JP2002167477A - Olefin-based resin composition for calender molding, and film and sheet using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an olefin-based resin composition excellent in calender moldability and to prepare a film and a sheet molded from the resin composition. SOLUTION: The olefin-based resin composition for calender molding is characterized in that, in the range of 80-200 deg.C, tanδ that is the ratio (G"/G') of a loss modulus G" to a storage modulus G', is 0.5 at frequency ω of 10 rad/s to 0.2-2 at frequency ω of 0.5-3,100 rad/s, the difference of logarithmic value (log(tanδω10)-log(tanδω100)) of tanδ(tanδω10) measured in 10 rad/s and tanδ(tanδω100) measured in 100 rad/s, is 0.05-0.3, the frequency ω at a crossing point Gc(G'=G") of the storage modulus G' and the loss modulus G", is 30 rad/s or above, or the crossing point Gc(G'=G") of the storage modulus G' and the loss modulus G" does not exist in the range of frequency ω of 0.1-500 rad/s.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an olefin resin composition excellent in calender moldability, and to a film and a sheet formed from the resin composition.

[0002]

2. Description of the Related Art Calender molding is a molding method in which a resin is molded into a sheet using a roll, and is characterized by higher productivity than extrusion sheet molding. For molding a plastic sheet, a four-roll calender is often used. It is said that most of the resins used for calendering are PVC resins, and olefinic resins are not suitable for calendering. Due to various problems, PVC
Conversion from olefin resins to olefin resins has been demanded, but olefin resins have poor moldability and conversion to olefin resins has not progressed.

[0003] The main problems in calendering are bank marks, thickness defects, pinholes, peeling defects, biting defects, and the like. The bank mark is a phenomenon in which a very thin V-shaped wavy pattern remains on the film and sheet surfaces. Thickness failure means that the thickness of the film or sheet becomes uneven. The pinhole means that the air entrapped in the resin is not defoamed even in the bank, and the air bubbles enter the film and sheet to form a hole. The peeling failure means that the resin does not separate from the roll and is wound around the roll. The poor bite means that the resin does not bite between the rolls, the bank becomes larger and the resin overflows. Among these, poor peeling and poor biting are not observed in the PVC calender molding, but are phenomena observed in the olefin-based resin, and are problems in molding.

The techniques relating to calender molding are described in Kenkichi Murakami, Rubber Digest, 17 (9), 47 (1964); Kaoru Ono,
Plastics, 27 (7), 46 (1965); Shigeharu Takazawa, Rubber Digest, 29 (4), 11 (1977); "Polyvinyl chloride"
The Kinki Chemical Association, Nikkan Kogyo Shimbun, and others mainly explain mechanical technology. In addition, calendering simulation was performed by E. Mitsoulis, J. Vlachopoulos, FA Mirz
a (Polym. Eng. Sci. 25 (1), 6 (1985)), but there are few studies on olefin resins for calendering.

[0005]

SUMMARY OF THE INVENTION An object of the present invention is to provide an olefin resin composition having excellent calender moldability, and a film and a sheet formed from the resin composition.

[0006]

The present inventors have conducted intensive studies to achieve the above object, and as a result, at the molding temperature of calender molding, the ratio tan δ, which is the ratio of the loss elastic modulus G ″ to the storage elastic modulus G ′, is reduced. An olefin-based resin composition that satisfies a predetermined relationship and has a frequency ω of a predetermined range of a point Gc (G ′ = G ″) where the storage elastic modulus G ′ and the loss elastic modulus G ″ intersect has excellent calender moldability. The inventors have found that the present invention has been achieved.

That is, the present invention includes the following inventions. (1) At any temperature in the range of 80 to 200 ° C., the ratio of the loss modulus G ″ to the storage modulus G ′ (G ″ /
G ′) is 0.5 to 3 at a frequency ω of 10 rad / s, 0.2 to 2 at 100 rad / s, and 1
Tanδ (tanδω ₁₀ ) measured at 0 rad / s and tanδ (tanδω measured at 100 rad / s)
₁₀₀ ) (log (tan δω ₁₀ ) −log
(Tan δω ₁₀₀ )) is 0.05 to 0.3, and a point Gc (G ′ = G ′ = G ′) where the storage elastic modulus G ′ and the loss elastic modulus G ″ intersect.
G ″) is at least 30 rad / s, or a point Gc (G ′) where the storage elastic modulus G ′ and the loss elastic modulus G ″ intersect within a frequency range of 0.1 to 500 rad / s.
= G ″) does not exist.

(2) A method for producing a film or sheet, comprising molding the olefin resin composition according to (1) by a calender molding method. (3) The production method according to (2), wherein the roll temperature at the time of calendering is a temperature of 80 to 200 ° C. in which the olefin resin composition to be used satisfies the condition described in (1).

(4) A film or sheet obtainable by the production method according to (2) or (3). The principle of measuring viscoelasticity is shown below. The measurement of viscoelasticity is to give a vibrating strain of a certain frequency as represented by a trigonometric function and measure the response (stress).

In the case of a completely elastic body, stress is generated immediately (without phase shift) with respect to oscillating strain. In the case of a viscous material (Newtonian fluid), the stress is generated (phase angle 90 degrees) with respect to the oscillating strain. A viscoelastic fluid exhibits a behavior intermediate between a completely elastic body and a viscous body, and has a phase of δ (0 <0
δ <90) and a stress is generated (see FIG. 1). From the phase δ, the magnitude of the elasticity and the magnitude of the viscosity of the polymer can be evaluated. From the stress equivalent to an ideal elastic body,
The loss elastic modulus G ″ is defined from the storage elastic modulus G ′ and the stress corresponding to the viscous material. The tan δ is the loss elastic modulus G ″.
And the storage modulus G ′ (G ″ / G ′).

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION The measurement of the dynamic viscoelastic function at the roll temperature during calendering of the olefin resin composition of the present invention shows the ratio of the loss elastic modulus G ″ to the storage elastic modulus G ′. At a frequency ω of 10 rad / s.
5-3, 0.2-2 at 100 rad / s, 10r
tan δ (tan δω ₁₀ ) measured in ad / s and 10
Tan δ (tan δω ₁₀₀ ) measured at 0 rad / s
(Log (tanδω ₁₀ ) −log (ta
nδω ₁₀₀ )) is 0.05 to 0.3, and a point Gc (G ′ = G ″) at which the storage modulus G ′ and the loss modulus G ″ intersect.
Is greater than 30 rad / s, or
A point Gc (G ′ = G ′ = intersection) where the storage elastic modulus G ′ and the loss elastic modulus G ″ intersect within the frequency ω of 0.1 to 500 rad / s.
G ") must not be present.

Specifically, the measurement of the dynamic viscoelastic function of the loss elastic modulus G ″ and the storage elastic modulus G ′ is performed by using a commercially available measuring device, for example, a mechanical spectrometer RMS800 or a stress rheometer SR-R manufactured by Rheometrics. The measurement can be performed using a parallel plate geometry or a cone plate geometry having a diameter of 2.5 mm such as 5000. The measurement temperature is a roll temperature at the time of calendering, and specifically, in the case of a four-roll calender, C4 80-200 ° C at the set temperature of the roll, preferably 100-1
80 ° C.

The measurement is a measurement of the frequency dispersion of dynamic viscoelasticity under strain control, and the frequency ω is 0.1 to 100 rad / s.
The measurement is performed in a range of 1 to 20% (500 depending on the device). Tan δ at molding temperature is 10 rad
/ S at a frequency ω of 0.5 to 3, preferably 1 to 3, more preferably 1.2 to 2, and 100 rad / s
Is 0.2 to 2, preferably 1 to 1.8 at the frequency ω.

Tan δ at a frequency ω of 10 rad / s is a property necessary for good moldability in a region where the molding speed is relatively low, and tan δ at a frequency ω of 10 rad / s is used.
If nδ is less than 0.5, poor biting will occur, and if nδ exceeds 3, peeling failure will occur, and it will easily wind around the roll, making molding difficult.

Tanδ at a frequency ω of 100 rad / s
Is a property necessary for good moldability in a region where the molding speed is high, and ta at a frequency ω of 100 rad / s
If nδ is less than 0.2, biting failure occurs and molding becomes difficult. If it exceeds 2, peeling of the resin composition from the roll is not stable, and the thickness and thickness accuracy of the resulting film and sheet are significantly deteriorated.

Tan δ (t measured at 10 rad / s
anδω ₁₀ ) and tanδ measured at 100 rad / s
(Tanδω ₁₀₀ ) logarithmic value difference (log (tanδω
₁₀ ) -log (tan δω ₁₀₀ )) is an index for obtaining good biteability into a calender roll. lo
g (tan δω ₁₀ ) -log (tan δω ₁₀₀ ) is 0.
When it is in the range of from 0.05 to 0.3, good moldability is exhibited. When the parameter is more than 0.3, poor penetration into the roll occurs, and high-speed calendering cannot be performed.

The frequency ω at the point Gc (G ′ = G ″) where the storage elastic modulus G ′ and the loss elastic modulus G ″ intersect is 30 rad / s or more, preferably 50 rad / s or more. The frequency ω of Gc is a property necessary to secure the stability of the resin bank in the calendering process. When the frequency ω of Gc (G ′ = G ″) is less than 30 rad / s, the size of the resin bank increases over time. The upper limit of the frequency ω of Gc is that the measurement limit ω of the viscoelasticity measuring device is 100 rad / s (500 rad depending on the device).
/ S), Gc may not appear in the measurable range, and the upper limit cannot be limited. Therefore,
A point Gc (G ′ = G ′ = intersection) where the storage elastic modulus G ′ and the loss elastic modulus G ″ intersect within the frequency ω of 0.1 to 500 rad / s.
G ") is not present in the present invention.

The relationship between dynamic viscoelasticity and calender moldability can be explained theoretically. In the dynamic viscoelasticity, when the storage elastic modulus G ′ is larger than the loss elastic modulus G ″ (G ′> G ″, tan δ <1), the resin behaves like a rubber because the elastic property is larger than the viscosity. Is shown. In this region, the peeling from the roll is good.

On the other hand, when G ′ <G ”(tan δ> 1)
Since the resin has a viscous property larger than the elasticity, the resin adheres well to the roll, so that the bite is improved. Since the frequency ω is related to the shear rate during calendering, a low frequency corresponds to a low forming rate, and a high frequency corresponds to a high forming rate. As a general property of olefin-based resins, G ">
Although G ′, G ′> G ″ at high frequencies. This is because peeling failure occurs in a region where the molding speed is low and biting failure occurs in a region where the molding speed is high. The property is such that G ′ = G ″ (ta
nδ = 1, referred to as Gc). That is, both the biting property and the peeling property are good. In order to realize such a state, the present inventors have conducted intensive studies on the molecular weight, molecular weight distribution, additives, and the like of the resin, and have reached the present invention.

In order to adjust tan δ at a frequency of ω10 rad / s at a molding temperature of calendering, a high molecular weight resin component is blended, or an organic or inorganic filler, a slip agent or the like is blended. To adjust tan δ at a frequency of ω100 rad / s, a low molecular weight resin component and a substance exhibiting tackiness are blended. That is, by widening the molecular weight distribution of the olefin resin and blending a slip agent, etc., ta
The frequency dependence of nδ can be controlled. By adjusting the frequency ω of Gc by a combination of the above methods, an olefin-based resin composition having excellent calender moldability is obtained. Further, the thickness of the film and sheet molded from the resin composition is good.

Resin Composition The resin used in the present invention includes, for example, high-density polyethylene, high-pressure low-density polyethylene, linear low-density polyethylene, ethylene / α-olefin copolymer, ethylene / vinyl acetate copolymer, Olefinic resins such as ethylene / styrene copolymer, ethylene / unsaturated carboxylic acid copolymer, polypropylene, propylene / α-olefin copolymer, polybutene-1, butene-1 / α-olefin copolymer, and the like. . Among them, a composition of the ethylene-based random copolymer (A) and the polyethylene resin (B) or a composition of the propylene-based copolymer and the ethylene-based random copolymer (A) is preferable. It is difficult to obtain the above-mentioned physical properties in the present invention simply by using a polymer obtained by a known production method alone, and the composition of the present invention is obtained by blending two kinds of polymers or a multi-stage polymerization method. You can get things. That is, it is necessary to obtain a resin having a different molecular weight, a resin having a different melting point, a melt blend of resins having different compositions, or multi-stage polymerization.

Here, the term "melt blending" refers to the melting and mixing of various kinds of resins with an extruder, a Banbury mixer, and the like. It means that the resin is continuously polymerized. The olefin-based resin composition of the present invention has a “maximum roll speed at which no biting failure occurs” measured by the method described in the Examples, and is usually 5.5 m / min or more, preferably 6 m / min or more, more preferably 6.5 m / min or more. Hereinafter, specific examples of the resin that can be used in the present invention will be described.

[Ethylene random copolymer (A)] The ethylene random copolymer (A) used in the present invention.
Comprises ethylene and an α-olefin having 3 to 20 carbon atoms. As the α-olefin having 3 to 20 carbon atoms, specifically, propylene, 1-butene, 1-pentene, 1-
Hexene, 1-heptene, 1-octene, 1-nonene,
1-decene, 1-undecene, 1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-octadecene, 1
-Nonadecene, 1-eicosene, 3-methyl-1-butene, 3-methyl-1-pentene, 3-ethyl-1-pentene, 4-methyl-1-pentene, 4-methyl-1-hexene, 4,4 -Dimethyl-1-hexene, 4,4-dimethyl-1-pentene, 4-ethyl-1-hexene,
-Ethyl-1-hexene, 9-methyl-1-decene, 1
1-methyl-1-dodecene, 12-ethyl-1-tetradecene, and combinations thereof. Among them,
An α-olefin having 3 to 10 carbon atoms is preferable, and an α-olefin having 3 to 8 carbon atoms is particularly preferable.

This ethylene-based random copolymer (A)
A density of 850~900kg / m ^3, preferably 85
0 to 895 kg / m ³ , more preferably 850 to 885
kg / m ³ . When the density of the ethylene-based random copolymer (A) is within the above range, a flexible sheet can be obtained.

Further, an ethylene random copolymer (A)
Is the melt flow rate (ASTMD 1238,19)
0 ° C., load 2.16 kg) is 0.1 to 50 g / 10 minutes,
Preferably it is in the range of 0.2 to 40 g / 10 minutes. The ethylene-based random copolymer (A) having a melt flow rate within the above-mentioned range has good bite into the roll and good peeling from the roll. Furthermore, the ethylene-based random copolymer (A) has a crystallinity of less than 40% as measured by an X-ray diffraction method. When the crystallinity of the ethylene-based random copolymer (A) is less than 40%, the flexibility is good.

The ethylene random copolymer (A) comprises 1
These can be used alone or in combination of two or more. Ethylene random copolymer (A) as described above
Can be prepared, for example, by subjecting ethylene and an α-olefin having 3 to 20 carbon atoms to random polymerization in the presence of an olefin polymerization catalyst comprising a soluble vanadium compound and an alkylaluminum halide compound.

Examples of the soluble vanadium compound include vanadium tetrachloride, vanadium oxytrichloride, vanadium triacetyl acetate, oxyvanadium triacetyl acetate, and the like. Examples of the alkylaluminum halide compound include ethylaluminum dichloride, diethylaluminum monochloride, ethylaluminum sesquichloride, diethylaluminum monobromide, diisobutylaluminum monochloride, and isobutylaluminum sesquichloride.

The random polymerization can be carried out in the form of a solution or a suspension or in the intermediate region thereof. In any case, it is preferable to use an inert solvent as a reaction medium.
Examples of such inert solvents include aliphatic hydrocarbons having about 3 to 12 carbon atoms, such as propane, butane, pentane, hexane, octane, nonane, decane, undecane, and dodecane; kerosene; methyl chloride, ethyl chloride, ethylene dichloride And the like.
These solvents can be used alone or in combination of two or more. The polymerization temperature is from 0 to 100 ° C.
In the present invention, the following linear or long-chain branched ethylene / α-olefin random copolymer is preferably used as the ethylene random copolymer (A).

<Linear ethylene / α-olefin random copolymer> The linear ethylene / α-olefin random copolymer preferably used in the present invention has a density of 850.
９００900 kg / m ³ , preferably 850-895 kg /
m ³ , more preferably in the range of 850 to 885 kg / m ³ , and the melt flow rate (ASTM D 1238,
190 ° C., load 2.16 kg) is 0.1 to 50 g / 10
Min, preferably in the range of 0.2 to 40 g / 10 min.

The linear ethylene / α-olefin random copolymer has a glass transition point (Tg) of -50 ° C. or lower, as determined by a differential scanning calorimeter (DSC). Furthermore,
This linear ethylene / α-olefin random copolymer has a crystallinity of less than 40%, preferably 30% or less, as measured by X-ray diffraction. When a linear ethylene / α-olefin random copolymer having a crystallinity of less than 40% is used, a resin composition having excellent flexibility can be obtained.

Further, the linear ethylene · alpha-olefin random copolymer, the molecular weight distribution determined from the GPC (Mw / Mn) of 3.0 or less, determined by ¹³ C-NMR method, comonomers It is preferable that the parameter B value indicating the randomness of the chain distribution is 1.0 to 1.4.
The B value in such a linear ethylene / α-olefin random copolymer is an index representing the composition distribution state of the structural unit derived from each monomer in the copolymer chain, and can be calculated by the following equation. it can.

B = P _OE / (2P _O · P _E ) [where P _E and P _O are the mole fraction of ethylene component and α, respectively, contained in the ethylene / α-olefin random copolymer. The mole fraction of the olefin component, P
_OE is the ratio of the number of alternating ethylene / α-olefin chains to the total number of dyads. These P _E , P _O and P _OE values are specifically determined as follows. About 20 in a 10mmφ test tube
A sample is prepared by uniformly dissolving 0 mg of an ethylene / α-olefin random copolymer in 1 ml of hexachlorobutadiene, and the ¹³ C-NMR spectrum of this sample is measured under the following measurement conditions.

[0033] [Measurement conditions] Measurement temperature: 120 ° C. Measurement Frequency: 20.05MHz spectral width: 1500 Hz Filter width: 1500 Hz Pulse repetition time: of 4.2 sec Pulse width: 7Myusec number of integrations: 2000 to 5000 times P _E, P _O and The P _OE value is
From the ¹³ C-NMR spectrum measured as described above, GJRay (Macromolecules, 10, 773 (1977)), JC
Randall (Macro-molecules, 15, 353 (1982)), K. Kimura
(Polymer, 25, 4418 (1984)) et al.

The B value obtained from the above equation is 2 when both monomers of the ethylene / α-olefin copolymer are alternately distributed, and both monomers are completely separated and polymerized. In the case of a complete block copolymer, it is 0. When a linear ethylene / α-olefin random copolymer having a B value within the above range is used, a polypropylene resin composition capable of providing a molded article having excellent heat resistance can be obtained. G obtained from the intrinsic viscosity [η] of the linear ethylene / α-olefin random copolymer as described above.
The η ^* value exceeds 0.95. This gη ^* value is defined by the following equation.

Gη ^* = [η] / [η] _blank (where [η] is the intrinsic viscosity measured in the above (b), and [η] _blank is the ethylene of the intrinsic viscosity [η]. Having the same weight average molecular weight (by light scattering method) as the α-olefin random copolymer and having an ethylene content of 7
It is an intrinsic viscosity of 0 mol% of a linear ethylene / propylene copolymer. )

From the linear ethylene / α-olefin random copolymer having the above-mentioned properties, a resin composition capable of providing a molded article having excellent mechanical strength properties and excellent heat resistance is obtained. be able to. The method for preparing the linear ethylene / α-olefin random copolymer will be described later.

<Long-chain branched ethylene / α-olefin random copolymer> The long-chain branched ethylene / α-olefin random copolymer preferably used in the present invention has a density of 850 to 900 kg / m ³ , preferably 850-89
5 kg / m ³ , more preferably 850-885 kg / m ³
And the melt flow rate (ASTM D 1
238, 190 ° C, load 2.16 kg) 0.1 to 50
g / 10 min, preferably in the range of 0.2 to 40 g / 10 min.

This long-chain branched ethylene / α-olefin random copolymer has a glass transition point (T
g) is −50 ° C. or less. Furthermore, the long-chain branched ethylene / α-olefin random copolymer has a crystallinity of less than 40%, preferably 30% or less, as measured by X-ray diffraction. When a long-chain branched ethylene / α-olefin random copolymer having a crystallinity of less than 40% is used, a resin composition having excellent flexibility can be obtained.

The long-chain branched ethylene / α-olefin random copolymer has a molecular weight distribution (Mw / Mn) of 3.0 or less as determined by GPC and a copolymer as determined by ¹³ C-NMR method. It is preferable that the parameter B value indicating the randomness of the monomer chain distribution is 1.0 to 1.4. When a long-chain branched ethylene / α-olefin random copolymer having a B value within the above range is used, a resin composition capable of providing a molded article having excellent heat resistance can be obtained.

This long-chain branched ethylene / α-olefin random copolymer has a gη ^* value of 0.2 to 0.95, preferably 0.4 to 0.9, more preferably 0.5 to 0.5.
85. When the gη ^* value of the ethylene / α-olefin random copolymer is 0.95 or less, it indicates that a long-chain branch is formed in the molecule.

<Linear and long-chain branched ethylene / α-
Method for Preparing Olefin Random Copolymer> A linear or long-chain branched ethylene / α-olefin random copolymer having the above-mentioned properties is obtained by adding ethylene to a metallocene-based catalyst containing a specific metallocene compound. And carbon number 3
~ 20 α-olefins can be prepared by random copolymerization.

The metallocene catalyst is not particularly limited except that it contains the metallocene compound [a]. For example, the metallocene compound [a] is reacted with the organoaluminum oxy compound [b] and / or the metallocene compound [a]. To form an ion pair (ionized ionic compound) [c]. Further, a metallocene compound [a] and an organic aluminum oxy compound [b]
And / or an organic aluminum compound [d] together with the compound [c] forming an ion pair.

Metallocene compound [a] First, linear ethylene.α preferably used in the present invention
-With regard to the metallocene compound [a1] used in the preparation of the olefin random copolymer, WO97 / 1
0296 is described in detail. In the present invention,
In particular, a compound represented by the following general formula [I] or [II] (the general formula [III] or [I
V]) are preferably used.

[0044]

Embedded image (In the formula, M is a transition metal atom of Group IVB of the periodic table, specifically, titanium, zirconium, or hafnium, and particularly preferably zirconium.)

R ¹¹ and R ¹² R ¹¹ and R ^{12 each} represent a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms which may be substituted by halogen, a silicon-containing group, an oxygen-containing group, and a sulfur-containing group. , A nitrogen-containing group or a phosphorus-containing group. R ¹¹ is particularly preferably a hydrocarbon group having 1 to 3 carbon atoms such as a methyl group, an ethyl group, and a propyl group. R ¹² is particularly preferably a hydrogen atom or a hydrocarbon group having 1 to 3 carbon atoms such as a methyl group, an ethyl group and a propyl group.

R ¹³ and R ¹⁴ R ¹³ and R ¹⁴ are an alkyl group having 1 to 20 carbon atoms.
R ¹³ is preferably a secondary or tertiary alkyl group. R ¹⁴ may contain a double bond or a triple bond.

X ¹ and X ² X ¹ and X ² represent a hydrogen atom, a halogen atom, a carbon number of 1 to 2
0 hydrocarbon group, halogenated hydrocarbon group having 1 to 20 carbon atoms, oxygen-containing group or sulfur-containing group. Among them,
A halogen atom and a hydrocarbon group having 1 to 20 carbon atoms are preferred.

[0048] Y Y is a divalent hydrocarbon group having 1 to 20 carbon atoms, 1 to carbon atoms
20 divalent halogenated hydrocarbon groups, divalent silicon-containing groups, divalent germanium-containing groups, -O-, -CO-,-
S -, - SO -, - SO 2 -, - NR 7 -, - P (R 7)
-, - P (O) ( R 7) -, - BR 7 - or -AlR ⁷ -
[However, R ⁷ is a hydrogen atom, a halogen atom, a carbon atom 1
To 20 hydrocarbon groups and halogenated hydrocarbon groups having 1 to 20 carbon atoms]. As Y, an alkylsilylene group, an alkylarylsilylene group, and an arylsilylene group are particularly preferable. The transition metal compound as described above can be synthesized from an indene derivative by a known method, for example, a method described in JP-A-4-268307.

[0049]

Embedded image(Wherein, M is a transition metal atom of Group IVB of the periodic table)
Specifically, titanium, zirconium, hafnium
And particularly preferably zirconium. R
^{twenty one}May be the same or different from each other, and represent a hydrogen atom,
A halogen atom, an optionally halogenated carbon number 1 to 1
10 alkyl groups, aryl groups having 6 to 10 carbon atoms, -N
R_Two, -SR, -OSiR_Three, -SiR_ThreeOr -PR_TwoBase
(Where R is a halogen atom, an alkyl having 1 to 10 carbon atoms)
Or an aryl group having 6 to 10 carbon atoms). )

[0050] R ²² to R ²⁸ may be the same or different, have the same atom or group as R ^21, these R ²² to R ²⁸
And at least two groups adjacent to each other may form an aromatic ring or an aliphatic ring together with the atoms to which they are bonded. X ³ and X ⁴ may be the same or different from each other, and include a hydrogen atom, a halogen atom, an OH group, and
0 alkyl group, C1-C10 alkoxy group, C6-C10 aryl group, C6-C10 aryloxy group, C2-C10 alkenyl group, C7-C4
0, an arylalkyl group having 7 to 40 carbon atoms, and an arylalkenyl group having 8 to 40 carbon atoms.

[0051]

Embedded image -Sn -, - O -, - S -, = SO, = SO 2, = NR
^29, = CO, a = PR ²⁹ or = P (O) R ^29. However, R ²⁹ and R ³⁰ may be the same or different from each other, and include a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, a fluoroalkyl group having 1 to 10 carbon atoms, and 6 carbon atoms.
An aryl group having 10 to 10 carbon atoms, a fluoroaryl group having 6 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an arylalkyl group having 7 to 40 carbon atoms,
Arylalkenyl group having 8 to 40 carbon atoms, 7 to 4 carbon atoms
0 is an alkylaryl group.

[0052] In addition to the R ²⁹ and R ^30, respectively, may form a ring together with the atoms connecting them. M ² is silicon, germanium or tin. The above-mentioned alkyl group is a linear or branched alkyl group, and the halogen (halogenated) is a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, particularly preferably a fluorine atom or a chlorine atom.

The compound represented by the general formula [II] is
P-549900 and Canada-2084017. Next, the metallocene compound [a] used in preparing the long-chain branched ethylene / α-olefin random copolymer preferably used in the present invention.
2] is described in detail in WO97 / 10295. In the present invention, in particular, the following general formula [II
The compound represented by the formula (I) (compound represented by the general formula [I] in WO97 / 10295) is preferably used.

[0054]

Embedded image (In the formula, M is a transition metal atom of Group IVB of the periodic table, specifically, titanium, zirconium, or hafnium, and particularly preferably zirconium.)

The substituent R ¹ R ¹ is a hydrocarbon group having 1 to 6 carbon atoms. R ¹ is preferably an alkyl group in which the carbon bonded to the indenyl group is primary, and particularly preferably a methyl group and an ethyl group. Substituents ^{R 2, R 4, R 5} , R 6 R 2, R 4, R 5, R 6 may each be identical or different, a hydrogen atom, the number the same carbon with a halogen atom or R ¹ 1 To 6 hydrocarbon groups.

The substituent R ³ R ³ is an aryl group having 6 to 16 carbon atoms. This aryl group may be substituted with a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or an organic silyl group. X ¹ and X ² X ¹ and X ² are a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms which may be substituted by halogen, an oxygen-containing group or a sulfur-containing group.

[0057] Y Y is a divalent hydrocarbon group having 1 to 20 carbon atoms, 1 to carbon atoms
20 divalent halogenated hydrocarbon groups, divalent silicon-containing groups, divalent germanium-containing groups, -O-, -CO-,-
S -, - SO -, - SO 2 -, - NR 7 -, - P (R 7)
-, - P (O) ( R 7) -, - BR 7 - or -AlR ⁷ -
(However, R ⁷ is a hydrogen atom, a halogen atom, a carbon atom 1
To 20 hydrocarbon groups and halogenated hydrocarbon groups having 1 to 20 carbon atoms).

Of these, Y is preferably a divalent silicon-containing group and a divalent germanium-containing group,
It is more preferably a divalent silicon-containing group, and particularly preferably an alkylsilylene group, an alkylarylsilylene group, or an arylsilylene group.

In the present invention, two or more of the above metallocene compounds can be used in combination. Such metallocene compounds are available from the Journal of Organometallic Ch.
em., 288 (1985), pp. 63-67, European Patent Application Publication No. 0,320,762.

Organic aluminum oxy compound [b] As the organic aluminum oxy compound [b], aluminoxane is preferably used. Specifically, the formula -A
Methylaluminoxane, ethylaluminoxane, methylethylaluminoxane or the like having a repeating unit represented by l (R) O- [where R is an alkyl group] usually having about 3 to 50 is used. Such an aluminoxane can be prepared by a conventionally known production method.

The ion reacts with the metallocene compound [a]
Compound forming a pair [c] Compound forming an ion pair by reacting with the metallocene compound [a] used in the present invention (ionized ionic compound)
The [c], for example, triphenylboron described in _{USP5321106, MgCl 2, Al 2 O} 3, Si
Lewis acids such as O ₂ —Al ₂ O ₃ are exemplified. The ionized ionic compound [c] can be used alone or in combination of two or more.

Organoaluminum Compound [d] The organoaluminum compound [d] optionally used in the present invention includes, for example, trialkylaluminum, dialkylaluminum halide, alkylaluminum sesquihalide, alkylaluminum dihalide and the like. Can be exemplified.

These organoaluminum compounds can be used alone or in combination of two or more.
The specific metallocene-based catalyst used in the present invention contains the metallocene compound [a] as described above. For example, it is formed from the metallocene compound [a] and the organic aluminum oxy compound [b] as described above. Can be.
Further, the metallocene compound [a] ([a1] or [a
2]) and a compound [c] which reacts with the metallocene compound [a] to form an ion pair. Further, together with the metallocene compound [a], an organoaluminum oxy compound [b] and a metallocene compound [ a] can be used in combination with a compound [c] that forms an ion pair by reacting with [a]. In these embodiments, it is particularly preferable to further use an organoaluminum compound [d] in combination.

In the present invention, ethylene and C 3-20
The metallocene compound [a] ([a1] constituting the metallocene catalyst when copolymerizing
Or [a2]), the organoaluminum oxy compound [b], the compound [c] forming an ion pair, and the organoaluminum compound [d] may be separately supplied to the polymerization reactor, or the metallocene may be supplied in advance. Compound [a]
May be subjected to a copolymerization reaction after preparing a metallocene-based catalyst.

In preparing the metallocene-based catalyst, a hydrocarbon solvent which is inactive with the catalyst component can be used. In the present invention, the copolymerization of ethylene and an α-olefin having 3 to 20 carbon atoms is usually performed at 40 to 200 ° C, preferably 50 to 150 ° C, and particularly preferably 60 to 120 ° C.
℃ at atmospheric pressure to 100 kg / cm ^2, preferably atmospheric pressure to 50 kg / cm ^2, particularly preferably atmospheric pressure ~30kg
/ Cm ² .

This copolymerization reaction can be carried out by various polymerization methods, but is preferably carried out by solution polymerization. At this time, the above-mentioned hydrocarbon solvent can be used as the polymerization solvent. The copolymerization can be performed by any of a batch system, a semi-continuous system, and a continuous system, but is preferably performed by a continuous system. Further, the polymerization can be carried out in two or more stages by changing the reaction conditions.

The linear or long-chain branched ethylene / α-olefin random copolymer used in the present invention is:
Obtained by the method as described above, the molecular weight of this copolymer can be adjusted by changing polymerization conditions such as polymerization temperature, and by controlling the amount of hydrogen (molecular weight regulator) used. It can also be adjusted.

In the present invention, the above-mentioned ethylene random copolymer (A) may be partially or completely modified with an unsaturated carboxylic acid or an anhydride thereof. The modified product of the ethylene-based random copolymer has an effect of further improving the overlap packaging property and the adhesiveness to a metal or the like.

[Polyethylene resin (B)] The polyethylene resin (B) used in the present invention may be a homopolymer of ethylene, and ethylene and an α-olefin, preferably ethylene and an α-olefin having 4 to 20 carbon atoms. -It may be a random copolymer with an olefin, and may be linear or branched.

As the α-olefin having 4 to 20 carbon atoms, specifically, 1-butene, 1-pentene, 1-pentene,
Hexene, 1-heptene, 1-octene, 1-nonene,
1-decene, 1-undecene, 1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-octadecene, 1
-Nonadecene, 1-eicosene, 3-methyl-1-butene, 3-methyl-1-pentene, 3-ethyl-1-pentene, 4-methyl-1pentene, 4-methyl-1-hexene, 4,4- Dimethyl-1-hexene, 4,4-dimethyl-1-pentene, 4-ethyl-1-hexene, 3-
Ethyl-1-hexene, 9-methyl-1-decene, 11
-Methyl-1-dodecene, 12-ethyl-1-tetradecene, and combinations thereof.

The polyethylene resin (B) used in the present invention generally has a MFR (melt flow rate; AST).
MD 1238, 190 ° C, 2.16 kg load) is 0.01 to 100 g / 10 min. In particular, this MFR is 0.1 to 50 g / 10 min, preferably 0.2 to 40 g / min.
When the time is 10 minutes, a molded article excellent in melt fluidity, that is, moldability, and excellent in balance between flexibility and heat resistance is obtained.

This polyethylene resin (B) has a density of 9
It is in the range of 01 to 970 kg / m ³ and the density is 901 k
In the range of g / m ³ or more and less than 940 kg / m ³ , a sheet excellent in flexibility is obtained, and in the range of 940-970 kg / m ³ , a sheet excellent in heat resistance is obtained.

The resin composition of the present invention contains the ethylene random copolymer (A) in an amount of 0.5 to 5000 parts by weight based on 100 parts by weight of the polyethylene resin (B). Such a resin composition is excellent in moldability and gives a molded article excellent in flexibility. Particularly, in the present invention, the ethylene random copolymer (A) is 67 to 2,000 parts by weight, more preferably 83 to 1,000 parts by weight, particularly preferably 10 to 100 parts by weight of the polyethylene resin (B).
When contained in an amount of 0 to 500 parts by weight, it is possible to provide a molded article excellent in balance between flexibility and heat resistance,
Moreover, a resin composition having excellent moldability can be obtained.

In other words, the polyethylene resin (B) is
2 to 200 parts by weight, preferably 5 to 150 parts by weight, based on 100 parts by weight of the ethylene-based random copolymer (A),
More preferably, 10 to 120 parts by weight, particularly preferably 2 parts by weight.
Desirably, it is contained in a proportion of 0 to 100 parts by weight.

Such a polyethylene resin (B) can be produced by a conventionally known method, and the above-mentioned ethylene / α-olefin copolymer comprises, for example, ethylene and α-olefin having 4 to 20 carbon atoms. -It can be obtained by copolymerizing an olefin with a transition metal catalyst. For example, the density of a linear ethylene / α-olefin copolymer is controlled by the type and amount of α-olefin, and the melt flow rate is controlled by the type of chain transfer agent and the amount used. .

There are no particular restrictions on the catalyst or polymerization method.
As the catalyst, for example, a Ziegler-Natta type catalyst, a Phillips type catalyst, a metallocene type catalyst or the like is used. As the Ziegler-Natta type catalyst, Ti-based, Zr-based, or periodic-based transition metal compounds belonging to Group IV of the periodic table are used. Examples of the olefin polymerization catalyst include a V-based transition metal compound of Table V and an organoaluminum compound, and the like. Examples of the polymerization method include a slurry polymerization method, a gas phase polymerization method, and a solution polymerization method. Is done. Additives such as a nucleating agent, a stabilizer, a lubricant, and an inorganic filler can be further added to the resin composition of the present invention, if necessary.

Representative examples of the nucleating agent include, for example, sodium benzoate, bisbenzylidene sorbitol, bis (p-methylbenzylidene) sorbitol, bis (p-
Ethylbenzylidene) sorbitol, sodium-2,2
-Methylenebis (4,6-di-t-butylphenyl) phosphite, talc, titanium oxide, aluminum hydroxy-di-pt-butylbenzoate, and the like. These may be used alone or in combination of two or more. Can be used.

Representative examples of the stabilizer include, for example, pentaerythrityl-tetrakis [3- (3,5-di-t-
Butyl-4-hydroxyphenyl) propionate],
Phenolic stabilizers such as triethylene glycol-bis [3- (3-t-butyl-5-methyl-4-hydroxyphenyl) propionate], tris (monononylphenyl) phosphite, tris (2,4-di- Examples include phosphorus-based stabilizers such as (t-butylphenyl) phosphite and sulfur-based stabilizers such as dilaurylthiodipropionate. These can be used alone or in combination of two or more.

Representative examples of the lubricant include sodium, calcium, and magnesium salts of saturated or unsaturated fatty acids such as lauric acid, palmitic acid, oleic acid, and stearic acid; oleamide, erucamide, and stearamide. And saturated or unsaturated fatty acid amides, and these can be used alone or in combination of two or more.

Representative examples of the inorganic filler include, for example, calcium carbonate, talc, glass fiber, magnesium carbonate, mica, kaolin, calcium sulfate, barium sulfate, titanium white, white carbon, carbon black, aluminum hydroxide, and aluminum oxide. , Magnesium hydroxide, silica, clay, zeolite and the like, and these can be used alone or in combination of two or more. The above composition is blended and kneaded with a usual kneader such as a roll, a Banbury mixer, a single-screw extruder, a twin-screw extruder or the like to prepare a composition. Usually, the composition is preferably formed into pellets.

The composition thus obtained is formed into a calender sheet or film by a calendering method, and is used for automobiles, especially for automobiles, especially floor materials, ceiling materials, instrument panels, door trims, interior sheets and the like. Used for exterior and interior materials, leisure sheets, gaskets, waterproof sheets, bags, notebook covers, notebook covers, belts, etc. Further, the resin sheet or film can be used for food containers, various industrial parts, and the like.

[0082]

EXAMPLES The present invention will be described below with reference to examples, but the present invention is not limited to these examples. In addition, the measuring method of the physical property performed about the olefin-type thermoplastic elastomer composition of an Example and a comparative example is as follows.

(Measurement of Dynamic Viscoelastic Function) A dynamic viscoelastic function at a roll temperature during calendering was measured using a commercially available viscoelasticity measuring instrument (rheometer) RMS800 manufactured by Rheometrics. did. The viscoelasticity was measured by measuring the frequency dependence of a predetermined temperature on a press sheet having a thickness of 2 mm and a diameter of 25 mm under the condition of a strain amount of 5%.

(Molecular weight distribution (Mw / Mn)) GPC-150C manufactured by Millipore was used, and the separation column was TSK CN.
H HT (column size: diameter 27 mm, length 600 m
m), the column temperature was 140 ° C., and the mobile phase was o-
Dichlorobenzene and BHT 0.02 as antioxidant
Using 5% by weight, the sample was moved at 1.0 ml / min, the sample concentration was 0.1% by weight, the sample injection amount was 500 ml, and a differential refractometer was used as a detector. Based on the obtained spectrum, Mw and Mn were obtained from a standard EPR sample.

(Examples 1 to 3, Comparative Examples 1 to 3) Tables 1 to 3
The calender molding was performed using the materials shown in (1) and (2). The roll temperature was C1 / C2 / C3 / C4 = 120 to 121/12 using an inverted L-type calendering machine with a roll diameter of 6 inches.
The temperature was 1 to 122/122/123 ° C, and a sheet having a thickness of 100 µm was prepared. The forming speed was controlled by the number of roll rotations, and the maximum speed at which the bank shape could be formed stably was defined as the "maximum roll speed at which biting failure did not occur".

[0086]

[Table 1] * Comonomer content: mole number of butene to total mole number of ethylene and butene (%)

[0087]

[Table 2]

[0088]

[Table 3]

(Example 4, Comparative Example 4) Calender molding was performed using the materials shown in Tables 4 to 6. The calendering was performed using the calendering machines described in Examples 1 to 3 and Comparative Examples 1 to 3, and the roll temperature was C1 / C2 / C3 /
C4 = 170/170 to 171/172/173 ° C.

[0090]

[Table 4] * Comonomer content: In PER1, the mole number of ethylene to the total mole number of propylene and ethylene (%); In the EPR1, the mole number of propylene to the total mole number of ethylene and propylene (%)

[0091]

[Table 5]

[0092]

[Table 6]

[0093]

According to the present invention, it is possible to provide an olefin resin composition having excellent calender moldability, and a film and a sheet molded from the resin composition.

[Brief description of the drawings]

FIG. 1 is a diagram showing a relationship between strain and stress in a viscoelastic body.

 ────────────────────────────────────────────────── ─── Continued on the front page (72) Inventor Satoshi Morita 2-1 Tango-dori, Minami-ku, Nagoya-shi, Aichi F-term (reference) in Mitsui Chemicals, Inc. 4F071 AA15X AA21X AA76 AF20 BB04 BC01 4F204 AA03 AG01 AM32 FA06 FB02 FN11 FN15 FQ26 4J002 BB03W BB03X BB05W BB06W BB12W BB12X BB15W BB17W

Claims (4)

[Claims] 1. At any temperature in the range of 80 to 200 ° C., the frequency ω of 10 rad / s, where tan δ, which is the ratio (G ″ / G ′) of the loss elastic modulus G ″ to the storage elastic modulus G ′, is 10 rad / s. Is 0.5 to 3 at 100 rad / s and 0.2 to 2 at 100 rad / s, and tan δ (tan δω
₁₀ ) and tan δ (tan) measured at 100 rad / s.
δω ₁₀₀ ) (log (tan δω ₁₀ ) −1
og (tanδω ₁₀₀₎₎ is 0.05 to 0.3,
Point Gc at which storage modulus G ′ and loss modulus G ″ intersect
(G ′ = G ″) where the frequency ω is equal to or higher than 30 rad / s, or a point G where the storage elastic modulus G ′ and the loss elastic modulus G ″ intersect within a frequency range of 0.1 to 500 rad / s.
An olefin resin composition for calender molding, wherein c (G ′ = G ″) does not exist. 2. A method for producing a film or sheet, comprising molding the olefin resin composition according to claim 1 by a calender molding method. 3. The production method according to claim 2, wherein the roll temperature at the time of calendering is a temperature of 80 to 200 ° C. in which the olefin resin composition used satisfies the conditions described in claim 1. 4. A film or sheet obtainable by the method according to claim 2.