JP2012158703A - Olefin resin composition, sheet, and thermoformed body - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an olefin resin composition suitable for production of a sheet excellent in the processability in thermoforming, and a balance between the room temperature impact strength and the low-temperature impact strength; and to provide a sheet and a thermoformed body composed of the same.SOLUTION: The olefin resin composition includes: 80 to 95 mass% of at least one propylene polymer (component (A)) selected from the group consisting of propylene homopolymers and propylene random copolymers; and 5 to 20 mass% of the following ethylene-α-olefin copolymer (component (B)) (here, the total mass of the component (A) and the component (B) is 100 mass%). The component (B) is an ethylene-α-olefin copolymer having a melt flow rate of 0.01 to 1.9 g/10 min, an activation energy of flow of 50 to 150 kJ/mol, and a molecular weight distribution as measured by gel permeation chromatography of 5 to 15.

Description

  The present invention relates to an olefin resin composition, a sheet, and a thermoformed article.

  Thermoformed bodies obtained by thermoforming a sheet made of a propylene polymer, such as vacuum forming or pressure forming, are used as containers for food packaging, pharmaceutical packaging and the like. Since the sheet | seat which consists of propylene polymers is not enough in the workability at the time of thermoforming, in order to improve workability, it mixes and uses a small amount of ethylene polymer, for example (refer patent document 1).

JP 52-136247 A

  However, a sheet made of a resin composition containing a propylene polymer and an ethylene polymer as described in Patent Document 1 is not sufficient in room temperature impact strength and low temperature impact strength. In view of the above problems, the present invention has sufficient workability during thermoforming, excellent room temperature impact strength and low temperature impact strength, and excellent balance between workability during thermoforming, room temperature impact strength and low temperature impact strength. An object is to provide an olefin resin composition suitable for manufacturing a sheet, a sheet comprising the resin composition, and a thermoformed article.

That is, the present invention relates to 80 to 95% by mass 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. An olefin resin composition containing 5 to 20% by mass of a polymer (component (B)) (however, the total mass of the component (A) and the component (B) is 100% by mass).
Component (B): Melt flow rate is 0.01 to 1.9 g / 10 min, flow activation energy is 50 to 150 kJ / mol, and molecular weight distribution measured by gel permeation chromatography is The ethylene-alpha-olefin copolymer which is 5-15.

  According to the present invention, there is provided an olefin resin composition suitable for manufacturing a sheet having a good balance between workability during thermoforming, room temperature impact strength and low temperature impact strength, a sheet comprising the resin composition, and a thermoformed article. Can be provided.

The present invention relates to 80 to 95% by mass 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)) is an olefin resin composition containing 5 to 20% by mass (provided that the total mass of the component (A) and the component (B) is 100% by mass).
Component (B): Melt flow rate is 0.01 to 1.9 g / 10 min, flow activation energy is 50 to 150 kJ / mol, and molecular weight distribution measured by gel permeation chromatography is The ethylene-alpha-olefin copolymer which is 5-15.
Details will be described below.

[Olefin resin composition]
<Propylene polymer (component (A))>
The propylene polymer (component (A)) 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)) is at least one propylene polymer 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 a copolymer of propylene as a main component and a small amount of a comonomer copolymerizable therewith, and when the mass of all monomers used for copolymerization is 100% by mass, For example, it is copolymerized at a ratio of 20% by mass or less, preferably 10% by mass or less. The mass of the comonomer is preferably 1% by mass or more, more preferably 2% by mass or more.

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 and a propylene / 1-butene random copolymer. 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)) has a melt flow rate (MFR) measured at a temperature of 230 ° C. and a load of 21.18 N in a range of 0.01 to 50 g / 10 min in accordance with JIS K 7210. 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)) 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)) is, for example, a solution polymerization method using an inert solvent typified by a hydrocarbon compound such as hexane, heptane, octane, decane, cyclohexane, methylcyclohexane, benzene, toluene, xylene, etc. Can be produced by a bulk polymerization method using the above monomer as a solvent or a gas phase polymerization method in which a gaseous monomer is polymerized as it is. Polymerization by these methods may be carried out batchwise or continuously.

<Ethylene-α-olefin copolymer (component (B))>
Examples of the ethylene-α-olefin copolymer (component (B)) include a copolymer of ethylene and one or more α-olefins having 3 to 12 carbon atoms. Examples of the α-olefin having 3 to 12 carbon atoms include propylene, 1-butene, 1-pentene, 4-methylpentene-1, 1-hexene, 1-octene and 1-decene. Among these, it is preferable to use propylene, 1-butene, 1-hexene, and 1-octene, and it is more preferable to use 1-butene and 1-hexene.

  Examples of the ethylene-α-olefin copolymer (component (B)) include an ethylene-propylene copolymer, an ethylene-1-butene copolymer, an ethylene-4-methylpentene-1 copolymer, and ethylene-1. -Hexene copolymer, ethylene-1-octene copolymer, ethylene-propylene-1-butene copolymer, ethylene-1-butene-1-hexene copolymer and the like. Among these, an ethylene-propylene copolymer, an ethylene-1-butene copolymer, an ethylene-1-hexene copolymer, an ethylene-1-octene copolymer, and an ethylene-1-butene-1-hexene copolymer are used. It is preferable to use, and it is more preferable to use an ethylene-1-butene copolymer, an ethylene-1-hexene copolymer, and an ethylene-1-butene-1-hexene copolymer.

The density of the ethylene-α-olefin copolymer (component (B)) (hereinafter sometimes referred to as “d”) is 880 to 940 kg / m ³ , and the resulting sheet or thermoformed machine From the viewpoint of increasing impact strength among strengths, 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 mechanical strength of the obtained sheet or thermoformed 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. In addition, the density of the ethylene-α-olefin copolymer (component (B)) should be changed depending on the content of monomer units based on ethylene in the ethylene-α-olefin copolymer (component (B)). Can do.

  The melt flow rate (hereinafter sometimes referred to as “MFR”) of the ethylene-α-olefin copolymer (component (B)) is 0.01 to 1.9 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 thermoformed article and from the viewpoint of enhancing the compatibility with the propylene polymer (component (A)). Further, from the viewpoint of increasing the mechanical strength of the obtained sheet or thermoformed product, it is preferably 1.7 g / 10 min or less, more preferably 1.5 g / 10 min or less, and even more preferably 0.8 g / 10 min or less. It is. 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 (component (B)) 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 sometimes referred to as “Mn”) of the ethylene-α-olefin copolymer (component (B)). The molecular weight distribution (hereinafter sometimes referred to as “Mw / Mn”) is 5 to 15. When Mw / Mn is 5 or more, the extrusion load during extrusion molding is low, which is preferable. Mw / Mn is preferably 6 or more. When Mw / Mn is 15 or less, the mechanical strength of the obtained sheet or thermoformed product is increased, and low molecular weight components that cause stickiness of the molded product are reduced, which is preferable. The amount of the sticky component can be quantified by measuring a cold xylene soluble part ratio (CXS) or the like. Mw / Mn is preferably 14 or less, more preferably 13 or less, and still more preferably 12 or less.

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

  From the viewpoint of further reducing the extrusion load during extrusion molding, the activation energy of the flow of the ethylene-α-olefin copolymer (component (B)) (hereinafter sometimes referred to as “Ea”) is as follows. 50 kJ / mol or more, preferably 60 kJ / mol or more. In addition, the activation energy of the flow is 150 kJ / mol or less, preferably 130 kJ / mol or less, more preferably 110 kJ / mol or less, from the viewpoint of increasing the mechanical strength of the sheet or thermoformed product. Preferably it is 90 kJ / mol, Most preferably, it is 80 kJ / mol or less.

The activation energy (Ea) of the flow is dependent on the angular frequency (unit: rad / sec) dependence of the melt complex viscosity (unit: Pa · sec) 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, the melt complex viscosity-angular frequency curve of the olefin polymer at temperatures of 130 ° C., 150 ° C., 170 ° C. and 190 ° C. (T, unit: ° C.) (the unit of melt complex viscosity is Pa · sec, the 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 device (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.

G * defined by the following formula (I) of the ethylene-α-olefin copolymer (component (B)) of the present invention is 0.50 to 0.95, preferably 0.70 to 0.90. Yes, more preferably from 0.73 to 0.85, and even more preferably from 0.74 to 0.81 (for g *, reference was made 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 (component (B)) and is defined by the following formula (I-I). [Η] _GPC was defined by the following formula (I-II). g _SCB * is 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 (component (B)).)
[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 (component (B)).)
g _SCB * = (1-A) ^1.725 (I-III)
(In the formula, A can be obtained directly from the measurement of the content of short chain branches in the ethylene-α-olefin copolymer (component (B)).]]

[Η] _GPC is a molecular weight distribution that is the same as that of the ethylene-α-olefin copolymer (component (B)), and the intrinsic viscosity of the polymer that is assumed to have a linear molecular chain ( (Unit: dl / g).
g _SCB * represents the contribution to g * caused by introducing short chain branches into the ethylene-α-olefin copolymer (component (B)).
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 ethylene-α-olefin copolymer (component (B)) has a relative viscosity (ηrel) of 100% of a tetralin solution containing 5% by weight of butylhydroxytoluene (BHT) as a thermal degradation inhibitor, and an ethylene-α-olefin copolymer. A sample solution is prepared by dissolving 100 mg of the union (component (B)) at 135 ° C., and using an Ubbelohde viscometer, the sample solution and a tetralin solution containing only 0.5% by weight of BHT as a thermal degradation inhibitor It is calculated from the descent time with the blank solution.

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 (component (B)) is the following formula (I-IV)

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

For A in formula (I-III), the number of short-chain branched carbon atoms is n (for example, n = 2 when butene is used as the α-olefin, n = 4 when hexene is used), When the number of short chain branches per 1000 carbon atoms determined by NMR or infrared spectroscopy is y,
A = ((12 × n + 2n + 1) × y) / ((1000−2y−2) × 14 + (y + 2) × 15 + y × 13)
As estimated.

  g * is an index representing the degree of contraction of molecules in a solution caused by long chain branching. When the amount of long chain branching is large, the contraction of molecular chains increases and g * decreases. The g * of the ethylene-α-olefin copolymer (component (B)) has a short relaxation time and sufficiently contains long chain branches, and is preferably 0 from the viewpoint of improving workability during thermoforming. .95 or less. Further, g * of the ethylene-α-olefin copolymer (component (B)) is preferably 0.50 or more from the viewpoint of improving mechanical strength.

  As a method for producing the ethylene-α-olefin copolymer (component (B)), for example, a promoter component such as an organoaluminum compound, an organoaluminum oxy compound, a boron compound, and an organozinc compound is supported on a particulate carrier. In the presence of a polymerization catalyst comprising a solid particle promoter component and a metallocene complex having a ligand having a structure in which two cyclopentadienyl type anion skeletons are bonded via a bridging group such as an alkylene group or a silylene group. And a method of copolymerizing ethylene and α-olefin.

  As content of each component in the olefin resin composition used in the present invention, the total amount of components (A) and (B) contained in the resin composition is 100% by mass, and the content of component (A) is It is 80-95 mass%, and content of a component (B) is 5-20 mass%. Preferably, the content of component (A) is 85 to 90% by mass, and the content of component (B) is 10 to 15% by mass. Olefin resin composition suitable for production of a sheet excellent in the balance between workability during thermoforming, room temperature impact strength and low temperature impact strength by adjusting the blending ratio of each component within the above range, the resin It becomes possible to provide the sheet | seat which consists of a composition, and a thermoforming body.

  The olefin resin composition includes an antioxidant, a neutralizing agent, a lubricant, an antistatic agent, a nucleating agent, an anti-ultraviolet agent, a plasticizer, a dispersing agent, an antifogging agent, an antibacterial agent, if necessary. It is possible to add a combination of additives such as organic porous powder and pigment.

  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, ultra low density polyethylene, high pressure method low density polyethylene, ethylene-vinyl acetate copolymer, ethylene- (meth) acrylic acid copolymer. Copolymers, ethylene- (meth) acrylic acid copolymer metal salts, polystyrene, ABS resins, styrene / butadiene block copolymers and hydrogenated products thereof, styrene / isoprene block copolymers and hydrogenated products thereof Polymers, polyesters such as polyethylene terephthalate and polybutylene terephthalate, polyamides such as nylon 6, nylon 66, nylon 11, nylon 12, nylon 6, 66, polycarbonate, polymethyl methacrylate, polyacetal, polyphenylenesulfur De, ethylene-propylene copolymer rubber, styrene-based thermoplastic elastomer, olefin-based thermoplastic elastomer, polyester thermoplastic elastomer, polyurethane thermoplastic elastomer, a polyamide-based thermoplastic elastomers.

  Examples of the method for producing the olefin resin composition include a method of dry blending or melt blending the component (A), the component (B) and other components such as additives as necessary. 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.

  Examples of the method for forming a sheet comprising 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.

  As a method for forming a sheet using the polyolefin-based resin of the present invention, a multilayer sheet may be formed by employing a coextrusion method, an extrusion coating method, or the like. Further, a gas or water vapor barrier layer such as oxygen; a sound absorbing layer; a light shielding layer; an oxygen absorbing layer; an adhesive layer; an adhesive layer; a colored layer; a conductive layer;

  The thickness of the sheet using the polyolefin resin 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.

  When the sheet of the present invention is thermoformed into a thermoformed 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.

  Examples of the thermoformed article of the present invention include various containers (bottles, trays, cups, bottles, lids, etc.), bubble cushioning materials and the like, and the sheet is suitably used for thermoforming containers. In addition, these thermoformed bodies are used as packaging materials such as food (butter, natto, bento, side dish, etc.), beverages, industrial parts, sundries, toys, daily necessities, office supplies, medical supplies and the like.

  EXAMPLES Hereinafter, although this invention is demonstrated in more detail based on an Example, this invention is not limited to these Examples. The physical properties were evaluated by the following methods.

(1) Melt flow rate of ethylene polymer and propylene polymer (MFR, unit: g / 10 min)
According to the method defined in JIS K 7210-1995, the measurement was performed under the conditions of a load of 21.18 N, an ethylene polymer at a temperature of 190 ° C., and a propylene polymer at a temperature of 230 ° C.

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

(3) Swell ratio (SR) of ethylene polymer
In the measurement of the melt flow rate in (1), the strand of ethylene polymer extruded at a length of about 15 to 20 mm from the orifice under the conditions of a temperature of 190 ° C. and a load of 21.18 N was cooled in air to obtain a solid state Strand was obtained. Next, the diameter D (unit: mm) of the strand at a position of about 5 mm from the upstream end of extrusion of the strand was measured, and the value obtained by dividing the diameter D by the orifice diameter 2.095 mm (D ₀ ) (D / D ₀ ) was calculated and used as the swell ratio.

(4) Density of ethylene polymer (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.

(5) Melting point (Tm, unit: ° C)
(5-1) Melting point of ethylene polymer A sample obtained by cutting out a specimen of about 10 mg from a sheet having a thickness of about 0.5 mm produced by hot pressing was used as a measurement sample, and a differential scanning calorimeter (Diamond, manufactured by PerkinElmer Co., Ltd.) DSC). In the measurement, the measurement sample was held at 150 ° C. for 5 minutes, then cooled to 40 ° C. at 1 ° C./minute, then held at 40 ° C. for 5 minutes, and then increased to 150 ° C. at a rate of 10 ° C./minute. Warm up. The melting point was determined from the melting peak of the melting curve obtained when the temperature was raised from 40 ° C. to 150 ° C. at a rate of 10 ° C./min.
(5-2) Melting point of propylene polymer A sample obtained by cutting out a specimen of about 10 mg from a sheet having a thickness of about 0.5 mm produced by hot pressing was used as a measurement sample, and a differential scanning calorimeter (Diamond, manufactured by PerkinElmer Co., Ltd.) DSC). In the measurement, the measurement sample was held at 220 ° C. for 5 minutes, then rapidly cooled to 150 ° C., held at 150 ° C. for 1 minute, and then cooled to 50 ° C. at a rate of 5 ° C./min. Then, after holding at 50 ° C. for 1 minute, the temperature was raised to 180 ° C. at 5 ° C./min, and the temperature of the maximum peak of the obtained melting endotherm curve was defined as the melting point (Tm).

(6) Molecular weight distribution of ethylene polymer (Mw / Mn)
Using a gel permeation chromatograph (GPC) method, the weight average molecular weight (Mw) and the number average molecular weight (Mn) are measured under the following conditions (1) to (8) to obtain Mw / Mn. It was. 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 refractometer
(8) Molecular weight reference material: Standard polystyrene

(7) Activation energy of flow of ethylene polymer (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 a melt complex viscosity-angular frequency curve at 190 ° C. was created, and activation energy (Ea) 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

(8) g * of ethylene polymer
G * was determined by the formula (I).
In addition, [η] represents the relative viscosity (ηrel) of the ethylene-α-olefin copolymer in 100 ml of a tetralin solution containing 5% by weight of butylhydroxytoluene (BHT) as a thermal degradation inhibitor, and the ethylene-α-olefin copolymer. A sample solution is prepared by dissolving 100 mg of a polymer at 135 ° C., and using a Ubbelohde viscometer, the sample solution and a blank solution composed of a tetralin solution 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 (6), g _SCB * was calculated | required by Formula (I-III) from the measurement of the number of short chain branches of the ethylene-alpha-olefin copolymer of (2).

(9) Sheet draw-down 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. The amount of the drawdown was measured by measuring the distance to the position where the clamp was fixed most downward in the vertical direction with the clamp fixing surface as the reference plane 50 minutes after the insertion. 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.

(10) Low temperature impact strength of sheet produced by bank molding (unit: J / mm)
A sample cut to a size of 100 mm × 100 mm from the center of the sheet produced by bank molding described later was cooled at 0 ° 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 as follows.
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

(11) Room temperature impact strength of sheet produced by bank molding (unit: J / mm)
The test was performed at 23 ° C. in the same manner as (10).

Each component used in the examples of the present invention is as follows.
Component (A): Propylene polymer Propylene homopolymer with MFR = 0.5 g / 10 min, melting point = 163 ° C.

Component (B): Ethylene-α-olefin copolymer PE (1):
(1) Preparation of solid catalyst component In a reactor equipped with a nitrogen-replaced stirrer, silica heat-treated at 300 ° C. under nitrogen flow (Sypolol 948 manufactured by Devison; 50% volume average particle size = 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 mass%) 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 cooled to 22 ° C., was added dropwise for 1.5 hours while maintaining the H ₂ O0.11kg the temperature of the reactor 22 ° C.. 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. Then, the solid catalyst component was obtained by drying.

(2) Preparation of prepolymerization catalyst component After adding 80 liters of butane to an autoclave with an internal volume of 210 liters which had been previously purged with nitrogen, 34.5 mmol of racemic-ethylenebis (1-indenyl) zirconium diphenoxide was added. 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 solid catalyst component described in (1) is added. Polymerization was started by adding 140 mmol of triisobutylaluminum. After 30 minutes while continuously supplying ethylene at 0.7 kg / Hr, the temperature was raised to 50 ° C., and ethylene and hydrogen were respectively 3.5 kg / Hr and 10.2 liters (room temperature and normal pressure volume) / Hr. A total of 4 hours of prepolymerization was carried out by continuous feeding. After the polymerization was completed, ethylene, butane, hydrogen gas and the like were purged and the remaining solid was vacuum dried at room temperature to obtain a prepolymerized catalyst component in which 15 g of polyethylene was prepolymerized per 1 g of the solid catalyst component.

(3) Production of ethylene-1-hexene-1-butene copolymer (PE (1)) Using the prepolymerized catalyst component obtained above, ethylene and 1-butene, 1 -Copolymerization of hexene was carried out to obtain a polymer powder. As polymerization conditions, the polymerization temperature was 84 ° C., the polymerization pressure was 2 MPa, the hydrogen molar ratio to ethylene was 1.04%, the 1-butene molar ratio to the total of ethylene, 1-butene and 1-hexene was 2.16%, The 1-hexene molar ratio was 0.73%. During the polymerization, ethylene, 1-butene, 1-hexene and hydrogen were continuously supplied in order to keep the gas composition constant. In addition, the prepolymerization catalyst component and triisobutylaluminum were continuously supplied, and the total powder mass of 80 kg in the fluidized bed was kept constant. The average polymerization time was 4 hours. The obtained polymer powder was fed using an extruder (LCM50 manufactured by Kobe Steel, Ltd.), feed rate 50 kg / hr, screw rotation speed 450 rpm, gate opening 50%, suction pressure 0.1 MPa, resin temperature 200-230 ° C. By granulating under the conditions, an ethylene-1-hexene-1-butene copolymer (hereinafter referred to as PE (1)) was obtained. The results of physical property evaluation of the obtained copolymer are shown in Table 1.

PE (2):
(1) Production of ethylene-1-hexene-1-butene copolymer (PE (2)) Continuous fluidized bed gas phase polymerization apparatus using the prepolymerized catalyst component obtained in (2) of PE (1) above Then, ethylene, 1-butene and 1-hexene were copolymerized to obtain a polymer powder. As polymerization conditions, the polymerization temperature was 84 ° C., the polymerization pressure was 2 MPa, the hydrogen molar ratio to ethylene was 1.4%, the 1-butene molar ratio to the total of ethylene, 1-butene and 1-hexene was 2.3%, The 1-hexene molar ratio was 1.0%. During the polymerization, ethylene, 1-butene, 1-hexene and hydrogen were continuously supplied in order to keep the gas composition constant. In addition, the prepolymerization catalyst component and triisobutylaluminum were continuously supplied, and the total powder mass of 80 kg in the fluidized bed was kept constant. The average polymerization time was 4 hours. The obtained polymer powder was fed using an extruder (LCM50 manufactured by Kobe Steel), feed rate 50 kg / hr, screw rotation speed 450 rpm, gate opening 50%, suction pressure 0.1 MPa, resin temperature 200-230 ° C. By granulating under the conditions, an ethylene-1-hexene-1-butene copolymer (hereinafter referred to as PE (2)) was obtained. The results of physical property evaluation of the obtained copolymer are shown in Table 1.

PE (3):
(1) Production of ethylene-1-hexene copolymer (PE (3)) Using the prepolymerized catalyst component obtained in (2) of PE (1) above, ethylene and 1 were prepared in a continuous fluidized bed gas phase polymerization apparatus. -Copolymerization of hexene was carried out to obtain a polymer powder. The polymerization conditions were a polymerization temperature of 80 ° C., a polymerization pressure of 2 MPa, a hydrogen molar ratio to ethylene of 0.4%, and a 1-hexene molar ratio to the total of ethylene and 1-hexene of 1.6%. During the polymerization, ethylene, 1-hexene and hydrogen were continuously supplied in order to keep the gas composition constant. In addition, the prepolymerization catalyst component and triisobutylaluminum were continuously supplied, and the total powder weight of 80 kg in the fluidized bed was kept constant. The average polymerization time was 4 hours. The obtained polymer powder was fed using an extruder (LCM50 manufactured by Kobe Steel), feed rate 50 kg / hr, screw rotation speed 450 rpm, gate opening 50%, suction pressure 0.1 MPa, resin temperature 200-230 ° C. By granulating under the conditions, an ethylene-1-hexene copolymer (hereinafter referred to as PE (3)) was obtained. The results of physical property evaluation of the obtained copolymer are shown in Table 1.

PE (4):
(1) Preparation of prepolymerization catalyst component 119 liters of butane was charged into an autoclave with an internal volume of 210 liters that had been previously purged with nitrogen, and then 131.7 mmol of racemic-ethylenebis (1-indenyl) zirconium diphenoxide was charged. The autoclave was heated to 50 ° C. and stirred for 2 hours. Next, after the temperature in 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 solid catalyst component 1. Obtained in (1) of PE (1) was obtained. 1 kg was charged, and then 794 mmol of triethylaluminum was charged to initiate polymerization. After 30 minutes while ethylene was continuously supplied at 1.1 kg / Hr, the temperature was raised to 50 ° C., and ethylene and hydrogen were 3.4 kg / Hr and 9.96 liters (room temperature and normal pressure volume) / Hr, respectively. A total of 9.3 hours of prepolymerization was carried out by continuous feeding. After the polymerization was completed, ethylene, butane, hydrogen gas and the like were purged and the remaining solid was vacuum dried at room temperature to obtain a prepolymerized catalyst component in which 28.6 g of polyethylene was prepolymerized per 1 g of the solid catalyst component.

(2) Production of ethylene-1-hexene copolymer (PE (4)) Using the prepolymerized catalyst component obtained above, copolymerization of ethylene and 1-hexene was carried out in a continuous fluidized bed gas phase polymerization apparatus. A polymer powder was obtained. As polymerization conditions, the polymerization temperature was 84 ° C., the polymerization pressure was 2 MPa, the hydrogen molar ratio to ethylene was 0.10%, 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. In addition, the prepolymerization catalyst component and triisobutylaluminum were continuously supplied, and the total powder mass of 80 kg in the fluidized bed was kept constant. The average polymerization time was 4 hours. The obtained polymer powder was fed using an extruder (LCM50 manufactured by Kobe Steel), feed rate 50 kg / hr, screw rotation speed 450 rpm, gate opening 50%, suction pressure 0.1 MPa, resin temperature 200-230 ° C. By granulating under the conditions, an ethylene-1-hexene copolymer (hereinafter referred to as PE (4)) was obtained. Table 1 shows the physical properties of the obtained copolymer.

PE (5):
(1) Production of ethylene-1-hexene-1-butene copolymer (PE (5)) Continuous fluidized bed gas phase polymerization apparatus using the prepolymerized catalyst component obtained in (2) of PE (1) above Then, ethylene, 1-butene and 1-hexene were copolymerized to obtain a polymer powder. As polymerization conditions, the polymerization temperature was 81.4 ° C., the polymerization pressure was 2 MPa, the hydrogen molar ratio to ethylene was 1.82%, and the 1-butene molar ratio to the total of ethylene, 1-butene and 1-hexene was 2.46. %, 1-hexene molar ratio was 0.76%.
During the polymerization, ethylene, 1-butene, 1-hexene and hydrogen were continuously supplied in order to keep the gas composition constant. In addition, the prepolymerization catalyst component and triisobutylaluminum were continuously supplied, and the total powder mass of 80 kg in the fluidized bed was kept 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 / hr, 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. By granulating under the condition of ° C., an ethylene-1-hexene-1-butene copolymer (hereinafter referred to as PE (5)) was obtained. Table 1 shows the physical properties of the obtained copolymer.

F101-1: manufactured by Sumitomo Chemical Co., Ltd., trade name “Sumikasen F101-1” (high-pressure low-density polyethylene, MFR (190 ° C.) = 0.3 g / 10 min, density = 922 kg / m ³ )

[Example 1 to Comparative Example 2]
After the component (A) and the component (B) are mixed together at the composition ratios shown in Table 2, the following is used using an extruder (manufactured by Sumitomo Heavy Industries, Ltd.) with a screw diameter of 65 mmφ and L / D = 33. Sheet processing was performed by bank molding under conditions. The evaluation results of the obtained sheet are shown in Table 2.
Processing temperature: 280 ° C
Roll temperature: C1 / C2 / C3 (60 ° C / 80 ° C / 80 ° C)
Form a bank between rolls C1 and C2 Spacer: 0.3 mm
T die width: 450mm
Lip opening: 1.2mm
Discharge rate: 37 kg / h
Take-off speed: 4.0 m / min

Claims (3)

80 to 95% by mass of one or more propylene polymers (component (A)) selected from the group consisting of propylene homopolymer and propylene random copolymer and the following ethylene-α-olefin copolymer (component (B )) Olefin resin composition containing 5 to 20% by mass (provided that the total mass of component (A) and component (B) is 100% by mass).
Component (B): Melt flow rate is 0.01 to 1.9 g / 10 min, flow activation energy is 50 to 150 kJ / mol, and molecular weight distribution measured by gel permeation chromatography is The ethylene-alpha-olefin copolymer which is 5-15. A sheet comprising the olefin resin composition according to claim 1. A thermoformed article obtained by thermoforming the sheet according to claim 2.