Specification
DESCRIPTION ETHYLENIC POLYMER AND MOLDED ARTICLE OBTAINED THEREFROM
[TECHNICAL FIELD]
[0001]
The present invention relates to an ethylene-α-olefin copolymer, and more specifically, to an ethylenic polymer which is excellent in moldability and is suitably used for molded articles including films excellent in transparency ' and mechanical strength, and to a molded article and a film obtained therefrom.
[BACKGROUND ART]
[0002]
Ethylenic copolymers require various properties depending on how they are molded or used. For example, ethylenic copolymers are formed into films by various molding methods and are used for wide applications in many fields. Types of the films vary depending on what they will contain, and the films show various properties depending on the types and amounts of monomer units constituting the ethylenic copolymer or depending on the production method of the ethylenic copolymer.
[0003]
For example, when an ethylenic copolymer is formed into
an inflation film at high speed, the copolymer should have a high melt tension (MT: melt tension) for its molecular weight in order to ensure stable high speed molding without fluttering or tearing of bubble. Similar characteristics are required in order to prevent sagging or tearing in blow molding, or to minimize width shortage in T-die molding. [0004]
Ziegler-catalyzed linear low-density
ethylene-1-butene copolymers give films excellent in transparency and surface smoothness. However, the films have low mechanical strength shown by dart impact strength and Elmendorf tear strength and have a low melt tension. Consequently, the films are easily broken during the molding and thus increasing the molding speed is limited. Japanese Patent Application Laid-Open Publication Nos. S56-90810 and S60-106806 disclose methods for improving moldability by improving the melt tension and blow ratio (die/swell ratio) of ethylenic polymers obtained with a Ziegler catalyst, especially a titanium-containing catalyst. [0005]
However, ethylenic polymers obtained using a
titanium-containing catalyst, especially linear
low-density ethylenic copolymers generally have a broad molecular weight distribution or composition distribution.
It is therefore desired to further reduce components which cause stickiness of molded articles such as films, and components such as low molecular weight components which bleed out and adhere in fine dots to the film surface. [0006]
Further, ethylenic polymers obtained with a chromium-containing catalyst have a relatively high melt tension but are desired to have higher heat stability. [0007]
On the one hand, linear low density polyethylene produced by gas-phase polymerization using a metallocene catalyst has a narrow molecular weight distribution, and films thereof do not cause blocking as known in the art. In particular, a linear low-density ethylene-1-hexene copolymer produced with a metallocene catalyst gives films having excellent properties such as mechanical strength, transparency and heat sealing properties. [0008]
However, the polymer has a low melt tension because of its narrow molecular weight distribution compared with that of Ziegler-catalyzed polymers, causing problems such as poor bubble stability in inflation molding and significant neck-in in extrusion molding (T-die molding). To cope with these problems, the performances of the polymer
are compensated for by adding a high pressure low density polyethylene with a high melt tension. [0009]
Moreover, the molding of the above polymer entails high resin pressure and high resin temperature, and gel-like products and die buildup are frequently caused during long-term film production. To eliminate these problems, a die and an extruder should be dismantled and cleaned or an additive should be added to suppress the gel-like products and die buildup.
[Patent Document 1] Japanese Patent Application Laid-Open Publication No. S56-90810
[Patent Document 2] Japanese Patent Application Laid-Open Publication No. S60-106806 [DISCLOSURE OF THE INVENTION] [PROBLEMS TO BE SOLVED BY THE INVENTION] [0010]
Therefore, there is desired the development of an ethylenic copolymer excellent in moldability and mechanical properties and a film or sheet composed of the ethylenic polymer. [0011]
Objects of the present invention are to provide an ethylenic polymer, specifically an ethylene-α-olefin
copolymer which is excellent in transparency and
moldability and which can form a molded article, especially
a film or sheet, excellent in mechanical strength, and to
provide a molded article, preferably a film or sheet,
comprising the ethylenic polymer. (In the following
explanation, the ethylene-α-olefin copolymer for a film or sheet of the present invention may be referred to as the "ethylene-α-olefin copolymer (E)" or simply as the "copolymer (E)" . )
[MEANS FOR SOLVING THE PROBLEMS] [0012]
The present invention relates to an ethylene-α-olefin copolymer (E) for a film or sheet characterized in that it satisfies the following requirements [1] to [5] simultaneously. [0013]
[1] The density (d) is in the range of 890 to 980 kg/m3. [0014]
[2] The intrinsic viscosity ([n]) measured at 135°C in decalin is in the range of 0.5 to 10 dl/g. [0015]
[3] The ratio of weight average molecular weight (Mw) to number average molecular weight (Mn) (Mw/Mn) measured by GPC is in the range of 2.0 to 50.
[0016]
[4] In an elution temperature-elution amount curve given by cross fractionation chromatography (CFC), the difference between a temperature at which the integrated elution amount is 1% by mass and a temperature at which the integrated elution amount is 40% by mass is 12°C or less, wherein the total elution amount is.100% by mass.
[0017]
[5] The amount of a component soluble in decane is 0.5% by mass or less.
[0018]
Further, the present invention relates to the above-mentioned ethylene-α-olefin copolymer characterized in that the above-mentioned ethylene-α-olef in copolymer (E) is composed of 80 to 20% by mass of the below-mentioned ethylene-α-olefin copolymer (A) and 20 to 80% by mass of the below-mentioned ethylene-α-olefin copolymer (B).
[0019]
Here, the ethylene-α-olefin copolymer (A) comprises ethylene and an α-olefin having 3 to 10 carbon atoms and satisfies the following requirements: the density (dA) is 910 to 980 kg/m3; the intrinsic viscosity ([n]A) is 0.5 to 3.0 dl/g as measured at 135°C in decalin; and the ratio of weight average molecular weight (Mw) to number average
molecular weight (Mn) (Mw/Mn) is 1.5 to 5.0 as measured by GPC.
The ethylene-α-olefin copolymer (B) comprises ethylene and an α-olefin having 3 to 10 carbon atoms and satisfies that the density (dB) is 880 to 950 kg/m3, the intrinsic viscosity ([n]B) is 1.0 to 10.0 dl/g as measured at 135°C in decalin and the ratio of weight average molecular weight (Mw) to number average molecular weight (Mn) (Mw/Mn) is 1.5 to 5.0 as measured by GPC.
In addition, the intrinsic viscosity of the ethylene-α-olef in copolymer (A) and that of the ethylene-α-olefin copolymer (B) satisfy the following relational equation (Eq-1). [0020]
( [ri]B)/( [n]A)>l ... (Eq-1)
Further, the present invention relates to the above-mentioned ethylene-α-olefin copolymer characterized in that the above-mentioned ethylene-α-olef in copolymer (E) has a melt tension (MT) at 190°C of 20 mN or more. [0021]
Moreover, the present invention relates to a film or
sheet obtained from the ethylene-α-olefin copolymer (E),
which preferably has (1) a thickness of 10 to 500 µm and
(2) a dart impact of 100 g or more in terms of a thickness
of 4 0 urn.
[0022]
Furthermore, the present invention relates to a wrapping bag, a sheet or a bag composed of the above-mentioned film or sheet.
[0023]
In addition, the present invention relates to a laminate comprising at least one layer of the above-mentioned film or sheet, wherein the film or sheet preferably has a dart impact of 130 g or more in terms of a thickness of 40 urn.
[EFFECT OF THE INVENTION]
[0024]
The ethylene-α-olefin copolymer (E) of the present invention is excellent in transparency and moldability and can produce a molded article, especially a film or sheet, which is excellent in mechanical strength properties such as dart impact.
[BEST MODE FOR CARRYING OUT THE INVENTION]
[0025]
Hereinafter, preferred embodiments of the
ethylene-α-olefin copolymers (E) of the present invention will be sequentially explained, followed by the description
of a method for producing the ethylene-α-olefin copolymers (E), films or sheets obtained from the ethylene-α-olefin copolymers (E) and various measurement methods, and finally working examples. In the present invention, the term "copolymers" is defined to refer to polymers including homopolymers obtained from a single olefin. [0026]
Ethylene-α-olefin Copolymer (E)
The ethylene-α-olefin copolymer (E) of the present invention is an ethylene homopolymer or a copolymer of ethylene and an α-olefin having 3 to 10 carbon atoms, for example, such as propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-l-pentene, 3-methyl-pentene, 1-heptene, 1-octene, 1-decene or the like, preferably propylene, 1-butene, 1-hexene, 4-methyl-l-pentene or 1-octene, and is preferably a copolymer containing 10% by mol or less of the α-olefin, or a mixture (composition) of these polymers, wherein:
[1] the density (d) is in the range of 890 to 980 kg/m3,
[2] the intrinsic viscosity ([n]) is in the range of 0.5 to 10 dl/g as measured at 135°C in decalin,
[3] the ratio of weight average molecular weight (Mw) to number average molecular weight (Mn) (Mw/Mn) is in the range of 2.0 to 50 as measured by GPC,
[4] in an elution temperature-elution amount curve
given by cross fractionation chromatography (CFC), the difference between a temperature at which the integrated elution amount is 1% by mass and a temperature at which the integrated elution amount is 40% by mass is 12CC or less, wherein the total elution amount is 100% by mass, and
[5] the amount of a component soluble in decane is 0.5% by mass or less. [0027]
The ethylene-α-olefin copolymer (E) of the present invention contains typically 10% by mol or less and preferably 0.2 to 10% by mol of constituent units derived from the α-olefin. [0028]
The ethylene-α-olefin copolymer (E) satisfying the above requirements [1] to [5] provides molded articles such as a film and the like which are excellent in moldability and mechanical strength properties such as dart impact strength and the like. Hereinafter, the requirements [1] to [5] are specifically explained. [0029]
Requirements [1] to [3]
The ethylene-α-olefin copolymer (E) of the present invention has a density (d) in the range of 890 to 980 kg/m3, preferably 900 to 975 kg/m3, more preferably 929 to 975 kg/m3
and further more preferably 929 to 945 kg/m3. [0030]
The ethylene-α-olefin copolymer (E) of the present invention has an intrinsic viscosity ([n]) in the range of 0.5 to 10.0 dl/g, preferably 0.5 to 8.0 dl/g, more preferably 0.5 to 7.0 dl/g, further more preferably 0.5 to 5.0 dl/g and especially preferably 1.0 to 4.0 dl/g, as measured at 135°C in decalin. An ethylene-α-olefin copolymer (El) having an intrinsic viscosity ([]) in the range of 0.5 to 5 dl/g as measured at 135°C in decalin is especially suitable for a film or sheet. [0031]
The ethylene-α-olefin copolymer (E) of the present invention has a ratio of weight average molecular weight (Mw) to number average molecular weight (Mn) (Mw/Mn) in the range of 2.0 to 50, preferably 2.5 to 30 and more preferably 3.0 to 25, as measured by GPC. [0032]
The ethylene-α-olefin copolymer having a density, an intrinsic viscosity and a molecular weight distribution in the above ranges is excellent in balance between mechanical properties and moldability. These parameters may be controlled to the above physical properties range by, for example, adjusting the feed ratio of hydrogen, ethylene and
α-olefin into a polymerization reactor. [0033]
Requirements [4] and [5]
In an elution temperature-elution amount curve given by cross fractionation chromatography (CFC) of the ethylene-α-olefin copolymer (E) of the present invention, the difference between a temperature at which the integrated elution amount is 1% by mass and a temperature at which the integrated elution amount is 40% by mass is 12°C or less and preferably 10°C or less, wherein the total elution amount is 100% by mass. [0034]
With the ethylene-α-olef in copolymer (E) of the present invention, the amount of a component soluble in decane is 0.5% by mass or less. [0035]
The ethylene-α-olefin copolymer (E) satisfying these requirements has a small amount of a high molecular component in whichα-olefins are copolymerized, or does not contain components having a relatively low molecular weight and a short branched chain. In this case, the polymer is excellent in balance between moldability and mechanical strength. [0036]
A preferred embodiment of the ethylene-α-olefin
copolymer (E) of the present invention is characterized in
that the copolymer satisfies the above requirements [1] to
[5] and has a melt tension (MT) at 190°C of 20 mN or more,
preferably 30 mN or more and more preferably 35 mN or more.
[0037]
In a preferred embodiment of the ethylene-α-olefin
copolymer (E) of the present invention, the
ethylene-α-olefin copolymer (E) comprises 80 to 20% by mass and preferably 70 to 30% by mass of an ethylene-α-olefin copolymer (A) and 20 to 80% by mass and preferably 30 to 70% by mass of an ethylene-α-olefin copolymer (B). The ethylene-α-olefin copolymer (E) of such preferred embodiment is excellent in moldability and melt tension, and the obtainable molded article is excellent in transparency and mechanical strength. [0038]
The above-mentioned ethylene-α-olefin copolymer (A) comprises ethylene and an α-olefin having 3 to 10 carbon atoms and has a density (dA) in the range of 910 to 980 kg/m3, preferably 915 to 975 kg/m3 and more preferably 920 to 975 kg/m3, an intrinsic viscosity ([]A) in the range of 0.5 to 3.0 dl/g, preferably 0.5 to 2.7 dl/g and more preferably 0.7 to 2.5 dl/g as measured at 135°C in decalin, and a ratio
of weight average molecular weight (Mw) to number average molecular weight (Mn) (Mw/Mn) in the range of 1.5 to 5.0, preferably 1.5 to 4.5 and more preferably 2.0 to 4.0 as measured by GPC. [0039]
The above-mentioned ethylene-α-olefin copolymer (B) comprises ethylene and an α-olefin having 3 to 10 carbon atoms and has a density (dB) in the range of 880 to 950 kg/m3, preferably 890 to 945 kg/m3 and more preferably 895 to 940 kg/m3, an intrinsic viscosity ([n]B) in the range of 1.0 to 10.0 dl/g, preferably 1.0 to 8.0 dl/g and more preferably 1.0 to 7.0 dl/g as measured at 135°C in decalin, and a ratio of weight average molecular weight (Mw) to number average molecular weight (Mn) (Mw/Mn) in the range of 1.5 to 5.0, preferably 1.5 to 4.5 and more preferably 2.0 to 4.0 as measured by GPC. [0040]
In addition, the intrinsic viscosities of the ethylene-α-olefin copolymer (A) and the ethylene-α-olefin copolymer (B) satisfy the following relationship. [0041]
The ratio ([]B)/([]A) is more than 1, preferably more than 1 and less than 6.0, more preferably 1.1 or more and less than 6.0 and further more preferably 1.2 or more and
less than 6.0.
[0042]
When the ethylene-α-olef in copolymer (E) of the present invention comprises the copolymer (A) and the copolymer (B) as mentioned above, the copolymer exhibits excellent film moldability and film transparency. However, even when the copolymer comprises a single copolymer, the copolymer falls within the scope of the claims of the present invention as long as the copolymer satisfies the above requirements [1] to [5]. The ethylene-α-olefin copolymer
(E) constituted of a single copolymer [hereinafter also referred to as the copolymer (E')] causes little gel-like products and die buildup during film production and forms a film with little fine dots bleeding out on the film surface.
[0043]
The copolymer (E') belongs to the ethylene-α-olefin copolymers (E) satisfying the above-mentioned requirements
[1] to [5] and satisfies the following requirements [1'] to [5' ] .
[0044]
The copolymer (E') is characterized in that [1' ] the density (d) is in the range of 910 to 980 kg/m3, preferably 920 to 975 kg/m3 and more preferably 925 to 970 kg/m3,
[2'] the intrinsic viscosity ([]) is in the range of 0.5 to 4.0 dl/g, preferably 0.5 to 3.5 dl/g and more preferably 0.5 to 3.0 dl/g as measured at 135°C in decalin,
[3'] the ratio of weight average molecular weight (Mw) to number average molecular weight (Mn) (Mw/Mn) is in the range of 1.5 to 5.0, preferably 1.5 to 4.5 and more preferably 2.0 to 4.0 as measured by GPC,
[4'] in an elution temperature-elution amount curve given by cross fractionation chromatography (CFC), the difference between a temperature at which the integrated elution amount is 5% by mass and a temperature at which the integrated elution amount is 50% by mass is 10°C or less and preferably 9°C or less, wherein the total elution amount is 100% by mass, and
[5'] the melt tension (MT) measured at 190°C is 5 mN or more, preferably 5 to 50 mN and more preferably 5 to 30 mN. [0045]
The copolymer (E') also satisfying the above requirements [1'] to [5'] causes little gel-like products and die buildup during film production and forms a film with little fine dots bleeding out on the film surface. Specifically, a film obtained from the copolymer (E' ) satisfies the following properties [a] to [c].
[0046]
[a] The total haze of a film having a thickness of 40
urn is 35% or less, preferably 30% or less and more preferably
25% or less.
[0047]
[b] The film impact strength measured at 23°C is 5 kJ/m
or more.
[0048]
[c] The visual evaluation value of the contamination
at a guide roll when a film is formed is score 3 or higher,
preferably score 4 or higher and more preferably score 5
by 5-grade evaluation.
[0049]
When a film is prepared by the cast film-forming
(details are explained in Examples) of an ethylene polymer, in general, a molten resin at 170 to 250°C extruded from a T-die is brought into contact with a chill roll at 20 to 100°C to solidify into a film. At that time, a powder may adhere to the surface of the film or guide rolls. In the present invention, the contamination was visually evaluated as follows: a black felt cloth was placed between a guide roll and the film and a powder which adhered to the felt cloth was observed after a fixed period of time.
[0050]
Further, the adhesion amount of the powder was evaluated as follows: a black felt cloth was pressure bonded under a fixed tension to a guide roll at the downstream of the chill roll and the white powder was allowed to adhere to the felt cloth by using the friction generated when the cast film passed through between a roll and the felt cloth. The film was brought into contact with the felt cloth while the film was drawn 500 m and then the black felt cloth was removed. The adhesion amount was visually evaluated in five grades according the adhesion amount of the white powder. [0051]
Score 5: No white powder adhered.
Score 4: A small amount of white powder adhered.
Score 3: The white powder adhered on about half of the area.
Score 2: Between score 3 and score 1
Score 1: The white powder adhered on almost the whole area.
Here, the result of Comparative Example 7 was used as the criterion of score 1. [0052]
The ethylene-α-olefin copolymer (E) of the present
invention may contain additives such as weathering
stabilizers, heat-stabilizers, anti-static agents,
workability improvers, anti-slip agents, anti-blocking agents, anti-fogging agents, lubricants, dyes, nucleating agents, plasticizers, anti-aging agents, hydrochloric acid absorbers, antioxidants and the like; pigments such as carbon black, titanium oxide, titanium yellow, phthalocyanine, isoindolinone, quinacridone compound, condensed azo compound, ultramarine blue, cobalt blue and the like; and additional polymers, if needed, as long as the object of the present invention is not impaired.
[0053]
The above-mentioned antioxidants specifically
include, for example, phenol anti-oxidants such as
2, 6-di-t-butyl-p-cresol (BHT),
tetrakis[methylene-3-(3,5-di-t-butyl-4-hydroxyphenyl)
propionate]methane (trade name: IRGANOX 1010, manufactured
by Ciba Specialty Chemicals),
n-octadecyl-3- (4'-hydroxy-3,5'-di-t-butylphenyl)propion
ate (trade name: IRGANOX 1076, produced by Ciba Specialty
Chemicals) and the like; phosphite anti-oxidants such as
bis(2,4-di-t-butylphenyl)pentaerythritol diphosphite,
tris(2,4-di-t-butylphenyl)phosphite,
2,4,8,10-tetrα-t-butyl-6-[3-(3-methyl-4-hydroxy-5-t-but ylphenyl)propoxy]dibenzo[d,f][1,3,2]dioxaphosphepine
(trade name: Sumilizer GP, manufactured by Sumitomo
Chemical Co., Ltd.) and the like. [0054]
The above-mentioned lubricants specifically include,
for example, a higher fatty acid amide, a higher fatty acid
ester and the like. The anti-static agents specifically
include, for example, a glycerin ester of a fatty acid having
8 to 22 carbon atoms, a sorbitan acid ester, a
polyethyleneglycol ester and the like. The workability
improvers specifically include, for example, a fatty acid
metal salts such as calcium stearate and the like, a
fluorine-based resin and the like. The anti-blocking
agents includes an inorganic anti-blocking agent and an
organic anti-blocking agent. The inorganic anti-blocking
agents specifically include, for example, silica, calcium
carbonate, talc and the like, and the organic anti-blocking
agents specifically include, for example, a powder of a
crosslinked methyl polymethacrylate, crosslinked
poly(methyl methacrylate-styrene)copolymer, crosslinked silicone and crosslinked polystyrene, and the like. [0055]
These additives including the antioxidant are arbitrarily added in amounts of 0.01 to 30 parts by mass depending on the kinds of the additives, based on 100 parts by mass of the ethylene-α-olefin copolymer (E).
[0056]
The additional polymers include polyolefin-based resins other than the ethylene-α-olefin copolymer (E) used in the present invention, and specific examples include a high-pressure low-density polyethylene and a linear low-density polyethylene (LLDPE) for improving moldability, transparency and the like, and an ethylene-based resin for improving flowability, strength, heat sealing properties and the like. These additional polymers may be typically added in an amount of 1 to 30 parts by mass based on 100 parts by mass of the ethylene-α-olefin copolymer (E). [0057]
Methods for mixing the additional resins and additives added as required include, for example, a method in which the ethylene-α-olefin copolymer (E) of the present invention, and the additional resins and additives are melt-kneaded using various kinds of mixers such as a single-screw extruder, a twin-screw extruder, a Bunbary mixer, a heating roller and the like, and then the mixture is shaped into a film; a method in which the ethylene-α-olefin copolymer (E) of the present invention, and the additional resins and additives are dry blended using various kinds of mixers such as a Henschel mixer, a tumbler mixer and the like, and then the blend is shaped
into a film; and a method in which at least one master batch is prepared from the additional resins and additives, and then the master batch and the ethylene-α-olefin copolymer
(E) of the present invention are dry blended using various kinds of mixers such as a Henschel mixer, a tumbler mixer and the like, and then the blend is shaped into a film.
[0058]
The ethylene-α-olefin copolymer (E) of the present
invention may be shaped into films by inflation molding,
cast molding, extrusion lamination molding and the like,
containers by extrusion molding, hollow articles such as
bottles and the like, pipes or profiles, foamed articles
by foam molding, molded articles by injection molding,
molded articles by rotational molding, molded articles by
calender molding and molded articles by roll molding. In
addition, the ethylene-α-olefin copolymer (E) of the
present invention may be used for fibers, monofilaments,
nonwoven fabrics and the like. These articles include
articles containing a part composed of the
ethylene-α-olef in copolymer (E) and a part composed of other
resins (laminates and the like). In addition, the
ethylene-α-olefin copolymer (E) of the present invention may be crosslinked during the molding process.
[0059]
Especially, the ethylene-α-olefin copolymer (E) of the present invention can provide films excellent in properties by inflation molding, cast molding, extrusion lamination molding and the like.
[0060]
Part of the ethylene-α-olef in copolymer (E) as mentioned above may be graft modified by a polar monomer. The polar monomers include hydroxyl group-containing ethylenic unsaturated compounds, amino group-containing ethylenic unsaturated compounds, epoxy group-containing ethylenic unsaturated compounds, aromatic vinyl compounds, unsaturated carboxylic acid compounds or derivatives thereof, vinyl ester compounds, vinyl chloride, vinyl group-containing organic silicon compounds and the like.
[0061]
The modified ethylene-α-olefin copolymer may be
obtained by graft polymerizing the polar monomer onto the
ethylene-α-olefin copolymer (E). In graft polymerizing
the polar monomer as mentioned above onto the
ethylene-α-olefin copolymer (E), the monomer is typically
used in an amount of 1 to 100 parts by mass and preferably
5 to 80 parts by mass, based on 100 parts by mass of the
ethylene-α-olefin copolymer (E). This graft
polymerization is typically carried out in the presence of
a radical initiator.
[0062]
As the radical initiator, an organic peroxide, an azo compound and the like may be used. The radical initiator may be directly mixed with the ethylenic polymer and the polar monomer, or may be used afterdissolved in a small amount of organic solvent. The organic solvent may be used without any particular limitations as long as it can dissolve the radical initiator.
[0063]
In addition, in graft polymerizing the polar monomer onto the ethylene-α-olefin copolymer (E), a reducing substance may be used. The use of the reducing substance may increase the grafting amount of the polar monomer.
[0064]
The graft modification of the ethylene-α-olefin
copolymer (E) with the polar monomer may be carried out by
a conventionally known method. For example, the
ethylene-α-olefin copolymer (E) is dissolved in an organic solvent and the polar monomer and the radical initiator are added to the solution, and then the mixture is reacted at 70 to 200°C, preferably at 80 to 190°C for 0.5 to 15 hours, preferably 1 to 10 hours to give the modified polymer.
[0065]
Alternatively, the modified ethylene-α-olefin copolymer may be produced by reacting the ethylene-α-olefin copolymer (E) and the polar monomer without a solvent using an extruder or the like. This reaction is preferably carried out at or above the melting point of the ethylene-α-olefin copolymer (E) , specifically at 120 to 250°C typically for 0.5 to 10 minutes. [0066]
The modification amount (grafting amount of the polar monomer) of the modified ethylene-α-olefin copolymer thus obtained is typically 0.1 to 50% by mass, preferably 0.2 to 30% by mass and more preferably 0.2 to 10% by mass. [0067]
When the above modified ethylene-α-olefin copolymer contains the ethylene-α-olefin copolymer (E) of the present invention, the adhesiveness and compatibility with other resins are excellent, and the wettability of the surface of the molded article obtained from the ethylene-α-olefin copolymer (E) may be improved. [0068]
Further, when the modified ethylene-α-olefin copolymer of the present invention is crosslinked, the polymer may be suitably used for a crosslinked electric wire and a crosslinked pipe.
[0069]
Method for Producing Ethylene-α-Olefin Copolymer (E) The ethylene-α-olefin copolymer (E) of the present invention may be obtained, for example, by copolymerizing ethylene with an α-olefin having 3 to 10 carbon atoms in the presence of a catalyst for olefin polymerization formed from
(A) a transition metal compound in which a
cyclopentadienyl group and a fluorenyl group are bonded by
covalent binding crosslinking containing a Group 14 atom;
(B) at least one compound selected from
(B-l) an organometallic compound, (B-2) an organoaluminum oxy compound and (B-3) a compound which reacts with the transition metal compound to form an ion pair; and
(C) a carrier.
[0070]
(A) Transition Metal Compound
The transition metal compound (A) is a compound represented by the general formulae (1) and (2) described below. [0071]
[Chemical Formula 1]
(Formula Removed)
[0073]
[In the above general formulae (1) and (2), R7, R8, R9, R10, R11, R12, R13, R14, R15, R16, R17, R18, R19 and R20 are selected from a hydrogen atom, a hydrocarbon group and a silicon-containing hydrocarbon group and may be the same or different, two adjacent substituents from R7 to R18 may be bonded together to form a ring, A is a divalent hydrocarbon
group having 2 to 20 carbon atoms which may contain a partially unsaturated bond and/or aromatic ring and forms a ring structure together with Y, A may contain two or more ring structures including the ring that it forms together with Y, Y is carbon or silicon, M is a metal selected from Group 4 in the Periodic Table, Q may be the same or different form each other and is selected from a halogen, a hydrocarbon group, an anionic ligand and a neutral ligand with a lone electron pair capable of coordinating, and j is an integer from 1 to 4 . ]
In the present invention, among the above-mentioned transition metal compounds, a compound in which R7 to R10 are each a hydrogen atom, Y is a carbon atom, M is Zr and j is 2, is preferably used.
[0074]
The transition metal compound (A) used in Examples described later is specifically represented by the following general formula (3) , but in the present invention, it is not at all limited to this transition metal compound.
[0075]
[Chemical Formula 3]
(Formula Removed)
[0076]
the structure of the transition metal compound represented by the above formula (3) was determined by using 270 MHz 1H-NMR (GSH-270, manufactured by JEOL Ltd.) and FD-Mass Spectrometer (SX-102A, manufactured by JEOL Ltd.). [0077]
(B-l) Organometallic Compound
The organometallic compounds (B-l) used as necessary in the present invention include, specifically an organic aluminum compound as described below. [0078]
General Formula
(Formula Removed)
(In the formula, Ra and Rb may be the same or different from each other and represent a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms, X represents a halogen atom, m is a number of 04x106 and a product of Pressure Chemical Co. for a molecular weight of 1,000≤Mw≤4x106. The molecular weight was determined in terms of polyethylene by means of universal calibration. [0132]
Intrinsic Viscosity ([])
This was a value measured at 135°C using decalin solvent. In detail, approximately 20 mg of the granulated pellets was dissolved in 15 ml of decalin and the specific viscosity sp was measured in an oil bath at 135°C. The dacalin solution was diluted by adding 5 ml of the decalin solvent and then the specific viscosity sp was measured in the same manner. The diluting operation was repeated twice further and the intrinsic viscosity was determined as sp/C which the concentration (C) is extraporated to 0 (see the following equation). [0133]
[]=lim (nsp/C) (C→0) Density (d)
Sheets having a thickness of 0.5 mm were formed under a pressure of 100 kg/cm2 using a hydraulic thermal press machine manufactured by SHINTO Metal Industries Corporation (Spacer-shape: a plate 240x240x0.5 mm having 9 holes of 45x45x0.5 mm) wherein the temperature was set at 190°C. The obtained sheets were compressed and cooled under a pressure of 100 kg/cm2 using another hydraulic thermal press machine manufactured by SHINTO Metal Industries Corporation wherein the temperature was set at 20°C. Specimens for measurement were thus prepared. The heating plate used was an SUS plate
having a thickness of 5 mm. The pressed sheets were heat treated at 120°C for one hour and were gradually and linearly cooled to room temperature in one hour, and then the density was measured using a density gradient column. [0134]
Melt Flow Rate (MFR)
The MFR was measured at 190°C under a load of 2.16 kg according to JIS K7210.
Melt Tension (MT)
The melt tension (MT) was measured with a melt tension tester manufactured by Toyo Seiki Seisaku-Sho, Ltd. The measurement conditions were as follows. [0135]
The nozzle used: L=8.000 mm, D=2.095 mm, measurement temperature: 190°C, resin extrusion rate: 15 mm/min, resin take-off speed: 10 m/min. [0136]
Measurement Conditions fot Film Properties
[1] Measurement of Dart Impact Strength (DI) (Unit:
g)
The DI was measured under the following conditions according to ASTM D1709. [0137]
Conditions : The specimen was fastened with an air clamp system and a hemispherical dart was dropped from a position at a fixed height. A load under which 50% of the specimen was broken was read out from a graph. The dropping was carried out 10 times with each load and method A was used. [0138]
[2] Measurement of Haze (Transparency, Unit: %) The total haze and internal haze were measured according to ASTM D1003. For the internal haze, the film was placed in a cell filled with cyclohexanol, and then the measurement was made using a haze meter in the same manner as in the haze. [0139]
[3] Measurement of Film Impact (FI) Strength The film was allowed to stand still at 23±2°C and a relative humidity of 50±5% for 48 hours or more and then was cut into a size of 100x100 mm. The film thickness of the film samples (n=10) was measured with a dial gauge or a continuous thickness meter and an average thickness was determined. [0140]
The size volume and shape of an impact head of a film impact tester manufactured by Toyo Seiki Seisaku-Sho, Ltd. was selected depending on the samples. (In a typical
measurement, the size volume of the impact head was 30 kg-cm and the shape of the impact head was 1/2 inch.)
The specimen was placed on a sample table of the film impact tester and fastened with air clamp. A pendulum was set at the starting position and an indicator needle was adjusted to the maximum scale. The stopper of the pendulum was removed and impact was applied to the sample and the sample was penetrated. The energy taken to break the sample was read out from the position of the needle to the 0.1 kg- cm. [0141]
The measurement was made for the ten samples and the film impact strength was calculated by the following equation. [0142]
FI=E/D
(FI: Film impact strength, E: Impact fracture energy, D: thickness of specimen)
Production Method for Film
[1] Inflation Molding (Monolayer)
The sample for measurement was shaped into a film having a thickness of 40 to 120 µm and a width of 320 mm by air-cooling inflation molding under the following molding conditions. [0143]
Molding machine: An inflation molding machine having a diameter of 50 mm 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: 200°C
Extrusion rate: 28.8 kg/h
Take-up speed: 20 m/min (in the molding to a thickness of 4 0 urn)
10 m/min (in the molding to a thickness of 80 urn)
6.7 m/min (in the molding to a thickness of 12 0 urn)
[2] Inflation Molding (Multilayer)
The sample for measurement was shaped into a multilayer film having a thickness of 40 to 120 µm and a width of 710 mm by air-cooling inflation molding under the following molding conditions. [0144]
Molding machine: A three-layer inflation molding machine (three extruders with a diameter of 50 mm:
manufactured by Alpine GmbH)
Screw: Barrier type screw
Die: 225 mm (diameter), 3.5 mm (lip width)
Air ring: 2-gap type
Molding temperature: 200°C
Extrusion rate: 100 kg/h (outermost layer: 25 kg/h, intermediate layer: 50 kg/h, innermost layer: 25 kg/h)
Take-up speed: 32 m/min (in the molding to a thickness of 4 0 urn)
10 m/min (in the molding to a thickness of 130 urn)
[3] Cast Molding (Monolayer)
The ethylene-α-olefin copolymer (E) or the ethylene-α-olefin copolymer (El) may be generally cast-film extruded by extruding a molten resin at 170 to 250°C from a T-die and bringing it into contact with a chill roll at 20 to 100°C to solidify the copolymer into a film. For example, the cast film-forming was carried out as follows.
A monolayer cast film was prepared under the following conditions using only an intermediate layer extruder (65 mm in diameter) of a high speed multi-layer cast molding machine (manufactured by SHI Modern Machinery Ltd.) [0145]
Screw: L/D=32, T-die: coat hanger type, width: 800 mm
Molding temperature: C1/C2/C3/C4/C5/AD/J =2 00/230/230/230/230/230/230°C
Extrusion rate: 70 kg/h
Chill roll temperature: 40°C, film thickness: 40 urn,
Take-up speed: 50 m/min.
[Synthesis Example 1]
[Preparation of Solid Catalyst Component (a)]
8.5 kg of silica dried at 200°C for 3 hours was suspended in 33 liters of toluene, and then 82.7 liters of a methylaluminoxane solution (Al=1.42 mol/L) was added dropwise over 30 minutes to the suspension. Next, the resulting mixture was heated to 115°C in 1.5 hours and allowed to react at that temperature for 4 hours. Subsequently, the reaction mixture was cooled to 60°C and the supernatant liquid was removed by decantation. The resulting solid catalyst component was washed with toluene three times, and was resuspended in toluene to give a solid catalyst component (a) (the total volume: 150 liters). [0146]
[Preparation of Supported Catalyst]
To a reactor in which the air had been sufficiently replaced with nitrogen, 19.60 mol (in terms of aluminum) of the above-mentioned solid catalyst component (α)
suspended in toluene was added. While stirring, to the
resulting suspension, 2 liters (61.12 mmol) of 31.06 mmol/L
solution of
di(p-tolyl)methylene(cyclopentadienyl)(octamethyloctahy drodibenzofluorenyl)zirconium dichloride was added at room temperature (20 to 25°C), and the mixture was stirred for 60 minutes. After termination of the stirring, the supernatant liquid was removed by decantation and the mixture was washed with 40 liters of n-hexane twice. The resulting supported catalyst was reslurried in n-hexane to give a solid catalyst component (y) as 25 liters of a catalyst suspension. [0147]
[Preparation of Solid Catalyst Component (5) by Prepolymerization of Solid Catalyst Component ()]
To a reactor equipped with a stirrer, under a nitrogen atmosphere, 15.8 liters of purified n-hexane and the above-mentioned solid catalyst component () were added, and then 5 mol of triisobutylaluminum was added. While stirring the resulting mixture, prepolymerization was carried out with ethylene so that 3 g of ethylene polymer was produced per gram of the solid component for 4 hours. The polymerization temperature was maintained at 20 to 25°C. After completion of the polymerization reaction, the
stirring was stopped, and then the supernatant liquid was removed by decantation. The residue was washed with 35 liters of n-hexane 4 times. The resulting supported catalyst was suspended in 20 liters of n-hexane to give a solid catalyst component (5) as a catalyst suspension.
[Example 1] [0148]
[Polymerization]
To a first polymerization reactor, 45 L/h of hexane, 0.050 mmol/h (in terms of Zr atom) of the solid catalyst component (5) obtained in Synthesis Example 1, 4 mmol/h of triethylaluminum, 8.1 kg/h of ethylene, 251 g/h of 1-hexene and 40 N-L/h of hydrogen were continuously supplied. Further, while continuously withdrawing the contents in the polymerization reactor so that the liquid level in the polymerization reactor was constant, polymerization was carried out under the conditions of a polymerization temperature of 75°C, a reaction pressure of 7.5 kg/cm2G and an average residence time of 2.5 hours. The unreacted ethylene and hydrogen were substantially removed from the contents continuously withdrawn from the first polymerization reactor in a flash drum maintained at an internal pressure of 0.30 kg/cm2G and at 65°C. [0149]
After that, the contents were continuously supplied to a second polymerization reactor, together with 43 L/h of hexane, 5.7 kg/h of ethylene, 4 N-L/h of hydrogen and 892 g/h of 1-hexene, and polymerization was continuously carried out under the conditions of a polymerization temperature of 72°C, a reaction pressure of 7 kg/cm2G and an average residence time of 1.5 hours. [0150]
In the second polymerization reactor too, the contents in the polymerization reactor were continuously withdrawn so that the liquid level in the polymerization reactor was constant, and the hexane and unreacted monomer in the contents were removed by a solvent separator and then the contents were dried to give a polymer. In order to prevent unintended polymerization, 2 L/h of methanol was supplied to the contents withdrawn from the polymerization reactor to deactivate the catalyst for polymerization. Subsequently, the hexane and unreacted monomer in the contents were removed by a solvent separator and then the contents were dried to give a polymer. [0151]
Then, to 100. parts by mass of the polymer particles,
0.2 part by mass of
6-[3-(3-t-butyl-4-hydroxy-5-methyl)propaxy]2,4,8,10-tet
rα-t-butylbenz[d,f][1,3,2]-dioxaphosphepine as an
antioxidant and 0.1 part by mass of calcium stearate were added. Next, a sample for measurement was prepared by pelletizing the resulting mixture at a temperature of 200°C and a resin extrusion rate of 25 kg/h using a single-screw extruder (a screw diameter of 65 mm, L/D=28) manufactured by Placo Co., Ltd. Further, a film was prepared by using the sample and the physical properties of the film were measured. The results are shown in Tables 1 and 2.
[Example 2] [0152]
[Polymerization]
To a first polymerization reactor, 45 L/h of hexane, 0.0110 mmol/h (in terms of Zr atom) of the solid catalyst component (5) obtained in Synthesis Example 1, 20 mmol/h of triethylaluminum, 8.1 kg/h of ethylene, 149 g/h of 1-hexene and 50 N-L/h of hydrogen were continuously supplied. Further, while continuously withdrawing the contents in the polymerization reactor so that the liquid level in the polymerization reactor was constant, polymerization was carried out under the conditions of a polymerization temperature of 75°C, a reaction pressure of 7 . 5 kg/cm2G and an average residence time of 2.5 hours. The unreacted ethylene and hydrogen were substantially removed from the
contents continuously withdrawn from the first polymerization reactor in a flash drum maintained at an internal pressure of 0.30 kg/cm2G and at 65°C. [0153]
Then, the contents were continuously supplied to a second polymerization reactor, together with 43 L/h of hexane, 49 kg/h of ethylene, 3 N-L/h of hydrogen and 204 g/h of 1-hexene, and polymerization was continuously carried out under the conditions of a polymerization temperature of 72°C, a reaction pressure of 7 kg/cm2G and an average residence time of 1.5 hours. [0154]
In the second polymerization reactor too, the contents in the polymerization reactor were continuously withdrawn so that the liquid level in the polymerization reactor was constant, and the hexane and unreacted monomer in the contents were removed by a solvent separator and then the contents were dried to give a polymer. In order to prevent unintended polymerization, 2 L/h of methanol was supplied to the contents withdrawn from the polymerization reactor to deactivate the catalyst for polymerization. Subsequently, the hexane and unreacted monomer in the contents were removed by a solvent separator and then the contents were dried to give a polymer.
[0155]
Then, 100 parts by mass of the polymer particles were mixed with the antioxidant and calcium stearate used in Example 1. A sample for measurement was prepared by pelletizing the resulting mixture using a single-screw extruder manufactured by Placo Co., Ltd. Further, a film was prepared using the sample and the physical properties of the film were measured. The results are shown in Tables 1 and 2.
[Example 3] [0156]
[Polymerization]
To a first polymerization reactor, 45 L/h of hexane, 0.20 mmol/h (in terms of Zr atom) of the solid catalyst component (5) obtained in Synthesis Example 1, 20 mmol/h of triethylaluminum, 6.3 kg/h of ethylene, 91 g/h of 1-hexene and 40 N-L/h of hydrogen were continuously supplied. Further, while continuously withdrawing the contents in the polymerization reactor so that the liquid level in the polymerization reactor was constant, polymerization was carried out under the conditions of a polymerization temperature of 75°C, a reaction pressure of 7 . 5 kg/cm2G and an average residence time of 2.5 hours. The unreacted ethylene and hydrogen were substantially removed from the
contents continuously withdrawn from the first polymerization reactor in a flash drum maintained at an internal pressure of 0.30 kg/cm2G and at 65°C.
[0157]
Then, the contents were continuously supplied to a second polymerization reactor, together with 43 L/h of hexane, 9.4 kg/h of ethylene, 4 N-L/h of hydrogen and 495 g/h of 1-hexene, and polymerization was continuously carried out under the conditions of a polymerization temperature of 72°C, a reaction pressure of 7 kg/cm2G and an average residence time of 1.5 hours.
[0158]
In the second polymerization reactor too, the contents in the polymerization reactor were continuously withdrawn so that the liquid level in the polymerization reactor was constant, and the hexane and unreacted monomer in the contents were removed by a solvent separator and then the contents were dried togive a polymer. In order to prevent unintended polymerization, 2 L/h of methanol was supplied to the contents withdrawn from the polymerization reactor to deactivate the catalyst for polymerization. Subsequently, the hexane and unreacted monomer in the contents were removed by a solvent separator and then the contents were dried to give a polymer.
[0159]
100 parts by mass of the polymer particles were mixed with the antioxidant and calcium stearate used in Example 1. A sample for measurement was prepared by pelletizing the resulting mixture using a single-screw extruder manufactured by Placo Co., Ltd. Further, a film was prepared using the sample and the physical properties of the film were measured. The results are shown in Tables 1 and 2 .
[Example 4] [0160]
[Polymerization]
To a first polymerization reactor, 45 L/h of hexane,
0.075 mmol/h (in terms of Zr atom) of the solid catalyst
component (5) obtained in Synthesis Example 1, 20 mmol/h
of triethylaluminum, 8.1 kg/h of ethylene and 50 N-L/h of
hydrogen were continuously supplied. Further, while
continuously withdrawing the contents in the polymerization reactor so that the liquid level in the polymerization reactor was constant, polymerization was carried out under the conditions of a polymerization temperature of 75°C, a reaction pressure of 7.5 kg/cm2G and an average residence time of 2 . 5 hours . The unreacted ethylene and hydrogen were substantially removed from the contents continuously
withdrawn from the first polymerization reactor in a flash drum maintained at an internal pressure of 0.30 kg/cm2G and at 65°C.
[0161]
Then, the contents were continuously supplied to a second polymerization reactor, together with 43 L/h of hexane, 10.2 kg/h of ethylene, 35 N-L/h of hydrogen and 1378 g/h of 1-hexene, and polymerization was continuously carried out under the conditions of a polymerization temperature of 72°C, a reaction pressure of 7 kg/cm2G and an average residence time of 1.5 hours.
[0162]
In the second polymerization reactor too, the contents in the polymerization reactor were continuously withdrawn so that the liquid level in the polymerization reactor was constant, and the hexane and unreacted monomer in the contents were removed by a solvent separator and then the contents were dried to give a polymer. In order to prevent unintended polymerization, 2 L/h of methanol was supplied to the contents withdrawn from the polymerization reactor to deactivate the catalyst for polymerization. Subsequently, the hexane and unreacted monomer in the contents were removed by a solvent separator and then the contents were dried to give a polymer.
[0163]
100 parts by mass of the polymer particles were mixed with the antioxidant and calcium stearate used in Example 1. A sample for measurement was prepared by pelletizing the resulting mixture using a single-screw extruder manufactured by Placo Co., Ltd. Further, a film was prepared using the sample and the physical properties of the film were measured. The results are shown in Tables 1 and 2 .
[Example 5] [0164]
[ Polymerization]
To a first polymerization reactor, 45 L/h of hexane, 0.080 mmol/h (in terms of Zr atom) of the solid catalyst component (5) obtained in Synthesis Example 1, 20 mmol/h of triethylaluminum, 8.1 kg/h of ethylene, 155 g/h of 1-hexene and 70 N-L/h of hydrogen were continuously supplied. Further, while continuously withdrawing the contents in the polymerization reactor so that the liquid level in the polymerization reactor was constant, polymerization was carried out under the conditions of a polymerization temperature of 75.5°C, a reaction pressure of 7.5 kg/cm2G and an average residence time of 2.5 hours. The unreacted ethylene and hydrogen were substantially removed from the
contents continuously withdrawn from the first polymerization reactor in a flash drum maintained at an internal pressure of 0.30 kg/cm2G and at 65°C. [0165]
Then, the contents were continuously supplied to a second polymerization reactor, together with 43 L/h of hexane, 10.2 kg/h of ethylene, 20 N-L/h of hydrogen and 1295 g/h of 1-hexene, and polymerization was continuously carried out under the conditions of a polymerization temperature of 72°C, a reaction pressure of 7 kg/cm2G and an average residence time of 1.5 hours. [0166]
In the second polymerization reactor too, the contents in the polymerization reactor were continuously withdrawn so that the liquid level in the polymerization reactor was constant, and the hexane and unreacted monomer in the contents were removed by a solvent separator and then the contents were dried to give a polymer. In order to prevent unintended polymerization, 2 L/h of methanol was supplied to the contents withdrawn from the polymerization reactor to deactivate the catalyst for polymerization. Subsequently, the hexane and unreacted monomer in the contents were removed by a solvent separator and then the contents were dried to give a polymer.
[0167]
100 parts by mass of the polymer particles were mixed with the antioxidant and calcium stearate used in Example 1. A sample for measurement was prepared by pelletizing the resulting mixture using a single-screw extruder manufactured by Placo Co., Ltd. Further, a film was prepared using the sample and the physical properties were measured. The results are shown in Tables 1 and 2.
[Example 6] [0168]
[Polymerization]
To a first polymerization reactor, 45 L/h of hexane, 0.080 mmol/h (in terms of Zr atom) of the solid catalyst component (5) obtained in Synthesis Example 1, 20 mmol/h of triethylaluminum, 8.1 kg/h of ethylene, 155 g/h of 1-hexene and 70 N-L/h of hydrogen were continuously supplied. Further, while continuously withdrawing the contents in the polymerization reactor so that the liquid level in the polymerization reactor was constant, polymerization was carried out under the conditions of a polymerization temperature of 75.5°C, a reaction pressure of 7.5 kg/cm2G and an average residence time of 2.5 hours. The unreacted ethylene and hydrogen were substantially removed from the contents continuously withdrawn from the first
polymerization reactor in a flash drum maintained at an
internal pressure of 0.30 kg/cm2G and at 65°C.
[0169]
Then, the contents were continuously supplied to a second polymerization reactor, together with 43 L/h of hexane, 10.2 kg/h of ethylene, 20 N-L/h of hydrogen and 1295 g/h of 1-hexene, and polymerization was continuously carried out under the conditions of a polymerization temperature of 72°C, a reaction pressure of 7 kg/cm2G and an average residence time of 1.5 hours. [0170]
In the second polymerization reactor too, the contents in the polymerization reactor were continuously withdrawn so that the liquid level in the polymerization reactor was constant, and the hexane and unreacted monomer in the contents were removed by a solvent separator and then the contents were dried to give a polymer. In order to prevent unintended polymerization, 2 L/h of methanol was supplied to the contents withdrawn from the polymerization reactor to deactivate the catalyst for polymerization. Subsequently, the hexane and unreacted monomer in the contents were removed by a solvent separator and then the contents were dried to give a polymer. [0171]
100 parts by mass of the polymer particles were mixed with the antioxidant and calcium stearate used in Example 1. A sample for measurement was prepared by pelletizing the resulting mixture using a single-screw extruder manufactured by Placo Co., Ltd. Further, a film was prepared using the sample and the physical properties were measured. The results are shown in Tables 1 and 3.
[Example 7] [0172]
[Pomymerization]
To a first polymerization reactor, 45 L/h of hexane, 0.080 mmol/h (in terms of Zr atom) of the solid catalyst component (5) obtained in Synthesis Example 1, 20 mmol/h of triethylaluminum, 8.1 kg/h of ethylene, 155 g/h of 1-hexene and 70 N-L/h of hydrogen were continuously supplied. And further, while continuously withdrawing the contents in the polymerization reactor so that the liquid level in the polymerization reactor was constant, polymerization was carried out under the conditions of a polymerization temperature of 75.5°C, a reaction pressure of 7.5 kg/cm2G and an average residence time of 2.5 hours. The unreacted ethylene and hydrogen were substantially removed from the contents continuously withdrawn from the first polymerization reactor in a flash drum maintained at an
internal pressure of 0.30 kg/cm2G and at 65°C. [0173]
Then, the contents were continuously supplied to a second polymerization reactor, together with 43 L/h of hexane, 10.2 kg/h of ethylene, 4 N-L/h of hydrogen and 1275 g/h of 1-hexene, and polymerization was continuously carried out under the conditions of a polymerization temperature of 72°C, a reaction pressure of 7 kg/cm2G and an average residence time of 1.5 hours. [0174]
In the second polymerization reactor too, the contents in the polymerization reactor were continuously withdrawn so that the liquid level in the polymerization reactor was constant, and the hexane and unreacted monomer in the contents were removed by a solvent separator and then the contents were dried to give a polymer. In order to prevent unintended polymerization, 2 L/h of methanol was supplied to the contents withdrawn from the polymerization reactor to deactivate the catalyst for polymerization. Subsequently, the hexane and unreacted monomer in the contents were removed by a solvent separator and then the contents were dried to give a polymer. [0175]
100 parts by mass of the polymer particles were mixed
with the antioxidant and calcium stearate used in Example 1. A sample for measurement was prepared by pelletizing the resulting mixture using a single-screw extruder manufactured by Placo Co., Ltd. Further, a film was prepared using the sample and the physical properties of the film were measured. The results are shown in Tables 1 and 3.
[Example 8] [0176]
[Polymerization]
To a first polymerization reactor, 45 L/h of hexane,
0.075 mmol/h (in terms of Zr atom) of the solid catalyst
component (5) obtained in Synthesis Example 1, 20 mmol/h
of triethylaluminum, 8.1 kg/h of ethylene and 50 N-L/h of
hydrogen were continuously supplied. Further, while
continuously withdrawing the contents in the polymerization reactor so that the liquid level in the polymerization reactor was constant, polymerization was carried out under the conditions of a polymerization temperature of 75.5°C, a reaction pressure of 7.5 kg/cm2G and an average residence time of 2 . 5 hours . The unreacted ethylene and hydrogen were substantially removed from the contents continuously withdrawn from the first polymerization reactor in a flash drum maintained at an internal pressure of 0.3 kg/cm2G and
at 65°C. [0177]
Then, the contents were continuously supplied to a second polymerization reactor, together with 43 L/h of hexane, 10.2 kg/h of ethylene, 35 N-L/h of hydrogen and 1378 g/h of 1-hexene, and polymerization was continuously carried out under the conditions of a polymerization temperature of 72°C, a reaction pressure of 7 kg/cm2G and an average residence time of 1.5 hours. [0178]
In the second polymerization reactor, the contents in the polymerization reactor were continuously withdrawn so that the liquid level in the polymerization reactor was constant, and the hexane and unreacted monomer in the contents were removed by a solvent separator and then the contents were dried to give a polymer. In order to prevent unintended polymerization, 2 L/h of methanol was supplied to the contents withdrawn from the polymerization reactor to deactivate the catalyst for polymerization. Subsequently, the hexane and unreacted monomer in the contents were removed by a solvent separator and then the contents were dried to give a polymer. [0179]
Then, 100 parts by mass of the polymer particles were
mixed with the antioxidant and calcium stearate used in Example 1. A sample for measurement was prepared by pelletizing the resulting mixture using a single-screw extruder manufactured by Placo Co., Ltd. Further, a film was prepared using the sample and the physical properties of the film were measured. The results are shown in Tables 1 and 4. [0180]
[Comparative Example 1] A linear low-density polyethylene (trade name: GD 1588, manufactured by Prime Polymer Co. , Ltd.) was used as a sample for measurement. The results are shown in Tables 1 and 2. [0181]
[Comparative Example 2]
A film was prepared using a high density polyethylene (trade name: HIZEX HZ3300F, manufactured by Prime Polymer Co. , Ltd. ) in the same manner as in Example 1 and the physical properties of the film were measured. The results are shown in Tables 1 to 3. [0182]
[Comparative Example 3]
A film was prepared using a linear low-density polyethylene (trade name: ULTZEX UZ4020L, manufactured by Prime Polymer Co., Ltd.) in the same manner as in Example
1 and the physical properties of the film were measured.
The results are shown in Tables 1 to 4.
[0183]
[Comparative Example 4]
A film was prepared using a linear low-density polyethylene (trade name: MORETEC 0168N, manufactured by Prime Polymer Co., Ltd.) in the same manner as in Example 1 and the physical properties of the film were measured. The results are shown in Tables 1, 2 and 4.
[0184]
(Table Removed)
[Example 9] [0188]
[Polymerization]
To a polymerization reactor, 45 L/h of hexane, 0.13
mmol/h (in terms of Zr atom) of the solid catalyst component
(5) obtained in Synthesis Example 1, 20 mmol/h of
triethylaluminum, 8.1 kg/h of ethylene and 50 N-L/h of
hydrogen were continuously supplied. Further, while
continuously withdrawing the contents in the polymerization
reactor so that the liquid level in the polymerization
reactor was constant, polymerization was carried out under
the conditions of a polymerization temperature of 75°C, a
reaction pressure of 8.5 kg/cm2G and an average residence
time of 2.5 hours. In order to prevent unintended
polymerization, 2 L/h of methanol was supplied to the contents withdrawn from the polymerization reactor to deactivate the catalyst for polymerization. Subsequently, the hexane and unreacted monomer in the contents were removed by a solvent separator and then the contents were dried to give a polymer. [0189]
To 100 parts by mass of the polymer particles, 0.2 part
by mass of
6-[3-(3-t-butyl-4-hydroxy-5-methyl)propoxy]2,4,8,10-tet
rα-t-butylbenz[d,f][1,3,2]-dioxaphosphepine as an
antioxidant and 0.1 part by mass of calcium stearate were added. Next, a sample for measurement was prepared by pelletizing the resulting mixture at a temperature of 200°C and a resin extrusion rate of 25 kg/h using a single-screw extruder (a screw diameter of 65 mm, L/D=28) manufactured by Placo Co., Ltd. Further, a film was prepared by using the sample and the physical properties of the film were measured. The property values of the polymer are shown in Tables 5 and 6 and the physical property values of the film are shown in Table 7. [Example 10]
[0190]
[Polymerization]
To a polymerization reactor, 45 L/h of hexane, 0.17 mmol/h (in terms of Zr atom) of the solid catalyst component
(5) obtained in Synthesis Example 1, 20 mmol/h of
triethylaluminum, 8.1 kg/h of ethylene and 50 N-L/h of
hydrogen were continuously supplied. Further, while
continuously withdrawing the contents in the polymerization reactor so that the liquid level in the polymerization reactor was constant, polymerization was carried out under the conditions of a polymerization temperature of 75°C, a reaction pressure of 8.5 kg/cm2G and an average residence
time of 2.5 hours. In order to prevent unintended
polymerization, 2 L/h of methanol was supplied to the contents withdrawn from the polymerization reactor to deactivate the catalyst for polymerization. Subsequently, the hexane and unreacted monomer in the contents were removed by a solvent separator and then the contents were dried to give a polymer.
[0191]
A sample for measurement was prepared by pelletizing the resulting mixture using a single screw extruder manufactured by Placo Co., Ltd. in the same manner used in Example 9. Further, a film was prepared by using the sample and the physical properties of the film were measured. The property values of the polymer are shown in Tables 5 and 6 and the physical property values of the film are shown in Table 7.
[Example 11]
[0192]
[Polymerization]
To a polymerization reactor, 45 L/h of hexane, 0.15 mmol/h (in terms of Zr atom) of the solid catalyst component
(5) obtained in Synthesis Example 1, 20 mmol/h of triethylaluminum, 8 . 1 kg/h of ethylene, 50 N-L/h of hydrogen and 117 g/h of 1-hexene were continuously supplied. Further,
while continuously withdrawing the contents in the polymerization reactor so that the liquid level in the polymerization reactor was constant, polymerization was carried out under the conditions of a polymerization temperature of 75°C, a reaction pressure of 8.5 kg/cm2G and an average residence time of 2.5 hours. In order to prevent unintended polymerization, 2 L/h of methanol was supplied to the contents withdrawn from the second polymerization reactor to deactivate the catalyst for polymerization. Subsequently, the hexane and unreacted monomer in the contents were removed by a solvent separator and then the contents were dried to give a polymer. [0193]
A sample for measurement was prepared by pelletizing the resulting mixture using a single-screw extruder manufactured by Placo Co., Ltd. in the same manner used in Example 9. Further, a film was prepared by using the sample and the physical properties of the film were measured. The property values of the polymer are shown in Tables 5 and 6 and the physical property values of the film are shown in Table 7.
[Example 12] [0194]
[Polymerization]
To a polymerization reactor, 45 L/h of hexane, 0.10 mmol/h (in terms of Zr atom) of the solid catalyst component (5) obtained in Synthesis Example 1, 20 mmol/h of triethylaluminum, 8.1 kg/h of ethylene, 100 N-L/h of hydrogen and 233 g/h of 1-hexene were continuously supplied. Further, while continuously withdrawing the contents in the polymerization reactor so that the liquid level in the polymerization reactor was constant, polymerization was carried out under the conditions of a polymerization temperature of 75°C, a reaction pressure of 8.5 kg/cm2G and an average residence time of 2.5 hours. In order to prevent unintended polymerization, 2 L/h of methanol was supplied to the contents withdrawn from the second polymerization reactor to deactivate the catalyst for polymerization. Subsequently, the hexane and unreacted monomer in the contents were removed by a solvent separator and then the contents were dried to give a polymer. [0195]
A sample for measurement was prepared by pelletizing the resulting mixture using a single-screw extruder manufactured by Placo Co., Ltd. in the same manner used in Example 9. Further, a film was prepared by using the sample and the physical properties of the film were measured. The property values of the polymer are shown in Tables 5 and
6 and the physical property values of the film are shown
in Table 7.
[0196]
[Comparative Example 5]
A film was prepared using a high density polyethylene (trade name: HIZEX HZ3300F, manufactured by Prime Polymer Co. , Ltd. ) in the same manner as in Example 9 and the physical properties of the film were measured. The property values of the polymer are shown in Tables 5 and 6 and the physical property values of the film are shown in Table 7. [0197]
[Comparative Example 6]
A film was prepared using a linear low-density polyethylene (trade name: ULTZEX UZ4020L, manufactured by Prime Polymer Co., Ltd.) in the same manner as in Example 9 and the physical properties of the film were measured. The property values of the polymer are shown in Tables 5 and 6 and the physical property values of the film are shown in Table 7. [0198]
[Comparative Example 7]
A film was prepared using a high density polyethylene (trade name: HIZEX HZ2200J, manufactured by Prime Polymer Co. , Ltd. ) in the same manner as in Example 9 and the physical
properties of the film were measured. The property values of the polymer are shown in Tables 5 and 6 and the physical property values of the film are shown in Table 7. [0199]
[Table 5]
(Table Removed)
Note) MT of mN (millinewton) unit is a product of MT of g
(gram) unit multiplied by 9.8. [0201]
[Table 7]
(Table Removed)
Note) Visual evaluation score
[Heavy] 1<2<3<4<5 [Minor]
[INDUSTRIAL APPLICABILITY] [0202]
The ethylene-α-olefin copolymer (E) of the present
invention may be shaped into films by inflation molding,
water-cooling inflation molding, cast molding, extrusion
lamination molding and the like, sheets, blow molded
articles, extrusion molded articles such as pipes, profiles
and the like, foamed molded articles, injection molded
articles and the like. In addition, the ethylene-α-olefin
copolymer (E) of the present invention may be used for fibers,
monofilaments, nonwoven fabrics and the like. These
articles include articles containing a part composed of the
ethylene-α-olefin copolymer and a part composed of other
resins (laminates and the like). Further, the
ethylene-α-olef in copolymer which is crosslinked during the
molding process may be used. The films of the
ethylene-α-olefin copolymer according to the present invention obtained by inflation molding, cast molding, extrusion lamination molding and the like has excellent properties, among the above molded articles.
[0203]
The film or sheet of the present invention is suitably used for a heavy-duty packaging film, a compression packaging film, a plastic shopping bag, a standardized bag, a laminate film, a retort film, a food film, a protect film
(including a process paper for electronic components and building materials), a film for packaging electronic components, a shrinkable film (including a label) , a medical film (including an infusion solution bag), a packaging material for industrial chemicals, a bag-in-box, an agricultural film (a greenhouse film, a rain-proof film, a multi-film), industrial materials (including a liner sheet),r-ray film and the like.
CLAIMS
1. An ethylene-α-olefin copolymer for a film or sheet
satisfying the following requirements [1] to [5]
simultaneously:
[1] the density (d) is in the range of 890 to 980 kg/m3;
[2] the intrinsic viscosity ([n]) measured at 135°C in decalin is in the range of 0.5 to 10 dl/g;
[3] the ratio of weight average molecular weight (Mw) to number average molecular weight (Mn) (Mw/Mn) measured by GPC is in the range of 2.0 to 50;
[4] in an elution temperature-eluation amount curve given by cross fractionation chromatography (CFC), the difference between a temperature at which the integrated elution amount is 1% by mass and a temperature at which the integrated elution amount is 40% by mass is 12°C or less, wherein the total elution amount is 100% by mass; and
[5] the amount of a component soluble in decane is 0.5% by mass or less.
2. The ethylene-α-olefin copolymer for a film or sheet
according to claim 1, wherein the copolymer comporises
80 to 20% by mass of the following ethylene-α-olefin copolymer (A), and
20 to 80% by mass of the following ethylene-α-olefin copolymer (B),
the ethylene-α-olefin copolymer (A) comprising ethylene and an a-olefin having 3 to 10 carbon atoms, and having a density (dA) of 910 to 980 kg/m3, an intrinsic viscosity ([n]A) of 0.5 to 3.0 dl/g as measured at 135°C in decalin, and a (Mw/Mn) of 1.5 to 5.0,
the ethylene-α-olefin copolymer (B) comprising a copolymer of ethylene and an a-olefin having 3 to 10 carbon atoms, and having a density (dB) of 880 to 950 kg/m3, an intrinsic viscosity ([n]B) of 1.0 to 10.0 dl/g as measured at 135°C in decalin, and a (Mw/Mn) of 1.5 to 5.0;
and further wherein the copolymer satisfies the following equation (Eq-1),
(Equation Removed)
3. The ethylene-α-olefin copolymer for a film or sheet according to claim 1 or 2, wherein the melt tension (MT) at 190°C is 20 mN or more.
4 . A film or sheet obtained from the ethylene-α-olefin copolymer (E) according to any of claims 1 to 3.
5. A wrapping bag, sheet or bag comprising the film or
sheet according to claim 4.
6. A laminate comprising at least one layer of the film or sheet according to claim 4.