl acetate copolymer [EVA; MFR (ASTM D 123)
8,190 ° C., load 2.16 kg) = 1 g / 10 min, vinyl acetate (VA) content = 10% by weight], and the extrusion conditions were changed to those shown in Table 1. hand,
A film having a thickness of 200 μm was formed.

The dirt impact strength of the obtained film was measured in the same manner as in Example 1. Table 1 shows the results. Thereafter, using the obtained film, a hot melt type traffic paint containing a polyethylene bag was produced in the same manner as in Example 1.

With respect to the obtained hot-melt type traffic paint, the melt viscosity, thixotropy, compressive strength, softening point and aggregate sedimentability were measured or evaluated according to the following methods. Table 2 shows the results.

[0076]

Comparative Example 3 In Example 1, the ethylene / 1-hexene copolymer [M-LLDPE (1)] obtained in Production Example 1
And high-pressure method low-density polyethylene, ethylene-acrylate copolymer [EEA; MFR (ASTM
D 1238, 190 ° C., load 2.16 kg) = 1 g / 10 min, acrylate (EA) content = 8% by weight], and the extrusion conditions shown in Table 1 were changed. Thus, a film having a thickness of 200 μm was formed.

The dart impact strength of the obtained film was measured in the same manner as in Example 1. Table 1 shows the results. Thereafter, using the obtained film, a hot melt type traffic paint containing a polyethylene bag was produced in the same manner as in Example 1.

The resulting hot melt type traffic paint was measured or evaluated for melt viscosity, thixotropy, compressive strength, softening point and aggregate sedimentation according to the following methods. Table 2 shows the results.

[0079]

[Table 1]

M-LLDPE (1); 2.2 × MFR ^−0.84 = 1.2 400 × d−248 = 1118.0 80 × exp (−100 (d−0.88)) + 0.1 = 7 ^{2.3 The} above M-LLDPE (2); 2.2 × MFR ^−0.84 = 1.4 400 × d−248 = ^1115.80 × exp (−100 (d−0.88)) + 0.1 = 5. 4 M-LLDPE (3) above; 2.2 x MFR ^-0.84 = 1.2 400 x d-248 = 116.0 80 x exp (-100 (d-0.88)) + 0.1 = 4.4. The above M-LLDPE (4); 2.2 × MFR ^−0.84 = 1.2 400 × d−248 = ^1116.80 × exp (−100 (d−0.88)) + 0.1 = 4.4

[0081]

[Table 2]

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification code FI Theme coat ゛ (Reference) C08L 23/08 C08L 23/08 4J100 // (C08L 23/08 23:06) B29K 23:00 B29L 7: 00 F-term (reference) 3E064 BA21 BA24 BC20 3E086 AD01 BA02 BA15 BB51 BB85 CA29 4F071 AA15 AA15X AA20 AA20X AA21 AA21X AA82 AA87 AA88 AF01Y AF05Y AF23Y AH04 BB01 BC014A01A013A01A13A01K GG00 4J100 AA02P AA03Q AA04Q AA07Q AA15Q AA16Q AA17Q AA19Q AA21Q CA04 DA24 DA36 DA40 DA42 JA58

Claims (9)

[Claims] An ethylene and a melt having a melt tension (MT (g)) at 190 ° C. and a melt flow rate (MFR (g / 10 minutes)) satisfying a relationship expressed by MT ≦ 2.2 × MFR− ^0.84. 3 to 2 carbon atoms
And a resin pressure P (kg / cm ² ) and a resin temperature T (° C.) at the time of forming a film comprising an ethylene / α-olefin copolymer (A1) comprising α-olefin of 0.
The resin extrusion rate K (kg / hour), the lip cross-sectional area A (cm ² ) of the film forming machine, and the melt flow rate (MFR (g / 10 minutes)) of the resin are 200 × [K ^{/ (MFR 1.5) / (T} -120) / A 0.2]
^0.2 ≦ P ≦ 450 × [K / (MFR ^1.5 ) / (T−120)
/ A ^0.2 ] A film for a melting bag, which is formed with a relationship represented by ^0.2 , and has a dart impact strength of 1000 g or more at a thickness of 200 μm. 2. The melt tension at 190 ° C. (MT)
(g)) and melt flow rate (MFR (g / 10 min))
^Satisfies the relationship expressed as MT> 2.2 × MFR ^-0.84 , and (ii) n-decane soluble component content ratio (W (% by weight)) and density (d (g / cm ³ )) at room temperature. When MFR ≦ 10 g / 10 min: W <80 × exp (−100 (d−0.88)) + 0.1 When MFR> 10 g / 10 min: W <80 × (MFR-9) ^0.26 × exp (−100 (d−
(Iii) the temperature (Tm (° C.)) and the density (d) at the maximum peak position of the endothermic curve measured by a differential scanning calorimeter (DSC).
(g / cm ³ )) and Tm <400 × d-248, satisfying the following relationship:
A resin pressure P (kg / cm ² ) consisting of an ethylene / α-olefin copolymer (A2) comprising α-olefin of 0 and forming a film
, Resin temperature T (° C.), resin extrusion amount K (kg / hour), and lip cross-sectional area A (cm ² ) of the film forming machine
And the melt flow rate of the resin (MFR (g / 10
Min)), but, 200 × [K / (MFR 1.5) / (T-120) / A 0.2]
^0.2 ≦ P ≦ 450 × [K / (MFR ^1.5 ) / (T−120)
/ A ^0.2 ] A film for a melting bag, which is formed with a relationship represented by ^0.2 , and has a dart impact strength of 1000 g or more at a thickness of 200 μm. 3. The ethylene / α-olefin copolymer (A2) satisfies the above relationships (i), (ii) and (iii), and (iv) is measured by a differential scanning calorimeter (DSC). The film for a molten bag according to claim 2, wherein the measured endothermic curve has at least two peaks. 4. The ethylene / α-olefin copolymer (A2) satisfies the above-mentioned relationships (i), (ii) and (iii), and (v) is 100% in a temperature rising dissolution test (TREF). 3. The film for a melting bag according to claim 2, wherein a component that is not eluted at a temperature lower than 0 ° C. is present, and the component is present in an amount of 10% or less of the whole. 5. The ethylene / α-olefin copolymer (A2) satisfies the above relationships (i), (ii) and (iii), and (vi) has 6 carbon atoms measured by NMR. The number of long chain branches is 3 per 1000 carbon atoms.
3. The film for a molten bag according to claim 2, wherein the number exceeds the number of pieces. 6. The ethylene / α-olefin copolymer (A2) satisfies the relationships (i), (ii) and (iii), and (vii) an α-olefin copolymerized with ethylene. When the number of carbon atoms exceeds 7, an ethylene / α-olefin copolymer in which the number of long-chain branches having 6 or more carbon atoms measured by NMR exceeds 3 per 1000 carbon atoms The film for a melting bag according to claim 5, characterized in that: 7. The ethylene / α-olefin copolymer (A2) satisfies the relationships (i), (ii) and (iii), and (viii) comprises an α-olefin copolymerized with ethylene. The method according to claim 2, wherein when the number of carbon atoms is 7 or less, the number of long-chain branches having 6 or more carbon atoms measured by NMR is 3 or less per 1000 carbon atoms. Packaging film. 8. The high-pressure low-density polyethylene (B) is blended in the ethylene / α-olefin copolymer (A1) or (A2) in an amount of 50% by weight or less. Item 8. The film for a melting bag according to any one of Items 1 to 7. 9. A melting bag formed from the film for a melting bag according to any one of claims 1 to 8.