KR100615935B1 - Polypropylene resin, and application of the polypropylene resin to a sheet - Google Patents

Abstract

This invention is a propylene polymer of propylene and ethylene or a C4-20 alpha-olefin, [1] The content of the structural unit derived from ethylene or a C4-20 alpha-olefin is 0.1-2.0 mol%. Range, [2] the melt flow rate (230 DEG C, 2.16 kg load) is 0.1 to 5.0 g / 10 minutes, [3] Mw / Mn measured by GPC method is 5.0 to 20, and [4] ¹³ C- The propylene polymer and the resin composition containing the polymer whose value of the stereoregularity index [M ₅ ] calculated | required by the following formula (Equation-1) from the absorption intensity of Pmmmm and Pw in an NMR spectrum are 0.960-0.990. The sheet obtained from is excellent in rigidity, heat resistance, and thermoforming, and can be suitably used as a material for thermoforming products.

(In formula, [Pmmmm] represents the absorption strength derived from the methyl group of the 3rd unit in the site | part which propylene unit continued isotactically bonding 5 units, and [Pw] shows the absorption strength derived from the methyl group of a propylene unit). .)

Polypropylene Resin, Resin Composition

Description

POLYPROPYLENE RESIN, AND APPLICATION OF THE POLYPROPYLENE RESIN TO A SHEET}

BRIEF DESCRIPTION OF THE DRAWINGS The figure which shows the change process of the shaping | molding sheet in the heating process at the time of vacuum shaping | molding.

[Description of the code]

1: Course 1, 2: Course 2, 3: Course 3, 4: Course 4

TECHNICAL FIELD The present invention relates to a propylene polymer and a resin composition containing the polymer, sheets and thermoforms thereof.

Since polypropylene sheets have characteristics such as high rigidity, high heat resistance, and recycling properties, they are widely used as various packaging materials such as food containers, industrial materials, and pharmaceuticals.

In recent years, sheet products have undergone various studies such as thinning, reducing filler amount, or foaming from environmental protection, light weight, and cost reduction, etc., and this is a phenomenon that further rigidity is required in terms of materials.

As a method of improving the rigidity of a sheet product, the method of using the polypropylene resin which raised the isotactic mesopentade fraction, the method of using the polypolypropylene resin composition which added the nucleating agent, etc. are known (for example, (Japanese Patent Application Laid-Open No. 7-33920, Japanese Patent Laid-Open No. 2001-089122).

However, since the above method further increases the melting point, as a result, the preheating time of the sheet in thermoforming is long, which adversely affects the productivity.

An object of the present invention is to provide a polypropylene resin having excellent stiffness and heat resistance and also having excellent thermoforming, a sheet and a thermoformed product made of the resin.

MEANS TO SOLVE THE PROBLEM The present inventors earnestly examined polypropylene resin in order to solve the said problem, and, as a result, the propylene polymer which combined specific range of comonomer content, specific range of melt flow rate, specific molecular weight distribution, and specific stereoregularity The polypropylene resin composition containing the sheet and the propylene-based polymer and polyethylene in a specific amount has very excellent rigidity and heat resistance, and also has good thermoformability, and the thermoform obtained from the sheet is conventionally rigid with that. It has been found that the heat resistance and heat resistance can be remarkably improved, and the present invention has been completed.

That is, this invention is the following propylene polymer (A), (A ') and (A "), resin composition (B) containing this, [In the following description, (A), (A'), (A "), (B) may be collectively called polypropylene resin." And the sheet and thermoforms (C1) and (C2) which become these are related.

(A) A propylene polymer of propylene and an propylene copolymer of ethylene or an alpha olefin having 4 to 20 carbon atoms, which satisfies the following requirements [1] to [4] simultaneously.

[1] The content of the structural unit derived from ethylene or an α-olefin having 4 to 20 carbon atoms is in the range of 0.1 to 2.0 mol%,

[2] the melt flow rate (230 DEG C, 2.16 kg load) is 0.1 to 5.0 g / 10 minutes;

[3] Mw / Mn measured by the GPC method is 5.0 to 20,

[4] The value of the stereoregularity index [M ₅ ] obtained by the following formula (Formula 1) from the absorption strengths of Pmmmm and Pw in the ¹³ C-NMR spectrum is in the range of 0.960 to 0.990.

(In formula, [Pmmmm] represents the absorption strength derived from the methyl group of the 3rd unit in the site | part which propylene unit continued isotactically bonding 5 units, and [Pw] shows the absorption strength derived from the methyl group of a propylene unit). .)

(A ') As said propylene polymer (A), the propylene polymer whose melting point measured by DSC is 150.0-163.0 degreeC and melt tension of 230 degreeC is 80-180 mN. In the following description, these two requirements are mentioned. May be referred to as Requirement [5] and Requirement [6], respectively.]

(A ") As said propylene polymer (A '), the propylene polymer whose tensile elasticity modulus of the thickness 0.6mm sheet measured in accordance with ASTM-D-882 is 1500-1900 Mpa. [In the following description, Sometimes the requirements are called requirements [7].]

(B) Polypropylene resin which consists of 70-98 weight% of said propylene polymers (A), (A '), or (A "), and polymer (Q) 2-30 weight% different from this propylene polymer Composition.

(C1) The polypropylene sheet which consists of said polypropylene resin (A), (A '), or (A "), or the molded object obtained by thermoforming this sheet.

(C2) The polypropylene sheet which becomes the said polypropylene resin composition (B), or the molded object obtained by thermoforming the sheet.

The sheet made of the propylene polymer or the resin composition of the present invention is excellent in rigidity, heat resistance, and thermoforming, and can be suitably used as a material for thermoforming products.

Best Mode for Carrying Out the Invention

The polypropylene resin of this invention is a resin composition (B) containing a propylene polymer (A)-this propylene polymer (A).

The propylene polymer (A) of the present invention is a polymer containing propylene as a structural unit and is a copolymer of propylene and ethylene or an alpha -olefin having 4 to 20 carbon atoms. Here, as an alpha olefin of 4-20 carbon atoms, for example, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene, etc. are mentioned. Among these, ethylene or α-olepin having 4 to 10 carbon atoms is preferable. The content of the structural unit derived from these α-olefins is preferably 0.1 to 2.0 mol%, preferably 0.2 to 0.8 mol% in the polypropylene resin.

The melt flow rate (MFR) of the propylene polymer of the present invention is in the range of 0.1 to 5.0 g / 10 minutes, preferably 0.3 to 1.0 g / 10 minutes. Since MFR is in this range, the extrusion property in sheet forming is excellent.

Next, Mw / Mn measured by GPC method of the propylene polymer (A) of this invention is 5.0-20, Preferably it is 7.0-14. Mw / Mn is an index indicating the molecular weight distribution, and if this value is within the above range, the polymer has a relatively wide molecular weight distribution, high melt tension, and good draw down property in thermoforming.

The value of the stereoregularity index [M ₅ ] obtained by the following formula (Formula 1) from the absorption strengths of Pmmmm and Pw in the ¹³ C-NMR spectrum of the propylene polymer (A) of the present invention is 0.960 to 0.990. It is preferably 0.970 to 0.990. By setting it as this range, a high rigidity and a high heat resistant sheet and a thermoformed body can be obtained.

In the formula (Equation-1), [Pmmmm] represents the absorption strength derived from the methyl group of the third unit at the site where the propylene units are continuously isotactically bonded 5 units, and [Pw] represents the methyl group of the propylene unit. It shows the absorption strength derived from

As for the preferable aspect of the propylene polymer (A) of this invention, melting | fusing point (Tm) measured by DSC is 150-163 degreeC, Preferably it is 157-162 degreeC (requirement [5]). Since the Tm of the polypropylene sheet currently used is about 163 degreeC, the preheating time of the sheet | seat in thermoforming does not become longer than before.

Moreover, the other preferable aspect of the propylene polymer (A) of this invention is 80-180 mN and preferably 90-180 mN of melt tension in 230 degreeC (requirement [6]). By setting the melt tension in this range, the draw down of the sheet in the thermoforming becomes small, and the deep draw property is good.

In the propylene polymer (A) of the present invention, in addition to the requirements [5] and [6] relating to the melting point and the melt tension, the thickness measured according to ASTM-D-882 (tensile speed 10 mm / min) is measured. The tensile modulus of the 0.6 mm sheet is preferably 1500 to 1900 MPa, preferably 1600 to 1900 MPa (requirement [7]). By setting it as this range, a high rigidity and high heat resistant sheet | seat and a thermoformed body can be obtained efficiently.

The above propylene polymers satisfying ethylene or α-olefin content having 4 to 20 carbon atoms, MFR, Mw / Mn, [M ₅ ], Tm and the like are supported titanium catalysts, for example magnesium-supported titanium catalysts. By using, the copolymerization of propylene and the above monomers is carried out by performing two or more stages of multistage polymerization.

Examples of the magnesium-supported titanium catalyst include solid titanium catalyst components containing magnesium, titanium, halogens and electron donors, catalysts containing organic metal compounds and electron donors.

The stereoregularity of the propylene-based polymer greatly influences the kind of the electron donor, and as the electron donor to obtain high stereoregularity, an organosilicon compound is preferable, and the direction of monomer insertion due to steric hindrance during polymerization can be regulated. As a result, stereoregularity improves.

The organosilicon compound used in the present invention is represented by the following general formula (I).

R ^a _n Si (OR ^b ) _4-n ---------- (I)

In the general formula (I), n is 1,2 or 3, when n is 1, R ^a is a secondary or tertiary hydrocarbon group, and when n is 2 or 3, at least one of R ^a is secondary or It is a tertiary hydrocarbon group, R ^<a> may be same or different, R <^b> is a C1-C4 hydrocarbon group, and when 4-n is 2 or 3, R <^b> may be same or different.

As an organosilicon compound represented by the said General formula (I), when n is 1, it is cyclopentyl trimethoxysilane, 2-methyl cyclopentyl trimethoxysilane, 2, 3- dimethyl cyclopentyl trimeth, for example. Methoxysilane, cyclopentyltriethoxysilane, iso-butyltriethoxysilane, t-butyltriethoxysilane, cyclohexyltrimethoxysilane, cyclohexyltriethoxysilane, 2-norbornanetrimethoxysilane, Trialkoxysilanes, such as 2-norbornane triethoxysilane, are mentioned.

In the general formula (I), when n is 2, for example, dicyclopentyl diethoxysilane, t-butylmethyldimethoxysilane, t-butylmethyldiethoxysilane, t-amylmethyldiethoxysilane, dicyclo And dialkoxysilanes such as hexyldimethoxysilane, cyclohexylmethyldimethoxysilane, cyclohexylmethyldiethoxysilane, and 2-norbornanemethyldimethoxysilane.

In the general formula (I), when n is 3, tricyclopentylmethoxysilane, tricyclopentylethoxysilane, dicyclopentylmethylmethoxysilane, dicyclopentylethylmethoxysilane, dicyclopentylmethylethoxy Monoalkoxysilanes, such as a silane, cyclopentyl dimethyl methoxysilane, cyclopentyl diethyl methoxysilane, cyclopentyl dimethyl ethoxysilane, and trimethyl methoxysilane, etc. are mentioned.

Of these, dimethoxysilanes are preferable, and specifically, dicyclopentyldimethoxysilane, di-t-butyldimethoxysilane, di (2-methylcyclopentyl) dimethoxysilane and di (3-methylcyclopentyl) Dimethoxysilane and di-t-amyldimethoxysilane are preferable.

Multistage polymerization means that the molecular weight distribution can be widened by, for example, producing a relatively high molecular weight polypropylene in a prepolymerization and a relatively low molecular weight polypropylene in a postpolymerization. It is a polymerization method.

Specifically, in the case of two-stage polymerization, the content in the polypropylene that finally obtains the polypropylene of intrinsic viscosity [η _1st ] of 3.0 to 4.5 dl / g, preferably 3.5 to 4.5 dl / g in the first stage is 10. Content in the polypropylene which manufactures in the quantity which becomes -60 weight%, and finally obtains the polypropylene of the intrinsic viscosity [η _2st ] of 0.1-5 dl / g, Preferably 0.3-3 dl / g in 2nd stage | paragraph. The amount is 90-40% by weight. At this time, copolymerization is performed at all stages or at either stage.

In this manner, when the intrinsic viscosity [η _1st ] of the polypropylene to be polymerized at the shear is within the above range, the amount of fish eye (propylene mass or the like) is suppressed and a sheet or thermoform having a good appearance is suppressed. You can get it.

In the present invention, another propylene polymer (Q) different from the polymer may be combined with the above propylene polymers (A) to (A ″). That is, the above propylene polymers (A) to (A ″). May be used alone or in the form of a resin composition blended with a polymer (Q) (hereinafter such a resin composition is referred to as a polypropylene resin composition (B)).

The polypropylene resin composition (B) of the present invention is a resin composition of the above propylene polymers (A) to (A '') and polymers (Q), the composition ratio of which is 70 to 98% by weight of the polypropylene polymer, Preferably it is 80 to 90 weight%, and the polymer (Q) is 2 to 30 weight%, Preferably it is 10 to 20 weight% The resin composition in this mixing ratio range improves the drawdown property in thermoformability further. As a result, since the productivity can be improved, such as the width | variety of a sheet | seat can be extended, and impact resistance also improves, it is preferable.

Polymer (Q) includes polyethylene; Poly alpha -olefins such as polybutene-1, polyisobutene, polypentene-1 and polymethylpentene-1; Ethylene or α-olefin-α-olefin copolymers such as ethylene / propylene copolymers having propylene content of less than 75% by weight, ethylene butene-1 copolymers, and propylene butene-1 copolymers having propylene content of less than 75% by weight; Ethylene or alpha-olefin, alpha-olefin, diene monomer copolymers, such as ethylene propylene 5-ethylidene-2-norbornene copolymer whose propylene content is less than 75 weight%; Vinyl monomers and diene monomer random copolymers such as styrene butadiene random copolymers; Vinyl monomers, diene monomers and vinyl monomer block copolymers such as styrene butadiene styrene block copolymers; Hydrogenation (vinyl monomer diene monomer random copolymer) such as hydrogenation (styrene butadiene random copolymer); Hydrogenation (vinyl monomer diene monomer vinyl monomer block copolymer), such as hydrogenation (styrene butadiene styrene block copolymer), etc. are mentioned.

Among these polymers (Q), polyethylene is preferable. The polyethylene which can be used has an MFR (190 DEG C, under 2.16 kg load) of 0.1 to 10 g / 10 minutes, preferably 0.1 to 5 g / 10 minutes. Specifically, a low density polyethylene having a long chain branch produced by a high pressure method, a low density polyethylene having a linear molecular structure, a high density polyethylene, or a mixture of two or more thereof can be suitably used.

When using a resin or rubber other than polyethylene as the polymer (Q), the amount of addition depends on the type of the resin to be added or the type of the rubber, and may be in a range that does not impair the object of the present invention as described above. It is about 10 weight% or less in propylene polymer (A)-(A ").

Moreover, when shape | molding the sheet (C1) or (C2) as a raw material using the polypropylene resin of this invention, you may add a filler in the range which does not deviate from the objective of this invention. As the filler, for example, talc, calcium carbonate, clay, mica, glass fiber, glass chips, glass beads, calcium silicate, silica, diatomaceous earth, alumina, titanium oxide, magnesium oxide, pumice powder, pumice balun, aluminum hydroxide, hydroxide Magnesium, basic magnesium carbonate, dolomite, calcium sulfate, potassium titanate, barium sulfate, calcium sulfite, montmorillonite, bentonite, graphite, aluminum powder, molybdenum sulfide, boron fiber, silicon carbide fiber, polyester fiber and polyamide fiber, etc. Can be mentioned.

The amount of the filler added varies depending on the type of filler to be added and may be in a range that does not impair the object of the present invention as described above, but is usually about 30% by weight or less in the propylene-based polymer or resin composition.

In the case where the sheet (C1) or (C2) is molded from the propylene-based polymer or the resin composition of the present invention as a raw material, antioxidants, ultraviolet absorbers, metal soaps, hydrochloric acid absorbers and the like can be used without departing from the object of the present invention. You may add additives, such as a stabilizer, a lubricating agent, a flame retardant, an antistatic agent, and a foaming agent.

The amount of the additive added varies depending on the type of the additive to be added, and may be in a range that does not impair the object of the present invention as described above, but is usually about 3 weights in the propylene polymer (A) to (A ″) or the resin composition (B). % Or less

Sheets made of propylene-based polymers or resin compositions having such physical properties or compositions have high rigidity and heat resistance, and have good thermoformability. The propylene-based polymer to resin composition supplied to the extruder is usually adjusted to a resin temperature of 170 to 280 ° C, preferably 200 to 250 ° C, extruded from a T die attached to the extruder tip, and preferably 30 ° C or more. It is taken out while cooling by the cooling roll adjusted to the temperature of 60-90 degreeC. It is preferable to carry out so that a pulling speed may be 0.2-10 m / min, and the thickness of the sheet which passed the cooling roll will be 0.1-10 mm. Moreover, this invention also includes the propylene sheet which used the mixture of the said propylene polymer and the said polypropylene resin composition as a raw material.

The polypropylene sheet includes an unstretched sheet, a multilayer sheet, uniaxial and biaxially oriented sheets. As a method of extending | stretching, the sequential biaxial stretching method by a tenter system and the simultaneous biaxial stretching method by a tubular system are mentioned.

When the said polypropylene sheet is a multilayer sheet, there is no limitation in layer constitution, and if a layer which consists of the propylene polymer or resin composition of this invention is contained even one layer, thermoforming will become favorable. The multilayer sheet is, for example, the polypropylene resin or the resin composition of the present invention is used for the core layer, and random PP having low melting point is used for the skin layer, and the heat sealing property is improved, or the innermost layer. The high performance sheet | seat using gas barrier resins, such as ethylene vinyl alcohol resin, etc. are mentioned.

Since the said polypropylene sheet is small in drawdown and heat time is short in thermoforming, such as vacuum forming and pressure forming, productivity is favorable. The obtained thermoform can be used for a wide range of applications as various packaging materials such as food containers, industrial materials, pharmaceuticals and the like.

Next, although this invention is demonstrated in detail based on an Example, this invention is not limited to these Examples. The measuring method of the physical property in an Example is as follows.

1) Melt Flow Rate (MFR)

Based on ASTM-D1238, it measured under 230 degreeC and a 2.16 kg load.

2) melt tension

Using capillary 1C manufactured by Toyo Seiki Co., Ltd., the tension applied when the strand extruded at 230 ° C. and 15 mm / min was taken at 15 m / min was measured by melt tension.

Capillary shape: L = 8mm, D = 2.095mm

3) Mw and Mn

It measured on condition of the following by GPC method.

Apparatus: 150Cv type manufactured by Waters, sample concentration: 7.5 mg / 4 ml, column: Shodex AD-806ms manufactured by Showa Denko Co., Ltd., measurement temperature: 135 ° C, solvent: o-dichlorobenzene, polystyrene conversion

4) Intrinsic Viscosity [η]

It measured in 135 degreeC tetralin solvent.

5) Isotactic pentax fraction ([M ₅ ])

The absorption intensity of Pmmmm and Pw in the ¹³ C-NMR spectrum was determined by the above formula (Equation-1). However, peak attribution was performed according to Polymer, 1993, Vol34, No14, 3129-3131.

6) melting point

Using DSC, the peak of the heat of fusion under a temperature rising rate of 10 ° C / min was taken as the melting point.

7) Tensile Modulus

Based on ASTM-D-882, it measured on the following conditions.

Test piece shape: 1 arc (thickness 0.6mm), between chucks: 100mm, tensile speed: 10mm / min

8) Dupont impact strength

Seat thickness: 0.6mm, tip diameter of dropping weight: 1/2 inch φ, pedestal diameter: 1/2 inch, temperature: 23 degrees Celsius

9) Load bending temperature

It measured according to ASTM-D-648. Load: 0.45MPa

10) Thermoforming (time to return taut and time to stretch 30mm)

The sheet molded by the sheet molding machine changes as shown in FIG. 1 in the preheating process of thermoforming. First, the sheet on which both ends are fixed is thermally expanded by heating of the upper and lower heaters, and irregular wrinkles are generated (process 1). It is further stretched by softening and thermal expansion (process 2), and when the whole sheet reaches near the melting point, it shrinks due to residual stress and returns to an instant tension (process 3). Upon further heating, the sheet melts completely and draws down by its own weight (process 4). Usually, between the processes 3-4, a sheet | seat is sent to a metal mold | die, and is shape | molded by vacuum suction etc. Herein, the thermosetting is improved as the sheet having a shorter time of returning to Step 3 and the sheet which is difficult to draw down.

The time until this tension was returned and the time until it extended | stretched after 30 mm was stretched were measured on condition of the following using the vacuum pressure forming machine by Asano Seisakusho.

Upper and lower heater temperature: 350 degrees Celsius, distance between upper and lower heaters: 200mm, size of sheet: 350 * 350mm, sheet thickness: 0.6mm

Example 1

As a propylene polymer, it is a supported titanium catalyst (high solid regular catalyst) using an electron donor as dicyclopentyldimethoxysilane, and random copolymerization in which the content of the ethylene structural unit is 0.6 mol% is performed by two-stage polymerization, Propylene-ethylene air having a molecular weight distribution widened by adjusting the high molecular weight body having an intrinsic viscosity [η] of 4.3 dl / g to 52% by weight and the low molecular weight body having an intrinsic viscosity [η] of 2.1 d1 / g to 48% by weight. Tetrakis [methylene-3 (3,5-di-t-butyl-4-hydroxyphenyl) propionate] methane (Chiba Specialty), which is a phenolic antioxidant, based on 100% by weight of the copolymer 0.1 parts by weight of Chemicals Co., Ltd., 2,2-methylenebis (4,6-di-t-butylphenyl) octyl phosphite (Asahi Denka Kogyo Co., Ltd.), which is a phosphorus antioxidant ), 0.1 parts by weight of the reaction product of 3-hydroxy-5.7-t-butyl-furan-2-one, a lactone-based antioxidant, and o-xylene 0.12 parts of calcium stearate (manufactured by Nippon Oil Holding Co., Ltd.) as a neutralizing agent and 0.02 parts by weight of Retiy Chemicals Co., Ltd. were mixed, melt-kneaded at a resin temperature of 230 ° C. using a single screw extruder, and granulated into pellets. (Iii). The physical properties measured about the obtained pellets are shown in Table 1.

The pellet obtained above was supplied to a sheet molding machine, adjusted to a resin temperature of 270 ° C, extruded from a T die, and formed into a sheet having a thickness of 0.6 mm at a pulling speed of 1.2 m / min using a cooling roll kept at 80 ° C. It was. The mechanical properties and thermoformability of the obtained sheet were evaluated, and the results are shown in Table 1.

Example 2

Instead of the propylene polymer used in Example 1, a supported titanium-based catalyst using an electron donor as dicyclopentyldimethoxysilane, and random copolymerization in which the content of the ethylene structural unit is 0.4 mol% by two-stage polymerization, A propylene-ethylene copolymer having a molecular weight distribution was adjusted by adjusting the high molecular weight having an intrinsic viscosity [η] of 4.3 dl / g to 51% by weight and the low molecular weight having an intrinsic viscosity [η] of 2.2 dl / g to 49 wt%. It carried out similarly to Example 1 except having used. The results are shown in Table 1 together.

Example 3

Instead of the propylene-based polymer used in Example 1, a supported titanium-based catalyst using an electron donor as dicyclopentyldimethoxysilane, and random copolymerization in which the content of the ethylene structural unit is 0.8 mol% is performed by two-stage polymerization. The propylene-ethylene copolymer which expanded the molecular weight distribution by adjusting the high molecular weight which has a viscosity [eta] of 4.2 dl / g to 51 weight%, and the low molecular weight whose intrinsic viscosity [η] is 2.2 dl / g to 49 weight% It carried out similarly to Example 1 except having used. The results are shown in Table 1 together.

Example 4

Instead of the propylene polymer used in Example 1, high-pressure method low density polyethylene (Mitsui Kagaku Co., Ltd.) whose MFR was 0.35 g / 10 min, measured under 80% by weight of the same propylene polymer as in Example 1, 190 ° C, and 2.16 kg load. Example 15 except that the resin composition composed of 15% by weight of Mirason 102 and 5% by weight of high density polyethylene (Hytax 5520B manufactured by Mitsui Chemical Co., Ltd.) having an MFR of 0.32 g / 10 minutes measured under the same conditions was used. It carried out similarly to 1. The results are shown in Table 1 together.

Example 5

It carried out similarly to Example 1 except having used the resin composition which consists of 85 weight% of propylene polymers similar to Example 1, and 15 weight% of high density polyethylenes similar to Example 4 instead of the propylene polymer used in Example 1. . The results are shown in Table 1 together.

Comparative Example 1

Instead of the propylene polymer used in Example 1, a supported titanium-based catalyst (intermediate regular catalyst) using an electron donor as cyclohexylmethyldimethoxysilane, the intrinsic viscosity [η] was 3.7 dl by two-stage polymerization. The same procedure as in Example 1 was repeated except that a propylene homopolymer having an increased molecular weight distribution was adjusted by adjusting the high molecular weight / g to 50% by weight and the low molecular weight having an intrinsic viscosity [η] of 2.6 dl / g to 50% by weight. It was done. This polymer is corresponded to the material currently used. The results are shown in Table 1 together.

Comparative Example 2

Instead of the propylene-based polymer used in Example 1, a supported titanium-based catalyst using an electron donor as dicyclopentyldimethoxysilane was used to prepare a high molecular weight body having an intrinsic viscosity [η] of 4.3 dl / g by two-stage polymerization. It carried out similarly to Example 1 except having adjusted the low molecular weight body with a weight% and intrinsic viscosity [(eta)] to 1.9 weight%, and used the propylene homopolymer which widened molecular weight distribution. The results are shown in Table 1 together.

Comparative Example 3

Instead of the propylene homopolymer used in Comparative Example 1, it was composed of 80% by weight of the same propylene homopolymer as in Comparative Example 1, 15% by weight of the same high pressure low density polyethylene as in Example 4, and 5% by weight of the same high density polyethylene as in Example 4. It carried out similarly to Example 1 except having used the resin composition. The results are shown in Table 1 together.

TABLE 1

The sheet obtained from the propylene resin or the resin composition of the present invention is excellent in rigidity, heat resistance, and thermoforming, and can be suitably used as a material for thermoforming products.

Claims (8)

As a propylene polymer obtained by random copolymerization of propylene and ethylene or C4-C20 alpha olefin, [1] The content of the structural unit derived from ethylene or an α-olefin having 4 to 20 carbon atoms is in the range of 0.1 to 2.0 mol%, [2] the melt flow rate (230 DEG C, 2.16 kg load) is 0.1 to 5.0 g / 10 minutes; [3] Mw / Mn measured by the GPC method is 5.0 to 20, [4] The value of the stereoregularity index [M ₅ ] obtained by the following formula (Formula 1) from the absorption strengths of Pmmmm and Pw in the ¹³ C-NMR spectrum is in the range of 0.960 to 0.990,

(In formula, [Pmmmm] represents the absorption strength derived from the methyl group of the 3rd unit in the site | part which propylene unit continued isotactically bonding 5 units, and [Pw] shows the absorption strength derived from the methyl group of a propylene unit). .) [5] melt tension at 230 ° C of 80 to 180 mN Propylene-based polymer, characterized in that. The method of claim 1, [6] A propylene polymer having a melting point of 150.0 to 163.0 ° C. measured by DSC. The method of claim 2, [7] A propylene polymer having a tensile modulus of 1500 to 1900 MPa as measured in accordance with ASTM-D-882 (tension rate of 10 mm / min). 70 to 98% by weight of the propylene polymer according to any one of claims 1 to 3, and Polyethylene; Poly α-olefins having a C 4 or more α-olefin as a repeating unit; Ethylene-α-olefin copolymers or α-olefin-α-olefin copolymers having a propylene content of less than 75% by weight; Ethylene-α-olefin-diene monomer copolymers or α-olefin-α-olefin-diene monomer copolymers having a propylene content of less than 75% by weight; Vinyl monomer diene monomer random copolymer; Vinyl monomer diene monomer vinyl monomer block copolymer; Hydrogenation (vinyl monomer diene monomer random copolymer); 2-30 weight% of polymer (Q) chosen from the group which consists of hydrogenation (vinyl monomer, diene monomer, vinyl monomer block copolymer) The polypropylene resin composition characterized by the above-mentioned. The method of claim 4, wherein Polypropylene resin composition, characterized in that the polymer (Q) is polyethylene. A propylene polymer according to any one of claims 1 to 3, wherein the polypropylene sheet or a molded product obtained by thermoforming the sheet. The polypropylene sheet which consists of a polypropylene resin composition of Claim 4, or the molded object obtained by thermoforming the sheet. The polypropylene sheet which consists of a polypropylene resin composition of Claim 5, or the molded object obtained by thermoforming the sheet.

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