JPH093266A - Ethylene / α-olefin copolymer composition - Google Patents

Abstract

(57) [Summary] [Purpose] Improved ethylene stability, color stability and corrosion resistance during processing, while maintaining excellent strength, resistance to environmental stress deterioration, transparency, etc. An olefin copolymer composition is provided. [Structure] Ethylene / α that satisfies the following (a) to (f)
-The olefin copolymer is blended with an antioxidant, more preferably a higher fatty acid metal salt or hydrotalcite, and further blended with a piperidyl group-containing hindered compound. (A) Density 0.86 to 0.96 g / cm ³ (b)
Melt flow rate (MFR) 0.01-50g / 1
0 min (c) molecular weight distribution (MW / Mn) 1.8-3.
5 (d) Composition distribution parameter Cb 1.10 to 2.00
(E) Ortho-dichlorobenzene (ODC at 25 ° C)
B) Amount X (% by weight) of soluble matter and density d and MFR satisfy a certain relationship. (F) Continuous temperature rising elution fractionation method (TRE
Multiple elution temperature-elution volume curves due to F)

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an ethylene / α-olefin copolymer composition, more specifically, while maintaining excellent strength, environmental stress deterioration resistance (ESCR), transparency, etc.
The present invention relates to an ethylene / α-olefin copolymer composition having improved heat stability during processing, color stability, corrosion resistance, etc., suitable for injection molding, blow molding, film molding,
The present invention relates to a composition suitable for use in various containers, lids, bottles, pipes, packaging materials and the like.

[0002]

2. Description of the Related Art Linear low-density polyethylene (LLDPE) produced by conventional Ziegler-type highly active catalyst is excellent in moldability and strength. Therefore, it can be molded into various containers and lids by injection molding, blow molding, film molding, etc. It is used for various purposes such as bottles, pipes, and packaging materials. In particular, linear low-density polyethylene polymer is branched low-density polyethylene (HPLDP
Since it is stronger and thinner than E), it can be used in a wider range of applications. However, recently, there is a demand to further reduce the thickness of the molded product to reduce the cost, and stronger strength is required. However, the one using the conventional Ziegler type catalyst has a wide composition distribution and still has insufficient strength, and there is a limit to thinning. There is also a drawback that the molded product is sticky because the low molecular weight component oozes out to the surface of the molded product.

In order to meet this demand, a so-called single-site catalyst has been developed, and an ethylene / α-olefin copolymer having a narrow molecular weight distribution and a narrow compositional distribution has been proposed. However, the ethylene / α-olefin copolymer has higher strength than conventional LLDPE, excellent low-temperature heat-sealing property and transparency, and has less stickiness on the film surface, but has a narrow molecular weight distribution. Since the viscosity is high, the heat generated during processing becomes intense, and gels are generated in the molded product due to heat deterioration,
This may cause a defective appearance of the molded product. Further, since the composition has a narrow composition distribution, the allowable range of molding process is narrow, and a short decrease in the molding temperature causes a short shot, which may cause poor appearance.

[0004]

The first object of the present invention is to obtain excellent impact strength, environmental stress deterioration resistance (ESCR),
Provided is an ethylene / α-olefin copolymer composition, which does not impair properties such as appearance, transparency, or a wide allowable range of molding conditions, has little thermal deterioration during processing, and does not cause deterioration of hue after long-term storage. Especially. The second purpose is to use the above composition to obtain impact strength, resistance to environmental stress deterioration, transparency, a wide range of allowable molding conditions, heat deterioration during processing, good hue, and corrosion of extruders and molds. The object is to provide a composition having low properties. A third object is to use the above composition and further synergistically improve the heat deterioration resistance without impairing the above properties.

[0005]

[Means for Solving the Problems] As a result of intensive studies to solve the above problems, the present inventors have found that a specific ethylene / α
-A composition that is less susceptible to thermal deterioration during processing without impairing properties such as impact strength, environmental stress deterioration resistance, and transparency from an olefin copolymer, and has excellent thermal stability and prevents yellowing during long-term storage, The present invention has been achieved by succeeding in obtaining a composition excellent in preventing metal corrosion.

That is, the present invention is, firstly, (A) (a) density 0.86 to 0.96 g / cm ³ , (b) melt flow rate (MFR) 0.01 to 50 g / 10 min,
(C) Molecular weight distribution parameter Mw / Mn 1.8-3.
5, (d) composition distribution parameter Cb 1.10 to 2.0
0, (e) Orthodichlorobenzene (O
DCB) Soluble content X (% by weight) and density d and MFR
Satisfies the following relation, a) d−0.008 × logM
When FR ≧ 0.93, X <2.0, b) d-0.00
When 8 × log MFR <0.93 X <9.8 × 10
³ x (0.9300-d + 0.008 x logMFR)
² + 2.0, (f) ethylene / α-olefin copolymer having plural peaks of elution temperature-elution amount curve by continuous temperature rising elution fractionation method (TREF), and (B) ethylene containing antioxidant -It is an α-olefin copolymer composition.

Secondly, the present invention provides (A) (a) density 0.8.
6 to 0.96 g / cm ³ , (b) melt flow rate (MFR) 0.01 to 50 g / 10 min, (c) molecular weight distribution parameter Mw / Mn 1.8 to 3.5, (d).
Composition distribution parameter Cb 1.10 to 2.00, (e)
The amount X (% by weight) of orthodichlorobenzene (ODCB) -soluble matter at 25 ° C., and the density d and MFR satisfy the following relationship: a) d−0.008 × log MFR ≧ 0.
In the case of 93 X <2.0, b) d−0.008 × log
When MFR <0.93 X <9.8 × 10 ³ × (0.
9300-d + 0.008 × logMFR) ² +2.
0, (f) Ethylene with multiple peaks on the elution temperature-elution volume curve by continuous temperature elution fractionation (TREF)
An ethylene / α-olefin copolymer composition comprising an α-olefin copolymer, (B) an antioxidant, and (C) one or more compounds selected from higher fatty acid metal salts or hydrotalcites.

Thirdly, the present invention is an ethylene / α-olefin copolymer composition comprising the above composition further containing (D) a hindered amine compound having a piperidyl group.

The details of the present invention will be described below.

The ethylene / α-olefin copolymer (A) in the present invention is a copolymer of ethylene and one or more kinds selected from α-olefins having 3 to 20 carbon atoms. The α-olefin having 3 to 20 carbon atoms is preferably one having 3 to 12 carbon atoms, specifically, propylene,
1-butene, 4-methyl-1-pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene and the like can be mentioned. The total content of these α-olefins is usually 30 mol% or less, preferably 20 mol%.
It is desirable to select within the following range.

The density (a) of the ethylene / α-olefin copolymer (A) of the present invention is 0.86 to 0.96 g / cm 3.
^3, preferably in the range of 0.88~0.945g / cm ^3, more preferably 0.90~0.93g / cm ^3. If the density is less than 0.86, the rigidity and heat resistance are poor, and
Impact resistance and environmental stress resistance deterioration (ESCR) when it exceeds 96
Is not enough.

The MFR (b) of the ethylene / α-olefin copolymer of the present invention is in the range of 0.01 to 50 g / 10 min, preferably 0.1 to 20 g / 10 min, more preferably 0.5 to 10 g / 10 min. Is desirable. If the MFR is less than 0.01 g / 10 min, the moldability is poor, and if it exceeds 50 g / 10 min, the impact resistance is
Mechanical strength such as environmental stress resistance deterioration decreases.

The method for calculating the molecular weight distribution Mw / Mn (c) of the ethylene / α-olefin copolymer of the present invention is to measure the weight average molecular weight (Mw) and the number average molecular weight (Mn) by gel permeation chromatography (GPC). ),
This ratio Mw / Mn is obtained.

The Mw / Mn of the ethylene / α-olefin copolymer of the present invention is 1.8 to 3.5, preferably 2.0 to 3.0, more preferably 2.2 to 2.8. It is desirable to be in the range. If Mw / Mn is less than 1.8, the moldability is poor, and if it exceeds 3.5, the impact resistance is poor.

The composition distribution parameter Cb (d) of the ethylene / α-olefin copolymer of the present invention is 1.10-2.
00, preferably 1.12 to 1.70, and more preferably 1.15 to 1.50. If it is less than 1.10, fluidity is apt to be deteriorated due to a decrease in molding temperature, and a defective appearance is apt to occur. If it is more than 2.00, transparency, shochu impact resistance, environmental stress deterioration resistance are deteriorated,
There are problems such as stickiness of the molded product, large heat shrinkage, and narrowing of the allowable range of molding conditions.

The method for measuring the composition distribution parameter Cb of the ethylene / α-olefin copolymer of the present invention is as follows.

A heat-resistant stabilizer is added to the sample, and the sample is heated and dissolved in ODCB at 135 ° C. so that the sample concentration becomes 0.2% by weight. This heated solution is transferred to a column filled with diatomaceous earth (Celite 545), filled, and then filled at 25 ° C at 0.1 ° C / min.
The sample is deposited and deposited on the surface of Celite. Next, while flowing ODCB at a constant flow rate through this column and gradually increasing the column temperature to 120 ° C. by 5 ° C., a solution in which the sample is dissolved is collected at each temperature. After cooling this solution, the sample is re-pillowed with methanol, filtered and dried to obtain a sample at each elution temperature. The weight fraction and the degree of branching (the number of branches per 1000 carbon atoms) of the separated sample are measured. 13C-
Determined by NMR.

For each fraction collected at 30 ° C. to 90 ° C. by such a method, the branching degree is corrected as follows. That is, the degree of branching measured against the elution temperature is plotted, and the correlation is approximated to a straight line by the least square method,
Create a calibration curve. The correlation coefficient of this approximation is large enough.
The value obtained from this calibration curve is defined as the degree of branching of each fraction. Note that, for a fraction collected at an elution temperature of 95 ° C. or higher, this correction is not performed because a linear relationship is not always established between the elution temperature and the degree of branching.

Next, the weight fraction w of each fraction
The i, the amount of change in the degree of branching _{b i} per the elution temperature 5 ° C. _{(b i}
-Bi _-1 ) to obtain the relative concentration c _i , and plot the relative concentration against the branching degree to obtain a composition distribution curve. This composition distribution curve is divided by a certain width, and the composition distribution parameter Cb is calculated from the following equation.

[0020]

(Equation 1)

Here, c _j and b _j are the relative density and branching degree of the j-th section, respectively. Composition distribution parameter Cb
Is 1.0 when the composition of the sample is uniform, and the value increases as the composition distribution spreads.

Many proposals have been made for the method of describing the composition distribution of the ethylene / α-olefin copolymer. For example, in Japanese Patent Application Laid-Open No. 60-88016, numerical processing is performed on the assumption that the cumulative weight fraction has a specific distribution (log normal distribution) with respect to the number of branches of each separated sample obtained by solvent separation of the sample. The ratio between the weight average branching degree (Cw) and the number average branching degree (Cn) is determined. The accuracy of this approximate calculation is low when the number of branches of the sample and the cumulative weight fraction deviate from the lognormal distribution, and the correlation coefficient R ² is considerably low when the measurement is performed on commercially available LLDPE, and the accuracy of the value is not sufficient. This Cw
/ Cn and Cb of the present invention have different definitions and measurement methods.

Amount X of ODCB-soluble component at 25 ° C. of the ethylene / α-olefin copolymer (A) of the present invention X
(E) shows the proportions of the highly branched component and the low molecular weight component contained in the ethylene / α-olefin copolymer, which is less because it causes a decrease in resistance and stickiness on the surface of the molded product. desirable. The amount of ODCB soluble matter is
It is affected by the α-olefin content and average molecular weight of the entire copolymer, that is, the density and MFR. Therefore, the amount X (wt%) of the ODCB soluble component is less than 2 wt%, preferably less than 1 wt%, when the relationship between the density d and MFR satisfies d−0.008 × logMFR ≧ 0.93. More preferably, it is less than 0.5% by weight.

The relationship between d and MFR is d-0.00.
X <9.8 when 8 × log MFR <0.93 is satisfied
× 10 ³ × (0.9300-d + 0.008 × logM
FR) ² +2.0, preferably X <7.
4 × 10 ³ × (0.9300-d + 0.008 × log
MFR) ² +1.0, more preferably X <5.6 × 1
^{0 3 × (0.9300-d +} 0.008 × logMF
R) ² +0.5.

The fact that the density, the MFR and the amount of the ODCB-soluble component satisfy the above-mentioned relations means that α contained in the whole copolymer.
-Indicates that the olefin is not ubiquitous.

The ODCB-soluble amount X at 25 ° C. is measured by the following method.

That is, 0.5 g of the sample is added to 20 ml of ODC.
In addition to B, heat at 135 ° C. for 2 hours to completely dissolve the sample, and then cool to 25 ° C. After leaving this solution at 25 ° C. overnight, the filtrate is collected by filtration through a Teflon filter. The absorption peak intensity near the wave number 2925 cm ⁻¹ of the asymmetric stretching vibration of methylene is measured for the filtrate, which is a sample solution, by an infrared spectroscope, and the sample concentration in the filtrate is calculated by a calibration curve prepared in advance. From this value, the ODCB-soluble matter at 25 ° C. is determined.

The ethylene / α-olefin copolymer of the present invention preferably has a plurality of peaks (f) in the elution temperature-elution amount curve determined by the continuous temperature rising elution fractionation method (TREF). 8 peaks on the high temperature side
It is particularly preferred that it is present between 5 ° C and 100 ° C.
The presence of this peak increases the melting point and the crystallinity, thereby improving the heat resistance and rigidity of the molded article. FIG. 1 shows the elution temperature-elution amount curve of the copolymer of the present invention, and FIG. 2 shows the elution temperature-elution amount curve of the copolymer with a commercially available metallocene catalyst. Both are significantly different.

The method of measuring TREF is as follows.
That is, a heat resistance stabilizer was added to the sample, and the sample was heated and dissolved in ODCB at 135 ° C. so that the sample concentration was 0.05% by weight.
After pouring 5 ml of this heated solution into a column filled with glass beads, it is cooled to 25 ° C. at a cooling rate of 0.1 ° C./min to deposit a sample on the surface of the glass beads. next,
While flowing ODCB through the column at a constant flow rate, the column temperature is raised at a constant rate of 50 ° C./hr, and samples that can be dissolved in the solution at each temperature are sequentially eluted. At this time, the sample concentration in the solvent was the wavenumber 29 of the asymmetric stretching vibration of methylene.
The absorption for 25 cm ⁻¹ is continuously detected with an infrared detector. From this concentration, an elution temperature-elution amount curve can be obtained.

Since the TREF analysis can continuously analyze the change in the elution rate with respect to the temperature change with a very small amount of sample, it is possible to detect a relatively fine peak which cannot be detected by the fractionation method.

The specific (A) ethylene / α-olefin copolymer of the present invention can be preferably produced by a polymerization method using the following catalysts E1 to E5.

That is, E1: general formula Me ¹ R ¹ _p (O
R ² ) _q X ¹ _4- pq A compound represented by the formula (Me ^{1 in the} formula)
Represents zirconium, titanium, and hafnium, R ¹ and R ² each represent a hydrocarbon group having 1 to 24 carbon atoms, X ¹ represents a halogen atom, and p and q each represent 0 ≦ P <4 and 0 ≦ p.
+ Q ≦ 4), E2: general formula M
_{^{e 2 R 3 m (OR 4}} ) n X 2 z-m-n compound represented by (wherein Me ² has periodic table I~III group element, ^{R 3} and ^{R 4} are each a carbon number 1 to 24 Hydrocarbon group, X ² is a halogen atom or a hydrogen atom (provided that when X ² is a hydrogen atom, Me ² is a group III element of the periodic table).
Where z is the valence of Me ² , and m and n are 0 respectively.
≦ m ≦ z, an integer satisfying the ranges of 0 ≦ n ≦ z, and 0 ≦ m + n ≦ z), E3: an organic cyclic compound having a conjugated heavy bond, and E4: an organic aluminum compound and water A modified organoaluminum compound having an Al-O-Al bond obtained by the reaction of E5: a catalyst obtained by bringing E5: an inorganic carrier and / or a particulate polymer carrier into contact with each other.

The general formula Me ¹ R ^{1 of the} above catalyst component (E1)
_In the formula of the compound represented by _p (OR ² ) _q X ¹ _4- pq, Me ¹ represents zirconium, titanium, or hafnium. The type of these transition metals is not limited, and a plurality thereof may be used, but it is particularly preferable that zirconium is contained from the viewpoint that the weather resistance of the copolymer is more excellent. R
¹ and R ² are each a hydrocarbon group having 1 to 24 carbon atoms, preferably 1 to 12 carbon atoms, and more preferably 1 to 12 carbon atoms.
8, specifically, an alkyl group such as a methyl group, an ethyl group, a propyl group, an isopropyl group, and a butyl group; an alkenyl group such as a vinyl group and an allyl group; a phenyl group, a tolyl group, a xylyl group; Aryl groups such as mesityl group, indenyl group and naphthyl group; and aralkyl groups such as benzyl group, trityl group, phenethyl group, styryl group, benzhydryl group, phenylbutyl group and neofuyl group. These may have branches. X
¹ represents a halogen atom such as fluorine, iodine, chlorine and bromine, and p and q are 0 ≦ p <4 and 0 ≦ q <, respectively.
4, satisfying a range of 0 ≦ p + q ≦ 4, preferably 0 ≦ p
The range is + q ≦ 4.

Examples of the compound represented by the general formula of the catalyst component (E1) include tetramethylzirconium, tetraethylzirconium, tetrabenzylzirconium,
Tetrapropoxy zirconium, tripropoxy monochloro zirconium, dipropoxy dichloro zirconium, tetrabutoxy zirconium, tributoxy monochloro zirconium, dibutoxy dichloro zirconium,
Examples thereof include tetrabutoxy titanium and tetrabutoxy hafnium, and two or more kinds of these may be mixed and used.

The above catalyst component (E2) has the general formula Me ² R ³
_m ^(OR ₄₎ n ^X ₂ wherein Me ² in the compound represented by the _x-m-n represents the periodic table I~III group element, lithium, sodium, potassium, magnesium, calcium, zinc, boron, Such as aluminum. R ³ and R ⁴ are each a hydrocarbon group having 1 to 24 carbon atoms, preferably a hydrocarbon group having 1 to 12 carbon atoms, more preferably a hydrocarbon group having 1 to 8 carbon atoms, and specifically, a methyl group, an ethyl group, Alkyl groups such as propyl group, isopropyl group and butyl group; alkenyl groups such as vinyl group and allyl group; aryl groups such as phenyl group, tolyl group, xylyl group, mesityl group, indenyl group and naphthyl group; benzyl group and trityl group , Phenethyl group, styryl group, benzhydryl group, phenylbutyl group, aralkyl group such as neophyll group, and the like. These may have branches. X ² is fluorine
It represents a halogen atom or hydrogen atom such as iodine, chlorine and bromine. However, when X ² is a hydrogen atom, Me ² is limited to a group III element of the periodic table exemplified by boron, aluminum and the like. Also, z
Represents the valence of Me ² , m and n are 0 ≦ m ≦ z,
An integer satisfying the range of 0 ≦ n ≦ z, and 0 ≦ m +
n ≦ z.

Examples of the compound represented by the general formula of the catalyst component (E2) include organic lithium compounds such as methyllithium and ethyllithium; dimethylmagnesium, diethylmagnesium, methylmagnesium chloride,
Organomagnesium compounds such as ethylmagnesium chloride; Organozinc compounds such as dimethylzinc and diethylzinc; Organoboron compounds such as trimethylboron and triethylboron; Trimethylaluminum, triethylaluminum, triisobutylaluminum, trihexylaluminum, tridecylaluminum, diethyl Examples thereof include derivatives of organic aluminum compounds such as aluminum chloride, ethyl aluminum dichloride, ethyl aluminum sesquichloride, diethyl aluminum ethoxide and diethyl aluminum hydride.

The organic cyclic compound having a conjugated double bond of the catalyst component (E3) is a cyclic ring having two or more conjugated double bonds, preferably 2 to 4 and more preferably 2 to 3. It has 1 or 2 or more, and the total carbon number is 4 to 2.
4, preferably 4 to 12 cyclic hydrocarbon compounds; wherein the cyclic hydrocarbon compounds are partially 1 to 6 hydrocarbon residues (typically, alkyl groups or aralkyl groups having 1 to 12 carbon atoms) A cyclic hydrocarbon compound substituted by; a compound having 2 or more, preferably 2 to 4, more preferably 2 to 3 rings having a conjugated double bond and having a total carbon number of 4 to 24 An organosilicon compound having a cyclic hydrocarbon group which is preferably 4 to 12; said cyclic hydrocarbon group being partly substituted with 1 to 6 hydrocarbon residues or an alkali metal salt (sodium or lithium salt) Includes organosilicon compounds. Particularly preferably, those having a cyclopentadiene structure in any of the molecules are desirable.

The preferred compounds include cyclopentadiene, indene, azulene and their alkyl, aryl, aralkyl, alkoxy or aryloxy derivatives. Moreover, the compound which these compounds couple | bonded (bridge | crosslink) through the alkylene group (The carbon number is 2-8 normally, Preferably 2-3) is also used suitably.

The organosilicon compound having a cyclic hydrocarbon group can be represented by the following general formula.

A _L SiR _4-L

Here, A represents the above-mentioned cyclic hydrogen group exemplified by a cyclopentadienyl group, a substituted cyclopentadienyl group, an indenyl group, and a substituted indenyl group, and R represents a methyl group, an ethyl group, a propyl group, an isopropyl group. Group, alkyl group such as butyl group; alkoxy group such as methoxy group, ethoxy group, propoxy group, butoxy group; aryl group such as phenyl group; aryloxy group such as phenoxy group;
It is represented by an aralkyl group such as a benzyl group and has 1 to 2 carbon atoms.
4, preferably 1 to 12 hydrocarbon residues or hydrogen, L is 1 ≦ L ≦ 4, preferably 1 ≦ L ≦ 3.

Specific examples of the organic cyclic hydrocarbon compound as the component (E3) include cyclopentadiene, methylcyclopentadiene, ethylcyclopentadiene and 1,3-.
Dimethylcyclopentadiene, indene, 4-methyl-
C7-C24 cyclopolyene or substituted cyclopolyene such as 1-indene, 4,7-dimethylindene, cycloheptatriene, methylcycloheptatriene, cyclooctatetraene, azulene, fluorene, methylfluorene, monocyclopentane Examples thereof include dienyl silane, biscyclopentadienyl silane, triscyclopentadienyl silane, monoindenyl silane, bisindenyl silane, and trisindenyl silane.

The modified organoaluminum compound having an Al--O--Al bond obtained by reacting the organoaluminum compound of the catalyst component (E4) with water is usually an aluminoxane by reacting an alkylaluminum compound with water. The modified organoaluminum referred to is obtained,
1 to 100, preferably 1 to 50 A's in the molecule
It contains an l-O-Al bond. The modified organoaluminum compound may be linear or cyclic.

The reaction of organoaluminum with water is usually carried out in an inert hydrocarbon. As the inert hydrocarbon,
Aliphatic, alicyclic and aromatic hydrocarbons such as pentane, hexane, heptane, cyclohexane, benzene, toluene and xylene are preferred.

The reaction ratio of water and the organoaluminum compound (water / Al molar ratio) is usually 0.25 / 1 to 1.2 / 1,
It is preferably 0.5 / 1 to 1/1.

Examples of the inorganic carrier and / or the particulate polymer carrier of the catalyst component (E5) include carbonaceous materials, metals, metal oxides, metal chlorides, metal carbonates or mixtures thereof, or thermoplastic resins, thermosetting resins. Etc. Suitable metals that can be used for the inorganic carrier include iron, aluminum, nickel and the like.

Specifically, SiO ₂ , Al ₂ O ₃ , Mg
O, ZrO ₂ , TiO ₂ , B ₂ O ₃ , CaO, ZnO,
BaO, ThO _2, etc. or a mixture thereof may be mentioned.
_{SiO 2 -Al 2 O 3, SiO} 2 -V 2 O 5, SiO 2
_{-TiO 2, SiO 2 -V 2 O} 5, SiO 2 -MgO,
Like SiO ₂ -Cr ₂ O ₃ and the like. Among these, those containing, as a main component, at least one component selected from the group consisting of SiO ₂ and Al ₂ O ₃ .

As the particulate polymer carrier, either a thermoplastic resin or a thermosetting resin can be used, and specifically, particulate polyolefin, polyester, polyamide, polyvinyl chloride, poly (meth) acrylic acid can be used. Methyl,
Examples include polystyrene, polynorbornene, various natural polymers, and mixtures thereof.

The above inorganic carrier and / or particulate polymer carrier can be used as they are, but preferably, as a pretreatment, these carriers are treated with an organoaluminum compound or a modified organoaluminum compound containing an Al--O--Al bond. It can also be used as the component (C5) after the contact treatment.

The ethylene / α-olefin copolymer of the present invention is produced by a gas phase method, a slurry method, a solution method or the like, and is not particularly limited to a one-step polymerization method or a multi-step polymerization method.

The first (A21) of the other ethylene-based polymer of (A2) of the present invention has a density obtained by a conventional Ziegler type catalyst or Phillips catalyst (generally called Ziegler type catalyst) by an ionic polymerization method. 0.86-0.96g /
cm ³ of ethylene / α-olefin copolymer,
Specific examples include linear medium density polyethylene (MDPE), linear low density polyethylene (LLDPE), and linear ultra low density polyethylene (VLDPE).

The linear medium / low density polyethylene (MDPE, LLDPE) produced by the Ziegler type catalyst of the present invention has a density of 0.91 to 0.96 g / cm ³ , preferably 0.91.
To 0.94 g / cm ³ (LLDPE), and M
FR is 0.1 to 20 g / 10 minutes, preferably 0.5 to 1
5 g / 10 minutes, more preferably 0.7 to 10 g / 10
Selected in the range of minutes. Melt tension is 0.3-15.0
g, preferably 0.4 to 7.0 g, more preferably 0.5 to 5.0 g. Mw / Mn is 2.5 to 6, preferably 3 to 5.5.

The linear ultra-low density polyethylene (VLDPE) using the Ziegler type catalyst of the present invention has a density of 0.86 to
Less than 0.91 g / cm ³ , preferably 0.88 to 0.9
05 g / cm ³ and MFR are selected in the range of 0.1 to 20 g / 10 minutes, preferably 0.5 to 10 g / 10 minutes.

The linear ultra low density polyethylene (VLDP
E) is linear low density polyethylene (LLDPE) and ethylene / α-olefin copolymer rubber (EPR, EPD)
M), which has polyethylene exhibiting properties intermediate to those of M),
The density is preferably 0.86 to 0.91 g / cm ³ , and the maximum peak temperature (T _m ) by differential scanning calorimetry (DSC).
Is 60 ° C. or higher, and preferably a specific ethylene.α-having a property of boiling n-hexane insoluble content of 10% by weight or more.
Olefin copolymer, at least titanium and / or
Alternatively, the high crystalline portion of the linear low density polyethylene and the amorphous portion of the ethylene / α-olefin copolymer rubber are polymerized by using a catalyst composed of a vanadium-containing solid catalyst component and an organoaluminum compound. It is a resin that has the characteristics of the former, such as mechanical strength and heat resistance, and the characteristics of the latter, such as rubber elasticity and low-temperature impact resistance, coexist in a well-balanced manner.

Ethylene / α-by the above Ziegler type catalyst
The α-olefin of the olefin copolymer has a carbon number of 3 to 12, preferably 3 to 10, specifically, propylene, butene-1,4-methylpentene-.
1, hexene-1, octene-1, decene-1, dodecene-1 and the like.

The content of these α-olefins is preferably selected in the range of 40 mol% or less.

Second ethylene-based polymer of the present invention
(A22) is a branched low-density polyethylene (HPLDPE) produced by high-pressure radical polymerization, an ethylene / vinyl ester copolymer, or a copolymer with ethylene / α, β-unsaturated carboxylic acid or a derivative thereof.

The above-mentioned HPLDPE has an MFR of 0.1 to 2
It is 0 g / 10 minutes, preferably 0.5 to 15 g / 10 minutes, and more preferably 1.0 to 10 g / 10 minutes. Within this range, the melt tension of the composition is in an appropriate range, and film formation is easy. The density is 0.91 to 0.94 g /
cm ³ , preferably 0.912 to 0.935 g / c
m ³ , more preferably 0.912 to 0.930 g / c
m ³ and the melt tension is 1.5 to 25 g, preferably 3
-20 g, more preferably 3-15 g. The melt tension is an elasticity item of the resin, and in the above range, it is easy to mold in the case of hollow molding or film molding.

The Mw / Mn is 3.0 to 10, preferably 4.0 to 8.0.

The ethylene / vinyl ester copolymer of the present invention means vinyl propionate, vinyl acetate, vinyl caproate, vinyl caprylate, vinyl laurate, stearin, which is produced by a high pressure radical polymerization method and contains ethylene as a main component. It is a copolymer with vinyl ester monomers such as vinyl acrylate and vinyl trifluoroacetate. Among them, particularly preferred is vinyl acetate (EVA). That is, a copolymer comprising 50 to 99.5% by weight of ethylene, 0.5 to 50% by weight of a vinyl ester, and 0 to 49.5% by weight of another copolymerizable unsaturated monomer is preferable. In particular, the vinyl ester content is in the range of 3 to 20% by weight, preferably 5 to 15% by weight.

The MFR of these copolymers is from 0.1 to 20.
g / 10 minutes, preferably 0.3-10 g / 10 minutes, and melt tension of 2.0-25 g, preferably 3-20 g.
It is.

A typical example of the copolymer of ethylene of the present invention with an α, β-unsaturated carboxylic acid or its derivative is ethylene / (meth) acrylic acid or its alkyl ester copolymer. These comonomers include acrylic acid, methacrylic acid, methyl acrylate,
Methyl methacrylate, ethyl acrylate, ethyl methacrylate, propyl acrylate, propyl methacrylate,
Isopropyl acrylate, isopropyl methacrylate,
-N-butyl acrylate, -n-butyl methacrylate,
Examples thereof include cyclohexyl acrylate, cyclohexyl methacrylate, lauryl acrylate, lauryl methacrylate, stearyl acrylate, stearyl methacrylate, glycidyl acrylate, and glycidyl methacrylate. Among these, (meta) is particularly preferable.
Examples thereof include alkyl esters of acrylic acid such as methyl and ethyl (EEA). In particular, the (meth) acrylic acid ester content is 3 to 20% by weight, preferably 5 to 15%.
% By weight.

The MFR of these copolymers is 0.1 to 20.
g / 10 minutes, preferably 0.3-10 g / 10 minutes, and melt tension of 2.0-25 g, preferably 3-20 g.
It is.

The mixing ratio of the above-mentioned component (A2) and component (A) (this is the component (A1)) is 100 (A1) component.
20% by weight or less, and 80% by weight or less of the component (A2). When importance is attached to impact strength, resistance to environmental stress deterioration, transparency, etc., it is desirable to use the component (A1) as the main component, but strength,
It is desirable to appropriately blend the component (A2) in consideration of processability and economic efficiency while having transparency to some extent. To obtain a molded product by extrusion molding, (A
Since the melt tension of the component (1) is small, the die swell tends to be small and the parison and the pipe at the time of melting tend to be unstable. It is desirable to blend the component (A2), and especially (A22).
It is desirable to add 5 to 10% by weight of the components. Also T-
In die molding or extrusion lamination, the thickness is uneven at both ends of the film due to neck-in, and the yield deteriorates.

As the antioxidant which is the component (B) used in the present invention, known antioxidants are used, and among them, hindered phenol compounds, organic phosphite compounds, organic phosphonite compounds and the like are preferably used. Is. Specific examples of the hindered phenol antioxidant include 2,6-di-t-butyl-4-methylphenol, 2-t-butyl-4-methoxy-phenol, n-octadecyl-3- (3 ′, 5'-di-t-butyl-4'-hydroxyphenyl) propionate,
2,2'-ethylidene-bis (2,4-t-butylphenol), 4,4'-thiobis (3-methyl-6-t-)
Butylphenol), 1,3,5-trimethyl-2,
4,6-Tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene, Tris (3,5-di-t-butyl-4-hydroxybenzyl) isocyanurate, Tris (4-t-butyl) -2,6-Di-methyl-3-hydroxybenzyl) isocyanurate, tetrakis- [methylene-3- (3 ', 5'-di-t-butyl) -4'-
Hydroxy-phenyl) propionate] methane, 3,
9-bis [1,1-di-methyl-2- {β- (3-t-
Butyl-4-hydroxy-5-methylphenyl) propionyloxy} ethyl] -2,4,8,10-tetraoxaspiro [5,5] undecane. Especially 3,
9-bis [1,1-di-methyl-2- {β- (3-t-
Butyl-4-hydroxy-5-methylphenyl) propionyloxy} ethyl] -2,4,8,10-tetraoxaspiro [5,5] undecane, tris (3,5-di-t-butyl-4-) Hydroxybenzyl) isocyanurate, 1,3,5-trimethyl-2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl)
Benzene is preferably used because it hardly changes in hue even during long-term storage. These are 0.01 to 1.0 with respect to 100 parts by weight of the ethylene / α-olefin copolymer composition.
Parts by weight, preferably 0.02 to 0.3 parts by weight are added and used. If the amount is less than 0.01 parts by weight, the resin does not have an antioxidant effect and the resin is apt to be thermally deteriorated.

Examples of the organic phosphite compound include organic phosphite compounds represented by the following general formula (II) or (III).

[0067]

Embedded image

(R ₁ , R ₂ and R ₃ represent hydrogen or an alkyl group, an aryl group, an alkaryl group, an aralkyl group or an alkylthio group which are the same or different from each other)

[0069]

Embedded image

(R ₄ and R ₅ are the same or different aryl groups or alkaryl groups)

Examples of the phosphite represented by the general formula (II) include trisisodecylphosphite, tristridecylphosphite, triphenylphosphite and tris (2,4-di-t-butylphenyl) phosphite. , Tris nonyl phenyl phosphite, tris (mixed mono, dinonyl phenyl) phosphite, tris biphenyl phosphite, tricyclohexyl phosphite, diphenyl isodecyl phosphite, trilauryl trithiophosphite, tris (octyl thiopropyl) phosphite , Dilauryl hydrogen phosphite and the like.

Examples of the phosphite represented by the general formula (III) include bistridecyl pentaerythritol diphosphite, distearyl pentaerythritol diphosphite, bis (nonylphenyl) pentaerythritol diphosphite, and di (2,4). -Di-t-butylphenyl) pentaerythritol diphosphite, di (2,2
6-di-t-butyl-4-methyl) pentaerythritol diphosphite and the like.

As the phosphite other than the general formulas (II) and (III), 4,4'-isopropylidene-diphenolalkylphosphite, tetratridecyl 4,
4'-butylidene bis (3-methyl-6-t-butylphenol) diphosphite, hexatridecyl 1,1,
3-Tris (2-methyl-4-hydroxy-5-t-butylphenyl) butane triphosphite and the like can be mentioned.

Examples of the organic phosphonite compound include phosphonite compounds represented by the following general formula (IV) or (V).

[0075]

Embedded image

[Wherein, R ₆ and R ₇ are the same or different hydrocarbons each having 1 to 4 carbon atoms]. ]

[0077]

Embedded image

[In the formula, R ₈ , R ₉ and R ₁₀ are the same or different hydrocarbons each having 1 to 4 carbon atoms. ]

A typical compound represented by the general formula (V) is tetrakis (2,4-di-butylphenyl).
-4,4'-biphenylene phosphonite is mentioned.

The blending ratio of the above components used in the present invention is
The amount is 0.005 to 5 parts by weight, preferably 0.01 to 2 parts by weight, based on 100 parts by weight of the polyolefin. 0.00
If the amount is less than 5 parts by weight, the resin does not have an antioxidant effect and the resin is easily deteriorated by heat, and if the amount exceeds 5 parts by weight, the effect reaches a ceiling and is uneconomical or causes deterioration of hue.

The above-mentioned organic phosphite compound and organic phosphonite compound may be used alone, but when they are used in combination with a phenolic antioxidant, the composition has a stability against heat due to a synergistic effect, particularly heat resistance during high temperature molding. Significantly improved. Further, the phenolic antioxidant is stored for a long time or yellows due to aging under high temperature and high humidity, but by using these organic phosphite compounds and organic phosphonite compounds together, the color stability is remarkably improved. Considering the effect of (1), it is desirable to add them together.

The higher fatty acid metal salt which is the component (C) used in the present invention includes lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, linoleic acid,
Examples thereof include salts of fatty acids such as linolenic acid and metals such as lithium, sodium, magnesium, calcium and zinc, and calcium stearate is particularly preferable. These fatty acid metal salts absorb chlorine contained in the catalyst residue and not only have a rust preventive effect on the extruder and the mold,
Further addition is preferable because it has the effect of reducing the friction between the molten resin and the metal and reducing the retention of the resin in the molding machine to prevent the generation of fish eyes due to thermal deterioration.
At the same time, these are also used as a mixture of a higher fatty acid metal salt and a fatty acid in order to prevent deterioration of the hue when the resin is heated. Examples of these fatty acids include the above fatty acids, and among these, a 1: 1 mixture of stearic acid and calcium stearate is most preferably used. The amount of component (C) used in the present invention is 0.05 to 5 parts by weight, preferably 0.1 to 2 parts by weight, based on 100 parts by weight of the polyolefin. If the amount is less than 0.05 parts by weight, the rust preventive effect is not obtained, and if the amount exceeds 5 parts by weight, the effect not only reaches a ceiling but also causes the generation of foreign matters and deterioration of hue.

The hydrotalcites as the component (C) used in the present invention are double salt compounds represented by the following formula.

(M ²⁺ ) _1-x Al _x (OH) ₂ (A
ⁿ⁻ ) _{x / n} · mH ₂ O

[0085] (where 0 <x ≦ 0.5, m: real number M ^2+: Mg, Ca or ^{Zn, A n-: n} value anion)

[0086] Any of natural products and synthetic products as these compounds are also used but, particularly ^{M 2+} is ^{Mg, A n-}
A synthetic product having CO ₃ ²⁻ is desirable. The blending composition of the above components used in the present invention is 0.01 to 1 part by weight, preferably 0.02 to 100 parts by weight of the polyolefin.
It is 0.08 part by weight. The carbonate in this compound is easily replaced with chlorine, and has a function of absorbing chlorine remaining as a catalyst component and reducing metal corrosion due to chlorine. 0.
If the amount is less than 01 parts by weight, the anticorrosive effect is not obtained, and if the amount is more than 1 part by weight, the effect not only reaches a level but also causes gelation and hue deterioration. Further, it is preferable that the component is used in combination with the metal salt of the higher fatty acid, because it has the effect of improving heat resistance deterioration with a smaller addition amount as compared with the case where it is used alone. When the polymerization is carried out using a catalyst containing no chlorine, the addition of this component can be omitted.

The (D) piperidyl group-containing hindered amine-based compound of the present invention synergistically improves the performance of the antioxidant when it is added in addition to at least the phenol-based antioxidant of the component (B). It is desirable to add in addition to the above components. Among these compounds, those having a 2,2,6,6-tetramethylpiperidyl group represented by the following general formula I are preferable.

[0088]

[Chemical 6]

(Wherein R ₁ is hydrogen, an alkyl, alkenyl, aralkyl or alkoxyl group, R ₂ is hydrogen,
Represents oxygen. )

When R _{2 of the} general formula I is hydrogen, it means H ₂ , and when oxygen, it means ═O. The residue to which the general formula I binds is not particularly limited, and examples thereof include a carboxylic acid residue and an amine residue.

Specific examples of the hindered amine compound having piperidyl include bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate and tetrakis (2,2,6,6-tetramethyl-4-). Piperidyl)-
1,2,3,4-butanetetracarboxylate, bis (2,2,6,6-pentamethyl-4-piperidyl)-
Di (tridecyl) -1,2,3,4-butanetetracarboxylate, 1- (2-hydroxyethyl) -2,
Polycondensate of 2,6,6-tetramethyl-4-piperidylethanol and dimethyl succinate, 1,6-bis (2,2
2,6,6-Tetramethyl-4-piperidylamino) hexane and 2,4-dichloro-6-t-octylamino-
Polycondensate of s-triazine, poly [{6- (1,1,
3,3-Tetramethylbutyl) imino-1,3,5-triazine-2,4-diyl)} {2,2,6,6-tetramethyl-4-piperidyl) imino} hexamethylene {2,2,2 6,6-Tetramethyl-4-piperidyl) imino}, bis- [1,2,2,6,6-pentamethyl-
4-piperidyl] sebacate, 2- {3,5-di-t-
Butyl-4-hydroxybenzyl) -2-butylmalonate bis 1,2,2,6,6-pentamethyl-4-piperidyl), mixed {1,2,2,6,6-pentamethyl-4-piperidyl / Tridecyl} -1,2,3,4-
Butane tetracarboxylate, mixed {1, 2,
2,6,6-pentamethyl-4-piperidyl / β, β,
β ′, β ′ Tetramethyl-3,9- [2,4,8,10
-Tetraoxazaspiro (5,5) undecane] diethyl} -1,2,3,4-butanetetracarboxylate, bis (1-octyloxy-2,2,6,6-tetramethyl-4-piperidyl) Sebacate etc. are mentioned.

By adding an ultraviolet absorber to the composition of the present invention, its weather resistance can be improved. Specific examples of the ultraviolet absorber include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone and 5,5′-methylenebis (2-hydroxy-4-methoxybenzophenone. ) And the like, 2-hydroxybenzophenones, 2- (2′-hydroxy-5′-methylphenyl) benzotriazole, 2- (2′-hydroxy-5′-t-octylphenyl) benzotriazole, 2- (2 ′) -Hydroxy-3 ', 5'-di-t-butylphenyl) -5-chlorobenzotriazole, 2-
(2'-Hydroxy-3'-t-butyl-5'-methylphenyl) -5-chlorobenzotriazole, 2,2 '
-Benzotriazoles such as methylenebis (4-t-octyl-benzotriazole) phenol, resorcinol monobenzoate, 2,4-di-t-butylphenyl-3'-5'-di-t-butyl-4'-hydroxy Benzoate, hexadecyl-3-5-di-t-butyl-
Examples thereof include benzoates such as 4-hydroxybenzoate.

The copolymer composition of the present invention is a composition which is less susceptible to heat deterioration and hue deterioration during molding, and is less likely to cause corrosion of the extruder screw, barrel or mold, and can be used for injection molding or hollow molding. Suitable for molding and film molding, used for various containers, lids, bottles, pipes, packaging materials, etc.

In the composition of the present invention, in addition to the above components, if necessary, a heavy metal deactivator, a nucleating agent, a metal soap,
An acid absorbent, a pigment, a filler, a plasticizer, an epoxy compound, a foaming agent, a flame retardant, a processing aid, a polar group-containing polyolefin and the like can be included.

[0095]

Next, the present invention will be described in more detail by way of examples, which should not be construed as limiting the invention thereto. The test methods performed are shown below.

(Physical Property Test Method) Density: According to JIS K6760. Melt flow rate: Based on JIS K6760. Thermal stability (deterioration time): Pellets were kneaded at 210 ° C. in an air stream using a Labo Plastomill manufactured by Toyo Seiki Co., Ltd., and the time until the torque sharply increased was measured as the oxygen induction period. Color stability: Pressed sheet with a thickness of 2 mm
After being exposed to a thermo-hygrostat at a temperature of 80 ° C. and a relative humidity of 90% for 2 weeks, the yellowness (according to JISK7103) was measured,
The one having a small change rate (color difference) from the initial yellowness before exposure is excellent. Rust test: Pellets were melted in a 230 ° C. oil bath under a nitrogen stream for 3 hours, a soft iron plate was immersed in a molten resin for 2 hours, the soft iron plate was taken out, and the resin adhering to the iron plate was peeled off, followed by 80 ° C. Then, the iron plate is left for 20 hours in a thermo-hygrostat having a relative humidity of 90% to promote rust. Further, it was dried in a desiccator containing silica gel for 1 day, and the weight increase amount (mg) of the soft iron plate was taken as the rust generation amount. Tensile Impact Test: A 1.5 mm-thick sheet injection-molded under the following conditions was prepared, S-type dumbbells were punched in the MD and TD directions, and the strength was measured according to ASTM D1822. Environmental stress deterioration resistance (ESCR): A sheet having a thickness of 3.0 mm was prepared by hot pressing and measured according to ASTM D1693. It was indicated by the time when half of all samples had cracks. Spiral flow test: This was performed as a measure of the susceptibility to a short shot due to a slight decrease in resin temperature. The mold for spiral flow was attached to the injection molding machine, and the fluidity in the mold was measured under the following injection conditions. The longer the spiral flow length, the less likely it is that the appearance will deteriorate.

(Injection molding conditions)

(Polymerization of Ethylene / α-Olefin Copolymer A) Preparation of Solid Catalyst Purified toluene was added to a catalyst preparation device (No. 1) equipped with an electromagnetic induction stirrer under nitrogen, and then dipropoxydichlorozirconium (Zr (OPr ) ₂ Cl ₂ ) (28 g) and methylcyclopentadiene (48 g) were added thereto, and 45 g of tridecylaluminum was added dropwise while maintaining the system at 0 ° C. After completion of the addition, the reaction system was maintained at 50 ° C. and stirred for 16 hours.
This solution is designated as solution A. Next, purified toluene was added to another catalyst preparation device with a stirrer (No. 2) under nitrogen, and the above solution A and then a 6.4 mol solution of methylaluminoxane in toluene were added and reacted. This is designated as solution B.

Next, under nitrogen, a preparer with a stirrer (No.
Purified toluene was added to 1) and then 400 ° C in advance.
After adding 1400 g of silica (manufactured by Fuji Devison Co., Ltd., grade # 952, surface area 300 m ² / g), which was calcined for a predetermined time, the whole amount of the solution B was added and stirred at room temperature. Then, the solvent was removed by nitrogen blowing to obtain a solid catalyst powder having good fluidity. This is designated as catalyst C.

Polymerization of Sample A1 Using a continuous fluidized bed gas phase polymerization apparatus, a polymerization temperature of 70
Copolymerization of ethylene and 1-butene was carried out at a temperature of 20 ° C. and a total pressure of 20 kgf / cm ² G. The polymerization was carried out by continuously supplying the catalyst C, and in order to keep the gas composition in the system constant, the polymerization was carried out while continuously supplying each gas.

The physical properties of the produced copolymer are shown below. Sample A1 MFR (g / 10 minutes): 8.0 Density (g / cm ³ ): 0.920 Maximum melting point (° C): 121 Molecular weight distribution (Mw / Mn): 2.5 ODCB soluble content (W%) ): 1.2 X (value of Formula 1) (W%): 4.8 Cb: 1.3 TREF peak number: multiple numbers

(Ethylene / α-olefin copolymer M1
Polymerization of) A stainless steel autoclave equipped with a stirrer was replaced with nitrogen, and purified toluene was added. Then, butene-
1 was added, and bus (n-butylcyclopentadienyl) zirconium dichloride (Zr 0.02 m
Mol) methylalumoxane [MAO] (MAO / Zr =
After adding a mixed solution of 100 [molar ratio]), the temperature was raised to 80 ° C. Next, ethylene was added to initiate polymerization. Polymerization was carried out for 1 hour while continuously polymerizing ethylene and maintaining the total pressure. In addition, these polymerizations were repeatedly produced in an amount necessary for Examples described later. Obtained ethylene butene
The physical properties of the 1 copolymer were as follows:

Sample M1 MFR (g / 10 min): 7.0 Density (g / cm ³ ): 0.920 Melting point (° C.): 113 Molecular weight distribution (Mw / Mn): 2.3 ODCB soluble content ( wt%): 0.3 X (value of Expression 1) (wt%): 4.6 Cb: 1.05 TREF peak number: Single

Resins used A1: the above A21: linear low density polyethylene by Ziegler catalyst (density = 0.923 g / cm ³ , MFR = 8.0 g / 1
0 minutes, trade name: Nisseki Linirex BJ5310 manufactured by Nippon Petrochemical Co., Ltd. A22: Low-density polyethylene by high-pressure radical polymerization (density = 0.920 g / cm ³ , MFR = 5.5 g / 1
0 minutes, product name: Nisseki Lexron J40, manufactured by Nippon Petrochemical Co., Ltd.) M1: The above

Additives Used Component (B) Hindered Phenol Antioxidant B-1: 2,6-Di-t-butyl-4-methylphenol (BHT, trade name of Yoshitomi Pharmaceutical Co., Ltd.) B- 2: Tetrakis- [methylene-3- (3 ', 5'-
Di-t-butyl) -4′-hydroxy-phenyl) propionate] methane (trade name Irganox 1010,
Ciba-Geigy Co., Ltd. phosphite-based antioxidant B-3: tris (2,4-di-t-butylphenyl) phosphite (trade name: Irgafos 168, Ciba-Geigy Co., Ltd.) phosphonite-based antioxidant B- 4: Tetrakis (2,4-di-t-butyl-5-methyl) -4,4'-biphenylene phosphonite (trade name GSY-P101, manufactured by Yoshitomi Pharmaceutical Co., Ltd.) Sulfur-based antioxidant AO-1 : Dilauryl-3,3 'thiodipropionate (trade name DLTP "Yoshitomi", manufactured by Yoshitomi Pharmaceutical Co., Ltd.) Component (C) C-1: Calcium stearate (manufactured by Kosei Co., Ltd.) C-2: Hydrotal Site (DHT-4A, manufactured by Kyowa Chemical Co., Ltd.) Component (D) D-1: poly [{6- (1,1,3,3-tetramethylbutyl) imino-1,3,5-triazine-2 , 4-ji )} {2,2,6,6-Tetramethyl-4-piperidyl) imino} hexamethylene {2,2,6,6-tetramethyl-4-piperidyl) imino} (trade name Chimassorb 944LD, Ciba Geigy (stock) )) D-2: mixed {1,2,2,6,6-pentamethyl-4-piperidyl / β, β, β ′, β ′ tetramethyl-3,9- [2,4,8,10 -Tetraoxazaspiro (5,5) undecane] diethyl} -1,2,3,4-
Butane tetracarboxylate (Product name ADEKA STAB L
A-63, manufactured by Asahi Denka Co., Ltd.

Experimental Example 1 In Experimental Examples 1 to 14 in Table 1, the component (B) was added and the effect on heat deterioration was examined.

In Experimental Example 1, 0.1 part by weight of (B1) was added to the powder of the copolymer (A1), the mixture was mixed by a Henschel mixer for about 30 seconds, and then granulated by an extruder. The heat deterioration time of the pellets was measured under the above conditions, and the rest was homogenized with a milling roll, cut into chips, and press-molded at 180 ° C. to obtain a sheet. About this sheet, color stability, tensile impact test, ES
CR and spiral flow tests were conducted. The results are shown in Table 1. The heat resistance stability, tensile impact strength, ESCR, and spiral flow tests are all good.

Experimental Example 2 The same operation as in Experimental Example 1 was performed with the composition shown in Table 1, and the results are also shown in Table 1. Heat resistance stability, tensile impact strength, E
Both SCR and spiral flow tests are good.

Experimental Examples 3 to 7 The same operation as in Experimental Example 1 was carried out with the composition shown in Table 1, and the results are also shown in Table 1. All of heat stability, color stability, tensile impact strength, ESCR, and spiral flow test are good. Experimental Examples 5 and 6 in which a phenol type and a phosphite type or a phosphonite type were used together as the B component are excellent in heat resistance stability.

Experimental Example 8 The same operation as in Experimental Example 1 was carried out without adding the component (B), and the results are shown in Table 1. The heat resistance stability is poor.

Experimental Example 9 (A21) was used as the resin component, the same operation as in Experimental Example 1 was carried out without adding the component (B), and the results are shown in Table 1.
Poor heat resistance and low tensile impact strength.

Experimental Example 10 The same operation as in Experimental Example 5 was performed using (A21) as a resin component, and the results are shown in Table 1. The tensile impact strength is poor.

Experimental Example 11 Using (A22) as the resin component, the same operation as in Experimental Example 1 was carried out without adding the component (B), and the results are shown in Table 1.
Heat resistance stability, tensile impact strength and ESCR are poor.

Experimental Example 12 Using (A22) as a resin component, the same operation as in Experimental Example 1 was performed, and the results are shown in Table 1. Tensile impact strength, ESC
R is bad.

Experimental Example 13 (M1) was used as a resin component, the same operation as in Experimental Example 1 was carried out without adding the component (B), and the results are shown in Table 1. The heat resistance is poor, the spiral flow length is short, and it is necessary to raise the molding temperature by about 20 ° C. in order to make the spiral flow length similar to that of Experimental Example 1, and the allowable range of molding conditions is narrow.

Experimental Example 14 Using (M1) as a resin component, the same operation as in Experimental Example 5 was performed, and the results are shown in Table 1. The spiral flow test is bad.

Experimental Examples 15 to 19 In Experimental Examples 15 to 19 of Table 2, the effect on the rust generation when the component (C) was further added was examined. Experimental Examples 15 to 17 are color stability, heat resistance stability, tensile impact strength, E
Rust generation is good together with SCR. In Experimental Example 18, Experimental Example 6 in which the component (C) is not added is Experimental Examples 13 to 1.
It is compared with 5. As shown in Table 2, the amount of rust generated is large. In Experimental Example 19, (A21) component, (B2) (B
4) consists of components. The tensile impact strength and the amount of rust generated are poor.

Experimental Examples 20 to 29 Experimental Examples 20 to 29 in Table 3 are for investigating the synergistic effect on the heat resistance stability when the component (D) is further added. Experimental Examples 20 to 21 have good color stability, ESCR, and rust generation, and heat resistance is even better than Experimental Example 22 in which the component (D) is not added. In Experimental Example 23, (D) was added to the one to which (AO-1) was added as the (C) component. The improvement in heat stability is slight. In Experimental Examples 24 to 27, resin components (B), (C),
The component (D) is added. The heat resistance, color stability, rust test, tensile impact strength, ESCR and spiral flow test are all good. In Experimental Example 28, (A21) was used as the (A) component, and the (B), (C), and (D) components were added. Poor tensile impact strength. Experimental example 29 is (A)
(M1) is used as a component, and (B), (C), and (D) components are added. The spiral flow test is bad.

[0119]

EFFECT OF THE INVENTION By adding an antioxidant to an ethylene / α-olefin copolymer having a narrow molecular weight distribution and a moderately wide composition distribution, excellent impact strength of the ethylene / α-olefin copolymer is obtained. It is an object of the present invention to provide a composition which does not deteriorate properties such as environmental stress deterioration resistance and transparency, has little heat deterioration during processing, and does not cause deterioration of hue after long-term storage. Further, the addition of a compound having a specific tetramethylpiperidyl group to these compositions is intended to synergistically improve heat resistance without impairing the above-mentioned properties. Further, by adding an acid absorbent to the composition, a composition having good impact strength, resistance to environmental stress deterioration, transparency, molding workability, heat deterioration during processing, good hue, and little corrosion of extruders and molds Can be provided.

[0120]

[Table 1]

[0121]

[Table 2]

[0122]

[Table 3]

[Brief description of drawings]

FIG. 1 is an elution temperature-elution amount curve obtained by TREF of the copolymer used in the present invention.

FIG. 2 is an elution temperature-elution amount curve obtained by TREF of a copolymer with a metallocene catalyst.

Claims (6)

[Claims] 1. An ethylene / α-olefin copolymer satisfying (A) the following (a) to (f), (a) a density of 0.86 to 0.96 g / cm ³ (b) a melt flow rate (MFR). ) 0.01 to 50 g / 10 min (c) Molecular weight distribution (Mw / Mn) 1.8 to 3.5 (d) Composition distribution parameter Cb 1.10 to 2.00 (e) Orthodichlorobenzene (ODCB) at 25 ° C. The amount X (% by weight) of the soluble component and the densities d and MFR satisfy the following relationships: a) d-0.008 × log MFR ≧ 0.93 X <2.0 b) d-0.008 When xlogMFR <0.93 X <9.8 × 10 ³ × (0.9300−d + 0.008 × logMFR) ² +2.0 Formula 1) (f) Elution by continuous temperature-rising elution fractionation (TREF) Multiple peaks on temperature-elution volume curve And (B) an ethylene · alpha-olefin copolymer composition characterized in that it comprises an antioxidant. 2. The composition according to claim 1, further comprising:
(C) An ethylene / α-olefin copolymer composition containing one or more compounds selected from higher fatty acid metal salts or hydrotalcites. 3. An ethylene / α-olefin copolymer composition, wherein the composition according to claim 1 or 2 further comprises (D) a hindered amine compound having a piperidyl group. 4. The hindered amine compound having a piperidyl group (D) is represented by the following general formula I:
The ethylene / α- according to claim 3, which is a hindered amine compound having a 6,6-tetramethylpiperidyl group.
Olefin polymer composition. Embedded image (However, R represents hydrogen, alkyl, alkenyl, aralkyl or alkoxyl group or oxygen bond, and R ₂ represents hydrogen or oxygen.) 5. The ethylene / α-olefin copolymer of (A) as a resin component, wherein the composition according to any one of claims 1 to 4 further comprises (A2) another ethylene-based polymer shown below. At least one selected from coalesce 0 to 80% by weight
An ethylene / α-olefin copolymer composition comprising: [Ethylene-based polymer] (A21) ethylene / α-olefin copolymerization resistance with a Ziegler-type catalyst having a density of 0.86 to 0.96 g / cm ³ (A22) low-density polyethylene by high-pressure radical polymerization, ethylene / vinyl ester copolymerization Copolymer of ethylene and α, β-unsaturated carboxylic acid or its derivative 6. The (B) antioxidant is one or more compounds selected from the group consisting of a hindered phenol compound, an organic phosphite compound, and an organic phosphonite compound. The ethylene / α-olefin copolymer composition described in 1.