JPH08325333A - Ethylene-alpha-olefin copolymer - Google Patents

Abstract

PURPOSE: To obtain the subject copolymer having relatively broad compositional distribution in spite of narrow molecular weight distribution, containing little low-molecular weight component and amorphous component and having excellent physical properties and processability. CONSTITUTION: This copolymer has a density of 0.86-0.96g/cm<3> , a melt flow rate of 0.01-200g/10min, a molecular weight distribution (Mw/Mn) of 1.8-3.5 and a compositional distribution parameter Cb of 1.10-2.00 and preferably satisfies the formulas X<2.0 when d-0.008×logMFR>=0.93 or X<9.8×10<3> ×(0.9300-d+0.008×logMFR)<2> +2.0 when d-0.08×logMFR<0.93 wherein X is amount (wt.%) of fraction soluble in o-dichlorobenzene(ODCB) at 25 deg.C and (d) is density. The copolymer is produced preferably by polymerizing the monomers in the presence of a catalyst composed of a compound of formula Me<1> R<1> p (OR<2> )q X<1> (4-p-q) (Me<1> is Zr, Ti, etc.; R<1> and R<2> are each a 1-24C hydrocarbon group; X<1> is a halogen; 0<=P<4; 0<=p+q<=4), etc.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a novel ethylene / α-olefin copolymer having excellent physical properties and processability. More specifically, despite having a narrow molecular weight distribution, it has a relatively wide composition distribution and a low content of low molecular weight components and amorphous components, and is excellent in mechanical properties, moldability, optical properties and heat resistance. , In particular, film molded products such as various packaging films and original films for laminating produced by T-die molding, inflation film molding, etc.
Various containers by injection molding, various containers by hollow molding, etc.
It is intended to provide an ethylene / α-olefin copolymer suitable for injection moldings such as lids and containers, or for coating electric wires, cables, steel pipes and the like.

[0002]

2. Description of the Related Art Ethylene / α obtained by Ziegler type catalyst
-Linear low-density polyethylene (LLDPE), which is an olefin copolymer, is a high-pressure low-density polyethylene (HPL).
Compared to DPE), it has higher strength and toughness and is used in various applications such as films, sheets, hollow moldings and injection moldings, but higher strength is required to reduce the weight of molded products. There is. In recent years, a high-strength ethylene / α-olefin copolymer having a very narrow molecular weight distribution and composition distribution has been developed using a metallocene catalyst. However, these metallocene ethylene / α-olefin polymers have some drawbacks. For example, since the composition distribution is very narrow, the changes in viscosity and strength with respect to temperature are extremely rapid, and therefore the applicable range of temperature and extrusion conditions during molding is narrow, and molding is difficult. Further, the molded product also has drawbacks such as a heat resistance, a narrow temperature range for exhibiting an appropriate heat seal strength or a good hot tack strength. For example, in the field of films, sheets, etc., heat sealing is easy, and therefore it is often used as a bag by heat sealing, and hot tack characteristics are required for such applications. That is, there is a case where the seal portion is pulled and a load is applied immediately after heat sealing, such as when filling the contents, and the seal portion is peeled off. In such a case, a seal having a wide temperature range that enables heat sealing exhibiting a strong value against peeling immediately after sealing is preferable.

As an attempt to improve such a hot tack property, an attempt has been made to mix a polyethylene resin with a plurality of Ziegler type catalysts (for example, Japanese Patent Laid-Open No. Hei 3).
-207736, JP-A-3-207737). However, in this method, since the molecular weight distribution is broadened at the same time, improvement in strength cannot be expected.

Next, as a method of improving the molding processability of the polymer by the metallocene catalyst, an attempt is made to improve the melting characteristics of the resin by keeping the composition distribution narrow by using the metallocene catalyst having a plurality of ligands. (For example, JP-A-6-206939). However, there is a problem that the strength is lowered due to the broadening of the molecular weight distribution or the formation of long chain branches. Attempts have also been made to improve molding processability by using a mixed system of a metallocene-based catalyst and a Ziegler-based catalyst (for example, Japanese Patent Laid-Open No. 6-157631), but the sacrifice of strength is accompanied by the broadening of the molecular weight distribution.

[0005]

The object of the present invention is to provide a mechanical strength superior to LLDPE with a Ziegler type catalyst,
It has optical properties and, at the same time, has a low temperature heat-sealing property equivalent to that of the metallocene ethylene / α-olefin copolymer and transparency, and therefore has a heat resistance superior to that of the metallocene ethylene / α-olefin copolymer, It is intended to provide an ethylene / α-olefin copolymer having hot tack characteristics and moldability.

[0006]

Means for Solving the Problems The inventors of the present invention have made earnest studies in accordance with the above-mentioned object, and as a result, have a relatively broad composition distribution despite having a narrow molecular weight distribution, and also have a low molecular weight component and an amorphous component. Ethylene / α- with low content of ingredients
An olefin copolymer was produced, and the above object was achieved thereby.

That is, the present invention is, firstly, (A) the density d is 0.86 to 0.96 g / cm ³ , (B) the MFR is 0.01 to 200 g / 10 min, and the (C) Mw / Mn is The ethylene / α-olefin copolymer has a composition distribution parameter Cb of 1.8 to 3.5 and (D) of 1.10 to 2.00.

Secondly, the present invention (A) has a density d of 0.8.
6 to 0.96 g / cm ³ , (B) MFR is 0.01 to 2
00 g / min, (C) Mw / Mn is 1.8 to 3.5,
(D) The composition distribution parameter Cb is 1.10 to 2.0
0, (E) The amount X (wt%) of the ODCB soluble component at 25 ° C, the density d and the MFR are a) d-0.008xl
When ogMFR ≧ 0.93, X <2.0, b) d−
If 0.008 × logMFR <0.93, X <9.
8 × 10 ³ × (0.9300−d + 0.008 × log
It is an ethylene / α-olefin copolymer characterized by satisfying MFR) ² +2.0.

Thirdly, the present invention provides (A) the density d or 0.8.
6 to 0.96 g / cm ³ , (B) MFR is 0.01 to 2
00g / 10min, (C) Mw / Mn is 1.8-3.
5, (D) composition distribution parameter Cb is 1.10-2.
00, (E) The amount X (wt%) of the ODCB soluble component at 25 ° C, the density d and the MFR are a) d-0.008 x
When logMFR ≧ 0.93, X <2.0, b) d−
If 0.008 × logMFR <0.93, X <9.
8 × 10 ³ × (0.9300−d + 0.008 × log
MFR) ² +2.0, elution temperature by (F) TREF-
It is an ethylene / α-olefin copolymer characterized by satisfying a plurality of peaks in an elution amount curve.

The present invention will be described in more detail below. The ethylene / α-olefin copolymer of 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. Also, these α-
It is desirable that the total content of olefins is selected in the range of usually 30 mol% or less, preferably 3 to 20 mol%.

The density (A) of the ethylene / α-olefin copolymer of the present invention is 0.86 to 0.96 g / cm ³ , preferably 0.88 to 0.945 g / cm ³ , and more preferably 0. It is in the range of 90 to 0.930 g / cm ³ . If the density is less than 0.86, the rigidity and heat resistance are poor, and if it is 0.96 or more, the impact resistance is insufficient.

The MFR (B) of the ethylene / α-olefin copolymer of the present invention is 0.01 to 200 g / 10 min,
It is preferably 0.1 to 100 g / 10 min, and more preferably 0.2 to 50 g / 10 min. When the MFR is less than 0.01, the moldability is poor, and when it is 200 or more, the mechanical strength such as impact resistance is lowered.

The method of calculating the molecular weight distribution Mw / Mn (C) of the ethylene / α-olefin copolymer of the present invention is carried out by gel permeation chromatography (GPC) by weight average molecular weight (Mw) and number average molecular weight (Mn). Seeking
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 the Mw / Mn is less than 1.8, the moldability is poor, and if it is 3.5 or more, 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, the hot tack property is poor, and 2.
When it is 00 or more, the transparency may be lowered, and a polymer gel may be formed in the molded product.

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 temperature becomes 0.2% by weight. This heated solution was transferred to a column packed with diatomaceous earth (Celite 545) and filled to 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 by 5 ° C. to 120 ° 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 this separated sample are measured. Measurement of branching degree is 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 method of least squares,
Create a calibration curve. The correlation coefficient of this approximation is sufficiently large.
The value obtained from this calibration curve is the branching degree of each fraction. This correction is not performed for the fractions collected at an elution temperature of 95 ° C or higher, because the elution temperature and the degree of branching do not always have a linear relationship.

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}
-B _i-1 ) to obtain the relative concentration c _i , plot the relative concentration against the branching degree, and obtain a composition distribution curve. This composition distribution curve is divided with a constant 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 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 JP-A-60-88016, numerical processing is performed assuming that the cumulative weight fraction has a specific distribution (logarithmic normal distribution) with respect to the number of branches of each fractionated sample obtained by solvent fractionation 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.

In the ethylene / α-olefin copolymer of the present invention, the amount X of the ODCB-soluble component at 25 ° C. is the ratio of the highly branched component and the low molecular weight component contained in the ethylene / α-olefin copolymer. However, it is desirable that the amount is small because it causes deterioration of heat resistance and stickiness of the surface of the molded product. The amount of ODCB-soluble component is α of the whole copolymer.
Influenced by olefin content and average molecular weight, ie density and MFR.

Therefore, the amount X (wt%) of the ODCB-soluble component has a relationship between the density d and the MFR: d-0.008 × lo
When gMFR ≧ 0.93 is satisfied, it is less than 2% by weight, preferably less than 1% by weight, and more preferably 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.
-Indicating that the olefins are not ubiquitous.

The ODCB-soluble component X at 25 ° C. is measured by the following method. That is, sample 0.
5 g is added to 20 ml of ODCB and heated at 135 ° C. for 2 hours to completely dissolve the sample, and then cooled to 25 ° C. The solution is left at 25 ° C. overnight and then filtered through a Teflon filter to collect the filtrate. The filtrate, which is a sample solution, was analyzed by infrared spectroscopy for the wave number 2925c of the asymmetric stretching vibration of methylene.
The absorption peak intensity around m ⁻¹ is measured, and the sample concentration in the filtrate is calculated from the calibration curve prepared in advance. From this value, the ODCB-soluble component 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). High temperature peak is 85 ℃
It is particularly preferred that it is present between 1 and 100 ° C. The presence of this peak raises the melting point and crystallinity, and improves the heat resistance and rigidity of the molded body. FIG. 1 shows an elution temperature-elution amount curve of the copolymer of the present invention,
FIG. 2 shows an elution temperature-elution amount curve of a copolymer with a so-called metallocene catalyst.

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. 5 ml of this heated solution was injected into a column filled with glass beads, and then 25 ° C. at a cooling rate of 0.1 ° C./min.
Cool to 0 ° C. and deposit sample on glass bead surface. Next, while flowing ODCB at a constant flow rate through this column, the column temperature is raised at a constant rate of 50 ° C./hr to sequentially elute the sample soluble in the solution at each temperature. At this time, as for the sample concentration in the solvent, the absorption of the asymmetric stretching vibration of methylene at a wave number of 2925 cm ⁻¹ is continuously detected by 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 production of the specific ethylene / α-olefin copolymer of the present invention is carried out according to the above (A) to (D), preferably (A) to (E), more preferably (A) to (F). As long as the properties are satisfied, Ziegler catalyst, Phillips catalyst,
It may be produced with a metallocene catalyst or the like, but it is preferable to polymerize with a catalyst having the following C1 to C5.

That is, C1: 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 Zr, Ti, Hf, R ¹ and R ² each represent a hydrocarbon group having 1 to 24 carbon atoms, X ¹ represents a halogen atom,
p, q and r are integers satisfying the ranges of 0 ≦ p <4 and 0 ≦ p + q ≦ 4, respectively, C2: general formula Me ² R ³
A compound represented by _{m (OR} 4 _{) n} X ² _z-mn (wherein Me ² is an element of Group I to III of the periodic table, R ³ and R ^4).
Are each a hydrocarbon group having 1 to 24 carbon atoms, X ² is a halogen atom or a hydrogen atom (provided that when X ² is a hydrogen atom, M is
e ² represents only a group III element of the periodic table)
z represents the valence of Me ² , and m and n are each 0 ≦ m ≦.
z, an integer satisfying the range of 0 ≦ n ≦ z, and 0 ≦
m + n ≦ z), C3: an organic cyclic compound having a conjugated double bond, and C4: a modified organoaluminum compound containing an Al—O—Al bond obtained by the reaction of an organoaluminum compound and water, C5: an inorganic carrier. And / or a catalyst obtained by bringing the particulate polymer supports into contact with each other.

The above catalyst component (C1) has the general formula Me ¹ R ¹
Me < ¹ > shows Zr, Ti, and Hf in the formula of the compound represented by _p (OR < ² >) _qX < ¹ _{> 4-} pq. The type of these transition metals is not limited, and a plurality of transition metals may be used, but it is particularly preferable that Zr 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,
More preferably, it is a hydrocarbon group having 1 to 8 carbon atoms, 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. Aryl groups such as tolyl group, xylyl group, mesityl group, indenyl group and naphthyl group; aralkyl groups such as benzyl group, trityl group, phenethyl group, styryl group, benzhydryl group, phenylbutyl group and neophyl group. These may have branches. X ¹ represents a halogen atom such as fluorine, iodine, chlorine and bromine, and p and q satisfy the ranges of 0 ≦ p <4, 0 ≦ q <4, 0 ≦ p + q ≦ 4, and preferably 0 ≦ p + q ≦ The range is 4.

Examples of the compound represented by the above general formula of the catalyst component (C1) include tetramethylzirconium, tetraethylzirconium, tetrabenzylzirconium, tetrapropoxyzirconium, tripropoxymonochlorozirconium, dipropoxydichlorozirconium,
Examples thereof include tetrabutoxyzirconium, tributoxymonochlorozirconium, dibutoxydichlorozirconium, tetrabutoxytitanium, and tetrabutoxyhafnium. These may be used as a mixture of two or more.

The above catalyst component (C2) has the general formula Me ² R ³
_m ^(OR ₄₎ wherein Me ² in n ^X compounds represented by _{2 z-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, and more preferably a hydrocarbon group having 1 to 8 carbon atoms, and specifically, methyl group, ethyl group. Groups, 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 Examples thereof include aralkyl groups such as a trityl group, a phenethyl group, a styryl group, a benzhydryl group, a phenylbutyl group, and a neophyll group. 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 (C2) 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 (C3) 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, one having a cyclopentadiene structure in any of the molecules is desirable.

Examples of the above-mentioned suitable compounds include cyclopentadiene, indene, azulene or 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.

ALSiR 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 of the above component (C3) include cyclopentadiene, methylcyclopentadiene, ethylcyclopentadiene, 1,3-dimethylcyclopentadiene, indene, 4-methyl-1-indene, 4, 7-Dimethylindene, cycloheptatriene, methylcycloheptatriene, cyclooctatetraene, azulene, fluorene, methylfluorene-containing cyclopolyene or substituted cyclopolyene, monocyclopentadienylsilane, biscyclo Examples thereof include pentadienylsilane, triscyclopentadienylsilane, monoindenylsilane, bisindenylsilane, and trisindenylsilane.

The modified organoaluminum compound containing an Al--O--Al bond obtained by the reaction of the catalyst component (C4) organoaluminum compound with water is usually referred to as an aluminoxane by reacting an alkylaluminum compound with water. The modified organoaluminum obtained is obtained, and usually 1 to 100, preferably 1 to 50 Al in the molecule.
It contains a —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 preferable.

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.

The catalyst component (C5) inorganic carrier and / or particulate polymer carrier means a carbonaceous material, a metal, a metal oxide, a metal chloride, a metal carbonate or a mixture thereof, or a thermoplastic resin, a thermosetting resin or the like. Is mentioned. Suitable metals that can be used for the inorganic carrier include
Examples include iron, aluminum and nickel.

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 organic compound, either a thermoplastic resin or a thermosetting resin can be used, and specifically, particulate polyolefin, polyester, polyamide, polyvinyl chloride, poly (meth) acrylate, Examples thereof 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 method for producing 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 such as a one-step polymerization method and a multi-step polymerization method.

In the present invention, antioxidants, as well as nucleating agents, lubricants, antistatic agents, antifog agents, and Known additives such as pigments, ultraviolet absorbers and dispersants can be added. Further, the ethylene / α-of the present invention
The olefin copolymer can also be used by blending with other thermoplastic resins, for example, polyolefins such as low density polyethylene, medium density polyethylene, high density polyethylene and polypropylene.

[0052]

The ethylene / α-olefin copolymer of the present invention has mechanical strength and optical characteristics superior to those of the Ziegler-catalyzed ethylene / α-olefin copolymer.
Moreover, it has excellent properties such as hot tack property while maintaining low-temperature heat-sealing property and transparency of the ethylene / α-olefin copolymer with a metallocene catalyst. Especially, various products produced by T-die molding, inflation film molding, etc. It is suitable as a film molded product such as a packaging film and a laminate original fabric. Further, the ethylene / α of the present invention
-Olefin copolymers are used for containers such as mayonnaise, tubular containers for wasabi, etc., thin containers for interior such as cardboard, hollow molded products such as containers for liquid detergent, stoppers, caps, container lids, injection of ski shoes, etc. It is also suitable for applications such as moldings, wires, cables, and steel pipes. The ethylene / α-olefin copolymer of the present invention can also be used as various multilayer films or laminated sheets by a dry laminating method, a coextrusion method, or an extrusion laminating method.

[0053]

The present invention will be described in more detail by way of examples, which should not be construed as limiting the invention.

The test method used in this experimental example is as follows. (Physical property test method) Density: Based on JIS K6760. MFR: Based on JIS K6760. Measurement by DSC: A sheet having a thickness of 0.2 mm is formed by hot pressing and a sample of about 5 mg is punched out at 230 ° C. for 10 minutes.
After holding for min, cool to 0 ° C at 2 ° C / min, and then 10 again
The temperature is raised to 170 ° C. at a rate of ° C./min, and the temperature at the peak of the highest temperature peak that appears is the highest peak temperature Tm. Mw / Mn: GPC Waters 150 type Solvent: ODCB 135 ° C Column: Toso-GMHHR-H (S)

(Inflation Film Molding) The polymerized copolymer powder was granulated, and a die with a diameter of 100 mmφ and a lip gap of 2 mm was attached to a 50 mmφ LLDPE film-only molding machine, a blow ratio of 1.9 and a take-up speed of 20 m / min. A film having a thickness of 30 μm was molded under the molding conditions of the molding temperature of 200 ° C.

(Film Performance Evaluation) Dirt Impact Strength: In accordance with ASTM D1709. Tensile modulus: Attach the sample to the tensile tester,
The tensile modulus was determined from the stress and the cross-sectional area when the sample was pulled at a speed of 5 mm / min and elongated by 1%. Haze: According to ASTM D1003-61. Gloss: Compliant with JIS Z8741. Hot tack property: A 15 μm nylon base film was coated with an ether anchor coating agent, and the copolymer film produced by the film forming method was dry-laminated to obtain a composite film. This film is 25mm
It was cut out in a width and sandwiched in a hot plate heat seal tester having a seal bar width of 5 mm. A load of 45 g is placed on one end of the composite film via a pulley. Seal pressure 2k
² g of composite film at g / cm ² and sealing time of 0.5 seconds
The sheets are stacked and heat-sealed, the seal bar is opened, and the sealing is completed. Sealing is performed by changing the sealing temperature at several points.
The relationship between the temperature and the peeled distance was investigated. The shorter the peeled distance was, the wider the seal temperature range was, and the better the hot tack property was.

(Sheet Forming Method) The copolymer was homogenized with a roll and then cut into chips, which were press-molded at 180 ° C. to obtain sheets. (Molding conditions of test piece by injection molding machine) Injection molding machine
: Japan Steel Works, Ltd. JSW100 Mold clamping force 10
0TON Molding resin temperature: 220 ° C. Cushion molding mold temperature: 50 ° C. (Evaluation of sheet and injection test piece) Tensile impact test: Determined according to ASTM D1822. Tensile modulus: Attach the sample to the tensile tester,
The tensile elastic modulus was determined from the stress and the cross-sectional area when stretched by 1% at a rate of 5 mm / min. Tensile yield strength, fracture strength and tensile elongation: determined in accordance with JIS K6760.

Samples A1 to A5 used in Examples 1 to 5 were polymerized by the following method.

(Preparation of Solid Catalyst) Purified toluene was added to a catalyst preparation device (No. 1) equipped with an electromagnetic induction stirrer under nitrogen,
Then dipropoxydichlorozirconium (Zr (OP
28 g of r) ₂ C ₁₂ ) and 48 g of methylcyclopentadiene were added, 45 g of tridecylaluminum was added dropwise while maintaining the system at 0 ° C., and after completion of the addition, the reaction system was adjusted to 50
The mixture was kept at 0 ° C. and stirred for 16 hours. This solution is referred to as solution A. Next, under nitrogen, another stirrer catalyst preparation device (No.
2) Purified toluene was added to 2 and the above solution A and then a toluene solution of 6.4 mol of methylaluminoxane 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, the polymerization temperature was 70 ° C. and the total pressure was 20 kgf / c.
Copolymerization of ethylene and 1-butene was carried out with m ² G. The gas composition in the system is 1-butene / ethylene molar ratio 0.12,
The ethylene concentration was 60 mol%. The catalyst C was continuously supplied to carry out polymerization, and each gas was continuously supplied to keep the gas composition in the system constant. The physical properties of the produced copolymer are shown in Table 1.

(Polymerization of Sample A2) Polymerization was carried out in the same manner as in (A1) except that the molar ratio of 1-butene / ethylene was changed. The physical properties of the copolymer are shown in Table 1 together with the experimental results.

(Polymerization of Samples A3 to A5) (A3), (A
4) and (A5) are comonomer 1-pentene,
Polymerization was performed in the same manner as in (A1) except that 1-hexene and 4-methyl-pentene-1 were used. The physical properties of the copolymer are shown in Table 1 together with the experimental results.

(Polymerization of Samples A7 to A10) 1-Butene /
Polymerization was performed in the same manner as in (A1) except that the molar ratio of ethylene was changed. The physical properties of the copolymer are shown in Table 2 or Table 3 together with the experimental results.

(Polymerization of Sample B2) 25 L of purified toluene was placed in a 50 L pressure reactor equipped with a stirrer and purged with nitrogen.
Next, 183 g of butene-1 was added, and bis (n-
A mixed solution of butylcyclopentadienyl) zirconium dichloride and methylalumoxane [MAO] (Al /
Zr molar ratio = 500) was added as Zr so as to be 0.33 mmol, and then the temperature was raised to 80 ° C. Next, the polymerization was initiated so that the ethylene content was 9 kg / cm ² G. The total pressure is 9 kg / cm while continuously polymerizing ethylene.
Polymerization was carried out by maintaining the temperature at ² G for 1 hour to produce a copolymer.
The physical properties of the copolymer are shown in Table 1 together with the experimental results.

(Polymerization of Sample B8) 410 g of 1-butene
Polymerization was performed in the same manner as in (B2) except that the addition was performed. The physical properties of the copolymer are shown in Table 3 together with the experimental results.

Samples (B1) and (B
3), (B7) and (B9) are LLDPE or VLDPE obtained by copolymerizing ethylene and 1-butene by a gas phase method or a slurry method using titanium tetrachloride and a triethylaluminum catalyst. Further, (B4) is a commercially available Ultzex 3010F (manufactured by Mitsui Petrochemical Co., Ltd.). The physical properties are shown in Tables 1 to 3 together with the experimental results.

Examples 1 to 5 Table 1 shows a comparison of various physical properties after granulation according to the above procedure and then blown film molding.

Comparative Examples 1 to 4 In order to make a comparison with Examples 1 to 5, the same operations were performed using the resins shown in Table 1. The results are shown in Table 1. Comparative Example 1 had a dart impact strength and transparency, Comparative Example 2 had a low melting point and poor heat resistance as shown in Table 1, and Comparative Examples 3 and 4 were carried out in consideration of the type of α-olefin used. The dirt strength and transparency are inferior to those of Examples 3 and 4.

Example 6, Comparative Examples 5 to 6 The hot tack characteristics were measured using the film obtained in Example 2, and the comparative example 5 was measured using the film obtained in Comparative Examples 1 and 2.
Compared to 6. The results are shown in Table 3. Example 6 has a wide seal temperature range with a short peel distance.

Examples 7 to 8 and Comparative Examples 7 to 8 Sheets were molded by the above-mentioned method and physical properties were tested. Comparative Example 7 is inferior in tensile impact strength, and Comparative Example 7 is inferior in heat resistance.

Examples 9 to 10 and Comparative Example 9 Test pieces by injection molding were molded by the above-mentioned method and the physical properties were tested. Comparative Example 9 is inferior in tensile impact strength and tensile fracture strength.

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[Table 1]

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[Table 2]

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[Table 3]

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[Table 4]

[Brief description of drawings]

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

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

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[Procedure amendment]

[Submission date] August 30, 1995

[Procedure Amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0010

[Correction method] Change

[Correction content]

The present invention will be described in more detail below. The ethylene / α-olefin copolymer of 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, 1-pentene, 4
-Methyl-1-pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene and the like. The total content of these α-olefins is usually 3
It is desirable to select 0 mol% or less, preferably 3 to 20 mol%.

[Procedure Amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0054

[Correction method] Change

[Correction content]

The test method used in this experimental example is as follows. (Physical property test method) Density: Based on JIS K6760. MFR: Based on JIS K6760. Measurement by DSC: A sheet having a thickness of 0.2 mm is formed by hot pressing and a sample of about 5 mg is punched out at 230 ° C. for 10 minutes.
After holding for min, cool to 0 ° C at 2 ° C / min, and then 10 again
The temperature is raised to 170 ° C. at a rate of ° C./min, and the temperature at the peak of the highest temperature peak that appears is the highest peak temperature Tm. Mw / Mn: GPC Waters 150 type Solvent: ODCB 135 ° C Column: Toso-GMHHR-H (S) Detector: Differential refractive index

[Procedure 3]

[Document name to be amended] Statement

[Correction target item name] 0059

[Correction method] Change

[Correction content]

(Preparation of Solid Catalyst) Purified toluene was added to a catalyst preparation device (No. 1) equipped with an electromagnetic induction stirrer under nitrogen,
Then dipropoxydichlorozirconium (Zr (OP
28 g of r) ₂ Cl ₂ ) and 48 g of methylcyclopentadiene were added, and 45 g of tridecylaluminum was added dropwise while maintaining the system at 0 ° C. After completion of the addition, the reaction system was adjusted to 50
The mixture was kept at 0 ° C. and stirred for 16 hours. This solution is referred to as solution A. Next, under nitrogen, another stirrer catalyst preparation device (No.
2) Purified toluene was added to 2, and the above solution A and then a toluene solution of 6.4 mol of methylaluminoxane were added and reacted. This is designated as solution B.

[Procedure amendment 4]

[Document name to be amended] Statement

[Correction target item name] 0071

[Correction method] Change

[Correction content]

Examples 7 to 8 and Comparative Examples 7 to 8 Sheets were molded by the above-mentioned method and physical properties were tested. Comparative Example 7 is inferior in tensile impact strength, and Comparative Example 8 is inferior in heat resistance.

[Procedure Amendment 5]

[Document name to be amended] Statement

[Correction target item name] 0073

[Correction method] Change

[Correction content]

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[Table 1]

Claims (3)

[Claims] 1. An ethylene / α-olefin copolymer satisfying the following (A) to (D): (A) Density 0.86 to 0.96 g / cm ³ (B) Melt flow rate (MFR) 0.01 to 200 g / 10 min (C) Molecular weight distribution (Mw / Mn) 1.8 to 3.5 (D) Composition distribution parameter Cb 1.10 to 2.00 2. An ethylene / α-olefin copolymer satisfying the following (A) to (E). (A) Density 0.86 to 0.96 g / cm ³ (B) Melt flow rate (MFR) 0.01 to 200 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 (ODC) at 25 ° C.
B) The amount X (% by weight) of the soluble content and the densities d and MFR satisfy the following relationships: a) In the case of d-0.008 × log MFR ≧ 0.93 X <2.0 b) d-0. When 008 × logMFR <0.93 X <9.8 × 10 ³ × (0.9300−d + 0.008
× logMFR) ² +2.0 (Equation 1) 3. An ethylene / α-olefin copolymer satisfying the following (A) to (F): (A) Density 0.86 to 0.96 g / cm ³ (B) Melt flow rate (MFR) 0.01 to 200 g / 10 min (C) Molecular weight distribution (Mw / Mn) 1.8 to 3.5 (D) Composition distribution parameter Cb 1.1-2.00 (E) Ortho-dichlorobenzene (ODC) at 25 ° C.
B) The amount X (% by weight) of the soluble content and the densities d and MFR satisfy the following relationships: a) In the case of d-0.008 × log MFR ≧ 0.93 X <2.0 b) d-0. When 008 × logMFR <0.93 X <9.8 × 10 ³ × (0.9300−d + 0.008
× logMFR) ² +2.0 (Equation 1) (F) Multiple peaks of elution temperature-elution amount curve by continuous temperature rising elution fractionation method (TREF)