JP2000198892A - Amorphous alpha-olefin-based copolymer composition and use thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject composition useful as a modifying agent, and capable of providing a thermoplastic resin excellent in balance in transparency, flexibility, heat-sealing property and impact strength by blending an amorphous α-olefinic copolymer with a nucleating agent in a specific ratio. SOLUTION: This amorphous α-olefin-based copolymer composition is obtained by blending (A) 100 pts.wt. amorphous α-olefinic copolymer containing 1-49 mol% ethylene component unit, 50-98 mol% propylene component unit and 1-49 mol% 4-20C α-olefin, having no melting peak measured by a differential scanning calorimeter, 0.01-10 dl/g intrinsic viscosity [η] measured in 135 deg.C decaline and <=4 molecular distribution by GPC with (B) 0.001-5 pt.wt. nucleating agent. A thermoplastic resin composition consisting of 1-60 pt.wt. above composition as the modifying agent with 40-99 pt.wt. thermoplastic resin is excellent in a balance of its transparency, flexibility, heat-sealing property and impact strength.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an amorphous .alpha.-olefin copolymer composition, a thermoplastic resin composition comprising the same and a thermoplastic resin, and a packaging material produced from the thermoplastic resin composition. To molded articles for use In particular, the amorphous α-olefin copolymer composition is a composition suitable for use in modifying thermoplastic resins.

[0002]

TECHNICAL BACKGROUND OF THE INVENTION Polyolefins, polyesters,
Thermoplastic resins such as polyamides and polyacetals have excellent processability, chemical resistance, electrical properties, mechanical properties, etc., and are therefore injection molded products, hollow molded products, films, sheets, etc. It is used for various purposes. However, in some applications, transparency, flexibility, heat sealability, impact resistance, and the like may not be sufficient.

As a method for improving the transparency, flexibility, heat sealability, impact resistance, and the like of a molded article made of such a thermoplastic resin, for example, a thermoplastic resin having a low crystalline ethylene / α-olefin is used. A method of blending a copolymer or the like as a modifier is known. However, in the conventional modifier, transparency, flexibility, and impact resistance are not well-balanced depending on the use.

[0004]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a thermoplastic resin composition having excellent balance of transparency, flexibility, heat sealability and impact resistance, and a molded article thereof. It is intended to provide a new polymer composition for a modifier.

[0005]

SUMMARY OF THE INVENTION That is, the present invention relates to a composition comprising 100 parts by weight of an amorphous α-olefin copolymer (A) and 0.001 to 5 parts by weight of a nucleating agent (B). And the amorphous α-olefin copolymer (A) is
(1) It contains 1 to 49 mol% of ethylene component units, 50 to 98 mol% of propylene component units, and 1 to 49 mol% of α-olefin component units having 4 to 20 carbon atoms (here, (2) the melting peak measured by a differential scanning calorimeter (DSC) is not substantially observed;
(3) its intrinsic viscosity [η] measured in decalin at 135 ° C. is in the range of 0.01 to 10 (dl / g);
(4) The present invention relates to an amorphous α-olefin copolymer composition having a molecular weight distribution of 4 or less as measured by GPC.

The above-mentioned amorphous α-olefin copolymer (A) comprises (1) a transition metal complex (a) represented by the formula (I) or (II), and (2) the above-mentioned (a) A catalyst system comprising at least one compound selected from a compound (b), an organoaluminum compound (c) and an organoaluminum oxy compound (d) capable of forming an ionic complex by reacting with a transition metal of Is a copolymer that can be produced in the presence of

Embedded image (Where M is Ti, Zr, Hf, Rn, Nd, Sm or Ru, and Cp ¹ and Cp ² are a cyclopentadienyl group, an indenyl group, a fluorenyl group or a derivative thereof which is π-bonded to M. X ¹ and X ² are
An anionic ligand or a neutral Lewis base ligand,
Y is a ligand containing a nitrogen atom, an oxygen atom, a phosphorus atom or a sulfur atom, and Z is C, O, B, S, Ge, S
i or Sn atom or a group containing those atoms. )

Further, the present invention relates to 1 to 60 parts by weight of the amorphous α-olefin copolymer composition,
With respect to a thermoplastic resin composition consisting of 0 to 99 parts by weight,
Further, the present invention relates to a molded article for a packaging material produced from the thermoplastic resin composition. The molded article is excellent in physical properties such as transparency, flexibility, heat sealability, impact resistance and the like.

[0008]

DETAILED DESCRIPTION OF THE INVENTION Next, the amorphous α-olefin copolymer composition according to the present invention, a thermoplastic resin composition containing the composition, and a molded article produced from the composition will be described. Will be explained. Here, the amorphous α-olefin copolymer composition comprises (A) the amorphous α-olefin copolymer and (B) a crystal nucleating agent.

< Amorphous α-olefin copolymer (A)
> Amorphous α-olefin copolymer (A) has an ethylene component unit of 1 to 49 mol% and a propylene component unit of 50%.
To 98 mol%, 1 to 49 mol% of α-olefin component units having 4 to 20 carbon atoms, and preferably 1 to 49 mol% of ethylene component units.
To 40 mol%, 50 to 98 mol% of a propylene component unit, 1 to 45 mol% of an α-olefin component unit (A) having 4 to 20 carbon atoms, and particularly preferably 1 to 45 mol% of an ethylene component unit.
-35 mol%, 50-98 mol% of propylene component units, and 1-40 mol% of α-olefin component units (A) having 4 to 20 carbon atoms. Here, the unit amount of all components in the copolymer is 100 mol%.

The amorphous α-olefin-based copolymer comprising the ethylene component, the propylene component, and the α-olefin component having 4 to 20 carbon atoms in such a proportion has good compatibility with the thermoplastic resin. . The obtained thermoplastic resin composition exhibits well-balanced properties such as transparency, flexibility, heat sealability, and impact strength.

The α-olefin constituting the amorphous α-olefin copolymer is a compound having a carbon number of 4 to 20, preferably 4 to 12, and is a linear compound. May also have a branch.

Specific examples of such α-olefins include 1-butene, 1-pentene, 1-hexene,
-Heptane, 1-octene, 1-nonene, 1-decene,
1-undecene, 1-dodecene, 3-methyl-1-butene, 3-methyl-1-pentene, 4-methyl-1-pentene, 4-methyl-1-hexene, 4,4-dimethyl-
1-hexene, 4,4-dimethyl-1-pentene, 4-
Ethyl-1-hexene, 3-ethyl-1-hexene and the like are exemplified. Among these, 1-butene, 1-hexene, 1-octene, 1-decene, and 4-methyl-1-pentene are preferable, and 1-butene, 1-hexene,
-Octene and 1-decene are preferred, and 1-butene is particularly preferred.

In the polymerization, these α-olefins may be used alone or in combination of two or more as long as they are within the above-mentioned ratio. For example, one kind of α-olefin (a) selected from α-olefins having 4 to 20 carbon atoms,
Α-olefin selected from the above,
Olefin (b) and (b) / (b) = 50 to 99 mol% /
It can be used in an amount ratio of 1 to 50 mol% ((a) + (b) = 100 mol%).

In this amorphous α-olefin-based copolymer, a polyene-based copolymer having two or more double bonds in addition to the α-olefin component unit as long as the object of the present invention is not impaired. It may contain a saturated compound (polyene) component unit, or a component unit composed of alcohol, carboxylic acid, amine and derivatives thereof.

[0015] The amorphous α-olefin copolymer is
Substantially no melting peak is measured as measured by a differential scanning calorimeter (DSC). Therefore, the amorphous α-olefin-based copolymer composition and the thermoplastic resin composition produced therefrom have excellent transparency and impact resistance.

The amorphous α-olefin copolymer is 13
Its intrinsic viscosity [η] measured in decalin at 5 ° C. is usually 0.01 to 10 (dl / g), preferably 0.05 to 10
It is desirable to be in the range of 10 (dl / g). When the intrinsic viscosity [η] is within the above range, an amorphous α-olefin copolymer having excellent properties such as weather resistance, ozone resistance, heat aging resistance, low temperature properties, and dynamic fatigue resistance is obtained. .

The molecular weight distribution measured by GPC is 4.0 or less, preferably 1 to 4, more preferably 1 to 4.
3. Here, the molecular weight distribution is represented by a weight average molecular weight (M
w) and the number (Mw / Mn) of the number average molecular weight (Mn), and the molecular weight is a value converted using standard polystyrene. When the molecular weight distribution is within this range, transparency, scratch resistance and impact resistance are improved, which is preferable.

This amorphous α-olefin-based copolymer is
It has a single glass transition temperature and the glass transition temperature Tg measured by a differential scanning calorimeter (DSC) is usually 40 ° C. or lower, preferably 20 ° C. or lower, particularly preferably 0 ° C. or lower. Is desirable. When the glass transition temperature Tg is in the above-mentioned range, excellent cold resistance and low-temperature properties are obtained.

The amorphous α-olefin copolymer has an iodine value of usually 0 to 150, preferably 0 to 150.
It is desirably in the range of 100. When it is within this range, when the thermoplastic resin composition containing the copolymer is partially or wholly crosslinked and used, the crosslinking speed is increased, so that the obtained molded article is Low temperature properties are improved.

< Amorphous α-olefin copolymer (A)
Production of Amorphous α-Olefin Copolymer (A) is a titanium catalyst comprising a solid titanium catalyst component and an organic aluminum compound, a vanadium catalyst comprising a soluble vanadium compound and an organic aluminum compound, It can be produced using a metallocene catalyst or the like. Preferred examples include ethylene, propylene,
An α-olefin having 4 to 20 carbon atoms and, if necessary, a monomer such as a polyene-based unsaturated compound having two or more double bonds (an ethylenically unsaturated compound) or the like coexists, and a metallocene-based compound to be described below is used. It can be produced by polymerizing in the presence of a catalyst.

The metallocene catalyst comprises the following components. (1): Transition metal complex (a) represented by formula (I) or (II) (2): Compound capable of forming an ionic complex by reacting with transition metal M in (a) (ionized ion (B), organoaluminum compound (c), and organoaluminum oxy compound (aluminoxane)
At least one compound selected from (d).

<Transition Metal Complex (a)> First, the transition metal complex (a) used in the present invention is represented by the formula (I) or (I)
It is a compound represented by I).

[0023]

Embedded image Here, M is Ti, Zr, Hf, Rn, Nd, Sm or Ru, preferably Ti, Zr, Hf.

Cp ¹ and Cp ² are ligands having a cyclopentadienyl skeleton such as a cyclopentadienyl group, an indenyl group, a fluorenyl group or a derivative group thereof bonded to M by π bond. The ligand having a dienyl skeleton is an alkyl group, a cycloalkyl group,
It may have a substituent such as a trialkylsilyl group or a halogen atom.

X ¹ and X ² are anionic ligands or neutral Lewis base ligands which may be the same or different from each other and are a hydrogen atom or a halogen atom,
Or a hydrocarbon group containing not more than 20 carbon atoms, silicon atoms or germanium atoms, an alkoxy group, an aryloxy group, a sulfonic acid-containing group (—SO ₃ Ra, wherein Ra is substituted with an alkyl group or a halogen atom. Alkyl, aryl, halogen-substituted aryl
An aryl group substituted with an alkyl group or an alkyl group), a silyl group or a germyl group.

Y is a ligand containing a nitrogen, oxygen, phosphorus or sulfur atom. Z is C, O,
It is a B, S, Ge, Si or Sn atom or a group containing these atoms. It is preferably any of carbon, oxygen and silicon, and Z may have a substituent such as an alkyl group or an alkoxy group, and the substituents of Z may combine with each other to form a ring. Z and Y may combine to form a condensed ring.

The following examples can be given as examples of the transition metal complex compound represented by the formula (I). (Dimethyl (t-
Butylamide) (tetramethyl-η5-cyclopentadienyl) silylene) titanium dichloride, ((t-butylamide) (tetramethyl-η5-cyclopentadienyl) -1,2-ethanediyl) titanium dichloride, (dimethyl (phenylamide) ) (Tetramethyl-η5-cyclopentadienyl) silylene) titanium dichloride, (dimethyl (t-butylamide) (tetramethyl-η5-cyclopentadienyl) silylene) titanium dimethyl, (dimethyl (4-methylphenylamide) ( Tetramethyl-η5
-Cyclopentadienyl) silylene) titanium dichloride, (dimethyl (t-butylamide) (η5-cyclopentadienyl) silylene) titanium dichloride, (tetramethyl (t-butylamide) (tetramethyl-η5-cyclopentadienyl) Disilylene) titanium dichloride.

The following examples can be given as examples of the transition metal complex compound represented by the formula (II). Cyclohexylidene-bis (indenyl) dimethylzirconium, cyclohexylidene-bis (indenyl) zirconium dichloride, isopropylidene-bis (indenyl) zirconium dichloride, isopropylidene (cyclopentadienyl-fluorenyl) zirconium dichloride, diphenylsilylene-bis ( Indenyl) zirconium dichloride, methylphenylsilylene-bis (indenyl)
Zirconium dichloride, rac-dimethylsilylene-bis (2-methyl-1-indenyl) zirconium dichloride, rac-dimethylsilylene-bis (4,7-dimethyl-1-
Indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2,4,7-trimethyl-1-indenyl)
Zirconium dichloride, rac-dimethylsilylene-bis (2,4,6-trimethyl-1-indenyl) zirconium dichloride,

Rac-dimethylsilylene-bis (4-phenyl-1-indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2-methyl-4-phenyl-1-
Indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2-methyl-4- (α-naphthyl) -1
-Indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2-methyl-4- (β-naphthyl)-
1-indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2-methyl-4- (1-anthryl)
1-indenyl) zirconium dichloride and the like.

In the above compounds, metallocene compounds in which zirconium metal is replaced by titanium metal or hafnium metal can also be exemplified. The above-mentioned metallocene compounds can be used alone or in combination of two or more.

The metallocene compound as described above can be used by being supported on a particulate carrier. Examples of the particulate carrier include SiO ₂ , Al ₂ O ₃ , B ₂ O ₃ , MgO, Zr
O ₂ , CaO, TiO ₂ , ZnO, SnO ₂ , BaO, T
inorganic carriers such as hO, polyethylene, polypropylene,
Organic carriers such as poly-1-butene, poly-4-methyl-1-pentene, and styrene-divinylbenzene copolymer can be used. These particulate carriers can be used alone or in combination of two or more.

<Ionized Ionic Compound (b)> The ionized ionic compound is a compound which reacts with the transition metal M in the transition metal complex (a) to form an ionic complex,
Examples of such ionized ionic compounds include Lewis acids, ionic compounds, borane compounds and carborane compounds.

As the Lewis acid, a compound represented by BR ₃ (where R is a phenyl group or a fluorine atom which may have a substituent such as a fluorine atom, a methyl group and a trifluoromethyl group) is used. No. For example, trifluoroboron, triphenylboron, tris (4-fluorophenyl) boron, tris (3,5-difluorophenyl) boron, tris (4-fluoromethylphenyl)
Boron, tris (pentafluorophenyl) boron, tris (p-tolyl) boron, tris (o-tolyl) boron, tris (3,5-dimethylphenyl) boron and the like can be used.

Examples of the ionic compound include trialkyl-substituted ammonium salts, N, N-dialkylanilinium salts,
Examples thereof include dialkyl ammonium salts and triaryl phosphonium salts. Specifically, as the trialkyl-substituted ammonium salt, for example, triethylammonium tetra (phenyl) boron, tripropylammonium tetra (phenyl) boron, tri (n-butyl) ammonium tetra (phenyl) boron and the like can be used.

Examples of the dialkylammonium salt include di (1-propyl) ammonium tetra (pentafluorophenyl) boron and dicyclohexylammonium tetra (phenyl) boron. Further, as an ionic compound, triphenylcarbenium tetrakis (pentafluorophenyl) borane
And N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, ferrocenium tetra (pentafluorophenyl) borate and the like can be used.

As the borane compound, decaborane (1
4), bis [tri (n-butyl) ammonium] nonaborate, bis [tri (n-butyl) ammonium] decaborate, bis [tri (n-butyl) ammonium] bis (dodecahydride dodecaborate) Metal borane anion salts such as nickelate (III) can be used.

The carborane compounds include 4-carbanonaborane (14) and 1,3-dicarbanonaborane (1
3), bis [tri (n-butyl) ammonium] bis (undecahydride-7-carboundecaborate)
G) Salts of metal carborane anions such as nickelate (IV).

These ionized ionic compounds can be used alone or in combination of two or more. The ionized ionic compound can be used by being supported on the above-mentioned particulate carrier.

<Organic Aluminum Compound (c)> As the organoaluminum compound to be added as required, a compound having at least one Al-carbon bond in the molecule can be used. Such compounds include, for example,
An organoaluminum compound represented by the general formula (III) is exemplified.

(R ¹ ) _m Al (O (R ² )) _n H _p X _q (III) (wherein, R ¹ and R ² each usually have 1 to 15 carbon atoms,
It preferably represents 1 to 4 hydrocarbon groups, which may be the same or different, X represents a halogen atom, and m represents 0
<M ≦ 3, n is 0 ≦ n <3, p is 0 ≦ p <3, and q is 0 ≦
q <3, and m + n + p + q =
3. )

<Organic aluminum oxy compound (aluminoxane) (d)>
A conventionally known aluminoxane may be used, or a benzene-insoluble organic aluminum oxy compound as exemplified in JP-A-2-78687.

The conventionally known aluminoxane (aluminoxane) is specifically a compound represented by the following general formula (IV) or (V).

Embedded image

In the formula, R ³ is a hydrocarbon group such as a methyl group, an ethyl group, a propyl group and a butyl group, preferably a methyl group, an ethyl group, particularly preferably a methyl group. m
Is an integer of 2 or more, preferably an integer of 5 to 40.

Here, the aluminoxane has the formula (OAl (R
⁴⁾⁾ represented alkyloxy aluminum units (where it alkyloxy aluminum units and formula represented by (OAl (R ^5)), but R ⁴ and R ⁵ are the same hydrocarbon group as R ^3, R ⁴ and R ⁵ represent different groups.). The organic aluminum oxy compound may contain a small amount of an organic compound of a metal other than aluminum.

The amorphous α-olefin-based copolymer is prepared by subjecting ethylene, propylene, an α-olefin having 4 to 20 carbon atoms and, if necessary, two or more double copolymers in the presence of the above-mentioned metallocene catalyst. It is usually obtained by copolymerization in a liquid phase in the presence of a polyene-based unsaturated compound having a bond. In this case, a hydrocarbon solvent is generally used, but the above-mentioned monomer may be used as the solvent. The copolymerization can be carried out by either a batch method or a continuous method.

When the copolymerization is carried out by a batch method using a metallocene catalyst, the concentration of the metallocene compound in the polymerization system is usually 0.00005 per liter of polymerization volume.
-1 mmol, preferably 0.0001-0.5 mmol.

The organoaluminum oxy compound is represented by the molar ratio (Al / M) of the aluminum atom (Al) to the transition metal atom (M) in the metallocene compound, and is 1 to 1
0000, preferably 10 to 5000.

The ionized ionic compound is represented by a molar ratio of the ionized ionic compound to the metallocene compound (ionized ionic compound / metallocene compound) of 0.1.
It is used in a ratio such that it becomes 5 to 20, preferably 1 to 10.

When an organoaluminum compound is used, it is used in a concentration of usually about 0 to 5 mmol, preferably about 0 to 2 mmol, per liter of polymerization volume.

The copolymerization reaction is usually carried out at a temperature of -20 to 15
0 ° C, preferably 0 to 120 ° C, more preferably 0 to
In the range of 100 ° C., the pressure exceeds 0 and is ~ 80 kg / cm
² , preferably above 0 and up to 50 kg / cm ² .

The reaction time (average residence time when the copolymerization is carried out by a continuous method) varies depending on conditions such as the catalyst concentration and the polymerization temperature, but is usually 5 minutes to 3 hours, preferably 10 minutes to 1.5 hours.

Monomers for copolymerization of ethylene, propylene, α-olefins having 4 to 20 carbon atoms and, if necessary, polyene unsaturated compounds having two or more double bonds.
Is ethylene / propylene / α having a specific composition as described above.
-Each is supplied to the polymerization system in such an amount that an olefin / polyene unsaturated compound copolymer (amorphous α-olefin copolymer) is obtained; In addition, at the time of copolymerization,
Molecular weight regulators such as hydrogen can also be used. The amorphous α-olefin-based copolymer is usually obtained as a polymerization solution containing the same, and is treated by a conventional method to obtain an amorphous α-olefin-based copolymer.

< Crystal nucleating agent (B) > As the crystal nucleating agent, conventionally known phosphorus-based, sorbitol-based,
Carboxylic acids, rosins and other compounds can be used arbitrarily. Next, these nucleating agents will be described. (1) Examples of the aromatic phosphate ester salt include compounds represented by the following general formula (VI).

[0054]

Embedded image

Wherein R ¹ is oxygen, sulfur or a divalent hydrocarbon group having 1 to 10 carbon atoms, R ² and R ³ are hydrogen or a hydrocarbon group having 1 to 10 carbon atoms, R ² and R ³ may be the same or different, and R ² may combine with each other, R ³ may combine with each other, or R ² and R ³ may combine to form a ring;
Is a 1 to 3 valent metal atom, and n is an integer of 1 to 3. )

Specifically, sodium-2,2'-methylene-bis (4,6-di-tert-butylphenyl) phospho-
G, 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.

(2) An aromatic phosphate ester salt represented by the following general formula (VII) can also be used.

Embedded image (Wherein R ⁴ is hydrogen or a hydrocarbon group having 1 to 10 carbon atoms, M is a metal atom having 1 to 3 valences, and n is 1 to 3)
It is an integer of 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 their 2
Mixtures of more than one species can be exemplified.

(3) A benzylidene-based sorbitol represented by the following general formula (VIII) can also be used.

Embedded image (In the formula, R ⁵ is hydrogen 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-
Ethyl benzylidene sorbitol, 1,3-p-methylbenzylidene-2,4-benzylidene sorbitol, 1,3-p-
Ethylbenzylidene-2,4-benzylidene sorbit
1,3-p-methylbenzylidene-2,4-p-ethylbenzylidenesorbitol, 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 (P-n-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-ethylbenzylidenesorbitol, 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 mixtures of two or more of these.

In particular, 1,3,2,4-dibenzylidene sorbite
1,3,2,4-di (p-methylbenzylidene) sorbitol
1,3,2,4-di (p-ethylbenzylidene) sorbitol
1,3-p-chlorobenzylidene-2,4-p-methylbenzylidene sorbitol, 1,3,2,4-di (p-chlorobenzylidene) sorbitol, and two or more thereof. Mixtures are preferred. Among these, 1,3,2,4-dibenzylidene sorbitol is more preferred.

Among the benzylidene sorbitols described above, a compound represented by the following formula (IX) can be mentioned as a preferred example.

Embedded image (In the formula, R ⁶ represents a methyl group or an ethyl group, and may be the same or different.)

(4) As the aromatic carboxylic acid compound,
Aluminum hydroxydi-p- represented by the following formula (X)
T-butyl benzoate and the like can be mentioned.

Embedded image

The metal salts of aromatic carboxylic acids and aliphatic carboxylic acids include aluminum benzoate, p-t-
Aluminum butyl benzoate, sodium adipate, sodium thiophenecarboxylate, sodium pyro-recarboxylate, and the like.

(5) Examples of the rosin-based crystal nucleating agent include a metal salt of rosin acid, which is a reaction product of rosin acid and a metal compound. Examples of rosin acids include natural rosins such as gum rosin, tall oil rosin and wood rosin; disproportionated rosin, hydrogenated rosin, dehydrogenated rosin, polymerized rosin, rosin modified with α, β-ethylenically unsaturated carboxylic acid, and the like. Various modified rosins; purified products of the natural rosin,
A purified product of the modified rosin can be exemplified.

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 acid,
Acrylic acid, methacrylic acid and the like can be mentioned.

Of these, at least one rosin acid selected from the group consisting of natural rosin, modified rosin, purified products of natural rosin, and purified products of modified rosin is preferable. Here, the rosin acid is a plurality of resin acids selected from pimaric acid, sandaracopimaric acid, parastolic 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 forms a metal salt by reacting with rosin acid include compounds having a metal element such as sodium, potassium and magnesium and forming a salt with the rosin acid. Specific examples include chlorides, nitrates, acetates, sulfates, carbonates, oxides, hydroxides, and the like of the above-mentioned metals.

(6) Examples of the high-melting polymer include polyvinylcycloalkanes such as polyvinylcyclohexane and polyvinylcyclopentane, poly-3-methyl-1-pentene, poly-3-methyl-1-butene, polyalkenylsilane and the like. .

(7) As inorganic compounds, silica, diatomaceous earth, alumina, titanium oxide, magnesium oxide, pumice powder, pumice balloon, aluminum hydroxide, magnesium hydroxide, basic magnesium carbonate, dolomite, calcium sulfate, titanium sulfate Examples include calcium oxide, barium sulfate, calcium sulfite, talc, clay, mica, asbestos, glass fiber, glass flake, glass beads, calcium silicate, montmorillonite, bentonite, graphite, aluminum powder, and molybdenum sulfide.

(8) Further, brominated biphenyl ether, cyclic triethylene glycol terephthalate and the like can be used as a crystal nucleating agent.

< Amorphous α-olefin-based copolymer composition > The amorphous α-olefin-based copolymer composition according to the present invention comprises (A) 100% by weight of the amorphous α-olefin-based copolymer. 0.001 to 5 parts by weight, preferably 0.01 to 2 parts by weight, of (B) a crystal nucleating agent is blended and formed.

Further, the composition may contain a weather-resistant stabilizer, a heat-resistant stabilizer, an antistatic agent, an anti-slip agent, an anti-blocking agent, an anti-fogging agent, a lubricant, Additives such as dyes, plasticizers, antioxidants, hydrochloric acid absorbents, antioxidants, and the like, or other synthetic resins and rubbers may be added as necessary.

The amorphous α-olefin copolymer composition of the present invention can be obtained by mixing the above-mentioned components at a fixed ratio. At the time of mixing, a method of mixing using a Henschel mixer, a V-blender, a ribbon blender, a tumbler blender, or the like, or thereafter, using a single-screw extruder, a twin-screw extruder, a kneader, a Banbury mixer, or the like. A method of melting and kneading can be adopted.

Such an amorphous α-olefin-based copolymer composition can be used by itself for various molded articles, but is preferably blended with various thermoplastic resins to form a thermoplastic resin. It is to be used as a resin modifier.
By blending in a thermoplastic resin, a thermoplastic resin composition having an improved balance of transparency, flexibility, heat sealability, impact resistance, and the like can be obtained.

< Thermoplastic Resin Composition > The thermoplastic resin composition according to the present invention comprises (1) 1 to 60 parts by weight, preferably 10 to 6 parts by weight of the above-mentioned amorphous α-olefin copolymer composition.
0 parts by weight and (2) 40 to 99 parts by weight of a thermoplastic resin, preferably 40 to 90 parts by weight.

As the thermoplastic resin, polyolefin,
Crystalline thermoplastic resins such as polyamide, polyester and polyacetal, and non-crystalline thermoplastic resins such as polystyrene, acrylonitrile-butadiene-styrene copolymer (ABS resin), polycarbonate and polyphenylene oxide are used. .

Further, these thermoplastic resins can be used widely from flexible resins to hard resins. For example, a tensile modulus measured by a tensile test is 600 or more, preferably 600 to 3500, more preferably 80
Those having a pressure of 0 to 3200 MPa can be suitably used.

As the polyolefin, polyethylene,
Examples thereof include olefin homopolymers such as polypropylene, poly 1-butene, polymethylpentene, and polymethylbutene, and olefin copolymers such as propylene / ethylene random copolymer. Among them, polyethylene, polypropylene, and poly-1 -Butene is preferred.

Examples of the polyester include aromatic polyesters such as polyethylene terephthalate, polyethylene naphthalate and polybutylene terephthalate, polycaprolactone, polyhydroxybutyrate and the like. Among them, polyethylene terephthalate is particularly preferred.

Examples of the polyamide include aliphatic polyamides such as nylon-6, nylon-66, nylon-10, nylon-12 and nylon-46, and aromatic polyamides produced from aromatic dicarboxylic acids and aliphatic diamines. Nylon-6 is particularly preferred.

Examples of polyacetals include polyformaldehyde (polyoxymethylene), polyacetaldehyde, polypropionaldehyde, polybutyraldehyde, etc., with polyformaldehyde being particularly preferred.

The polystyrene may be a homopolymer of styrene or a binary copolymer of styrene with acrylonitrile, methyl methacrylate, and α-methylstyrene. The ABS resin contains a structural unit derived from acrylonitrile in an amount of 20 to 35 mol%, a structural unit derived from butadiene in an amount of 20 to 30 mol%, and a structural unit derived from styrene. From 40 to
Those containing in an amount of 60 mol% are preferably used.

Examples of the polycarbonate include bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, 2,2-bis (4-hydroxyphenyl) propane, and 2,2- Examples thereof include those obtained from bis (4-hydroxyphenyl) butane and the like.
Polycarbonates obtained from bis (4-hydroxyphenyl) propane are particularly preferred. As the polyphenylene oxide, it is preferable to use poly (2,6-dimethyl-1,4-phenylene oxide).

Among these thermoplastic resins, polyolefins are preferable, and propylene or ethylene homopolymers and copolymers are more preferable. Especially ASTM
The melt flow rate measured under a load of 2.16 kg according to D-1238 is 0.1 to 200 (g / 10 min).
A propylene-based or ethylene-based polymer is preferable.

The above-mentioned thermoplastic resins may be used alone or in combination of two or more. Further, other thermoplastic resins may be used in combination with the above-mentioned thermoplastic resin. Further, additives that may be blended with the amorphous α-olefin copolymer composition may be blended as necessary within a range that does not impair the object of the present invention.

The thermoplastic resin composition of the present invention can be produced by any known method, for example, an amorphous α-olefin copolymer (A), a crystal nucleating agent (B) And a thermoplastic resin, and other components added as desired, by melt-kneading using a single-screw or twin-screw extruder, a kneader, a Banbury mixer, or the like. In the present invention, an amorphous α-olefin-based copolymer composition is first prepared from an amorphous α-olefin-based copolymer and a crystal nucleating agent, and then a thermoplastic resin is blended with the amorphous α-olefin-based copolymer composition. It is preferable to prepare a resin composition.

[0093] In <adult form body> The present invention can be produced various molded articles of a thermoplastic resin composition described above. In particular, sheets, films, bottles, tubes, pipes, filaments and the like used in the field of packaging materials are suitable, and they are easily manufactured by extrusion molding, blow molding, injection molding, vacuum molding and the like. can do.
These molded articles may be used in an unstretched state or may be used after being stretched uniaxially or biaxially. The molded article is excellent in transparency and mechanical strength and has high heat sealing strength, and thus is particularly suitable for films and sheets.

The thermoplastic resin composition according to the present invention is transparent and flexible, and has excellent heat sealability and impact resistance, so that it can be suitably used for the following applications, for example. (1) Film: multilayer stretched film, multilayer unstretched film, laminate film, shrink film, stretch film, wrap film, protect film,
Retort film, porous film, barrier film, metallized film, agricultural film (2) Sheets and sheet molded products: wallpaper, foamed sheet,
Wire covering materials, prestar packaging materials, trays, stationery supplies, food containers, toys, cosmetic containers, medical equipment, detergent containers, flooring materials, cushion flooring materials, decorative sheets, shoe soles

(3) Blow molded product: bottle (4) Extruded product: tube, wire coating material, cable coating material, pipe, gasket material (5) Fiber: fiber, flat yarn (6) Nonwoven fabric and nonwoven fabric product: nonwoven fabric , Filters (7) Injection molded products: automotive interior skin materials, automotive exterior materials,
Sundries, home appliances, caps, containers, pallets (8) Modifiers: adhesives, lubricant additives, hot melt adhesives, toner release agents, pigment dispersants, asphalt modifiers (9 ) Others: Sealant, vacuum formed body, powder slash body

[0096]

The amorphous α-olefin copolymer composition according to the present invention is a composition excellent in transparency, flexibility, heat sealability and impact resistance by itself. It can be used for applications such as films. In addition, it can be used as a modifier for various thermoplastic resins. From the composition mixed with the thermoplastic resin, transparency, flexibility, heat sealability, and excellent balance of impact resistance are obtained. A molded article, particularly a molded article suitable for use in a packaging material is obtained.

[0097]

Next, the present invention will be described more specifically based on examples, but the present invention is not limited to these examples. First, the physical property test method will be described.

1. Tensile modulus (MPa) According to JIS K6301, use a JIS No. 3 dumbbell, span 30 mm, tensile speed 30 (mm / m
in) at 23 ° C.

2. Heat seal strength (g / 15mm
Width) Using a cast film molding machine, cylinder temperature 23
0 ° C, chill roll temperature 20 ° C, screw rotation speed 80rp
Under the condition of m, a test film having a width of 250 mm and a thickness of 50 μm was prepared. Next, using this film, a heat seal temperature of 120 ° C. and a heat seal pressure of 2 (kg / c) were used.
m ² ), heat-sealing was performed under the conditions of a heat-sealing time of 1 (sec), peeled off under the condition of a tensile speed of 300 (mm / min), and the heat-sealing strength was measured.

3. Film impact strength (J / m) Using a cast film molding machine, cylinder temperature 23
0 ° C, chill roll temperature 20 ° C, screw rotation speed 80rp
Under the condition of m, a test film having a width of 250 mm and a thickness of 50 μm was prepared. Next, the film impact strength was measured at 0 ° C. according to ASTM D-3420.

4. Haze (%) Cylinder temperature 23
0 ° C, chill roll temperature 20 ° C, screw rotation speed 80rp
Under the condition of m, a test film having a width of 250 mm and a thickness of 50 μm was prepared. Using a digital turbidimeter “NDH-20D” manufactured by Nippon Denshoku Industries Co., Ltd., ASTM D-1003
The haze of this film was measured in accordance with 5. JIS A hardness Based on JIS K7215.

6. Melting point (Tm) and glass transition temperature (Tg) (° C.) An endothermic curve of DSC is determined, and the temperature at the maximum peak position is defined as melting point Tm. When the base line is curved, the intersection between the initial base line and the curved line is defined as a glass transition point Tg. For the measurement, the sample was packed in an aluminum pan, heated to 200 ° C. at 100 ° C./min, kept at 200 ° C. for 5 minutes, and then cooled to −150 ° C. at 10 ° C./min.
/ Min was determined from an endothermic curve when the temperature was raised.

7. Intrinsic viscosity [η] (dl / g) Measured in decalin at 135 ° C. 8. Molecular weight distribution (Mw / Mn) The weight average molecular weight (Mw) and the number average molecular weight (Mn) were determined by GPC (gel permeation chromatography) using an orthodichlorobenzene solvent.
It was measured under the condition of ° C. From the values of Mw and Mn, M
The w / Mn value was calculated and determined.

(Synthesis Example 1) (Synthesis of Amorphous Ethylene / Propylene / 1-Butene Copolymer (A-1)) A 1.5-liter autoclave dried under reduced pressure and purged with nitrogen. Then, 675 ml of heptane was added at room temperature, and then 0.3 ml of a 1.0 mmol / ml toluene solution of triisobutylaluminum was converted to 0.3 mmol of aluminum atoms, and propylene was added with stirring. 28.5 liters (25 ° C., 1 atm), 1-butene 10 liters (2
(5 ° C., 1 atm), and the temperature was raised to reach 60 ° C.

Thereafter, the system was purged with ethylene at 5.9 kg / c.
The pressure was adjusted to m ² G, and a toluene solution (0.0001 mM / ml) of (dimethyl (t-butylamide) (tetramethyl-η5-cyclopentadienyl) silane) dichloride titanium synthesized by a known method was added. .6 ml,
(Triphenylcarbenium tetra (pentafluorophenyl) borate) in toluene solution (0.001 mM /
ml), and ethylene, propylene and 1-
Copolymerization of butene was started. At this time, the catalyst concentration was such that (dimethyl (t-butylamide) (tetramethyl-η5-cyclo-pentadienyl) silane) dichloride titanium was 0.00075 (mmol / liter) and triphenylcarbenium tetra (pentane) Fluorophenyl) borate was 0.0027 (mmol / liter).

During the polymerization, the internal pressure was maintained at 5.9 kg / cm ² G by continuously supplying ethylene. Fifteen minutes after the start of the polymerization, the polymerization reaction was stopped by adding methyl alcohol. After the depressurization, the polymer solution was taken out, and the polymer solution was washed with the aqueous solution obtained by adding 5 ml of concentrated hydrochloric acid to 1 liter of water at a ratio of 1: 1. The catalyst residue was transferred to the aqueous phase.

After allowing the catalyst mixed solution to stand, the aqueous phase was separated and removed, and further washed twice with distilled water, and the polymerization liquid phase was separated into oil and water. Next, the polymerization liquid phase separated from the oil and water was brought into contact with three times the volume of acetone under vigorous stirring to precipitate a polymer, which was then sufficiently washed with acetone, and a solid part (copolymer) was collected by filtration. 130 ° C, 350mm under nitrogen flow
Dried at Hg for 12 hours.

The yield of the ethylene / propylene / 1-butene copolymer (A-1) thus obtained was 110
g. The intrinsic viscosity [η] measured in decalin at 135 ° C. is 1.3 (dl / g), and the glass transition temperature T
g was -29 ° C, ethylene content was 30 mol%, 1-butene content was 11 mol, and molecular weight distribution (Mw / Mn) measured by GPC was 2.9. Under the above-mentioned DSC measurement conditions, substantially no melting peak was observed.

(Synthesis Example 2) (Synthesis of Amorphous Ethylene / Propylene / 1-Butene Copolymer (A-2)) In Synthesis Example 1, the amount of 1-butene was 13 liters (25 ° C., 1 atm), The same operation as in Synthesis Example 1 was performed except that the pressure of ethylene was changed to 5.5 kg / cm ² .

The yield of the obtained ethylene / propylene / 1-butene copolymer (A-2) was 103 g. 1
The intrinsic viscosity [η] measured in decalin at 35 ° C. is 1.
1 (dl / g), and the glass transition temperature Tg is -19 ° C.
The ethylene content was 22 mol%, the 1-butene content was 19 mol%, and the molecular weight distribution by GPC was 2.8. Under the above-mentioned DSC measurement conditions, substantially no melting peak was observed.

Example 1 Amorphous ethylene / propylene / 1-butene copolymer (A-1) 1 obtained in Synthesis Example 1
00 parts by weight and 1,3,2,4-di (p-methylbenzylidene)
And 1 part by weight of sorbitol and mixed by melt kneading to obtain an amorphous ethylene / propylene / butene copolymer composition (C-
1) A pellet was obtained.

Using the pellets, a hot plate temperature of 190 ° C.
After forming a sheet under the conditions of 6 minutes of residual heat and 2 minutes of pressurization (100 kg / cm ² ), the sheet was transferred to a press forming machine at a hot plate temperature of 20 ° C. and cooled by pressurization (100 kg / cm ² ) to obtain a 1 mm thick A sheet was prepared. Table 1 shows the physical properties of the obtained sheet.

(Example 2) In Example 1, the amorphous ethylene / propylene / 1-butene copolymer (A-1) was used instead of the amorphous ethylene / propylene / 1-butene copolymer (A-1). Except that 2) was used, an amorphous ethylene / propylene / 1-butene copolymer composition (C-2) was obtained in the same manner as in Example 1. Table 1 shows the physical properties of the obtained sheet.

Comparative Example 1 A 1 mm thick sheet of the amorphous ethylene / propylene / 1-butene copolymer (A-1) obtained in Synthesis Example 1 was prepared. Table 1 shows the physical properties of the sheet.

Comparative Example 2 A 1 mm thick sheet of the amorphous ethylene / propylene / 1-butene copolymer (A-2) obtained in Synthesis Example 2 was prepared. Table 1 shows the physical properties of the sheet.

(Example 3) 70 parts by weight of a propylene random copolymer (trade name: Grand Polypro F327BV) (PP) manufactured by Grand Polymer Co., Ltd., and the amorphous ethylene / propylene obtained in Example 1 -30 parts by weight of the 1-butene copolymer composition (C-1) was mixed and melt-kneaded to obtain a thermoplastic resin composition.

This composition had a tensile modulus of 140 MPa and a heat seal strength of 240 MPa at a seal temperature of 120 ° C.
(G / 15mm width) and the film impact strength is 60K
The haze was 1.1% in J / m.

(Embodiment 4) In Embodiment 3, Embodiment 1
The amorphous ethylene-propylene / 1-butene copolymer composition (C-1) obtained in Example 2 from the amorphous ethylene-propylene / 1-butene copolymer composition (C-1) obtained in
Except having changed to -2), the thermoplastic resin composition was obtained like Example 3.

This composition had a tensile modulus of 155 MPa and a heat seal strength of 200 at a seal temperature of 120 ° C.
(G / 15mm width) and the film impact strength is 45K
The haze was 1.3% in J / m.

Comparative Example 3 70 parts by weight of a propylene random copolymer manufactured by Grand Polymer Co., Ltd. (trade name: Grand Polypro F327BV) (PP) and the amorphous ethylene / propylene obtained in Synthesis Example 1 -30 parts by weight of 1-butene copolymer (A-1) were mixed and melt-kneaded to obtain a thermoplastic resin composition.

This composition has a tensile modulus of 135 MPa.
The heat seal strength is 24 at a seal temperature of 120 ° C.
0 (g / 15 mm width) and the film impact strength is 50
In KJ / m, the haze was 1.7%.

[0122]

[Table 1]

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08K 5/098 C08K 5/098 5/521 5/521 C08L 101/16 C08F 210/06 // C08F 210 / 06 C08L 101/00 (C08L 101/16 23:14) (C08F 210/06 210: 02 210: 08 210: 14)

Claims (9)

[Claims] An amorphous α-olefin copolymer (A) 1
A composition in which 0.001 to 5 parts by weight of a crystal nucleating agent (B) is blended with respect to 00 parts by weight, wherein the amorphous α-olefin-based copolymer (A) comprises (1) an ethylene component 1 unit
To 49 mol%, 50 to 98 mol% of propylene component units, and 1 to 4 of α-olefin component units having 4 to 20 carbon atoms.
9 mol% (here, the total amount of the components in the copolymer is assumed to be 100 mol%), and (2) its melting peak measured by differential scanning calorimetry (DSC). (3) Its intrinsic viscosity [η] measured in decalin at 135 ° C. is 0.01 to 10 (dl /
g), and (4) an amorphous α-olefin-based copolymer composition having a molecular weight distribution measured by GPC of 4 or less. 2. The method according to claim 1, wherein the α-olefin component having 4 to 20 carbon atoms is at least one selected from the group consisting of 1-butene, 4-methyl-1-pentene, 1-hexene, 1-octene and 1-decene. The amorphous α-olefin-based copolymer composition according to claim 1, which is a kind of olefin. 3. The amorphous α-olefin copolymer composition according to claim 1, wherein the α-olefin component having 4 to 20 carbon atoms is 1-butene. 4. The amorphous α-olefin-based copolymer (A) comprises (1) a transition metal complex (a) represented by the formula (I) or (II), and (2) It comprises at least one compound selected from a compound (b) capable of forming an ionic complex by reacting with the transition metal of a), an organic aluminum compound (c) and an organic aluminum oxy compound (d). The amorphous α-olefin-based copolymer composition according to any one of claims 1 to 3, which is a copolymer that can be produced in the presence of a catalyst system. Embedded image (Where M is Ti, Zr, Hf, Rn, Nd, Sm or Ru, and Cp ¹ and Cp ² are a cyclopentadienyl group, an indenyl group, a fluorenyl group or a derivative thereof which is π-bonded to M. X ¹ and X ² are
An anionic ligand or a neutral Lewis base ligand,
Y is a ligand containing a nitrogen atom, an oxygen atom, a phosphorus atom or a sulfur atom, and Z is C, O, B, S, Ge, S
i or Sn atom or a group containing those atoms. ) 5. The method according to claim 1, wherein the nucleating agent (B) is at least one compound selected from the group consisting of aromatic phosphate ester salts, benzylidene sorbitol compounds, aromatic carboxylate salts and metal rosinate salts. The amorphous α-olefin-based copolymer composition according to any one of claims 1 to 4, wherein 6. The benzylidene-based sorbitol nucleating agent is 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-methylbenzylidene sorbitol, and at least one compound selected from the group consisting of 1,3,2,4-di (p-chlorobenzylidene) sorbitol. The amorphous α- according to claim 5,
Olefin copolymer composition. 7. The amorphous α according to claim 1,
-A thermoplastic resin composition comprising 1 to 60 parts by weight of an olefin-based copolymer composition and 40 to 99 parts by weight of a thermoplastic resin. 8. The method according to claim 1, wherein said thermoplastic resin is ASTM D-1.
9. The heat according to claim 7, wherein the melt flow rate measured under a load of 2.16 kg according to 238 is a propylene-based or ethylene-based polymer in the range of 0.1 to 200 (g / 10 minutes). Plastic resin composition. 9. A molded article for a packaging material, which is formed from the thermoplastic resin composition according to claim 7.