JP2014040563A - Olefine resin composition, sheet and molding - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an olefine resin composition that provides sheets having a small sagging of sheet at sheet heating during thermoforming and a high low-temperature impact strength.SOLUTION: The olefine resin composition contains propylene polymer in an amount of 50 to 99 weight % and ethylene-α-olefine copolymer shown below in an amount of 1 to 50 weight %. Ethylene-α-olefine copolymer: the ethylene-α-olefine copolymer has a monomer unit based on ethylene and a monomer unit based on α-olefine having the number of carbon atoms of 3 to 20, has a density of 880 to 940 kg/m, a melt flow rate of 0.01 to 10 g/10 minutes, a molecular weight distribution of 4.5 to 13, an activation energy of fluidity of 40 to 100 kJ/mol, a long chain branching content of 0.29 to 0.50 carbon atoms per the number of 1,000 carbon atoms, and a g* defined by expression (I) of 0.76 to 0.88. g*=[η]/([η]×g*) (I).

Description

  The present invention relates to an olefin resin composition, a sheet comprising the resin composition, and a molded body.

  A molded body obtained by thermoforming a sheet made of a propylene polymer, such as vacuum forming or pressure forming, is used as a container for food packaging, pharmaceutical packaging and the like. In thermoforming, the sheet is heated and then shaped, but if the sheet hangs down too much when the sheet is heated, wrinkles and uneven thickness are generated in the resulting molded product. In order to prevent the sheet from dripping too much when the sheet is heated during thermoforming, for example, Patent Document 1 includes a propylene polymer and a low density polyethylene having a melt flow rate of 0.1 to 1.0 g / 10 min. It describes that a sheet made of a resin composition is used for thermoforming.

JP 52-136247 A

  However, the sheet made of the resin composition still has a large sheet sag when heated, and the low-temperature impact strength is not sufficient. In view of the above problems, the present invention provides an olefin resin composition that provides a sheet having a low low-temperature impact strength and a low sag during heating, and a sheet sag during heating during thermoforming. Is to provide a sheet having a small size and high low-temperature impact strength, and a molded body obtained by thermoforming the sheet.

That is, the present invention relates to 50 to 99% by weight of one or more propylene polymers (component (A)) selected from the group consisting of propylene homopolymers and propylene random copolymers, and the following ethylene-α-olefin copolymer. This relates to an olefin resin composition containing 1 to 50% by weight of the coalescence (component (B)) (provided that the total weight of the component (A) and the component (B) is 100% by weight).
Ethylene-α-olefin copolymer (component (B)): having a monomer unit based on ethylene and a monomer unit based on an α-olefin having 3 to 20 carbon atoms, and a density of 880-940 kg / m ³ , the melt flow rate (MFR) is 0.01 to 10 g / 10 min, the molecular weight distribution (Mw / Mn), which is the ratio of the weight average molecular weight to the number average molecular weight, is 4.5 to 13, The flow activation energy (Ea) is 40 to 100 kJ / mol, the long chain branching amount measured by NMR is 0.29 to 0.50 per 1000 carbon atoms, and is defined by the following formula (I) Ethylene * alpha-olefin copolymer whose g * is 0.76-0.88.
g * = [η] / ([η] _GPC × g _SCB *) (I)
[Wherein [η] represents the intrinsic viscosity (unit: dl / g) of the ethylene-α-olefin copolymer, and is a value defined by the following formula (I-I). [Η] _GPC is a value defined by the following formula (I-II). g _SCB * is a value defined by the following formula (I-III).
[Η] = 23.3 × log (ηrel) (II)
(In the formula, ηrel represents the relative viscosity of the ethylene-α-olefin copolymer.)
[Η] _GPC = 0.00046 × Mv ^0.725 (I-II)
(In the formula, Mv represents the viscosity average molecular weight of the ethylene-α-olefin copolymer.)
g _SCB * = (1-A) ^1.725 (I-III)
(In the formula, A is a value defined by the following formula (IV).)
A = {(14n + 1) × y} / 14002 (IV)
(In the formula, n represents the number of short-chain branched carbon atoms derived from the monomer unit based on the α-olefin of the ethylene-α-olefin copolymer, and y is a short number per 1000 carbon atoms. Represents the amount of chain branching.)]

  According to the present invention, the olefin resin composition that gives a sheet with high low-temperature impact strength when the sheet is heated at the time of thermoforming is small, the sag of the sheet when the sheet is heated at the time of thermoforming is low, and low temperature It is possible to provide a sheet having high impact strength and a molded body obtained by thermoforming the sheet.

It is the figure which plotted the value of long chain branching amount _NLCB (pieces / 1000C) with respect to the value of MFR (g / 10min) about the ethylene-alpha-olefin copolymer of the polymerization example (PE1-8). It is the figure which showed the melting curve obtained by the differential scanning calorimetry of the ethylene-alpha-olefin copolymer of PE1 and PE7. It is the figure which plotted the value of characteristic relaxation time (tau) ₀ (s < ^-1 >) with respect to the value of MFR (g / 10min) about the ethylene-alpha-olefin copolymer of the polymerization example (PE1-8). It is the figure which plotted the value of oligomer amount (SIGMA) Cn; n = 12-18 (ppm) with respect to the value of MFR (g / 10min) about the ethylene-alpha-olefin copolymer of the polymerization example (PE1-8). In the sheet | seat which consists of a resin composition of Example 1, 2 and Comparative example 1, 2, it is the figure which plotted the value of the low-temperature impact strength of a sheet | seat with respect to the value of MFR (g / 10min) of each component (B). is there. It is the figure which plotted the value of the drawdown of the sheet | seat with respect to the value of MFR (g / 10min) of each component (B) about the sheet | seat which consists of a resin composition of Examples 1, 2 and Comparative Examples 1, 2.

[Propylene polymer (component (A))]
The propylene polymer (component (A)) of the present invention is one or more propylene polymers selected from the group consisting of a propylene homopolymer and a propylene random copolymer.
The propylene homopolymer is obtained by homopolymerizing propylene.
The propylene random copolymer is obtained by random copolymerization of comonomer mainly composed of propylene and copolymerizable therewith. As the propylene random copolymer, a random copolymer having a monomer unit based on propylene and a monomer unit based on olefin selected from the group consisting of ethylene and an α-olefin having 4 to 20 carbon atoms is used. Can be mentioned.

The comonomer of the propylene random copolymer is preferably ethylene or an α-olefin having 4 to 20 carbon atoms. Examples of the α-olefin having 4 to 20 carbon atoms include 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-dodecene and 4-methyl. Examples include -1-pentene and 4-methyl-1-hexene.
The ethylene or α-olefin having 4 to 20 carbon atoms is more preferably ethylene, 1-butene, 1-pentene, 1-hexene and 1-octene from the viewpoint of copolymerizability, especially 1-butene and 1 -Hexene is particularly preferred. Moreover, the said ethylene or C4-C20 alpha olefin may be used independently, and may use 2 or more types together.

Specific examples of the propylene random copolymer include a propylene-ethylene random copolymer, a propylene / ethylene / 1-butene random copolymer, and a propylene-1-butene random copolymer.
The content of the monomer unit based on olefin selected from the group consisting of ethylene and an α-olefin having 4 to 20 carbon atoms contained in the propylene random copolymer is 100% by weight of the propylene random copolymer. When it is, it is preferably 20% by weight or less, more preferably 10% by weight or less. Moreover, it is preferably 1% by weight or more, more preferably 2% by weight or more.
In the propylene / ethylene random copolymer and propylene / 1-butene random copolymer, the content of the monomer unit based on ethylene and the content of the monomer unit based on 1-butene are, for example, “Polymer Analysis Handbook” "(1995, published by Kinokuniya Shoten), page 616, can be obtained by measuring infrared (IR) spectrum.

  The propylene polymer (component (A)) of the present invention has a melt flow rate (MFR) measured at a temperature of 230 ° C. and a load of 21.18 N in accordance with JIS K 7210, 0.01 to 50 g / 10 min. It is preferable that it exists in the range of 0.1-10 g / 10min from the point of the workability at the time of thermoforming.

  The stereoregularity of the propylene polymer (component (A)) of the present invention may be any of isotactic, syndiotactic, and atactic. In the present invention, a syndiotactic or isotactic propylene polymer is preferably used from the viewpoint of heat resistance.

  The propylene polymer (component (A)) of the present invention can be produced by a method of homopolymerizing propylene, a method of copolymerizing propylene and another copolymerizable comonomer, or the like. As the polymerization catalyst, for example, (a) a Ti—Mg-based catalyst comprising a solid catalyst component containing magnesium, titanium and halogen as essential components, and (b) a solid catalyst component comprising magnesium, titanium and halogen as essential components, Examples thereof include a catalyst system in which an organoaluminum compound is combined with a third component such as an electron donating compound as required, and (c) a metallocene catalyst.

  The propylene polymer (component (A)) of the present invention uses, for example, an inert hydrocarbon solvent typified by a hydrocarbon compound such as hexane, heptane, octane, decane, cyclohexane, methylcyclohexane, benzene, toluene, and xylene. A slurry polymerization method, a solvent polymerization method, a liquid phase polymerization method without a solvent, a gas phase polymerization method and the like can be mentioned, and a gas phase polymerization method is preferable. Furthermore, the above polymerization methods are combined and a method for continuously performing them, for example, a polymerization by these methods including a liquid phase-gas phase polymerization method, etc., may be performed in a batch mode or a continuous mode. May be.

[Ethylene-α-olefin copolymer (component (B))]
The ethylene-α-olefin copolymer (component (B)) of the present invention has ethylene-α- having a monomer unit based on ethylene and a monomer unit based on an α-olefin having 3 to 20 carbon atoms. It is an olefin copolymer. Examples of the α-olefin include propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-dodecene, 4-methyl-1-pentene, 4 -Methyl- 1-hexene etc. are mention | raise | lifted and these may be used independently and 2 or more types may be used together. As the α-olefin, 1-butene, 1-hexene, 4-methyl-1-pentene, and 1-octene are preferably used, and 1-butene and 1-hexene are more preferably used.

The ethylene-α-olefin copolymer of the present invention (component (B)) is necessary in addition to the above-described monomer units based on ethylene and monomer units based on α-olefins having 3 to 20 carbon atoms. Accordingly, it may have a monomer unit based on another monomer. Examples of other monomers include conjugated dienes (for example, butadiene and isoprene), non-conjugated dienes (for example, 1,4-pentadiene), acrylic acid, acrylic acid esters (for example, methyl acrylate and ethyl acrylate), and methacrylic acid. Methacrylic acid esters (for example, methyl methacrylate and ethyl methacrylate), vinyl acetate and the like.

  Content of the monomer unit based on ethylene in the ethylene-α-olefin copolymer (component (B)) of the present invention is based on the total weight (100% by weight) of the ethylene-α-olefin copolymer. Usually, it is 50 to 99.5% by weight. The content of the monomer unit based on the α-olefin is usually 0.5 to 50% by weight with respect to the total weight (100% by weight) of the ethylene-α-olefin copolymer.

  The ethylene-α-olefin copolymer (component (B)) of the present invention is preferably a copolymer having a monomer unit based on ethylene and a monomer unit based on an α-olefin having 4 to 20 carbon atoms. More preferably, it is a copolymer having a monomer unit based on ethylene and a monomer unit based on an α-olefin having 5 to 20 carbon atoms, and more preferably a single unit based on ethylene. It is a copolymer having a monomer unit and a monomer unit based on an α-olefin having 6 to 8 carbon atoms.

  Examples of the ethylene-α-olefin copolymer (component (B)) of the present invention include an ethylene-1-butene copolymer, an ethylene-1-hexene copolymer, and an ethylene-4-methyl-1-pentene copolymer. Polymer, ethylene-1-octene copolymer, ethylene-1-butene-1-hexene copolymer, ethylene-1-butene-4-methyl-1-pentene copolymer, ethylene-1-butene-1- Examples include octene copolymer, ethylene-1-hexene-1-octene copolymer, and the like, preferably ethylene-1-hexene copolymer, ethylene-4-methyl-1-pentene copolymer, ethylene-1- They are a butene-1-hexene copolymer, an ethylene-1-butene-1-octene copolymer, and an ethylene-1-hexene-1-octene copolymer.

The density of the ethylene-α-olefin copolymer (component (B)) of the present invention (hereinafter sometimes referred to as “d”) is 880 to 940 kg / m ³ , and the obtained sheet or molded product From the standpoint of increasing the impact strength, it is preferably 930 kg / m ³ or less, more preferably 925 kg / m ³ or less. From the viewpoint of increasing the rigidity of the obtained sheet or molded article, it is preferably 890 kg / m ³ or more, more preferably 900 kg / m ³ or more, and further preferably 910 kg / m ³ or more. The density is measured according to the method defined in Method A of JIS K7112-1980 after annealing described in JIS K6760-1995. Moreover, the density of the ethylene-α-olefin copolymer (component (B)) of the present invention can be changed by the content of monomer units based on ethylene in the ethylene-α-olefin copolymer.

  The melt flow rate (hereinafter sometimes referred to as “MFR”) of the ethylene-α-olefin copolymer (component (B)) of the present invention is 0.01 to 10 g / 10 min. The melt flow rate is preferably 0.05 g / 10 min or more from the viewpoint of enhancing the surface smoothness of the sheet or the molded article and enhancing the compatibility with the propylene polymer (component (A)). Further, from the viewpoint of increasing the mechanical strength of the obtained sheet or molded product, it is preferably 3.0 g / 10 min or less, more preferably 1.5 g / 10 min or less, and even more preferably 0.7 g / 10 min or less. is there. The melt flow rate is a value measured by Method A under the conditions of a temperature of 190 ° C. and a load of 21.18 N in the method defined in JIS K7210-1995. In the measurement of the melt flow rate, usually, an ethylene-α-olefin copolymer previously blended with about 1000 ppm of an antioxidant is used.

  The weight average molecular weight (hereinafter sometimes referred to as “Mw”) and the number average molecular weight (hereinafter referred to as “Mn”) of the ethylene-α-olefin copolymer (component (B)) of the present invention. The molecular weight distribution (hereinafter sometimes referred to as “Mw / Mn”), which is a ratio to the ratio, is 4.5 to 13. From the viewpoint of lowering the extrusion load at the time of extrusion molding, it is preferably 4.7 or more, more preferably 4.9 or more, still more preferably 5.1 or more, particularly preferably 5.3 or more. From the viewpoint of increasing the mechanical strength of the obtained sheet or molded body or reducing the low molecular weight component that causes stickiness of the obtained sheet or molded body, it is preferably 10 or less, more preferably 8 or less. The amount of the sticky component can be quantified by measuring a cold xylene soluble part ratio (CXS) or the like.

Mw / Mn is a value (Mw / Mn) obtained by measuring the weight average molecular weight (Mw) and the number average molecular weight (Mn) by gel permeation chromatography (GPC), and dividing Mw by Mn. . Moreover, as measurement conditions by GPC method, the following conditions can be mention | raise | lifted, for example.
(1) Equipment: Waters 150C manufactured by Waters
(2) Separation column: TOSOH TSKgelGMH6-HT
(3) Measurement temperature: 140 ° C
(4) Carrier: Orthodichlorobenzene
(5) Flow rate: 1.0 mL / min
(6) Injection volume: 500 μL
(7) Detector: Differential refractometer
(8) Molecular weight reference material: Standard polystyrene

  The flow activation energy of the ethylene-α-olefin copolymer (component (B)) of the present invention (hereinafter sometimes referred to as “Ea”) is 40 kJ / mol to 100 kJ / mol. From the viewpoint of further reducing the extrusion load during extrusion molding, it is 45 kJ / mol or more, more preferably 55 kJ / mol or more, still more preferably 60 kJ / mol or more, and even more preferably 65 kJ / mol or more. . The flow activation energy is preferably 90 kJ / mol or less from the viewpoint of increasing the mechanical strength of the sheet or molded body. In the production method described later, the flow activation energy can be changed, for example, depending on polymerization conditions such as hydrogen concentration, organoaluminum compound concentration, ethylene pressure, and polymerization temperature.

The activation energy (Ea) of the flow is dependent on the angular frequency (unit: rad / second) dependence of the melt complex viscosity (unit: Pa · second) at 190 ° C. based on the temperature-time superposition principle. It is a numerical value calculated by the Arrhenius type equation from the shift factor (a _T ) when creating the master curve shown, and is a value obtained by the method shown below. That is, melt complex viscosity-angular frequency curve of olefin polymer at temperatures of 130 ° C., 150 ° C., 170 ° C. and 190 ° C. (T, unit: ° C.) (unit of melt complex viscosity is Pa · second, unit of angular frequency) Is rad / sec.) For each melt complex viscosity-angular frequency curve at each temperature (T) based on the temperature-time superposition principle, the melt complex viscosity-angle of the olefin polymer at 190 ° C. seek shift factor (a _T) at each temperature (T) obtained when superimposed on the frequency curve, and each of the temperature (T), from a shift factor (a _T) at each temperature (T), A linear approximate expression (formula (II) below) of [ln (a _T )] and [1 / (T + 273.16)] is calculated by the method of least squares. Next, Ea is obtained from the slope m of the linear expression and the following expression (III).
ln (a _T ) = m (1 / (T + 273.16)) + n (II)
Ea = | 0.008314 × m | (III)
a _T : Shift factor Ea: Activation energy of flow (unit: kJ / mol)
T: Temperature (unit: ° C)
For the calculation, commercially available calculation software may be used. As the calculation software, Rheos V. manufactured by Rheometrics is used. 4.4.4 etc. are mentioned.
The shift factor (a _T ) is obtained by moving the logarithmic curve of the melt complex viscosity-angular frequency at each temperature (T) in the log (Y) = − log (X) axis direction (however, the Y axis Is the complex viscosity of the melt, and the X axis is the angular frequency.), And the amount of movement when superposed on the melt complex viscosity-angular frequency curve at 190 ° C., in the superposition, melting at each temperature (T) The logarithmic curve of complex viscosity-angular frequency shifts the angular frequency by a _T times and the melt complex viscosity by 1 / a _T times for each curve. Moreover, the correlation coefficient when calculating | requiring (II) Formula by the least squares method from the value of four points | pieces, 130 degreeC, 150 degreeC, 170 degreeC, and 190 degreeC is usually 0.99 or more.

  The melt complex viscosity-angular frequency curve is measured using a viscoelasticity measuring apparatus (for example, Rheometrics Mechanical Spectrometer RMS-800 manufactured by Rheometrics), and usually geometry: parallel plate, plate diameter: 25 mm, plate interval: 1. It is performed under the conditions of 5 to 2 mm, strain: 5%, angular frequency: 0.1 to 100 rad / sec. The measurement is performed in a nitrogen atmosphere, and it is preferable that an appropriate amount (for example, 1000 ppm) of an antioxidant is added to the measurement sample in advance.

The amount of long chain branching (LCB amount; sometimes referred to as “N _LCB ”) measured by NMR of the ethylene-α-olefin copolymer (component (B)) of the present invention is 1000 carbon atoms. 0.29 to 0.50. The amount of LCB per 1000 carbon atoms (N _LCB ) is preferably 0.30 or more, more preferably 0.31 or more, further preferably 0.32 or more from the viewpoint of improving workability. Particularly preferred is 0.33 or more, and most preferred is 0.34 or more. Moreover, from a viewpoint of raising mechanical strength, Preferably it is 0.45 or less, More preferably, it is 0.42 or less. In the production method described later, the amount of LCB can be changed, for example, depending on polymerization conditions such as hydrogen concentration, organoaluminum compound concentration, ethylene pressure, polymerization temperature, and the like.

The amount of LCB (N _LCB ) is determined by the carbon nuclear magnetic resonance ( ¹³ C-NMR) method, the carbon nuclear magnetic resonance ( ¹³ C-NMR) spectrum of the polymer under the measurement conditions described later, and determined by the calculation method described later. The number of long chain branches per 1000 carbon atoms in the polymer.

LCB amount (N _LCB ) measurement condition device: AVANCE 600 manufactured by Bruker
Measurement probe: 10 mm cryoprobe Measurement solvent: 1,2-dichlorobenzene / 1,2-dichlorobenzene-d4
= 75/25 (volume ratio) mixed solution measurement temperature: 130 ° C.
Measurement method: proton decoupling method Pulse width: 45 degrees Pulse repetition time: 4 seconds Measurement standard: Tetramethylsilane window function: Exponential or Gaussian integration number: 2500

Calculation method of long chain branching amount (LCB amount) In NMR spectrum in which window function is treated with Gaussian, 7 or more carbon atoms when sum of peak areas of all peaks having peak top at 5 to 50 ppm is 1000 The peak area of the peak derived from the methine carbon to which these branches are bonded is defined as the long-chain branch amount (the number of branches having 7 or more carbon atoms). Under these measurement conditions, the peak area of a peak having a peak top in the vicinity of 38.22 to 38.27 ppm when the sum of peak areas of all peaks having a peak top at 5 to 50 ppm is 1000 is a long chain branch. Amount (number of branches having 7 or more carbon atoms). The peak area of the peak was defined as the area of the signal in the range from the chemical shift of the valley with the adjacent peak on the high magnetic field side to the chemical shift of the valley with the adjacent peak on the low magnetic field side. In this measurement condition, a branch having 7 or more carbon atoms is a long chain branch. Therefore, a branch having 6 or less carbon atoms is not regarded as a long chain branch. For example, a hexyl branch (branch having 6 carbon atoms) derived from 1-octene of an ethylene-1-octene copolymer is not regarded as a long chain branch. In the measurement of the ethylene-1-octene copolymer, the position of the peak top of the peak derived from the methine carbon bonded with the hexyl branch is 38.21 ppm, and is not included in the peak used for calculating the LCB amount. .

G * of the ethylene-α-olefin copolymer (component (B)) of the present invention is 0.76 to 0.88. g * is an index representing the degree of contraction of a molecule in a solution due to long chain branching. If the amount of long chain branching is large, the molecular chain is more easily contracted and g * becomes smaller. From the viewpoint of reducing the workability during thermoforming and reducing the sag of the resin, it is preferably 0.85 or less, more preferably 0.84 or less, still more preferably 0.83 or less, and particularly preferably 0.8. 82 or less. Further, g * of the ethylene-α-olefin copolymer is preferably 0.77 or more, more preferably 0.78 or more, from the viewpoint of improving mechanical strength.
g * can be lowered, for example, by carrying out prepolymerization under suitable conditions.

g * is a value defined by the following formula (I) (g * was referred to the following document: Developments in Polymer Characterisation-4, JV. Dawkins, Ed., Applied Science, London, 1983, Chapter. I, “Characterization. Of. Long Chain Branching in Polymers,” by Th. G. Scholte.
g * = [η] / ([η] _GPC × g _SCB *) (I)
[Wherein [η] represents the intrinsic viscosity (unit: dl / g) of the ethylene-α-olefin copolymer, and is a value defined by the following formula (I-I). [Η] _GPC is a value defined by the following formula (I-II). g _SCB * is a value defined by the following formula (I-III).
[Η] = 23.3 × log (ηrel) (II)
(In the formula, ηrel represents the relative viscosity of the ethylene-α-olefin copolymer.)
[Η] _GPC = 0.00046 × Mv ^0.725 (I-II)
(In the formula, Mv represents the viscosity average molecular weight of the ethylene-α-olefin copolymer.)
g _SCB * = (1-A) ^1.725 (I-III)
(In the formula, A is a value defined by the following formula (IV).
A = {(14n + 1) × y} / 14002 (IV)
(In the formula, n represents the number of short-chain branched carbon atoms derived from the monomer unit based on the α-olefin of the ethylene-α-olefin copolymer, and y is a short number per 1000 carbon atoms. Represents the amount of chain branching.)]

[Η] _GPC is the intrinsic viscosity (unit: dl / g) of a polymer assuming that the molecular weight distribution is the same as that of the ethylene-α-olefin copolymer and the molecular chain is linear. Represents.
g _SCB * represents the contribution to g * produced by introducing short chain branching into the ethylene-α-olefin copolymer.
As the formula (I-II), the formula described in Journal of Polymer Science, 36, 130 (1959) pp. 287-294 by LH Tung was used.

  The relative viscosity (ηrel) of the ethylene-α-olefin copolymer was determined by adding 100 mg of an ethylene-α-olefin copolymer at 135 ° C. to 100 ml of a tetralin solution containing 5% by weight of butylhydroxytoluene (BHT) as a thermal degradation inhibitor. A sample solution is prepared by dissolution, and is calculated from the falling time of the sample solution and a blank solution made of a tetralin solution containing only 0.5% by weight of BHT as a thermal degradation inhibitor using an Ubbelohde viscometer.

で定義され、a＝０．７２５とした。ここで分子量Ｍ_μの分子数をｎ_μとする。 The viscosity-average molecular weight (Mv) of the ethylene-α-olefin copolymer is the following formula (I-IV)

And a = 0.725. Here, the number of molecules having a molecular weight M _μ is defined as n _μ .

A in the formula (I-III) is a value defined by the following formula (IV). N in the formula (IV) represents the number of short-chain branched carbon atoms derived from the monomer unit based on the α-olefin of the ethylene-α-olefin copolymer (for example, butene as α-olefin). When used, n = 2, and when using hexene, n = 4), y represents the amount of short chain branching per 1000 carbon atoms, and is a value determined by NMR or infrared spectroscopy.
A = {(12n + 2n + 1) × y} / {(1000−2y−2) × 14 + (y + 2) × 15 + 13y} = {(14n + 1) × y} / 14002 (IV)
When the ethylene-α-olefin copolymer has monomer units derived from different types of α-olefins, A is a value defined by the following formula (IV ′).
type of α- olefin as is m type, the number of carbon atoms of short chain branches derived from the monomer unit based on each α- olefin, respectively, n _{1, n 2,} and · · · n _m, the α- olefins from monomer unit based on the short-chain branching, y ₁ the short chain branching of several per 1000 carbon _atoms, y _2, ··· y _m, all short chain branching number per 1000 carbon atoms When the number is ytotal,
A = {(12n ₁ + 2n ₁ +1) × y ₁ + (12n ₂ + 2n ₂ +1) × y ₂ +... + (12n _m + 2n _m +1) × y _m } / {(1000-2ytotal-2) × 14+ (ytotal + 2) × 15 + 13ytotal}
= {(14n ₁ +1) × y ₁ + (14n ₂ +1) × y ₂ +... + (14n _m +1) × y _m } / 14002 (IV ′)

The ethylene-α-olefin copolymer (component (B)) used in the present invention is obtained from differential scanning calorimetry of the ethylene-α-olefin copolymer from the viewpoint of improving the heat resistance of the sheet and the molded product. In the melting curve showing the relationship between temperature and heat flow, a plurality of melting peaks are shown in the range from 25 ° C. to 150 ° C., and the maximum melting peak is higher than the maximum melting peak with the highest melting peak height (heat flow). It is preferable to show a melting peak different from.
Here, the melting peak means a point where the peak height (heat flow) shows a maximum value in the melting curve or a point where the peak height (heat flow) shows the following shoulder.
A shoulder means that there is no local maximum between two inflection points, and the melting curve between the two inflection points is convex upward, the inflection point on the low temperature side and the high temperature side inflection point. It is a convex vertex that connects inflection points with a straight line to form a base line, and the base line is the base.
The inflection point is a point at which the tangent slope at a certain point of the melting curve starts from increasing to decreasing, or a tangential slope from the decreasing to increasing point.
Two melting peaks are shown in the range from 25 ° C. to 150 ° C., and the melting curve of PE1 of Polymerization Example 1 in which one melting peak shows the shoulder is shown in FIG. Moreover, the melting curve of PE7 of Polymerization Example 7 showing only one melting peak in the range from 25 ° C. to 150 ° C. is also shown in FIG.
The ethylene-α-olefin copolymer showing a melting peak different from the maximum melting peak at a temperature higher than the maximum melting peak having the largest peak height is the same density as the ethylene-α-olefin copolymer, It means that the ethylene-α-olefin copolymer having rigidity and having only one melting peak contains a component having high crystallinity. A component having high crystallinity can improve the moldability at the time of melt molding, and can improve the heat resistance of the resulting sheet and molded product. In addition, the number of melting peaks can be changed by, for example, the organoaluminum compound concentration or the polymerization temperature in the production method described later. When the organoaluminum compound or the polymerization temperature is increased, the ethylene-α-olefin copolymer is increased. A melting peak area different from the maximum melting peak is increased.

  In addition, the melting curve of the ethylene-α-olefin copolymer is measured by using a differential scanning calorimeter (for example, a differential scanning calorimeter DSC-7 manufactured by Perkin Elmer), for example, an aluminum pan in which about 10 mg of a sample is sealed. (1) held at 150 ° C. for 5 minutes, (2) lowered from 150 ° C. to 20 ° C. at 5 ° C./minute, (3) held at 20 ° C. for 2 minutes, and (4) 20 at 5 ° C./minute. It is obtained from the differential scanning calorimetry curve obtained by measuring from (4) by raising the temperature from 0 ° C to the melting end temperature + about 20 ° C (usually about 150 ° C).

The characteristic relaxation time of the ethylene-α-olefin copolymer (component (B)) of the present invention (hereinafter sometimes referred to as “τ ₀ ”) is the same as that of the ethylene-α-olefin copolymer of the present invention. From the viewpoint of improving the appearance of the sheet formed using, preferably the following formula (a-1)
τ ₀ <3.8 × MFR ^−0.62 formula (a-1)
More preferably, formula (a-2) is satisfied, further preferably formula (a-3) is satisfied, particularly preferably formula (a-4) is satisfied, and most preferably formula (a-) is satisfied. 5) is satisfied.
τ ₀ <3.7 × MFR ^−0.62 (a-2)
τ ₀ <3.6 × MFR ^−0.62 (a-3)
τ ₀ <3.5 × MFR ^−0.62 (a-4)
τ ₀ <3.4 × MFR ^−0.62 (a-5)

In general, it is known that the following formula is established for a polymer having sufficient entanglement.
τ ₀ = A · η ₀ formula (2)
Further, in FIG. 14 of Macromolecules, 33, 7489 (2000) (PM Wood-Adams et al.), In a metallocene polyethylene containing long chain branches, log-log plots of η ₀ and Mw can be expressed by straight lines. It is reported that this is a polyethylene containing long chain branches and the following formula η ₀ = B · Mw ^ε formula (3)
Strongly suggests that Substituting this equation (3) into equation (2), the following equation (4) can be derived.
τ ₀ = C · MFR ^ε formula (4)
In order to define the range of τ ₀ of the ethylene-α-olefin copolymer used in the sheet of the present invention, the inequality of formula (a) was used.
τ ₀ <C ₁ · MFR ^ε1 formula (a)

The plot of τ ₀ and MFR of PE1 to PE6 shown in Table 1 that satisfies the requirements of the component (B) of the present invention was fitted by using Equation (4) using Microsoft Excel. MFR and relaxation time of PE1 to PE6 were used for fitting. In view of the accuracy of data, -0.62 was obtained as ε1. Also from the equation (a-1) is a inequalities multiplied by a constant a C ₁ in the following manner to obtain a formula (a-5).
To give equation (a-1) as the _{C 1} to 1.235 times the value of the obtained C by fitting. To give equation (a-2) as a _{C 1} to 1.202 times the value of the obtained C by fitting. To give equation (a-3) as a _{C 1} to 1.170 times the value of the obtained C by fitting. The value of C obtained by fitting is multiplied by 1.137 to obtain C ₁ as formula (a-4)
Got. The value of C obtained by fitting is multiplied by 1.105 to obtain C ₁ as the formula (a-5
)

Similarly, the inequality of formula (b) was used to define the preferred range of τ ₀ of the ethylene-α-olefin copolymer of component (B) of the present invention.
τ ₀ > C ₂ · MFR ^ε2 formula (b)

From the viewpoint of stably producing a sheet having a uniform thickness, τ ₀ of the ethylene-α-olefin copolymer used in the sheet of the present invention is preferably the following relational formula (b-1):
τ ₀ > 1.5 × MFR ^−0.62 (b-1)
Is satisfied, more preferably the relational expression of the formula (b-2) is satisfied, and still more preferably the relational expression of the formula (b-3) is satisfied.
τ ₀ > 2.0 × MFR ^−0.62 (b-2)
τ ₀ > 2.5 × MFR ^−0.62 (b-3)

The plot of τ ₀ and MFR of PE1 to PE6 shown in Table 1 that satisfies the requirements of the component (B) of the present invention was fitted by using Equation (4) using Microsoft Excel. MFR and relaxation time of PE1 to PE6 were used for fitting. In view of the accuracy of the data, -0.62 was obtained as ε2. Also the following manner inequalities that constant multiple of C ₂ formula (b-1) was obtained formula (b-3).
To give formula (b-1) as a _{C 2} to 0.478 times the value of the obtained C by fitting. To give formula (b-2) as a _{C 2} to 0.650 times the value of the obtained C by fitting. To give formula (b-3) as a _{C 2} to 0.812 times the value of the obtained C by fitting.

The characteristic relaxation time (τ ₀ ) is a numerical value related to the molecular weight of the ethylene-α-olefin copolymer and the length of the long chain branch (the number of carbon atoms of the long chain branch), and the molecular weight is small or the long chain branch When the is short, the characteristic relaxation time becomes a small value, and when the molecular weight is large or long chain branching is long, the characteristic relaxation time becomes a large value. In order to obtain a high melt tension and a high strain hardening property, it is necessary that a long chain branch having a sufficient amount or a sufficient length is introduced into the molecular chain, and preferably has a certain relaxation time or more. On the other hand, a polymer having a too long relaxation time has high strain hardening characteristics, but the take-up property of the molten resin with respect to the melt tension is deteriorated, that is, the balance between the melt tension and the take-up property is deteriorated. In the production method described later, the characteristic relaxation time can be changed, for example, depending on polymerization conditions such as hydrogen concentration, ethylene pressure, and polymerization temperature, and the characteristic relaxation time of the ethylene-α-olefin copolymer can be changed.

The characteristic relaxation time is calculated from a master curve showing the dependence of the melt complex viscosity (unit: Pa · second) at 190 ° C on the angular frequency (unit: rad / second), which is created based on the temperature-time superposition principle. It is a numerical value. Specifically, the melt complex viscosity-angular frequency curve of the ethylene-α-olefin copolymer at each temperature (T, unit: ° C.) at 130 ° C., 150 ° C., 170 ° C. and 190 ° C. (unit of melt complex viscosity is (Pa · sec, unit of angular frequency is rad / sec.) Is superposed on the melt complex viscosity-angular frequency curve at 190 ° C based on the temperature-time superposition principle to obtain a master curve. It is a value calculated by approximating the master curve by the following formula (5).
η = η ₀ / [1+ (τ ₀ × ω) ⁿ ] (5)
η: melt complex viscosity (unit: Pa · sec)
ω: angular frequency (unit: rad / sec)
τ ₀ : Characteristic relaxation time (unit: s ⁻¹ )
η ₀ : Constant determined for each ethylene-α-olefin copolymer (unit: Pa · second)
n: Constant determined for each ethylene-α-olefin copolymer For the above calculation, commercially available calculation software may be used. As the calculation software, Rhios V. manufactured by Rheometrics Co., Ltd. may be used. 4.4.4.

  The melt complex viscosity-angular frequency curve is measured using a viscoelasticity measuring device (for example, Rheometrics Mechanical Spectrometer RMS-800 manufactured by Rheometrics), and usually geometry: parallel plate, plate diameter: 25 mm, plate interval: 1.5. ˜2 mm, strain: 5%, angular frequency: 0.1-100 rad / sec. Note that the measurement is performed in a nitrogen atmosphere, and it is preferable that an appropriate amount (for example, 1000 ppm) of an antioxidant is added to the measurement sample in advance.

  The melt flow rate ratio of the ethylene-α-olefin copolymer (component (B)) of the present invention (hereinafter sometimes referred to as “MFRR”) is from the viewpoint of further reducing the extrusion load during molding. , Preferably it is 60 or more, More preferably, it is 65 or more, More preferably, it is 70 or more. Moreover, from a viewpoint of raising the mechanical strength of the sheet | seat obtained more, Preferably it is 150 or less, More preferably, it is 130 or less. The MFRR is a melt flow rate (hereinafter sometimes referred to as “H-MFR”) measured under conditions of a load of 211.82 N and a temperature of 190 ° C. in the method defined in JIS K7210-1995. In the method defined in JIS K7210-1995, it is a value divided by the melt flow rate (MFR) measured under conditions of a load of 21.18 N and a temperature of 190 ° C. In addition, MFRR can be changed by, for example, the hydrogen concentration in the production method described later. When the hydrogen concentration is increased, the MFRR of the ethylene-α-olefin copolymer is decreased.

  The ratio (Mz / Mw) of polystyrene-equivalent z-average molecular weight (Mz) and weight-average molecular weight (Mw) of the ethylene-α-olefin copolymer (component (B)) of the present invention is 2.2 to 3.5. It is preferable that In order to obtain a sheet having good mechanical strength, the Mz / Mw of the ethylene-α-olefin copolymer is preferably 3.0 or less, more preferably 2.9 or less, and still more preferably 2. 7 or less. Moreover, from a viewpoint of reducing the extrusion load at the time of a shaping | molding process more, Preferably it is 2.3 or more, More preferably, it is 2.4 or more.

The dynamic complex viscosity (η ^{* 100} , unit: Pa · sec) of the ethylene-α-olefin copolymer (component (B)) of the present invention at a temperature of 190 ° C. and an angular frequency of 100 rad / sec increases the extrusion processability. From the viewpoint, it is preferably 1500 Pa · sec or less. It is preferably 1300 Pa · sec or less, more preferably 1200 Pa · sec or less, further preferably 1150 Pa · sec or less, and most preferably 1100 Pa · sec or less. Further, from the viewpoint of increasing mechanical strength, it is preferably 300 Pa · second or more, more preferably 400 Pa · second or more, and further preferably 500 Pa · second or more. The angular frequency of 100 rad / sec is an angular frequency close to the shear rate when an ethylene-α-olefin copolymer is processed with a general processing machine, and can be used as an index of workability.

  The melt tension at 190 ° C. of the ethylene-α-olefin copolymer (component (B)) of the present invention is preferably 4 to 30 cN from the viewpoint of stably producing a sheet having a uniform thickness. More preferably, it is 4.5 cN or more, More preferably, it is 4.7 cN or more, More preferably, it is 4.9 cN or more. Moreover, from a viewpoint of the production efficiency at the time of manufacturing a sheet | seat, Preferably it is 25 cN or less, More preferably, it is 20 cN or less.

The amount of oligomer contained in the ethylene-α-olefin copolymer (component (B)) of the present invention (hereinafter sometimes referred to as ΣCn; n = 12-18) has high cleanliness of the sheet, and the molded product. From the viewpoint of preventing the contents and contact materials from being contaminated, suppressing fuming generated during melt molding, reducing the amount of fuming components adhering to the sheet, and suppressing contamination of the contents, etc. (c- 1)
ΣCn; n = 12−18 <310 × ln (MFR) +1200 formula (c−1)
It is preferable to satisfy.
More preferably, the formula (c-2) is satisfied, and still more preferably the formula (c-3) is satisfied.
ΣCn; n = 12−18 <310 × ln (MFR) +1150 Formula (c-2)
ΣCn; n = 12−18 <310 × ln (MFR) +1000 formula (c-3)
Here, the oligomer means a hydrocarbon having 12 to 18 carbon atoms.

The amount of oligomer is affected by the concentration of hydrogen supplied during the polymerization of the ethylene-α-olefin copolymer. Similarly, the MFR value controlled by the hydrogen concentration during the polymerization and the ethylene-α-olefin copolymer Shows a certain relational expression (6).
ΣCn; n = 12−18 = D × ln (MFR) + E Formula (6)
This is because, generally, the larger the MFR (the smaller the molecular weight), the greater the amount of oligomer.
Here, the amount of oligomer was converted from the gas chromatography detection peak area of hydrocarbons having 12 to 18 carbon atoms obtained under the measurement conditions described later to hydrocarbon concentration (ppm) of 18 carbon atoms. Value.
In order to define a preferable range of the oligomer amount of the ethylene-α-olefin copolymer of the component (B) of the present invention, the inequality of the formula (c) was used.
ΣCn; n = 12−18 <D ₁ × ln (MFR) + E ₁ formula (c)

Fitting of equation (1) was performed using Microsoft Excel against the plots of oligomer amounts and MFR of PE1 to PE6 listed in Table 1 that satisfy the requirements of component (B) of the present invention. MFR and oligomer amount of PE1-6 were used for fitting. Etc. In view of the accuracy of the data, to obtain a _{D 1} as 310. The yield of formula (c-3) from the formula (c-1) is a inequalities multiplied by a constant to E ₁ in the following manner.
The value of E obtained by fitting was multiplied by 1.216 to obtain E ₁ to obtain formula (c-1). The value of E obtained by fitting was multiplied by 1.165 to obtain E ₁ to obtain formula (c-2). It was obtained (c-3) as _{E 1} and 1.013 times the value of the resulting E by fitting.

  Preferably, the amount of oligomer (ΣCn; n = 12-18) contained in the ethylene-α-olefin copolymer (component (B)) used in the present invention is 1000 ppm or less.

The amount of oligomer (ΣCn; n = 12-18) contained in the ethylene-α-olefin copolymer (component (B)) of the present invention can be measured using gas chromatography. The oligomer can be extracted by an ultrasonic method. The GC measurement device and each measurement condition are as follows.
GC measuring device manufactured by SHIMADZU GC-2010
DB-1 made by J & W
(Film thickness 0.15 μm, length 15 m, inner diameter 0.53 mm) Connection detector (FID) temperature 310 ° C.
Measurement column temperature Hold at 100 ° C. for 1 minute, then increase to 310 ° C. at 10 ° C./min. The total of the detection peak areas of hydrocarbons having 12 to 18 carbon atoms in the obtained gas chromatogram chart is the number of carbon atoms. Converted to a hydrocarbon concentration of 18 (ppm).

Production method of ethylene-α-olefin copolymer (component (B)) As a production method of the ethylene-α-olefin copolymer used in the sheet of the present invention, for example, diethyl zinc (hereinafter referred to as component (a) and ), 3,4,5-trifluorophenol (hereinafter referred to as component (b)), water (hereinafter referred to as component (c)), and inorganic compound particles (hereinafter referred to as component (d). )) In a toluene solvent, and two ligands having a cyclopentadienyl skeleton and a solid particle promoter support (hereinafter referred to as component (A)). A metallocene complex (hereinafter referred to as component (B)) having a structure in which the two ligands are bonded by a crosslinking group such as an alkylene group or a silylene group; and an organoaluminum compound (hereinafter referred to as component (C)). As a catalyst component. And a method of copolymerizing ethylene and α-olefin in the presence of the polymerization catalyst used.

Component (d) is 1,1,1,3,3,3-hexamethyldisilazane (((CH ₃ ) ₃ Si) ₂ NH) (hereinafter referred to as component (e)) as necessary. You may carry out contact processing with.

  The inorganic compound particles of component (d) are preferably silica gel.

The amount of component (a), component (b), and component (c) used is not particularly limited, but the molar ratio of the amount of each component used is component (a): component (b): component (c) = 1: When the molar ratio of y: z is used, it is preferable that y and z substantially satisfy the following formula (1).
0.5 <y + 2z <5 (1)
In the above formula (1), y is preferably a number of 0.5 to 4, more preferably a number of 0.6 to 3, further preferably a number of 0.8 to 2.5, and most preferably. Is a number from 1 to 2. Z in the above formula (1) is a positive number larger than 0, and can arbitrarily take a range determined by y and the above formula (1).

Examples of the order in which the component (a), the component (b), the component (c), the component (d), and the component (e) are brought into contact include the following orders.
<1> After contacting component (d) and component (e), contact component (b), then contact component (a), and then contact component (c).
<2> After contacting component (d) and component (e), contact component (a), then contact component (b), and then contact component (c).
<3> Component (d) and component (a) are contacted, then component (b) is contacted, and then component (c) is contacted.
<4> Component (d) and component (b) are contacted, then component (a) is contacted, and then component (c) is contacted.
The contact order is preferably <1>.

  The contact treatment of component (a), component (b), component (c), component (d) and component (e) is preferably carried out in an inert gas atmosphere. The treatment temperature is usually −100 to 300 ° C., preferably −80 to 200 ° C. The treatment time is usually 1 minute to 200 hours, preferably 10 minutes to 100 hours.

  As a metal atom (M) of the metallocene complex of the said component (B), a periodic table group IV atom is preferable, and a zirconium atom and a hafnium atom are more preferable.

  As a crosslinking group of the metallocene complex of the said component (B), a methylene group, a dimethylmethylene group, and an ethylene group are preferable, More preferably, it is an ethylene group.

  As the remaining substituents that the metal atom of the metallocene complex of the component (B) has, a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, an alkyl group having 1 to 20 carbon atoms, a carbon atom number of 3 10 cycloalkyl groups, aralkyl groups having 7 to 20 carbon atoms, aryl groups having 6 to 20 carbon atoms, alkoxy groups having 1 to 20 carbon atoms, aralkyloxy groups having 7 to 20 carbon atoms, carbon atoms 6-20 aryloxy group, silyl group optionally having 1-20 carbon atoms hydrocarbyl group as a substituent, hydrocarbyl group having 1-20 carbon atoms as a substituent The amino group which may be sufficient is mentioned. Preferably, a chlorine atom, a bromine atom, an iodine atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an aryloxy group having 6 to 10 carbon atoms, or an alkyl group having 1 to 6 carbon atoms An amino group optionally having a hydrocarbyl group as a substituent, particularly preferably a chlorine atom, a bromine atom, an iodine atom, an alkoxy group having 1 to 10 carbon atoms, or an aryl having 6 to 10 elementary atoms An amino group which may have an oxy group or a hydrocarbyl group having 1 to 6 carbon atoms as a substituent. Specifically, phenoxy group, 4-methylphenoxy group, 2,3,4-trimethylphenoxy group, 2,3,5-trimethylphenoxy group, 2,3,6-trimethylphenoxy group, 2,4,6- Examples include trimethylphenoxy group, 3,4,5-trimethylphenoxy group, methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, sec-butoxy group, isobutoxy group, dimethylamino group, and diethylamino group. Particularly preferred are a phenoxy group and a dimethylamino group.

（式中、

Ｒ^１およびＲ^２は、同一または相異なり、
ハロゲン原子を置換基として有していてもよい炭素原子数１〜２０のアルキル基、
ハロゲン原子を置換基として有していてもよい炭素原子数３〜１０のシクロアルキル基、
ハロゲン原子を置換基として有していてもよい炭素原子数２〜２０のアルケニル基、
ハロゲン原子を置換基として有していてもよい炭素原子数２〜２０のアルキニル基、
ハロゲン原子を置換基として有していてもよい炭素原子数７〜２０のアラルキル基、または
ハロゲン原子を置換基として有していてもよい炭素原子数６〜２０のアリール基を表し、Ｒ^３およびＲ^４は、同一または相異なり、水素原子、
ハロゲン原子を置換基として有していてもよい炭素原子数１〜２０のアルキル基、
ハロゲン原子を置換基として有していてもよい炭素原子数３〜１０のシクロアルキル基、
ハロゲン原子を置換基として有していてもよい炭素原子数２〜２０のアルケニル基、
ハロゲン原子を置換基として有していてもよい炭素原子数２〜２０のアルキニル基、
ハロゲン原子を置換基として有していてもよい炭素原子数７〜２０のアラルキル基、または
ハロゲン原子を置換基として有していてもよい炭素原子数６〜２０のアリール基を表し、
Ｒ^５からＲ^８は、同一または相異なり、水素原子、
ハロゲン原子を置換基として有していてもよい炭素原子数１〜２０のアルキル基、
ハロゲン原子を置換基として有していてもよい炭素原子数３〜１０のシクロアルキル基、
ハロゲン原子を置換基として有していてもよい炭素原子数２〜２０のアルケニル基、
ハロゲン原子を置換基として有していてもよい炭素原子数２〜２０のアルキニル基、
ハロゲン原子を置換基として有していてもよい炭素原子数７〜２０のアラルキル基、
ハロゲン原子を置換基として有していてもよい炭素原子数６〜２０のアリール基、
ハロゲン原子を置換基として有していてもよい炭素原子数１〜２０のアルコキシ基、
ハロゲン原子を置換基として有していてもよい炭素原子数７〜２０のアラルキルオキシ基
、
ハロゲン原子を置換基として有していてもよい炭素原子数６〜２０のアリールオキシ基、炭素原子数１〜２０のハイドロカルビル基もしくはハロゲン化ハイドロカルビル基を置換基として有していてもよいシリル基、
炭素原子数１〜２０のハイドロカルビル基もしくはハロゲン化ハイドロカルビル基を置換基として有していてもよいアミノ基、または
ヘテロ環式化合物残基を表し、
Ｒ^１およびＲ^３、Ｒ^２およびＲ^４、Ｒ^５およびＲ^６、Ｒ^５およびＲ^７、Ｒ^７およびＲ^８は
、連結して環を形成してもよく、該環は置換基を有していてもよい。） As a ligand having a cyclopentadienyl skeleton of the metallocene complex of the component (B)

(Where

R ¹ and R ² are the same or different,
An alkyl group having 1 to 20 carbon atoms which may have a halogen atom as a substituent,
A cycloalkyl group having 3 to 10 carbon atoms which may have a halogen atom as a substituent,
An alkenyl group having 2 to 20 carbon atoms which may have a halogen atom as a substituent,
An alkynyl group having 2 to 20 carbon atoms which may have a halogen atom as a substituent,
An aralkyl group having 7 to 20 carbon atoms which may have a halogen atom as a substituent, or an aryl group having 6 to 20 carbon atoms which may have a halogen atom as a substituent, R ³ and R ⁴ is the same or different and is a hydrogen atom,
An alkyl group having 1 to 20 carbon atoms which may have a halogen atom as a substituent,
A cycloalkyl group having 3 to 10 carbon atoms which may have a halogen atom as a substituent,
An alkenyl group having 2 to 20 carbon atoms which may have a halogen atom as a substituent,
An alkynyl group having 2 to 20 carbon atoms which may have a halogen atom as a substituent,
An aralkyl group having 7 to 20 carbon atoms which may have a halogen atom as a substituent, or an aryl group having 6 to 20 carbon atoms which may have a halogen atom as a substituent;
R ⁵ to R ⁸ are the same or different and each represents a hydrogen atom,
An alkyl group having 1 to 20 carbon atoms which may have a halogen atom as a substituent,
A cycloalkyl group having 3 to 10 carbon atoms which may have a halogen atom as a substituent,
An alkenyl group having 2 to 20 carbon atoms which may have a halogen atom as a substituent,
An alkynyl group having 2 to 20 carbon atoms which may have a halogen atom as a substituent,
An aralkyl group having 7 to 20 carbon atoms which may have a halogen atom as a substituent,
An aryl group having 6 to 20 carbon atoms which may have a halogen atom as a substituent;
An alkoxy group having 1 to 20 carbon atoms which may have a halogen atom as a substituent;
An aralkyloxy group having 7 to 20 carbon atoms which may have a halogen atom as a substituent;
The aryloxy group having 6 to 20 carbon atoms which may have a halogen atom as a substituent, the hydrocarbyl group or halogenated hydrocarbyl group having 1 to 20 carbon atoms as a substituent Good silyl group,
An amino group optionally having a hydrocarbyl group having 1 to 20 carbon atoms or a halogenated hydrocarbyl group as a substituent, or a heterocyclic compound residue;
R ¹ and R ³ , R ² and R ⁴ , R ⁵ and R ⁶ , R ⁵ and R ⁷ , R ⁷ and R ⁸ may be linked to form a ring, and the ring has a substituent. It may be. )

Preferred examples of the metallocene complex of the component (B) include the following compounds (B-1) and (B-2). From the viewpoint of mechanical strength such as tensile impact strength, more preferably (B-1 ).

  Moreover, the compound which changed the phenoxy group of these compounds into the dimethylamino group or the diethylamino group, and the compound which changed the zirconium atom into the hafnium atom are also mentioned preferably.

  The organoaluminum compound of component (C) is preferably triisobutylaluminum, trinormal octylaluminum, triethylaluminum, or trimethylaluminum.

The amount of the metallocene complex used as the component (B) is preferably 5 × 10 ^{−6 to} 5 × 10 ⁻⁴ mol with respect to 1 g of the promoter support of the component (A). The amount of the organoaluminum compound used as the component (C) is preferably a ratio of the number of moles of aluminum atoms in the organoaluminum compound as the component (C) to the number of moles of metal atoms in the metallocene complex as the component (B) (Al / M ) And 1 to 5000.

  In the polymerization catalyst obtained by contacting the promoter support (A), the metallocene complex (B) and the organoaluminum compound (C), the promoter support (A) and the metallocene complex (B ) And the organoaluminum compound (C) may be a polymerization catalyst obtained by contacting the electron donating compound (D). Specific examples of the electron donating compound (D) include tertiary amines and secondary amines. Tertiary amines are preferable, and specific examples include triethylamine and trinormaloctylamine.

  From the viewpoint of increasing the molecular weight distribution of the obtained ethylene-α-olefin copolymer, the electron donating compound (D) is preferably used, and the amount of the electron donating compound (D) used is an organoaluminum compound. The amount is more preferably 0.1 mol% or more, still more preferably 1 mol% or more, relative to the number of moles of aluminum atoms in (C). In addition, from the viewpoint of increasing the polymerization activity, the amount used is preferably 30 mol% or less, and more preferably 20 mol% or less.

  The ethylene-α-olefin copolymer (component (B)) of the present invention can be polymerized by a continuous gas phase polymerization method, although the practice of the present invention is not particularly limited. The gas phase polymerization reaction apparatus used in the polymerization method is usually an apparatus having a fluidized bed type reaction tank, and preferably an apparatus having a fluidized bed type reaction tank having an enlarged portion. A stirring blade may be installed in the reaction vessel.

  As a method of supplying each component of the polymerization catalyst used for the production of the ethylene-α-olefin copolymer (component (B)) of the present invention to a reaction vessel, usually an inert gas such as nitrogen or argon, hydrogen, A method using ethylene or the like to supply in a moisture-free state, or a method in which each component is dissolved or diluted in a solvent and supplied in a solution or slurry state is used. Each component of the catalyst may be supplied individually, or arbitrary components may be supplied in contact in advance in an arbitrary order. For the production of the ethylene-α-olefin copolymer used in the resin composition of the present invention, it is preferable to carry out prepolymerization and to use the prepolymerized prepolymerized catalyst component as the catalyst component or catalyst of the main polymerization. .

  The polymerization temperature of the ethylene-α-olefin copolymer (component (B)) of the present invention is preferably 60 to 100 ° C, more preferably 65 to 90 ° C, still more preferably 70 to 90 ° C, and still more preferably. It is 75-90 degreeC, Most preferably, it is 80-90 degreeC. By increasing the polymerization temperature, the molecular weight distribution can be narrowed.

  For the purpose of adjusting the melt fluidity of the ethylene-α-olefin copolymer (component (B)) of the present invention, hydrogen may be added as a molecular weight regulator in the polymerization reactor.

  Multi-stage polymerization may be performed for the purpose of widening the molecular weight distribution of the ethylene-α-olefin copolymer (component (B)) of the present invention.

[Olefin resin composition]
The content of each component in the olefin resin composition of the present invention is such that the total amount of components (A) and (B) contained in the resin composition is 100% by weight, and the content of component (A) is 50. -99 weight%, and content of a component (B) is 1-50 weight%. Preferably, the content of component (A) is 80 to 95% by weight, and the content of component (B) is 5 to 20% by weight. More preferably, the content of the component (A) is 85 to 90% by weight, and the content of the component (B) is 10 to 15% by weight.

  If necessary, the olefin resin composition of the present invention comprises an antioxidant, a neutralizing agent, a lubricant, an antistatic agent, a nucleating agent, an ultraviolet inhibitor, a plasticizer, a dispersant, an antifogging agent, an antibacterial agent, an organic It is possible to add additives such as porous powder and pigment alone or in combination of two or more.

  The olefin resin composition of this invention may contain the thermoplastic resin different from a propylene polymer (component (A)) and an ethylene-alpha-olefin copolymer (component (B)) as needed. Examples of the thermoplastic resin include linear low density polyethylene, high density polyethylene, medium density polyethylene, very low density polyethylene, high pressure method low density polyethylene, and ethylene-α-olefin having a flow activation energy of less than 40 kJ / mol. Copolymer, ethylene-vinyl acetate copolymer, ethylene- (meth) acrylic acid copolymer, metal salt of ethylene- (meth) acrylic acid copolymer, polystyrene, ABS resin, styrene-butadiene block copolymer, and Its hydrogenated products, styrene polymers such as styrene / isoprene block copolymers and their hydrogenated products, polyesters such as polyethylene terephthalate and polybutylene terephthalate, nylon 6, nylon 66, nylon 11, nylon 12, nylon 6, Polyamide such as 66 Polycarbonate, polymethyl methacrylate, polyacetal, polyphenylene sulfide, ethylene / propylene copolymer rubber, styrene thermoplastic elastomer, olefin thermoplastic elastomer, polyester thermoplastic elastomer, polyurethane thermoplastic elastomer, polyamide thermoplastic elastomer, etc. Can be mentioned.

  Examples of the method for producing the olefin resin composition of the present invention include a method of dry blending or melt blending the component (A), the component (B) and other components such as additives as necessary. Can be mentioned. Examples of the dry blending method include a method using various blenders such as a Henschel mixer and a tumbler mixer. Examples of the melt blending method include a single screw extruder, a twin screw extruder, a Banbury mixer, a hot roll, and the like. The method of melt-kneading using these various mixers is mentioned.

[Sheet]
A sheet can be obtained from the olefin resin composition of the present invention. The sheet of the present invention may be a single layer sheet made of the olefin resin composition or a multilayer sheet having a layer made of the olefin resin composition and a layer different from the layer. In the case of a multi-layer sheet, a layer different from the layer made of the olefin resin composition, such as a barrier layer of a gas such as oxygen or water vapor; a sound absorbing layer; a light shielding layer; an oxygen absorbing layer; an adhesive layer; Layer; Recycled resin-containing layer; Foam layer and the like may be provided.
The sheet of the present invention is suitably used for thermoforming containers.

Examples of the method for forming a sheet made of the olefin resin composition of the present invention include an extrusion method such as an inflation method and a T-die cast method, an injection molding method, a compression molding method, and a calendar molding method.
When the sheet of the present invention is a multilayer sheet, it can be formed by a coextrusion method, an extrusion coating method or the like.

  The thickness of the sheet comprising the olefin resin composition of the present invention varies depending on the purpose, application, etc., but is usually 100 μm to 5 mm, preferably 200 μm to 2 mm, more preferably 300 μm to 1 mm, and even more preferably 400 μm. ˜900 μm.

[Molded body]
The sheet of the present invention can be thermoformed into a formed body. Examples of the thermoforming method include a vacuum forming method, a pressure forming method, and a vacuum / pressure forming method. Specifically, free drawing method, plug and ring molding method, ridge molding method, matched mold molding method, straight molding method, drape molding method, reverse draw molding method, air slip molding method, plug assist molding method, plug assist reverse Examples thereof include a draw molding method and a contact heating / pressure forming method.

  The molded body of the present invention is suitably used as various containers (bottles, trays, cups, bottles, lids, etc.) and bubble cushioning materials. Further, these molded products are used as packaging materials for food (butter, natto, bento, side dish, etc.), beverages, industrial parts, sundries, toys, daily necessities, office supplies, medical supplies and the like. Since the ethylene-α-olefin copolymer (component (B)) contained in the molded article of the present invention is also excellent in oil resistance, the molded article of the present invention is suitable for food packaging materials, for example.

Hereinafter, the present invention will be described with reference to examples and comparative examples.
The physical properties in Examples and Comparative Examples were measured according to the following methods.

(1) Density of ethylene-α-olefin copolymer (d, unit: kg / m ³ )
It measured according to the method prescribed | regulated to A method among JISK7112-1980. The sample was annealed according to JIS K6760-1995.

(2) Melt flow rate of ethylene-α-olefin copolymer (MFR, unit: g / 10 min)
In the method defined in JIS K7210-1995, measurement was performed by the A method under the conditions of a load of 21.18 N and a temperature of 190 ° C.

(3) Melt flow rate ratio (MFRR) of ethylene-α-olefin copolymer
In the method specified in JIS K7210-1995, the test load is 211.82N, the melt flow rate (H-MFR) measured at a measurement temperature of 190 ° C., and the method specified in JIS K7210-1995 is the load 21 The melt flow rate (MFR) measured under the conditions of .18 N and a temperature of 190 ° C. was measured and obtained as a value obtained by dividing H-MFR by MFR.

(4) Molecular weight distribution of ethylene-α-olefin copolymer (Mw / Mn, Mz / Mw)
Using gel permeation chromatograph (GPC) method, measure z-average molecular weight (Mz), weight-average molecular weight (Mw) and number-average molecular weight (Mn) under the following conditions (1) to (8) Mw / Mn and Mz / Mw were obtained. The baseline on the chromatogram is a stable horizontal region with a sufficiently long retention time than the appearance of the sample elution peak and a stable horizontal region with a sufficiently long retention time than the solvent elution peak was observed. A straight line formed by connecting the points.
(1) Equipment: Waters 150C manufactured by Waters
(2) Separation column: TOSOH TSKgelGMH6-HT
(3) Measurement temperature: 140 ° C
(4) Carrier: Orthodichlorobenzene
(5) Flow rate: 1.0 mL / min
(6) Injection volume: 500 μL
(7) Detector: Differential refraction
(8) Molecular weight reference material: Standard polystyrene

(5) Long chain branching amount (LCB amount; N _LCB ), short chain branching amount (SCB; N _SCB ) of ethylene-α-olefin copolymer (unit: piece / 1000 C)
The number of long-chain branches or short-chain branches per 1000 carbon atoms is determined by the carbon nuclear magnetic resonance ( ¹³ C-NMR) method and the carbon nuclear magnetic resonance ( ¹³ C-NMR) of the polymer according to the following measurement conditions. The spectrum was measured, and the number of long chain branches or short chain branches per 1000 carbon atoms in the polymer was determined by the following calculation method.

(Measurement condition)
Apparatus: AVANCE600 manufactured by Bruker
Measurement probe: 10 mm cryoprobe Measurement solvent: 1,2-dichlorobenzene / 1,2-dichlorobenzene-d4
= 75/25 (volume ratio) mixed solution measurement temperature: 130 ° C.
Measurement method: proton decoupling method Pulse width: 45 degrees Pulse repetition time: 4 seconds Measurement standard: Tetramethylsilane window function: Exponential or Gaussian integration number: 2500

Calculation method of long chain branching amount (LCB amount) In NMR spectrum in which window function is processed with Gaussian, carbon atom number is 7 or more when sum of peak areas of all peaks having peak top at 5 to 50 ppm is 1000 The peak area of the peak derived from the methine carbon to which the branches were bonded was determined as the amount of long-chain branching (number of branches having 7 or more carbon atoms). Under these measurement conditions, the peak area of a peak having a peak top in the vicinity of 38.22 to 38.27 ppm was determined as the amount of long chain branching (number of branches having 7 or more carbon atoms). The peak area of the peak was defined as the area of the signal in the range from the chemical shift of the valley with the adjacent peak on the high magnetic field side to the chemical shift of the valley with the adjacent peak on the low magnetic field side. In this measurement condition, in the measurement of the ethylene-1-octene copolymer, the peak top position of the peak derived from the methine carbon to which the hexyl branch was bonded was 38.21 ppm.

Calculation method of short chain branching amount (SCB amount) When the comonomer is hexene, a branch having 4 carbon atoms is bound when the sum of the peak areas of all peaks having a peak top at 5 to 50 ppm is 1000 in the NMR spectrum obtained by treating the window function with an exponential. The peak area derived from the methine carbon was calculated as the amount of short chain branching. In this measurement condition, it calculated | required from the total value of the area of a peak of 38.0-38.21 ppm and the area of a peak of 35.85-36.00 ppm.
2. When the comonomer is hexene and butene, in the NMR spectrum in which the window function is processed with the exponential, the branching with 2 carbon atoms when the sum of the peak areas of all peaks having a peak top at 5 to 50 ppm is 1000 The peak area derived from the methine carbon bonded to the methine carbon and the peak area derived from the methine carbon bonded to the branch having 4 carbon atoms were calculated as the amount of short chain branching. In this measurement condition, it calculated | required from the total value of the area of 39.60-39.85 ppm, the area of the peak of 38.00-38.21 ppm, and the area of the peak of 35.85-36.00 ppm.

(6) g * of ethylene-α-olefin copolymer
G * was determined by the formula (I).
[Η] represents the relative viscosity (ηrel) of the ethylene-α-olefin copolymer in 100 ml of tetralin containing 0.5% by weight of butylhydroxytoluene (BHT) as a thermal degradation inhibitor, and ethylene-α-olefin. A sample solution was prepared by dissolving 100 mg of the copolymer at 135 ° C., and using a Ubbelohde viscometer, the sample solution and a blank solution composed of tetralin containing only 0.5% by weight of BHT as a thermal degradation inhibitor Calculated from the fall time and determined by the formula (II), [η] _GPC is determined by the formula (I-II) from the measurement of the molecular weight distribution of the ethylene-α-olefin copolymer of (4), g _SCB * was calculated | required by Formula (I-III) from the measurement of the amount of short chain branches of the ethylene-alpha-olefin copolymer of (5).

(7) Differential scanning calorimetry
The ethylene-α-olefin copolymer was pressed at a pressure of 10 MPa for 5 minutes with a 150 ° C. hot press machine, then cooled for 5 minutes with a 30 ° C. cooling press machine, and formed into a sheet having a thickness of about 100 μm. About 10 mg of sample was cut from the sheet and sealed in an aluminum pan. Next, the aluminum pan in which the sample was sealed was held at a differential scanning calorimeter (differential scanning calorimeter DSC-7 manufactured by Perkin Elmer Co., Ltd.) (1) at 150 ° C. for 5 minutes, and (2) 5 ° C. (3) Hold at 20 ° C. for 2 minutes, (4) Increase the temperature from 20 ° C. to 150 ° C. at 5 ° C./minute, and calculate the melting curve in (4) It was measured. From the obtained melting curve, the number of melting peaks existing in the range from 25 ° C. to 150 ° C. and the temperature showing the maximum melting peak with the highest peak height were determined. In addition, when there were a plurality of melting peaks, a temperature showing a melting peak different from the maximum melting peak was also obtained.

(8) Flexural modulus of ethylene-α-olefin copolymer (unit: MPa)
The flexural modulus was measured at 23 ° C. using a 75 mm × 25 mm × 1 mm thick sample piece according to ASTM D747. The sample piece was molded by hot pressing at 150 ° C., stored in a temperature-controlled room at 23 ° C. and 50% humidity for 24 hours or more, and then used for measurement. It shows that rigidity is so high that this value is high.

(9) Flow activation energy of ethylene-α-olefin copolymer (Ea, unit: kJ / mol)
Using a viscoelasticity measuring device (Rheometrics Mechanical Spectrometer RMS-800 manufactured by Rheometrics), a melt complex viscosity-angular frequency curve at 130 ° C., 150 ° C., 170 ° C. and 190 ° C. was measured under the following measurement conditions. From the obtained melt complex viscosity-angular frequency curve, calculation software Rhios V. Using 4.4.4, a master curve of the melt complex viscosity-angular frequency curve at 190 ° C. was created, and the activation energy (Ea) of the flow was determined.
<Measurement conditions>
Geometry: Parallel plate Plate diameter: 25mm
Plate spacing: 1.5-2mm
Strain: 5%
Angular frequency: 0.1 to 100 rad / sec Measurement atmosphere: Nitrogen

(10) Melt complex viscosity of ethylene-α-olefin copolymer (η *, unit: Pa · sec)
In the measurement of the flow activation energy of (9), the melt complex viscosity measured at a temperature of 190 ° C. and an angular frequency of 100 rad / sec was determined. The lower the melt complex viscosity, the smaller the extrusion load during extrusion molding, and the better the extrusion moldability.

(11) Characteristic relaxation time of ethylene-α-olefin copolymer (τ ₀ , unit: s ⁻¹ )
Τ ₀ was obtained by approximating the master curve of the melt complex viscosity-angular frequency curve at 190 ° C. obtained in the measurement of the flow activation energy of (9) by the following formula (5).
η = η ₀ / [1+ (τ ₀ × ω) ⁿ ] (5)
η: melt complex viscosity (unit: Pa · sec)
ω: angular frequency (unit: rad / sec)
τ ₀ : Characteristic relaxation time (unit: seconds)
η ₀ : Constant determined for each ethylene-α-olefin copolymer (unit: Pa · second)
n: Constant determined for each ethylene-α-olefin copolymer

(12) Melt tension of ethylene-α-olefin copolymer (MT, unit: cN)
Using a melt tension tester manufactured by Toyo Seiki Seisakusho, an ethylene-α-olefin copolymer was melt-extruded from an orifice having a diameter of 2.095 mm and a length of 8 mm at a temperature of 190 ° C. and an extrusion speed of 0.32 g / min. The melted ethylene-α-olefin copolymer was drawn into a filament by a take-up roll at a take-up rate of 6.3 (m / min) / min, and the tension during take-up was measured. The maximum tension from the start of take-up until the filamentous ethylene-α-olefin copolymer was cut was defined as the melt tension.
The higher this value is, the more stable the melt before entering the sizing at the time of forming the sheet, and it becomes easier to obtain a sheet having a uniform thickness.

(13) Maximum take-up speed of ethylene-α-olefin copolymer (MTV, unit: m / min)
In the measurement of the melt tension of (12), the take-up speed when the filamentous ethylene-α-olefin copolymer was cut was defined as the maximum take-up speed. The higher this value, the better the take-up property at the time of extrusion molding.

(14) Impact strength of ethylene-α-olefin copolymer (unit: kJ / m ² )
The measurement of impact strength was performed at 23 ° C. in an S-type dumbbell shape according to ASTM D1822-61T. The sample piece was molded by hot pressing at 150 ° C., stored in a temperature-controlled room at 23 ° C. and 50% humidity for 24 hours or more, and then used for measurement. The larger this value, the better the impact resistance.

(15) Cold xylene soluble part of ethylene-α-olefin copolymer (unit:% by weight)
In a 200 mL flat bottom flask equipped with a reflux condenser, about 0.5 g of an ethylene-α-olefin copolymer sample and 100 mL of xylene were charged and refluxed for 30 minutes. After refluxing, the flat bottom flask was allowed to stand in an atmosphere of about 25 ° C. for 20 minutes, and then left in a water bath adjusted to 25 ° C. for 1 hour. After standing, the solution in the flat bottom flask was filtered with a filter paper (for No. 50 chromatography). The obtained filtrate was subjected to liquid chromatographic analysis under the following conditions (1) to (7), the amount of the copolymer dissolved in the solution was calculated, and the cold xylene-dissolved component ratio was determined from the sample weight.
(1) Apparatus: Degasser DG-2080-53 manufactured by JASCO Corporation
(2) Column: SHODEX GPC KF-801
(3) Column oven: CO-2065Plus manufactured by JASCO Corporation, setting 30 ° C
(4) Eluent: Tetrahydrofuran (for liquid chromatograph)
(5) Flow rate: 1.0 mL / min
(6) Injection volume: 110 μL
(7) Detector: differential refractometer The smaller this value, the better the solvent resistance.

(16) Amount of oligomer of ethylene-α-olefin copolymer (ΣCn; n = 12-18, unit: ppm)
The ethylene-α-olefin copolymer is pressed for 5 minutes at a pressure of 10 MPa with a hot press at 150 ° C. and then cooled for 5 minutes with a cooling press at 30 ° C. to form a sheet having a thickness of about 100 μm to 200 μm. did. About 1 g of a sample was cut out from the sheet, and the oligomer component was extracted by ultrasonic extraction using 10 ml of THF solvent. The oligomer component was quantified by the GC method. The measuring apparatus and each measurement condition are as follows.
<Measurement conditions>
GC measuring device: GC-2010 manufactured by SHIMADZU
Column: DB-1 manufactured by J & W
(Thickness 0.15μm, length 15m, inner diameter 0.53mm)
Detector (FID) temperature: 310 ° C
Measurement column temperature: held at 100 ° C. for 1 minute, then heated up to 310 ° C. at 10 ° C./minute, the total of detection peak areas of hydrocarbons having 12 to 18 carbon atoms in the gas chromatogram chart is the carbon atom This was converted to the hydrocarbon concentration (ppm) of Equation 18.
The smaller this value is, the higher the cleanliness of the sheet, the less likely it is to contaminate the contents and contacts of the molded body, the suppression of fuming that occurs during melt molding, the amount of fuming components adhering to the sheet is reduced, the contents, etc. Contamination can be suppressed.

(17) Smokeability of ethylene-α-olefin copolymer (unit: Count / min)
Covers the die outlet of a T-die sheet molding machine (Union Plastics, USV30 non-vent type extruder, T-die width 250 mm, die lip opening 1 mm) with a digital dust meter (Shibata) Science Co., Ltd., LD-5D, light scattering type) was connected. The number of fuming particles generated from the resin extruded from the T-die sheet molding machine was measured for 1 minute under the conditions of a die temperature of 260 ° C., a cylinder temperature of 260 ° C., and a screw rotation speed of 100 rpm.
The obtained numerical value (unit: Count / min) was used as the evaluation value of smoke generation. The smaller this value is, the less smoke is generated during extrusion molding.

(18) Oil resistance (solvent extraction rate)
The ethylene-α-olefin copolymer was pressed at a pressure of 10 MPa for 5 minutes by a 150 ° C. hot press machine, then cooled for 5 minutes by a 30 ° C. cooling press machine, and formed into a sheet having a thickness of about 1 mm. A sample piece of about 2 cm × 2 cm was cut out from the sheet, put into about 1.3 g of cylindrical filter paper, and subjected to Soxhlet extraction for 2 hours so that the number of reflux was 6 times / 1 hour. As the solvent, ethanol or ethanol / heptane (= 3/7 (volume ratio)) was used. Thereafter, a sample piece was taken out from the cylindrical filter paper and air-dried at 80 ° C., and then the solvent extraction rate was obtained from the following formula. The smaller the solvent extraction rate, the better the oil resistance.

Solvent extraction rate (%) = 100 × (“weight of ethylene-α-olefin copolymer before extraction” − “weight of ethylene-α-olefin copolymer after extraction”) / “ethylene-α before extraction” -Weight of olefin copolymer "

(19) Drawdown of the sheet produced by bank molding (unit: mm)
A sample cut into a size of 90 mm × 90 mm from the center of a sheet produced by bank molding described later was sandwiched between outer frame 125 mm × 125 mm and inner frame 65 mm × 65 mm spacers and fixed with a clamp. Next, the oven was heated to 190 ° C., and the sample was charged. Thirty minutes after the loading, the distance to the position where the clamp fixing surface was the most downward in the vertical direction was measured to measure the amount of drawdown (the amount of sheet sag). If the degree of this drawdown is too large, the molded product may be wrinkled, and the smaller the degree, the better the workability during thermoforming.

(20) Low temperature impact strength of sheet produced by bank molding (unit: J / mm)
A sample cut into a size of 100 mm × 100 mm from the center of the sheet produced by bank molding described later was cooled at −20 ° C. for 2 hours. The cooled sample was tested with a DuPont impact tester (manufactured by Toyo Seiki Seisakusho) to determine 50% fracture energy (J). The obtained energy was divided by the sheet thickness (mm) to obtain the low temperature impact strength (J / mm). Details of the test conditions are shown below.
Conditions for measuring the low temperature impact strength of the sheet:
Sample fixing: Air cylinder tightening method Usage method: Stair case method Test piece tray: Inner diameter 50 mmφ
Diameter of impact core tip: 12.7 mmφ
Weight: 0.5kg

Each component used in the examples and comparative examples of the present invention is as follows.
Component (A): Propylene polymer Sumitomo Nobrene D101 (manufactured by Sumitomo Chemical Co., Ltd .; propylene homopolymer, MFR = 0.5 g / 10 min) was used.

Component (B): Ethylene-α-olefin copolymer Polymerization Example 1 (PE1) and Polymerization Example 2 (PE2), which will be described later, are used as Examples, Polymerization Example 7 (PE7), and Polymerization Example 8 (PE8) are used as Comparative Examples. used.

Synthesis of Polymerization Example 1 (PE1) (1) Preparation of Solid Component (a-1) Silica (Sypolol 948 manufactured by Devison, Inc .; 50), which was heat-treated at 300 ° C. under nitrogen flow in a reactor equipped with a nitrogen-replaced stirrer % Volume average particle diameter = 55 μm; pore volume = 1.67 ml / g; specific surface area = 325 m ² / g) 2.8 kg and 24 kg of toluene were added and stirred. Thereafter, after cooling to 5 ° C., a mixed solution of 0.9 kg of 1,1,1,3,3,3-hexamethyldisilazane and 1.4 kg of toluene was maintained for 30 minutes while maintaining the reactor temperature at 5 ° C. It was dripped at. After completion of dropping, the mixture was stirred at 5 ° C. for 1 hour, then heated to 95 ° C., stirred at 95 ° C. for 3 hours, and filtered. The obtained solid product was washed 6 times with 20.8 kg of toluene. Thereafter, 7.1 kg of toluene was added to form a slurry, which was allowed to stand overnight.

To the slurry obtained above, 1.73 kg of diethylzinc in hexane (diethylzinc concentration: 50% by weight) and 1.02 kg of hexane were added and stirred. Then, after cooling to 5 ° C., a mixed solution of 0.78 kg of 3,4,5-trifluorophenol and 1.44 kg of toluene was added dropwise over 60 minutes while maintaining the temperature of the reactor at 5 ° C. After completion of dropping, the mixture was stirred at 5 ° C. for 1 hour, then heated to 40 ° C. and stirred at 40 ° C. for 1 hour. Then, it cooled to 22 degreeC and 0.11 kg of water was dripped in 1.5 hours, keeping the temperature of a reactor at 22 degreeC. After completion of dropping, the mixture was stirred at 22 ° C. for 1.5 hours, then heated to 40 ° C., stirred at 40 ° C. for 2 hours, further heated to 80 ° C., and stirred at 80 ° C. for 2 hours. After stirring, at room temperature, the supernatant was withdrawn to a residual amount of 16 L, charged with 11.6 kg of toluene, then heated to 95 ° C. and stirred for 4 hours. After stirring, the supernatant liquid was extracted at room temperature to obtain a solid product. The obtained solid product was washed 4 times with 20.8 kg of toluene and 3 times with 24 liters of hexane. Thereafter, the solid component was obtained by drying (hereinafter referred to as promoter support (a-1)).

(2) Preparation of pre-polymerization catalyst component (b-1) After 80 liters of butane was introduced into an autoclave with a stirrer having an internal volume of 210 liters that had been previously purged with nitrogen, 8-tetrahydro-5,5,8,8-tetramethylbenz [f] indenyl) zirconium diphenoxide (101 mmol) was added, and the autoclave was heated to 50 ° C. and stirred for 2 hours. Next, after the temperature of the autoclave is lowered to 30 ° C. and the system is stabilized, 0.03 MPa of ethylene is charged at the gas phase pressure in the autoclave, and 0.7 kg of the promoter support (a-1) is added. Polymerization was started by adding 158 mmol of triisobutylaluminum. After 30 minutes while continuously supplying ethylene at 0.7 kg / hour, the temperature was raised to 50 ° C., and ethylene and hydrogen were supplied at 3.5 kg / hour and 5.5 liters (room temperature and normal pressure volume) / hour, respectively. A total of 4 hours of prepolymerization was carried out by continuous feeding. After completion of the polymerization, ethylene, butane, hydrogen gas, etc. are purged and the remaining solid is vacuum-dried at room temperature. b-1) was obtained.

(3) Production of ethylene-1-hexene copolymer (PE1) Using the prepolymerized catalyst component (b-1) obtained above, ethylene and 1-hexene were copolymerized in a continuous fluidized bed gas phase polymerization apparatus. This was carried out to obtain a polymer powder. As polymerization conditions, the polymerization temperature was 87 ° C., the polymerization pressure was 2 MPa, the hydrogen molar ratio to ethylene was 0.52%, and the 1-hexene molar ratio to the total of ethylene and 1-hexene was 1.30%. During the polymerization, ethylene, 1-hexene and hydrogen were continuously supplied in order to keep the gas composition constant. Moreover, the said prepolymerization catalyst component (b-1), triisobutylaluminum, and triethylamine (3% of molar ratio with respect to triisobutylaluminum) were supplied continuously, and the total powder weight of 80 kg of the fluidized bed was maintained constant. The average polymerization time was 4 hours. The obtained polymer powder was fed using an extruder (LCM50 manufactured by Kobe Steel, Ltd.) at a feed rate of 50 kg / hour, a screw speed of 450 rpm, a gate opening of 50%, a suction pressure of 0.1 MPa, and a resin temperature of 200 to 230 ° C. By granulating under the conditions, an ethylene-1-hexene copolymer (PE1) was obtained. Tables 1 and 2 show the results of physical property evaluations of the obtained copolymers. Moreover, the melting curve of the obtained copolymer was shown in FIG.

Synthesis of Polymerization Example 2 (PE2) (1) Production of ethylene-1-hexene copolymer (PE2) Using the prepolymerized catalyst component (b-1) obtained by the same method as in Polymerization Example 1, continuous fluidized bed gas Copolymerization of ethylene and 1-hexene was performed in a phase polymerization apparatus to obtain a polymer powder. As polymerization conditions, the polymerization temperature was 87 ° C., the polymerization pressure was 2 MPa, the hydrogen molar ratio to ethylene was 0.98%, and the 1-hexene molar ratio to the total of ethylene and 1-hexene was 1.39%. During the polymerization, ethylene, 1-hexene and hydrogen were continuously supplied in order to keep the gas composition constant. Moreover, the said prepolymerization catalyst component (b-1), triisobutylaluminum, and triethylamine (molar ratio 30% with respect to triisobutylaluminum) were supplied continuously, and the total powder weight of 80 kg of a fluid bed was maintained constant. The average polymerization time was 4 hours. The obtained polymer powder was fed using an extruder (LCM50 manufactured by Kobe Steel, Ltd.) at a feed rate of 50 kg / hour, a screw speed of 450 rpm, a gate opening of 50%, a suction pressure of 0.1 MPa, and a resin temperature of 200 to 230 ° C. By granulating under the conditions, an ethylene-1-hexene copolymer (PE2) was obtained. Tables 1 and 2 show the results of physical property evaluations of the obtained copolymers.

Synthesis of Polymerization Example 3 (PE3) (1) Production of Ethylene-1-hexene Copolymer (PE3) Using a prepolymerized catalyst component (b-1) obtained by the same method as in Polymerization Example 1, continuous fluidized bed gas Copolymerization of ethylene and 1-hexene was performed in a phase polymerization apparatus to obtain a polymer powder. As polymerization conditions, the polymerization temperature was 87 ° C., the polymerization pressure was 2 MPa, the hydrogen molar ratio to ethylene was 0.98%, and the 1-hexene molar ratio to the total of ethylene and 1-hexene was 1.34%. During the polymerization, ethylene, 1-hexene and hydrogen were continuously supplied in order to keep the gas composition constant. Moreover, the said prepolymerization catalyst component (b-1), triisobutylaluminum, and triethylamine (3% of molar ratio with respect to triisobutylaluminum) were supplied continuously, and the total powder weight of 80 kg of the fluidized bed was maintained constant. The average polymerization time was 4 hours. The obtained polymer powder was fed using an extruder (LCM50 manufactured by Kobe Steel, Ltd.) at a feed rate of 50 kg / hour, a screw speed of 450 rpm, a gate opening of 50%, a suction pressure of 0.1 MPa, and a resin temperature of 200 to 230 ° C. By granulating under the conditions, an ethylene-1-hexene copolymer (PE3) was obtained. Tables 1 and 2 show the results of physical property evaluations of the obtained copolymers.

Synthesis of Polymerization Example 4 (PE4) (1) Production of Ethylene-1-hexene Copolymer (PE4) Using a prepolymerized catalyst component (b-1) obtained by the same method as in Polymerization Example 1, continuous fluidized bed gas Copolymerization of ethylene and 1-hexene was performed in a phase polymerization apparatus to obtain a polymer powder. As polymerization conditions, the polymerization temperature was 87 ° C., the polymerization pressure was 2 MPa, the hydrogen molar ratio to ethylene was 0.71%, and the 1-hexene molar ratio to the total of ethylene and 1-hexene was 1.31%. During the polymerization, ethylene, 1-hexene and hydrogen were continuously supplied in order to keep the gas composition constant. Moreover, the said prepolymerization catalyst component (b-1), triisobutylaluminum, and triethylamine (3% of molar ratio with respect to triisobutylaluminum) were supplied continuously, and the total powder weight of 80 kg of the fluidized bed was maintained constant. The average polymerization time was 4 hours. The obtained polymer powder was fed using an extruder (LCM50 manufactured by Kobe Steel, Ltd.) at a feed rate of 50 kg / hour, a screw speed of 450 rpm, a gate opening of 50%, a suction pressure of 0.1 MPa, and a resin temperature of 200 to 230 ° C. By granulating under the conditions, an ethylene-1-hexene copolymer (PE4) was obtained. Tables 1 and 2 show the results of physical property evaluations of the obtained copolymers.

Synthesis of Polymerization Example 5 (PE5) (1) Production of ethylene-1-hexene copolymer (PE5) Using the prepolymerized catalyst component (b-1) obtained by the same method as in Polymerization Example 1, continuous fluidized bed gas Copolymerization of ethylene and 1-hexene was performed in a phase polymerization apparatus to obtain a polymer powder. As polymerization conditions, the polymerization temperature was 87 ° C., the polymerization pressure was 2 MPa, the hydrogen molar ratio to ethylene was 1.11%, and the 1-hexene molar ratio to the total of ethylene and 1-hexene was 1.45%. During the polymerization, ethylene, 1-hexene and hydrogen were continuously supplied in order to keep the gas composition constant. Moreover, the said prepolymerization catalyst component (b-1), triisobutylaluminum, and triethylamine (molar ratio 30% with respect to triisobutylaluminum) were supplied continuously, and the total powder weight of 80 kg of a fluid bed was maintained constant. The average polymerization time was 4 hours. The obtained polymer powder was fed using an extruder (LCM50 manufactured by Kobe Steel, Ltd.) at a feed rate of 50 kg / hour, a screw speed of 450 rpm, a gate opening of 50%, a suction pressure of 0.1 MPa, and a resin temperature of 200 to 230 ° C. By granulating under the conditions, an ethylene-1-hexene copolymer (PE5) was obtained. Tables 1 and 2 show the results of physical property evaluations of the obtained copolymers.

Synthesis of Polymerization Example 6 (PE6) (1) Production of Ethylene-1-hexene Copolymer (PE6) Continuous fluidized bed gas using the prepolymerized catalyst component (b-1) obtained by the same method as in Polymerization Example 1 Copolymerization of ethylene and 1-hexene was performed in a phase polymerization apparatus to obtain a polymer powder. As polymerization conditions, the polymerization temperature was 80 ° C., the polymerization pressure was 2 MPa, the hydrogen molar ratio to ethylene was 1.04%, and the 1-hexene molar ratio to the total of ethylene and 1-hexene was 1.26%. During the polymerization, ethylene, 1-hexene and hydrogen were continuously supplied in order to keep the gas composition constant. Moreover, the said prepolymerization catalyst component (b-1), triisobutylaluminum, and triethylamine (molar ratio 30% with respect to triisobutylaluminum) were supplied continuously, and the total powder weight of 80 kg of a fluid bed was maintained constant. The average polymerization time was 4 hours. The obtained polymer powder was fed using an extruder (LCM50 manufactured by Kobe Steel, Ltd.) at a feed rate of 50 kg / hour, a screw speed of 450 rpm, a gate opening of 50%, a suction pressure of 0.1 MPa, and a resin temperature of 200 to 230 ° C. By granulating under the conditions, an ethylene-1-hexene copolymer (PE6) was obtained. Tables 1 and 2 show the results of physical property evaluations of the obtained copolymers.

Synthesis of Polymerization Example 7 (PE7) (1) Preparation of Preliminary Polymerization Catalyst Component (b-2) Into an autoclave with a stirrer having an internal volume of 210 liters that had been previously purged with nitrogen, 80 liters of butane was added, and then racemic-ethylenebis ( 1-indenyl) zirconium diphenoxide (101 mmol) was added, the autoclave was heated to 50 ° C. and stirred for 2 hours. Next, after the temperature of the autoclave was lowered to 30 ° C. and the system was stabilized, 0.03 MPa of ethylene was charged at the gas phase pressure in the autoclave, and the promoter support (a-1) 0 obtained by the same method as in Polymerization Example 1 was obtained. Polymerization was started by charging 0.7 kg followed by 158 mmol of triisobutylaluminum. After 30 minutes while continuously supplying ethylene at 0.7 kg / hour, the temperature was raised to 50 ° C., and ethylene and hydrogen were supplied at 3.5 kg / hour and 5.5 liters (room temperature and normal pressure volume) / hour, respectively. A total of 4 hours of prepolymerization was carried out by continuous feeding. After completion of the polymerization, the remaining solids purged with ethylene, butane, hydrogen gas and the like are vacuum-dried at room temperature, and a prepolymerized catalyst component (20 g of polyethylene preliminarily polymerized per 1 g of the promoter support (a-1) ( b-2) was obtained.

(2) Production of ethylene-1-hexene copolymer (PE7) Using a prepolymerization catalyst component (b-2) obtained by the same method as in Reference Example 1, ethylene and 1- Hexene copolymerization was carried out to obtain a polymer powder. As polymerization conditions, the polymerization temperature was 87 ° C., the polymerization pressure was 2 MPa, the hydrogen molar ratio to ethylene was 1.30%, and the 1-hexene molar ratio to the total of ethylene and 1-hexene was 1.34%. During the polymerization, ethylene, 1-hexene and hydrogen were continuously supplied in order to keep the gas composition constant. Moreover, the said prepolymerization catalyst component (b-2), triisobutylaluminum, and triethylamine (3% of molar ratio with respect to triisobutylaluminum) were supplied continuously, and the total powder weight of 80 kg of the fluidized bed was maintained constant. The average polymerization time was 4 hours. The obtained polymer powder was fed using an extruder (LCM50 manufactured by Kobe Steel, Ltd.) at a feed rate of 50 kg / hour, a screw speed of 450 rpm, a gate opening of 50%, a suction pressure of 0.1 MPa, and a resin temperature of 200 to 230 ° C. By granulating under the conditions, an ethylene-1-hexene copolymer (PE7) was obtained. The results of physical property evaluation of the obtained copolymer are shown in Table 3 and Table 4. Moreover, the melting curve of the obtained copolymer was shown in FIG.

Synthesis of Polymerization Example 8 (PE8) (1) Production of ethylene-1-butene-1-hexene copolymer (PE8) Continuously using the prepolymerized catalyst component (b-2) obtained in the same manner as in Reference Example 1 Copolymerization of ethylene, 1-butene and 1-hexene was carried out in a fluidized bed gas phase polymerization apparatus to obtain a polymer powder. As polymerization conditions, the polymerization temperature is 87 ° C., the polymerization pressure is 2 MPa, the hydrogen molar ratio to ethylene is 1.10%, the 1-hexene molar ratio to the total of ethylene, 1-hexene and 1-butene is 0.90%, The 1-butene molar ratio relative to the total of ethylene, 1-hexene and 1-butene was 1.75%. During the polymerization, ethylene, 1-hexene, 1-butene and hydrogen were continuously supplied in order to keep the gas composition constant. Moreover, the said prepolymerization catalyst component (b-2), triisobutylaluminum, and triethylamine (3% of molar ratio with respect to triisobutylaluminum) were supplied continuously, and the total powder weight of 80 kg of the fluidized bed was maintained constant. The average polymerization time was 4 hours. The obtained polymer powder was fed using an extruder (LCM50 manufactured by Kobe Steel, Ltd.) at a feed rate of 50 kg / hour, a screw speed of 450 rpm, a gate opening of 50%, a suction pressure of 0.1 MPa, and a resin temperature of 200 to 230 ° C. By granulating under the conditions, an ethylene-1-butene-1-hexene copolymer (PE8) was obtained. The amount of short chain branching derived from 1-butene of the ethylene-1-butene-1-hexene copolymer (PE8) is 6.3 / 1000 C per 1000 carbon atoms, and the amount of short chain branching derived from 1-hexene. Was 10.7 / 1000 C per 1000 carbon atoms. The results of other physical property evaluations of the obtained copolymer are shown in Tables 3 and 4.

Example 1
As a component (A), Sumitomo Nobrene D101 (manufactured by Sumitomo Chemical Co., Ltd.) was 85% by weight, and as a component (B) PE1 described in Polymerization Example 1 was 15% by weight. 32 extruders (manufactured by Plastics Engineering Laboratory), extruder set temperature 280 ° C., roll temperature C1 / C2 / C3 (70 ° C./80° C./80° C.), spacer 0.5 mm, T die width 350 mm, Bank forming was performed under the conditions of a lip opening of 1.2 mm, a discharge rate of 30.9 kg / hour, and a take-up speed of 2.39 m / min, and sheet processing was performed. The evaluation results of the obtained sheet are shown in Table 5.

Example 2
In the same manner as in Example 1 except that Sumitomo Nobrene D101 (manufactured by Sumitomo Chemical Co., Ltd.) was 85% by weight as component (A) and PE2 described in Polymerization Example 2 was 15% by weight as component (B). Sheet processing was performed. The evaluation results of the obtained sheet are shown in Table 5.

Comparative Example 1
The same method as in Example 1 except that Sumitomo Nobrene D101 (manufactured by Sumitomo Chemical Co., Ltd.) was 85% by weight as component (A) and PE7 described in Polymerization Example 7 was 15% by weight as component (B). Sheet processing was performed. The evaluation results of the obtained sheet are shown in Table 5.

Comparative Example 2
In the same manner as in Example 1, except that Sumitomo Nobrene D101 (manufactured by Sumitomo Chemical Co., Ltd.) was 85% by weight as component (A) and PE8 described in Polymerization Example 8 was 15% by weight as component (B). Sheet processing was performed. The evaluation results of the obtained sheet are shown in Table 5.

For the ethylene-α-olefin copolymer of PE1-8, a diagram in which the value of long chain branching amount N _LCB (pieces / 1000 C) is plotted against the value of MFR (g / 10 min) is shown in FIG. ◆ the polymerization examples to meet all requirements of the component (B) of the present invention (PE1~6), □ the _{N LCB} ethylene -α- olefin copolymer is less than 0.29, an ethylene -α- olefin copolymerization It is a polymerization example (PE7, 8) in which the coalescence does not satisfy the requirements of the component (B) of the present invention.

  The figure which showed the melting curve obtained by the differential scanning calorimetry of the ethylene-alpha-olefin copolymer of PE1 and PE7 is shown in FIG.

FIG. 3 is a diagram in which the value of the characteristic relaxation time τ ₀ (s ⁻¹ ) is plotted against the value of MFR (g / 10 minutes) for the ethylene-α-olefin copolymer of PE1-8. ◆ the polymerization examples to meet all requirements of the component (B) of the present invention (PE1~6), □ the _{N LCB} ethylene -α- olefin copolymer is less than 0.29, an ethylene -α- olefin copolymerization It is a polymerization example (PE7, 8) in which the coalescence does not satisfy the requirements of the component (B) of the present invention.

For the ethylene-α-olefin copolymer of PE1-8, a diagram in which the value of oligomer amount ΣCn; n = 12-18 (ppm) is plotted against the value of MFR (g / 10 min) is shown in FIG. ◆ the polymerization examples to meet all requirements of the component (B) of the present invention (PE1~6), □ the _{N LCB} ethylene -α- olefin copolymer is less than 0.29, an ethylene -α- olefin copolymerization It is a polymerization example (PE7, 8) in which the coalescence does not satisfy the requirements of the component (B) of the present invention.

  The sheet | seat which consists of the resin composition of Example 1, 2 and Comparative Example 1, 2 plotted the value of the low temperature impact strength of a sheet | seat with respect to the value of MFR (g / 10min) of each component (B). As shown in FIG. ♦ are Examples 1 and 2, and □ are Comparative Examples 1 and 2.

The figure which plotted the value of the drawdown of a sheet | seat with respect to the value of MFR (g / 10min) of each component (B) about the sheet | seat which consists of a resin composition of Examples 1, 2 and Comparative Examples 1, 2. It is shown in FIG. ♦ are Examples 1 and 2, and □ are Comparative Examples 1 and 2. Comparison was made between sheets made of a resin composition containing an ethylene-α-olefin copolymer having the same MFR. The sheet of Example 1 is a comparative example in which the MFR value of the ethylene-α-olefin copolymer is close to the sheet of Comparative Example 2 in which the MFR value of the ethylene-α-olefin copolymer is close. Each sheet has a small drawdown, less sagging of the sheet during thermoforming, and excellent thermoformability.

1 Point indicating shoulder 2 Inflection point 3 Inflection point

Claims (4)

50 to 99% by weight of one or more propylene polymers (component (A)) selected from the group consisting of propylene homopolymers and propylene random copolymers and the following ethylene-α-olefin copolymers (component (B)) ) Olefin resin composition containing 1 to 50 wt% (provided that the total weight of component (A) and component (B) is 100 wt%).
Ethylene-α-olefin copolymer (component (B)): having a monomer unit based on ethylene and a monomer unit based on an α-olefin having 3 to 20 carbon atoms, and a density of 880-940 kg / m ³ , the melt flow rate (MFR) is 0.01 to 10 g / 10 min, the molecular weight distribution (Mw / Mn), which is the ratio of the weight average molecular weight to the number average molecular weight, is 4.5 to 13, The flow activation energy (Ea) is 40 to 100 kJ / mol, the long chain branching amount measured by NMR is 0.29 to 0.50 per 1000 carbon atoms, and is defined by the following formula (I) Ethylene * alpha-olefin copolymer whose g * is 0.76-0.88.
g * = [η] / ([η] _GPC × g _SCB *) (I)
[Wherein [η] represents the intrinsic viscosity (unit: dl / g) of the ethylene-α-olefin copolymer, and is a value defined by the following formula (I-I). [Η] _GPC is a value defined by the following formula (I-II). g _SCB * is a value defined by the following formula (I-III).
[Η] = 23.3 × log (ηrel) (II)
(In the formula, ηrel represents the relative viscosity of the ethylene-α-olefin copolymer.)
[Η] _GPC = 0.00046 × Mv ^0.725 (I-II)
(In the formula, Mv represents the viscosity average molecular weight of the ethylene-α-olefin copolymer.)
g _SCB * = (1-A) ^1.725 (I-III)
(In the formula, A is a value defined by the following formula (IV).)
A = {(14n + 1) × y} / 14002 (IV)
(In the formula, n represents the number of short-chain branched carbon atoms derived from the monomer unit based on the α-olefin of the ethylene-α-olefin copolymer, and y is a short number per 1000 carbon atoms. Represents the amount of chain branching.)] The olefin resin composition according to claim 1, wherein the ethylene-α-olefin copolymer (component (B)) has a characteristic relaxation time (τ) satisfying the formula (a-1).
τ <3.8 × MFR ^−0.62 (a-1) A sheet comprising the olefin resin composition according to claim 1. The molded object formed by thermoforming the sheet | seat of Claim 3.

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