JPH09183872A - Ethylene copolymer composition for film casting and sheet extrusion and cast film and extruded sheet using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an ethylene copolymer composition for film casting excellent in transparency, elasticity modulus and mechanical strength by blending a specific ethylene-α-olefin copolymer with a crystallization promoter in specific ratio. SOLUTION: This composition comprises (A) 100 pts.wt. of a copolymer of ethylene and a 4-20C α-olefin such 1-butene, etc., having (i) density of 0.880-0.950g/cm<3> , (ii) melt flow rate of 0.1-100g/10min at 190 deg.C under 2.16kg load, and (iii) the temperature of maximum peak [Tm( deg.C)] observed by differential scanning calorimeter(DSC) and density [d(g/cm<3> )] which satisfy the equation; Tm<400×d-250 and (B) 0.001-5 pts.wt. of a crystallization promoter such as metallic resinates (e.g.; sodium rosinate, etc.) expressed in formula I and II (R<1> -R<3> are each H, an alkyl, a cycloalkyl or an aryl).

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to an ethylene-based copolymer composition for cast films and extruded sheets, and a cast film and extruded sheet comprising this composition, and more specifically, it has excellent transparency and mechanical strength. The present invention relates to an ethylene-based copolymer composition from which a cast film and an extruded sheet can be obtained, and a cast film and an extruded sheet comprising the composition.

[0002]

BACKGROUND OF THE INVENTION Ethylene copolymers such as ethylene / α-olefin copolymers are molded by various molding methods and used for various purposes. The ethylene copolymer has different required properties depending on the molding method and the application.

By the way, when a cast film or an extruded sheet is molded from such an ethylene copolymer, the transparency or elastic modulus may be insufficient, and depending on the application, the transparency and elastic modulus may be different from each other. Sometimes the balance was not good.

As a result of intensive studies in view of such circumstances, the present inventors have found that an ethylene-based copolymer composition comprising a specific ethylene / α-olefin copolymer and a crystal nucleating agent is
The present invention has been completed by finding that a cast film and an extruded sheet having an excellent balance of transparency and elastic modulus can be obtained by molding the cast film and the extruded sheet.

[0005]

The present invention provides an ethylene copolymer composition capable of producing a cast film and an extruded sheet having excellent transparency and mechanical strength, and a cast film and an extruded sheet obtained from the composition. The purpose is to do.

[0006]

SUMMARY OF THE INVENTION An ethylene-based copolymer composition for cast films and extruded sheets according to the present invention is a copolymer of (A) ethylene and an α-olefin having 4 to 20 carbon atoms. , (I) density is 0.880 ~
In the range of 0.950 g / cm ³ , (ii) 190 ° C,
2. Melt flow rate under a load of 16 kg is 0.1
The temperature (Tm (° C.)) and the density (d (g / cm ³ )) at the maximum peak position of the endothermic curve measured by a differential scanning calorimeter (DSC). Is 100 parts by weight of an ethylene / α-olefin copolymer satisfying the relationship represented by Tm <400 × d-250, and (B) a crystal nucleating agent: 0.001 to 5 parts by weight. .

In the present invention, the crystal nucleating agent is preferably a metal salt of rosin acid, more preferably at least one rosin acid selected from the group consisting of natural rosin, modified rosin and purified products thereof. More preferably, it is at least one rosin acid selected from dehydroabietic acid, dihydroabietic acid or dihydropimaric acid, or a derivative thereof, and a rosin acid represented by the following formula (ia) and the following formula (i-a) Particularly preferred is at least one rosin acid selected from rosin acids represented by i-b).

[0008]

Embedded image

(In the formula, R ¹ , R ² and R ³ represent a hydrogen atom, an alkyl group, a cycloalkyl group or an aryl group and may be the same or different). Also,
In the present invention, the metal salt of rosin acid is preferably at least one metal salt of rosin acid selected from the group consisting of sodium salt, potassium salt and magnesium salt of rosin acid.

From the ethylene-based copolymer composition of the present invention,
When a cast film or extruded sheet is molded, a film or sheet excellent in transparency and mechanical strength can be obtained.

The cast film according to the present invention is characterized by comprising the above ethylene copolymer composition. The cast film of the present invention is excellent in transparency and mechanical strength.

The extruded sheet according to the present invention is characterized by comprising the above ethylene-based copolymer composition. The extruded sheet of the present invention is excellent in transparency and mechanical strength.

[0013]

DETAILED DESCRIPTION OF THE INVENTION The ethylene-based copolymer composition for cast films and extruded sheets and the cast film and extruded sheet comprising the composition according to the present invention will be specifically described below.

The ethylene-based copolymer composition for cast films and the ethylene-based copolymer composition for extruded sheets according to the present invention are (A) an ethylene / α-olefin copolymer as described below, and (B). It is formed from a crystal nucleating agent.

First, each component forming the ethylene-based copolymer composition will be described. Ethylene / α-olefin copolymer (A) The ethylene / α-olefin copolymer (A) used in the present invention is a random copolymer of ethylene and an α-olefin having 4 to 20 carbon atoms. .

Ethylene / α-olefin copolymer (A)
Then, the structural unit derived from ethylene is 55 to 99% by weight, preferably 65 to 98% by weight, more preferably 7
It exists in a proportion of 0 to 96% by weight and has 4 to 20 carbon atoms.
The structural unit derived from the α-olefin of 1 to 45% by weight, preferably 2 to 35% by weight, more preferably 4 to 3% by weight.
It is present in a proportion of 0% by weight.

Here, as the α-olefin having 4 to 20 carbon atoms, 1-butene, 1-pentene, 1-hexene, 4-
Methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene and the like can be mentioned.

The ethylene / α-olefin copolymer has a density of 0.880 to 0.950 g / cm ³ ,
It is preferably in the range of 0.890 to 0.935 g / cm ³ , and more preferably 0.905 to 0.930 g / cm ³ .

Further, the melt flow rate at 190 ° C. under a load of 2.16 kg is 0.01 to 100 g / 10 minutes,
It is preferably in the range of 0.05 to 50 g / 10 minutes, more preferably 0.1 to 10 g / 10 minutes.

The ethylene / α-olefin copolymer used in the present invention has a temperature (Tm (° C)) at the maximum peak position of an endothermic curve measured by a differential scanning calorimeter (DSC).
And density (d (g / cm ³ )) are: Tm <400 × d-250, preferably Tm <450 × d-297, more preferably Tm <500 × d-344, and most preferably Tm <550 × d-391. Meets the relationship indicated by.

Such an ethylene / α-olefin copolymer (A) can be obtained by, for example, (a) a transition metal compound of Group IV of the periodic table containing a ligand having a specific cyclopentadienyl skeleton, (b) ) Organoaluminum oxy compounds,
A copolymer capable of obtaining ethylene and an α-olefin having 4 to 20 carbon atoms in the presence of (c) a fine particle carrier and, if necessary, (d) an olefin polymerization catalyst formed from an organoaluminum compound. Has a density of 0.880-0.
It can be produced by copolymerization so that the amount becomes 950 g / cm ³ .

The olefin polymerization catalyst and each catalyst component will be described below. The transition metal compound (a) (hereinafter sometimes referred to as “component (a)”) is a transition metal compound represented by the following formula (I).

ML _x (I) In the formula, M is a transition metal atom selected from Group IVB of the periodic table, specifically zirconium, titanium or hafnium, preferably zirconium.

X is the valence of the transition metal atom M and represents the number of L coordinated to the transition metal atom. L is a ligand that coordinates to a transition metal atom M, and at least two of these ligands L are a cyclopentadienyl group, a methylcyclopentadienyl group, and an ethylcyclopentadienyl group. Or a substituted cyclopentadienyl group having at least one substituent selected from a hydrocarbon group having 3 to 10 carbon atoms, and the ligand L other than the (substituted) cyclopentadienyl group is , A hydrocarbon group having 1 to 12 carbon atoms, an alkoxy group, an aryloxy group, a halogen atom,
It is a trialkylsilyl group or a hydrogen atom.

The substituted cyclopentadienyl group may have two or more substituents, and the two or more substituents may be the same or different. The substituted cyclopentadienyl group has at least 1 when it has two or more substituents.
Each of the substituents may be a hydrocarbon group having 3 to 10 carbon atoms, and the other substituent is a methyl group, an ethyl group or a hydrocarbon group having 3 to 10 carbon atoms. Further, the substituted cyclopentadienyl groups coordinated to M may be the same or different.

Specific examples of the hydrocarbon group having 3 to 10 carbon atoms include an alkyl group, a cycloalkyl group, an aryl group and an aralkyl group. More specifically, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, t-butyl group, pentyl group, hexyl group, octyl group, 2-ethylhexyl group,
Examples thereof include alkyl groups such as decyl group; cycloalkyl groups such as cyclopentyl group and cyclohexyl group; aryl groups such as phenyl group and tolyl group; aralkyl groups such as benzyl group and neophyll group.

Of these, alkyl groups are preferable, and n-propyl group and n-butyl group are particularly preferable. In the present invention, the (substituted) cyclopentadienyl group which coordinates to the transition metal is preferably a substituted cyclopentadienyl group, more preferably a cyclopentadienyl group substituted with an alkyl group having 3 or more carbon atoms. A disubstituted cyclopentadienyl group is more preferable, and a 1,3-substituted cyclopentadienyl group is particularly preferable.

In the above formula (I), the ligand L other than the substituted cyclopentadienyl group coordinated to the transition metal atom M is a hydrocarbon group having 1 to 12 carbon atoms, an alkoxy group or an aryloxy group. , A halogen atom, a trialkylsilyl group or a hydrogen atom.

Examples of the hydrocarbon group having 1 to 12 carbon atoms include an alkyl group, a cycloalkyl group, an aryl group and an aralkyl group, and more specifically,
Methyl group, ethyl group, n-propyl group, isopropyl group,
alkyl groups such as n-butyl group, isobutyl group, sec-butyl group, t-butyl group, pentyl group, hexyl group, octyl group, 2-ethylhexyl group and decyl group; cycloalkyl groups such as cyclopentyl group and cyclohexyl group; An aryl group such as a phenyl group and a tolyl group; and an aralkyl group such as a benzyl group and a neophyl group can be exemplified.

As the alkoxy group, methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, isobutoxy group, sec-butoxy group, t-butoxy group, pentoxy group, hexoxy group, octoxy group and the like. Can be illustrated.

Examples of the aryloxy group include a phenoxy group and the like. Examples of the halogen atom include fluorine, chlorine, bromine and iodine.

Examples of the trialkylsilyl group include trimethylsilyl group, triethylsilyl group and triphenylsilyl group. Examples of the transition metal compound represented by the general formula (I) include bis (cyclopentadienyl) zirconium dichloride, bis (methylcyclopentadienyl) zirconium dichloride, bis (ethylcyclopentadienyl) zirconium dichloride, and bis. (N-propylcyclopentadienyl)
Zirconium dichloride, bis (n-butylcyclopentadienyl) zirconium dichloride, bis (n-hexylcyclopentadienyl) zirconium dichloride, bis (methyl-n-propylcyclopentadienyl) zirconium dichloride, bis (methyl-n- Butylcyclopentadienyl) zirconium dichloride, bis (dimethyl-n
-Butylcyclopentadienyl) zirconium dichloride, bis (n-butylcyclopentadienyl) zirconium dibromide, bis (n-butylcyclopentadienyl)
Zirconium methoxy chloride, bis (n-butylcyclopentadienyl) zirconium ethoxy chloride, bis (n-butylcyclopentadienyl) zirconium butoxycyclolide, bis (n-butylcyclopentadienyl) zirconium ethoxide, bis (n- Butylcyclopentadienyl) zirconium methyl chloride, bis (n-butylcyclopentadienyl) zirconium dimethyl, bis (n-butylcyclopentadienyl) zirconium benzyl chloride, bis (n-butylcyclopentadienyl) zirconium dibenzyl , Bis (n-butylcyclopentadienyl) zirconium phenyl chloride, bis (n-butylcyclopentadienyl) zirconium hydride chloride and the like. In the above example, the di-substituted cyclopentadienyl ring includes 1,2- and 1,3-substituted compounds, and the tri-substituted compound includes 1,2,3- and 1,2,4-substituted compounds. Including. In the present invention, a transition metal compound in which zirconium metal is replaced with titanium metal or hafnium metal in the above zirconium compound can be used.

Among these transition metal compounds represented by the general formula (I), bis (n-propylcyclopentadienyl) zirconium dichloride, bis (n-butylcyclopentadienyl) zirconium dichloride, bis (1 Particularly preferred are -methyl-3-n-propylcyclopentadienyl) zirconium dichloride and bis (1-methyl-3-n-butylcyclopentadienyl) zirconium dichloride.

The organoaluminum oxy compound (b) (hereinafter sometimes referred to as "component (b)") may be a conventionally known benzene-soluble aluminoxane, and it is also disclosed in JP-A-2-276807. It may be a benzene-insoluble organoaluminum oxy compound as disclosed in the publication.

The conventionally known aluminoxane is obtained by bringing an organoaluminum compound as described below into contact with water such as adsorbed water, crystallization water, ice or steam, or an organoaluminum compound as described below It can be produced by reacting tin oxide.

The particulate carrier (c) is an inorganic or organic material.
The compound having a particle size of 10 to 300 μm, preferably
Is a solid of 20 to 200 μm in the form of granules or fine particles.
used. Of these, porous oxides are used as the inorganic carrier.
Preferably, specifically, SiO _Two, Al_TwoO_Three, MgO,
ZrO_Two, TiO_Two, B_TwoO_Three, CaO, ZnO, Ba
O, ThO_TwoOr mixtures thereof, such as SiO_Two-
MgO, SiO_Two-Al_TwoO_Three, SiO_Two-TiO_Two, Si
O_Two-V_TwoO_Five, SiO_Two-Cr_TwoO_Three, SiO_Two-TiO_Two-M
Examples thereof include gO. Among these SiO_Two
And Al_TwoO_ThreeAt least one selected from the group consisting of
Those containing the above component as the main component are preferable.

The above inorganic oxide contains a small amount of Na ₂ C.
O ₃ , K ₂ CO ₃ , CaCO ₃ , MgCO ₃ , Na ₂ SO
₄ , Al ₂ (SO ₄ ) ₃ , BaSO ₄ , KNO ₃ , Mg
(NO ₃ ) ₂ , Al (NO ₃ ) ₃ , Na ₂ O, K ₂ O, Li
_It may contain carbonate, sulfate, nitrate and oxide components such as ₂ O.

The type of the particulate carrier (c) is
And the properties differ depending on the production method, but are preferably used in the present invention.
The particulate carrier to be used has a specific surface area of 50 to 1000 m.
^Two/ G, preferably 100 to 700 m^Two/ G, which is fine
Pore volume 0.3-2.5 cm ^ThreeDesired to be / g
Yes. The fine particle carrier may be 100 to 1000 as needed.
℃, preferably 150-700 ℃
You.

Further, examples of the fine particle carrier which can be used in the present invention include granular or fine particle solids of an organic compound having a particle size of 10 to 300 μm. As these organic compounds, ethylene, propylene, 1-butene, 4-methyl-1-pentene, etc. (co) polymers containing 2 to 14 carbon atoms as the main component (co) polymer or vinylcyclohexane, styrene The polymer or copolymer as the main component can be exemplified.

The olefin polymerization catalyst used for producing the ethylene / α-olefin copolymer is the above-mentioned component (a),
Although it is formed from the fine particle carrier of the components (b) and (c), the organoaluminum compound (d) may be used if necessary.

Examples of the (d) organoaluminum compound (hereinafter sometimes referred to as "component (d)") which is used as necessary include, for example, the organoaluminum compounds represented by the following general formula (III). can do.

R ¹ _n AlX _3-n (III) (wherein, R ¹ represents a hydrocarbon group having 1 to 12 carbon atoms, X represents a halogen atom or a hydrogen atom, and n represents 1 to 1).
3. ) In the above general formula (III), R ¹ has ¹ to 10 carbon atoms.
12 hydrocarbon groups such as an alkyl group, a cycloalkyl group or an aryl group, specifically, a methyl group,
Examples include ethyl group, n-propyl group, isopropyl group, isobutyl group, pentyl group, hexyl group, octyl group, cyclopentyl group, cyclohexyl group, phenyl group, and tolyl group.

Specific examples of such an organoaluminum compound include the following compounds. Trialkylaluminums such as trimethylaluminum, triethylaluminum, triisopropylaluminum, triisobutylaluminum, trioctylaluminum, tri2-ethylhexylaluminum; alkenylaluminums such as isoprenylaluminum; dimethylaluminum chloride, diethylaluminium chloride, diisopropylaluminum chloride, diisobutyl. Dialkyl aluminum halides such as aluminum chloride and dimethyl aluminum bromide; alkyl aluminum sesquihalides such as methyl aluminum sesquichloride, ethyl aluminum sesquichloride, isopropyl aluminum sesquichloride, butyl aluminum sesquichloride, ethyl aluminum sesquibromide; methyl Aluminum dichloride, ethyl aluminum dichloride, isopropyl aluminum dichloride, alkyl aluminum dihalides such as ethyl aluminum dibromide; diethylaluminum hydride, and alkyl aluminum hydride such as diisobutyl aluminum hydride.

Further, as the organoaluminum compound (d), a compound represented by the following general formula (IV) can be used. During ^{_{R 1 n AlY 3-n ...}} (IV) ( wherein, R ¹ represents the same hydrocarbon and R ¹ in the general formula (III), Y is -OR ² group, -OSiR ³ ₃ group, -
OAlR ⁴ ₂ group, -NR ⁵ ₂ group, -SiR ⁶ ₃ group or -
Shows the N (R ⁷⁾ AlR ⁸ ₂ group, n is 1-2,
R ² , R ³ , R ⁴ and R ⁸ are a methyl group, an ethyl group, an isopropyl group, an isobutyl group, a cyclohexyl group, a phenyl group and the like, and R ⁵ is a hydrogen atom, a methyl group, an ethyl group, an isopropyl group, a phenyl group. , Trimethylsilyl group and the like, and R ⁶ and R ⁷ are methyl group, ethyl group and the like. ) Among such organoaluminum compounds, R ¹ _n
A compound represented by Al (OAlR ⁴ ₂ ) _3-n , such as Et
₂ AlOAlEt ₂ , (iso-Bu) ₂ AlOAl (iso-
Bu) _{2 and the} like are preferred.

[0045] Among the organic aluminum compounds represented by the general formula (III) and (IV), the general formula R ¹ ₃ Al
The compound represented by is preferable, and the compound in which R ¹ is an isoalkyl group is particularly preferable.

When the ethylene / α-olefin copolymer is produced, the above-mentioned component (a), component (b) and particulate carrier (c) and, if necessary, component (d) are brought into contact with each other. The catalyst prepared is used.

The contact of each of the above components can be carried out in an inert hydrocarbon solvent. Specific examples of the inert hydrocarbon medium used for preparing the catalyst include propane, butane, pentane, hexane, heptane and octane. Aliphatic hydrocarbons such as decane, dodecane and kerosene; Alicyclic hydrocarbons such as cyclopentane, cyclohexane and methylcyclopentane; Aromatic hydrocarbons such as benzene, toluene and xylene; Ethylene chloride, chlorobenzene, dichloromethane etc. Examples thereof include halogenated hydrocarbons and mixtures thereof.

The catalyst used in the production of the ethylene / α-olefin copolymer contains the above-mentioned component (a), component (b), particulate carrier (c) and, if necessary, component (d). It may be a prepolymerization catalyst obtained by prepolymerizing an olefin below. The prepolymerization is carried out by introducing an olefin into an inert hydrocarbon solvent in the presence of the above-mentioned component (a), component (b), particulate carrier (c) and optionally component (d). It can be carried out.

As the olefin used in the prepolymerization, ethylene and 4 to 2 carbon atoms as described above are used.
Examples thereof include 0-α-olefin and the like. Among these, ethylene or a combination of ethylene and an α-olefin used in the polymerization is particularly preferable.

The prepolymerization can be carried out batchwise or continuously, and can be carried out under reduced pressure, normal pressure or under pressure. In the prepolymerization,
Intrinsic viscosity [η] measured in decalin of at least 135 ° C. in the presence of hydrogen in the range of 0.2 to 7 dl / g,
It is desirable to produce a prepolymer such that it is preferably 0.5-5 dl / g.

Ethylene / α-olefin copolymer (A)
Can be obtained by copolymerizing ethylene with an α-olefin having 4 to 20 carbon atoms as described above in the presence of the above-mentioned olefin polymerization catalyst or prepolymerization catalyst.

In the present invention, the copolymerization of ethylene and α-olefin is carried out in the gas phase or in the slurry liquid phase. In slurry polymerization, an inert hydrocarbon may be used as a solvent, or an olefin itself may be used as a solvent.

Specific examples of the inert hydrocarbon solvent used in the slurry polymerization include butane, isobutane, pentane, hexane, octane, decane, dodecane, hexadecane, octadecane, and other aliphatic hydrocarbons; cyclopentane, methylcyclopentane. , Cyclohexane,
Alicyclic hydrocarbons such as cyclooctane; aromatic hydrocarbons such as benzene, toluene and xylene; gasoline;
Examples include petroleum fractions such as kerosene and light oil. Among these inert hydrocarbon media, aliphatic hydrocarbons, alicyclic hydrocarbons, petroleum fractions and the like are preferred.

When carrying out the slurry polymerization method or the gas phase polymerization method, the olefin polymerization catalyst or the prepolymerization catalyst as described above is usually used in a concentration of transition metal atoms of 10 ⁻⁸ to 10 ^−. It is desirable to use an amount of ³ gram atom / liter, preferably 10 ⁻⁷ to 10 ⁻⁴ gram atom / liter.

In addition, the same organoaluminumoxy compound and / or organoaluminum compound (d) as the component (b) may be added during the polymerization. At this time, the atomic ratio of the aluminum atom (Al) derived from the organoaluminum oxy compound and the organoaluminum compound and the transition metal atom (M) derived from the transition metal compound (a) (A
1 / M) is in the range of 5-300, preferably 10-200, more preferably 15-150.

When carrying out the slurry polymerization method, the polymerization temperature is usually in the range of -50 to 100 ° C, preferably 0 to 90 ° C, and when carrying out the gas phase polymerization method, the polymerization temperature is It is usually in the range of 0 to 120 ° C, preferably 20 to 100 ° C.

The polymerization pressure is usually atmospheric pressure to 100 kg /
It is under a pressure condition of cm ² , preferably ² to 50 kg / cm ² , and the polymerization can be carried out in any of batch system, semi-continuous system and continuous system.

It is also possible to carry out the polymerization in two or more stages under different reaction conditions. (B) Crystal Nucleating Agent As the crystal nucleating agent, various conventionally known crystal nucleating agents for olefins can be used without any limitation. Among them, the aromatic phosphoric acid ester salts, benzylidene sorbitol, and rosin listed below are particularly usable. Crystal nucleating agents such as metal salts of acids are preferred.

[0059]

Embedded image

(Wherein R ⁴ represents an oxygen atom, a sulfur atom or a hydrocarbon group having 1 to 10 carbon atoms, and R ⁵ and R ⁶ represent a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms. R ⁵ and R ⁶ may be the same or different and may be R ^{5 s} , R ^{6 s,} or R ⁵ and R ⁶ may be bonded to form a ring, and M is 1 ~ Represents a trivalent metal atom, and n is an integer of 1 to 3.) Specifically, sodium-2,2'-methylene-bis (4,6-di-
(t-butylphenyl) phosphate, sodium-2,2'-
Ethylidene-bis (4,6-di-t-butylphenyl) phosphate, lithium-2,2'-methylene-bis- (4,6-di-t-butylphenyl) phosphate, lithium-2,2 ' -Ethylidene-bis (4,6-di-t-butylphenyl) phosphate, sodium-2,2'-ethylidene-bis (4-i-propyl-
6-t-butylphenyl) phosphate, lithium-2,2'-
Methylene-bis (4-methyl-6-t-butylphenyl) phosphate, lithium-2,2'-methylene-bis (4-ethyl-6-
t-butylphenyl) phosphate, calcium-bis [2,2'-thiobis (4-methyl-6-t-butylphenyl) phosphate], calcium-bis [2,2'-thiobis (4-ethyl-6 -t-butylphenyl) phosphate], calcium-bis [2,2'-thiobis- (4,6-di-t-butylphenyl) phosphate], magnesium-bis [2,2'-thiobis (4, 6-di-t-butylphenyl) phosphate],
Magnesium-bis [2,2'-thiobis- (4-t-octylphenyl) phosphate], sodium-2,2'-butylidene-bis (4,6-di-methylphenyl) phosphate, sodium-2, 2'-butylidene-bis (4,6-di-t-butylphenyl) phosphate, sodium-2,2'-t-octylmethylene-bis (4,6-di-methylphenyl) phosphate, sodium-2 , 2'-t-octylmethylene-bis (4,6-
Di-t-butylphenyl) phosphate, calcium
Bis- (2,2'-methylene-bis (4,6-di-t-butylphenyl) phosphate), magnesium-bis [2,2'-methylene-bis (4,6-di-t-butylphenyl) ) Phosphate], barium-bis [2,2'-methylene-bis (4,6-di-t-
Butylphenyl) phosphate], sodium-2,2'-
Methylene-bis (4-methyl-6-t-butylphenyl) phosphate, sodium-2,2'-methylene-bis (4-ethyl-
6-t-butylphenyl) phosphate, sodium (4,
4'-dimethyl-5,6'-di-t-butyl-2,2'-biphenyl) phosphate, calcium-bis [(4,4'-dimethyl-6,6'-
Di-t-butyl-2,2'-biphenyl) phosphate], sodium-2,2'-ethylidene-bis (4-m-butyl-6-t-butylphenyl) phosphate, sodium-2,2 ' -Methylene-bis (4,6-di-methylphenyl) phosphate, sodium-2,2'-methylene-bis (4,6-di-ethylphenyl) phosphate, potassium-2,2'-ethylidene-bis (4,6-Di-t-butylphenyl) phosphate, calcium-bis [2,2'-ethylidene-bis (4,6-di-t-butylphenyl) phosphate], magnesium-bis [2,2 '-
Ethylidene-bis (4,6-di-t-butylphenyl) phosphate], barium-bis [2,2'-ethylidene-bis (4,6
-Di-t-butylphenyl) phosphate], aluminum-tris [2,2'-methylene-bis (4,6-di-t-butylfell) phosphate] and aluminum-tris [2,
2′-ethylidene-bis (4,6-di-t-butylphenyl) phosphate] and mixtures of two or more thereof. Particularly preferred is sodium-2,2'-methylene-bis (4,6-di-t-butylphenyl) phosphate.

[0061]

Embedded image

(In the formula, R ⁷ represents a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, M represents a metal atom having a valence of 1 to 3, and n is an integer of 1 to 3.) Specifically, sodium-bis (4-t-butylphenyl)
Phosphate, sodium-bis (4-methylphenyl) phosphate, sodium-bis (4-ethylphenyl) phosphate, sodium-bis (4-i-propylphenyl) phosphate, sodium-bis (4-t-
Octylphenyl) phosphate, potassium-bis (4
-t-butylphenyl) phosphate, calcium-bis (4-t-butylphenyl) phosphate, magnesium
-Bis (4-t-butylphenyl) phosphate, lithium-bis (4-t-butylphenyl) phosphate, aluminum-bis (4-t-butylphenyl) phosphate and mixtures of two or more thereof can do. Particularly, sodium-bis (4-t-butylphenyl) phosphate is preferable.

[0063]

[Chemical 6]

(In the formula, R ⁸ represents a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms.) Specifically, 1,3,2,4-dibenzylidene sorbitol, 1,
3-benzylidene-2,4-p-methylbenzylidene sorbitol, 1,3-benzylidene-2,4-p-ethylbenzylidene sorbitol, 1,3-p-methylbenzylidene-2,4-benzylidene sorbitol, 1,3- p-ethylbenzylidene-2,4-benzylidenesorbitol, 1,3-p-methylbenzylidene-2,4
-p-ethylbenzylidene sorbitol, 1,3-p-ethylbenzylidene-2,4-p-methylbenzylidene sorbitol,
1,3,2,4-di (p-methylbenzylidene) sorbitol, 1,
3,2,4-di (p-ethylbenzylidene) sorbitol, 1,3,
2,4-di (pn-propylbenzylidene) sorbitol, 1,
3,2,4-di (pi-propylbenzylidene) sorbitol,
1,3,2,4-di (pn-butylbenzylidene) sorbitol,
1,3,2,4-di (ps-butylbenzylidene) sorbitol,
1,3,2,4-di (pt-butylbenzylidene) sorbitol,
1,3,2,4-di (2 ', 4'-dimethylbenzylidene) sorbitol, 1,3,2,4-di (p-methoxybenzylidene) sorbitol, 1,3,2,4-di (p- Ethoxybenzylidene) sorbitol, 1,3-benzylidene-2-4-p-chlorobenzylidene sorbitol, 1,3-p-chlorobenzylidene-2,4-benzylidene sorbitol, 1,3-p-chlorobenzylidene-2,4- p-methylbenzylidene sorbitol, 1,3-p-chlorobenzylidene-2,4-p-ethylbenzylidene sorbitol, 1,3-p-
Methylbenzylidene-2,4-p-chlorobenzylidene sorbitol, 1,3-p-ethylbenzylidene-2,4-p-chlorobenzylidene sorbitol and 1,3,2,4-di (p-chlorobenzylidene) sorbitol and these And a mixture of two or more of 1,3,2,4-dibenzylidene sorbitol, 1,3,2,4-di (p-methylbenzylidene) sorbitol, 1,3,2,4-di ( p-Ethylbenzylidene) sorbitol, 1,3-p-chlorobenzylidene-2,4-p-methylbenzylidenesorbitol, 1,3,2,4-di (p-chlorobenzylidene) sorbitol and mixtures of two or more thereof Is preferred.

The metal salt of rosin acid used as a crystal nucleating agent in the present invention means a reaction product of rosin acid and a metal compound. As rosin acid, natural rosin such as gum rosin, tall oil rosin and wood rosin; disproportionated rosin, hydrogenated rosin, dehydrogenated rosin, polymerized rosin, α,
Various modified rosins such as β-ethylenically unsaturated carboxylic acid modified rosin; purified products of the above-mentioned natural rosin, purified rosins, and the like. The unsaturated carboxylic acid used for preparing the α, β-ethylenically unsaturated carboxylic acid-modified rosin includes, for example, maleic acid, maleic anhydride, fumaric acid, itaconic acid, itaconic anhydride, citraconic acid, acrylic acid. , Methacrylic acid and the like. Among these, at least one rosin acid selected from the group consisting of natural rosin, modified rosin, purified product of natural rosin, and purified product of modified rosin is preferable. Here, rosin acid is a plurality of resin acids selected from pimaric acid, sandaracopimaric acid, parastophosphoric acid, isopimaric acid, abietic acid, dehydroabietic acid, neoabietic acid, dihydropimaric acid, dihydroabietic acid, tetrahydroabietic acid, and the like. Contains.

Examples of the metal compound which reacts with the rosin acid to form a metal salt include compounds having a metal element such as sodium, potassium and magnesium and forming a salt with the rosin acid. Specific examples thereof include chlorides, nitrates, acetates, sulfates, carbonates, oxides and hydroxides of the above metals.

The crystal nucleating agent used in the present invention is a metal salt of at least one rosin acid selected from dehydroabietic acid, dehydroabietic acid derivatives, dihydroabietic acid, dihydroabietic acid derivatives, dihydropimaric acid and dihydropimaric acid derivatives. Preferably there is.

In the present invention, the rosin acid is represented by the following formula (i
at least one rosin acid selected from rosin acid represented by formula (a) and a rosin acid represented by the following formula (i-b): [compound (i-a)] It is preferable.

[0069]

Embedded image

In formula (i-a) and formula (i-b), R ¹ and R
² and R ³ may be the same or different from each other;
It is a hydrogen atom, an alkyl group, a cycloalkyl group or an aryl group.

Specific examples of the alkyl group include methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl,
Examples include alkyl groups having 1 to 8 carbon atoms such as tert-butyl, pentyl, heptyl, and octyl, and these groups may have a substituent such as a hydroxyl group, a carboxyl group, an alkoxy group, and a halogen. .

Specific examples of the cycloalkyl group include cycloalkyl groups having 5 to 8 carbon atoms such as cyclopentyl, cyclohexyl and cycloheptyl. These groups include hydroxyl group, carboxyl group, alkoxy group, halogen and the like. It may have a substituent.

Examples of the aryl group include aryl groups having 6 to 10 carbon atoms such as a phenyl group, a tolyl group and a naphthyl group. These groups are substituents such as a hydroxyl group, a carboxyl group, an alkoxy group and a halogen. May have.

Such compounds (ia) and compounds
In (i-b), R¹, R^TwoAnd R^ThreeEach
Preferred are rosin acids that are the same or different alkyl groups.
R ¹Is an i-propyl group, R^TwoAnd R^ThreeBut
More preferred is a rosin acid that is a chill group. Such a logic
The metal salt of acid is especially effective in improving the crystallization rate of crystalline resins.
The fruit is excellent.

Specific examples of the compound (i-a) include dehydroabietic acid, and specific examples of the compound (i-b) include dihydroabietic acid.
Of such compounds (i-a) and compounds (i-b), for example, the rosin acid represented by the formula (i-a) disproportionates natural rosins such as gum rosin, tall oil rosin, and wood rosin. Alternatively, it is obtained by dehydrogenation and then purification. In addition, natural rosin is usually a plurality of resin acids such as pimaric acid, sandaracopimaric acid, parastophosphoric acid, isopimaric acid, abietic acid, dehydroabietic acid, neoabietic acid, dihydropimaric acid, dihydroabietic acid, and tetrahydroabietic acid. Seed included.

Examples of the metal salt of the compound (i-a) include compounds represented by the following formula (ii-a) [compound (ii-a)], and examples of the metal salt of the compound (i-b) include , The following formula (ii-b)
A compound [compound (ii-b)] represented by

[0077]

Embedded image

In the formulas (ii-a) and (ii-b), R ¹ and R ²
And R ³ are the same as the above formula (i-a) and formula (i-b). M is a monovalent metal ion such as lithium, sodium, potassium, rubidium and cesium; and divalent metal such as beryllium, magnesium, calcium, strontium, barium and zinc. Metal ions; trivalent metal ions such as aluminum. Of these, monovalent or divalent metal ions are preferable, and sodium ions, potassium ions, and magnesium ions are more preferable.

N is the same integer as the valence of the metal ion M, and is an integer of 1 to 3. Among the compounds (ii-a) and (ii-b), R ¹ , R ² and R ³ are the same or different alkyl groups, respectively, a rosin acid metal salt, or M is a monovalent or divalent group. A rosin acid metal salt which is a metal ion is preferred, and R ¹ is an i-propyl group, and R ² and R ³ are methyl groups, a rosin acid metal salt, or M is a sodium ion, potassium ion or magnesium ion. A metal salt of rosin acid is more preferable, R ¹ is an i-propyl group, and R ² and R ^{3 are}
Is a methyl group, and M is a sodium ion, potassium ion or magnesium ion, and a rosin acid metal salt is particularly preferred. Such a rosin acid metal salt is
Especially, the effect of improving the crystallization rate is excellent.

Specific examples of the compound (ii-a) include lithium dehydroabietic acid, sodium dehydroabietic acid, potassium dehydroabietic acid, beryllium dehydroabietic acid, magnesium dehydroabietic acid, calcium dehydroabietic acid, and zinc dehydroabietic acid. , A metal salt of dehydroabietic acid such as aluminum dehydroabietic acid, and the like, and sodium dehydroabietic acid, potassium dehydroabietic acid, and magnesium dehydroabietic acid are preferable.

Specific examples of the compound (ii-b) include lithium dihydroabietic acid, sodium dihydroabietic acid, potassium dihydroabietic acid, beryllium dihydroabietic acid, magnesium dihydroabietic acid, calcium dihydroabietic acid, and zinc dihydroabietic acid. , A metal salt of dihydroabietic acid such as aluminum dihydroabietic acid, and the like, and sodium dihydroabietic acid, potassium dihydroabietic acid, and magnesium dihydroabietic acid are preferable.

As a method for producing the above-mentioned metal salt of rosin acid, a conventionally known method can be adopted. Such metal salts of rosin acid may be used alone or in combination of two or more. As a combination of two or more kinds, a combination with a rosin acid metal salt having the same rosin acid and a different metal, a combination of rosin acid metal salts having a different rosin acid and the same metal, and a rosin acid different rosin acid and a different metal A combination of metal salts may be mentioned. Among these, at least 2 metal salts of rosin acid having the same rosin acid but different metals are used.
It is preferred to use seed-containing rosin acid metal salts.

The amount ratio of the rosin metal salt in the at least two rosin acid partial metal salts is arbitrary, but one kind of rosin metal salt in the at least two rosin acid partial metal salts is used. Of rosin acid metal salt of 1 mol% or more, preferably 5 to 95 mol%, and other rosin acid metal salt of 99%
It is desirable to combine them so that the ratio is less than mol%, preferably 95 to 5 mol%.

The combination of at least two rosin acid partial metal salts is preferably a combination of a rosin acid partial potassium salt and a rosin acid partial sodium salt or a rosin acid partial magnesium salt. Further, potassium rosinate is 20 mol% or more, preferably 40 to 99 mol%, more preferably 45 to 80 mol%, and rosin acid based on the total amount of the rosin acid metal salt in the two types of rosin acid partial metal salts. Sodium salt or magnesium rosin acid salt is less than 80 mol%, preferably 60 to 1 mol%, more preferably 55 to 55 mol%.
It is desirable to combine them in a proportion of 20 mol%.

Such a rosin acid partial metal salt containing at least two metals is superior in dispersibility in an ethylene / α-olefin copolymer as compared with a rosin acid partial metal salt containing only one metal.

Among the crystal nucleating agents containing a metal salt of rosin acid as a main component as described above, a partial metal salt of rosin acid is preferable.
Here, the rosin acid partial metal salt means both a mixture of a rosin acid metal salt and an unreacted rosin acid, and a rosin acid metal salt containing no unreacted rosin acid. In the rosin acid partial metal salt, the rosin acid metal salt is 10 to 100 mol%, preferably 20 to 70 mol%, and particularly preferably 30.
It is desirable that the content is ˜50 mol%.

Examples of the other crystal nucleating agent include metal salts of aromatic carboxylic acids and aliphatic carboxylic acids. Specific examples include aluminum benzoate, aluminum pt-butylbenzoate, sodium adipate and thio. Examples thereof include sodium phenecarboxylate and sodium pyrrolecarboxylate.

Inorganic compounds such as talc can also be exemplified. Ethylene-based copolymer composition The ethylene-based copolymer composition for cast film and the extruded sheet- based ethylene-based copolymer composition according to the present invention,
(A) an ethylene / α-olefin copolymer; 100 parts by weight; and (B) a crystal nucleating agent; 0.001 to 5 parts by weight, preferably 0.01 to 2 parts by weight.

The ethylene-based copolymer composition for cast films and extruded sheets of the present invention contains a weather resistance stabilizer, a heat resistance stabilizer, an antistatic agent, an antislip agent, as long as the object of the present invention is not impaired. If necessary, additives such as an anti-blocking agent, an antifogging agent, a lubricant, a pigment, a dye, a plasticizer, an antiaging agent, a hydrochloric acid absorbent, and an antioxidant may be added. In addition, a small amount of another polymer compound can be blended without departing from the spirit of the present invention.

As a method for producing the ethylene-based copolymer composition for cast films and extruded sheets, any known method can be adopted. For example, the ethylene / α-olefin copolymer (A) and the crystal nucleus are used. A method of melt-kneading the agent (B) and, if necessary, the above-mentioned additives using an extruder, a kneader or the like can be mentioned.

The ethylene copolymer composition for cast films and extruded sheets of the present invention is suitable for use in films and sheets obtained by cast molding and extrusion molding. Conventionally known methods and conditions are adopted when producing cast films and extruded sheets by cast molding and extrusion molding.

The cast film and the extruded sheet thus obtained are excellent in transparency and elastic modulus.

[0093]

INDUSTRIAL APPLICABILITY The ethylene-based copolymer composition for cast films and extruded sheets according to the present invention provides cast films and extruded sheets excellent in transparency and elastic modulus.

The cast film and extruded sheet according to the present invention are excellent in transparency and elastic modulus. Next, the definition of the physical properties used in the present invention, the measuring method, and the molding method will be shown. (1) Granulation of ethylene-based copolymer Powdery ethylene-based copolymer 1 obtained by gas phase polymerization
To 100 parts by weight, tri (2,4-
0.05 parts by weight of di-t-butylphenyl) phosphate, and n-octadecyl-3- (4'hydroxy-3 ', 5'-di-t-butylphenyl) propionate as a heat-resistant stabilizer were added in an amount of 0.
1% by weight and 0.05 part by weight of calcium stearate as a hydrochloric acid absorbent are mixed. Thereafter, a conical taper type twin-screw extruder manufactured by Haake Co. is used and melt-extruded at a preset temperature of 180 ° C. to prepare granulated pellets. (2) Density The strand obtained at the time of measuring the melt flow rate under a load of 2.16 kg at 190 ° C. is heat-treated at 120 ° C. for 1 hour, gradually cooled to room temperature over 1 hour, and then measured with a density gradient tube. (3) Composition of copolymer Determined by ¹³ C-NMR. That is, ¹³ C of a sample prepared by uniformly dissolving about 200 mg of copolymer powder in 1 ml of hexachlorobutadiene in a 10 mmφ sample tube.
-It is determined by measuring the NMRR spectrum under the measuring conditions of a measuring temperature of 120 ° C, a measuring 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) Maximum peak temperature (Tm) by DSC The measurement was performed using a DSC-7 type apparatus manufactured by Perkin Elmer. Temperature (Tm) at the maximum peak position on the endothermic curve
Packs about 5 mg of sample in an aluminum pan at 20 ° C / min.
After raising the temperature to 0 ° C and holding at 200 ° C for 5 minutes, 10
It is determined from the endothermic curve when the temperature is lowered to room temperature at ° C / min and then the temperature is raised at 10 ° C / min. (6) Film or sheet processing method (a) Cast molding 30 mmφ, L / D = 25 single screw extruder, lip width 0.7
mm, a processing temperature of 210 ° C., an extrusion rate of about 22 g, a roll temperature of 40 ° C., and a take-up speed of 2.4 m / min.

(B) Extrusion molding Using granulated pellets of the copolymer as a sample, 20 mmφ · L /
D = 28 single screw extruder, 25 mmφ die, lip width 0.7 mm, single slit air ring, air flow rate =
90 liter / min. , Extrusion rate = 9 g / min. , Blow ratio = 1.8, take-up speed = 2.4 m / min. ,
A film having a thickness of 30 μm was extruded at a processing temperature of 200 ° C. (7) Film physical property evaluation method (a) Haze (cloudiness): Measured according to ASTM-D-1003-61.

(B) Gloss (Gloss): Measured according to JIS Z8741. (C) Elastic modulus: A dumbbell having a size according to JIS K6718 is punched out from the film to be a test piece. MD is the case where the film is punched in parallel with the direction in which the film is taken, and TD is the case where the film is punched in a direction perpendicular to the direction in which the film is taken.

Set on an air chuck of an Instron type universal material testing machine, chuck distance 86 mm, pulling speed 2
A tensile test is performed at 00 mm / min, and the slope of the initial stress with respect to the displacement is taken as the elastic modulus.

[0098]

EXAMPLES Hereinafter, the present invention will be described more specifically based on examples, but the present invention is not limited to these examples.

[0099]

[Production Example] Production of ethylene / α-olefin copolymer (A) [Preparation of catalyst] Silica 10 dried at 250 ° C for 10 hours
After suspending the suspension in 154 liters of toluene,
Cooled to ° C. Thereafter, a toluene solution of methylaminooxane (Al = 1.33 mol / liter) 57.5.
One liter was added dropwise over one hour. At this time, the temperature in the system is set to 0
C. Subsequently, the reaction was carried out at 0 ° C. for 30 minutes, then the temperature was raised to 95 ° C. over 1.5 hours, and the reaction was carried out at that temperature for 20 hours. Then, the temperature was lowered to 60 ° C., and the supernatant was removed by the decantation method. After the solid component thus obtained was washed twice with toluene, toluene 100
Resuspended in liters. Bis (1-methyl-3
16.8 L of a toluene solution of (-n-butylcyclopentadienyl) zirconium dichloride (Zr = 27.0 mmol / L) was dropped at 80 ° C. for 30 minutes, and further reacted at 80 ° C. for 2 hours. Then, the supernatant was removed, and the solid catalyst was washed twice with hexane to obtain a solid catalyst containing 3.5 mg of zirconium per 1 g.

[Preparation of prepolymerization catalyst] 870 g of the solid catalyst obtained above and 260 g of 1-hexene were added to 87 liters of hexane containing 2.5 mol of triisobutylaluminum, and ethylene preliminarily was added at 35 ° C. for 5 hours. By carrying out the polymerization, a prepolymerized catalyst in which 10 g of polyethylene was prepolymerized per 1 g of the solid catalyst was obtained.

[Polymerization] Copolymerization of ethylene and 1-hexene was carried out using a continuous fluidized bed gas phase polymerization apparatus at a total pressure of 20 kg / cm ² -G and a polymerization temperature of 80 ° C. 0.33 mmol of the prepolymerized catalyst prepared above in terms of zirconium atoms
/ H, triisobutylaluminum 10 mmol / h
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.
02, hydrogen / ethylene = 4.6 × 10 ⁻⁴ , ethylene concentration = 70%).

The yield of the obtained ethylene / α-olefin copolymer (A-1) was 60.0 kg / hr, the density was 0.926 g / cm ³ , and the MFR was 4.2 g / 10.
The temperature of the maximum peak position of the endothermic curve measured by DSC is 117.2 ° C., the temperature of the peak position on the lowest temperature side is 106.7 ° C., and the decane-soluble portion at room temperature is 0. It was 13 parts by weight.

[0103]

Example 1 Ethylene / α-olefin copolymer (A-
1) 0.3 parts by weight of potassium / sodium salt of dehydroabietic acid (metal salt having 15% of potassium metal equivalent and 15% of sodium metal equivalent to the equivalent of carboxyl machine) per 100 parts by weight. It was blended and pelletized by melt-kneading.

A film having a thickness of 40 μm was inflation-molded using the above pellets. The physical properties of the copolymer composition and the film are shown in Tables 1 and 2.

[0105]

[Reference Example 1] Ethylene / α-olefin copolymer (A-
1) was pelletized by melt-kneading, and a film having a thickness of 40 μm was cast-molded using the pellet. The physical properties of the copolymer composition and the film are shown in Tables 1 and 2.

[0106]

[Examples 2 to 6] Production examples except that the gas composition was changed so that the density and MFR were the ethylene / α-olefin copolymers (A-2) to (A-6) shown in Table 1. Similarly, ethylene / α-olefin copolymers (A-2) to (A-6)
I got However, only (A-4) had a polymerization temperature of 70 ° C.

0.5 wt% of the same potassium / sodium salt of dehydroabietic acid as used in Example 1 was added to these ethylene / α-olefin copolymers (A-2) to (A-6). Parts were mixed and pelletized by melt-kneading.

A film having a thickness of 40 μm was inflation-molded using the above pellets. The physical properties of the copolymer composition and the film are shown in Tables 1 and 2.

[0109]

[Reference Examples 2 to 6] The ethylene / α-olefin copolymers (A-2) to (A-6) were pelletized by melt-kneading and the pellets were used to cast a film having a thickness of 40 µm. The physical properties of the copolymer composition and the film are shown in Tables 1 and 2.

[0110]

[Table 1]

[0111]

[Table 2]

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Office reference number FI technical display area C08L 93:04) B29K 23:00 B29L 7:00

Claims (16)

[Claims] 1. (A) Ethylene and 4 to 20 carbon atoms.
Of the α-olefin of (i) having a density in the range of 0.880 to 0.950 g / cm ³ ,
i) The melt flow rate at 190 ° C. under a load of 2.16 kg is in the range of 0.1 to 100 g / 10 minutes, and (ii)
i) Temperature (Tm (° C)) and density (d) at the maximum peak position of the endothermic curve measured by a differential scanning calorimeter (DSC)
(G / cm ³ )) satisfies the relationship represented by Tm <400 × d-250: 100 parts by weight of ethylene / α-olefin copolymer, and (B) crystal nucleating agent: 0.001 to 5 parts by weight. An ethylene-based copolymer composition for a cast film, comprising: 2. The ethylene-based copolymer composition for cast films according to claim 1, wherein the crystal nucleating agent is a metal salt of rosin acid. 3. The ethylene copolymer composition for a cast film according to claim 2, wherein the rosin acid is at least one rosin acid selected from the group consisting of natural rosin, modified rosin and purified products thereof. 4. The rosin acid is dehydroabietic acid, dihydroabietic acid or dihydropimaric acid,
The ethylene copolymer composition for cast films according to claim 2, which is at least one rosin acid selected from these derivatives. 5. The rosin acid is at least one rosin acid selected from rosin acids represented by the following formula (ia) and rosin acids represented by the following formula (ib). Two
An ethylene-based copolymer composition for a cast film according to any one of the above; (Wherein, R ¹ , R ² and R ³ represent a hydrogen atom, an alkyl group, a cycloalkyl group or an aryl group, which may be the same or different). 6. The ethylene-based cast film according to claim 5, wherein in the formulas (i-a) and (i-b), R ¹ is an isopropyl group and R ² and R ³ are methyl groups. Copolymer composition. 7. The metal salt of rosin acid is at least one metal salt of rosin acid selected from the group consisting of sodium salt, potassium salt and magnesium salt of rosin acid. An ethylene-based copolymer composition for a cast film as described above. 8. A cast film obtained from the ethylene-based copolymer composition for a cast film according to claim 1. 9. (A) ethylene and 4 to 20 carbon atoms
Of the α-olefin of (i) having a density in the range of 0.880 to 0.950 g / cm ³ ,
i) The melt flow rate at 190 ° C. under a load of 2.16 kg is in the range of 0.1 to 100 g / 10 minutes, and (ii)
i) Temperature (Tm (° C)) and density (d) at the maximum peak position of the endothermic curve measured by a differential scanning calorimeter (DSC)
(G / cm ³ )) satisfies the relationship represented by Tm <400 × d-250: 100 parts by weight of ethylene / α-olefin copolymer, and (B) crystal nucleating agent: 0.001 to 5 parts by weight. An ethylene-based copolymer composition for an extruded sheet, comprising: 10. The ethylene copolymer composition for an extruded sheet according to claim 9, wherein the crystal nucleating agent is a metal salt of rosin acid. 11. The ethylene copolymer composition for an extruded sheet according to claim 10, wherein the rosin acid is at least one rosin acid selected from the group consisting of natural rosin, modified rosin and purified products thereof. 12. The rosin acid is dehydroabietic acid, dihydroabietic acid or dihydropimaric acid,
Alternatively, the ethylene copolymer composition for an extruded sheet according to claim 10, which is at least one kind of rosin acid selected from these derivatives. 13. The rosin acid is at least one rosin acid selected from rosin acids represented by the following formula (i-a) and rosin acids represented by the following formula (i-b): The ethylene copolymer composition for an extruded sheet according to item 10; (Wherein, R ¹ , R ² and R ³ represent a hydrogen atom, an alkyl group, a cycloalkyl group or an aryl group, which may be the same or different). 14. The formula (i-a) and the formula (i-b)
In the formula, R ¹ is an isopropyl group, and R ² and R ³
The ethylene-based copolymer composition for an extruded sheet according to claim 13, wherein is a methyl group. 15. The metal salt of rosin acid is at least one metal salt of rosin acid selected from the group consisting of sodium salt, potassium salt and magnesium salt of rosin acid. An ethylene-based copolymer composition for an extruded sheet as described above. 16. An extruded sheet obtained from the ethylene-based copolymer composition for an extruded sheet according to any one of claims 9 to 15.