JP2012046198A - Thermoformed container - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a deep-drawn thermoformed container that can sustain retort processing.SOLUTION: A thermoformed container is formed by solid phase pressure forming a crystalline propylene polymer sheet having following characteristics (a)-(c), and has a deep drawn structure in which a ratio of a depth to a diameter is 1 or larger. A thermal contraction percentage of the container at 125°C is 3% or smaller. (a) In a measurement of a temperature rising elution fractionation (TREF) using orthodichlorobenzene as a solvent, components eluted at a temperature of 40°C or lower are 1 wt.% or smaller and a temperature (Tp) at which the eluted component amount is the largest value is between 113°C and 125°C. (b) When 10times of an inverse number of storage elastic modulus value (unit: Pa) at an intersection Gc of a frequency ω relevancy curve G'(ω) of the storage elastic modulus and a frequency ω relevancy curve G"(ω) of a loss elastic modulus in a dynamic viscoelastic measurement is indicated as PI, the PI is 4.0 or larger. (c) A melt flow rate (MFR) measured based on JIS K7210 (at a temperature of 230°C and under a load of 2.16 kg) is 0.2-1 g/10 minutes.

Description

  The present invention relates to a thermoformed container, and more particularly, to a deep-drawn thermoformed container that can withstand retort processing, and to a thermoformed container obtained by solid-phase pressure forming a polypropylene sheet at a temperature below the melting peak temperature. .

  Conventionally, containers using thermoplastic resins such as polystyrene, polyethylene terephthalate, and polypropylene have been manufactured. Among thermoplastic resins, the propylene-based resin composition is excellent in heat resistance, rigidity, impact resistance, or hygiene, and thus is suitably used as a container for foods, and in particular, has high heat resistance. The range of use is expanding to range-up containers in necessary microwave ovens, containers that require high-temperature filling, and the like.

As a food container, a container having a long main body for storing contents relative to the caliber of the container, that is, a so-called deep-drawn container, is effective in that it can have a larger internal capacity than the caliber and is easy to hold.
Such a deep drawn container may be formed by injection molding. Injection molding is suitable for deep-drawn container molding because it can be easily molded into a desired shape depending on the mold used.
However, the injection molding has problems that the mold cost is high when a large number of pieces are taken, the production speed is slower than that of a thermoformed container, and it is difficult to produce a thin molded product.

On the other hand, after extruding a thermoplastic resin into a sheet, the sheet is reheated to obtain the desired container. Thermoforming methods such as vacuum forming, vacuum pressure forming, and solid pressure forming are easy to mold and productivity. Since it is high, it is suitable for mass production and it is easy to obtain multi-layered products.
However, the thermoforming method in which the container is formed in a state where the sheet is melted, such as vacuum forming or vacuum / pressure forming, is reheated to a temperature equal to or higher than the melting point, so that a deep drawn container having a large depth / caliber ratio is used. It is difficult to obtain and it is difficult to form a container that is valuable as a product.

  In recent years, packaging materials that can withstand high-temperature retort processing have been demanded in order to ensure food safety, and various film materials that have both heat resistance and sealing properties have been proposed (Patent Document 1). And Patent Document 2). On the other hand, various materials have been proposed for thermoformed containers from sheets (see Patent Document 3 and Patent Document 4), but they are satisfactory as retort heat-resistant sheet materials that can be formed into deep-drawn containers by solid-state pressure forming. There is a need for a deep-drawn thermoformed container that is not sufficient for retort processing.

JP 2006-150892 A JP 2006-307120 A JP 2006-282259 A JP 2008-207818 A

An object of the present invention is to provide a thermoformed container having a deep-drawing structure that can be produced by pressure forming a polypropylene-based sheet at a temperature equal to or lower than the melting peak temperature in view of the above-described problems of the prior art. It is to provide.
The thermoformed container of the present invention is widely used as a deep-drawn thermoformed container having a high commercial value because a deep-drawn container having a large depth / caliber ratio can be solid-phase pressure-molded and can withstand high temperature retort processing. be able to.

  As a result of intensive studies to solve the above problems, the present inventor, when a polypropylene sheet made of a specific crystalline propylene polymer is subjected to solid-state pressure molding at a temperature lower than the melting peak temperature, the heat resistance against retort treatment As a result, the present invention has been completed.

That is, the first invention of the present invention is obtained by solid-state pressure molding a sheet of crystalline propylene polymer (A) satisfying the following (a) to (c), and the ratio of the depth / caliber of the container Is a thermoformed container having a deep drawing structure of 1 or more, wherein the heat shrinkage rate at 125 ° C. is 3% or less.
(A) In the measurement of temperature rising elution fractionation (TREF) using orthodichlorobenzene as a solvent, the temperature (Tp) when the component eluted at a temperature of 40 ° C. or less is 1% by weight or less and the amount of the eluted component is the largest 113 ° C. or more and 125 ° C. or less (b) Storage at the intersection Gc between the frequency ω dependency curve G ′ (ω) of the storage elastic modulus and the frequency ω dependency curve G ″ (ω) of the loss elastic modulus by dynamic viscoelasticity measurement. the value of the elastic modulus (unit: Pa) when the ¹⁰⁵ times the reciprocal of the PI, melt flow rate PI of 4.0 or more (c) JIS K7210 (230 ℃ , 2.16kg load) was measured on the basis of (MFR) is 0.2-1 g / 10 min

  Further, according to the second invention of the present invention, in the first invention, the crystalline propylene polymer (A) sheet comprises a nucleating agent with respect to 100 parts by weight of the crystalline propylene polymer (A). A thermoformed container characterized by containing 0.01 to 0.5 part by weight is provided.

  According to the third invention of the present invention, in the first or second invention, the crystalline propylene polymer (A) comprises one or more bulk polymerization steps and one or more gas phase polymerization steps. A crystalline propylene polymer produced by multistage polymerization of two or more stages and having a lower melt flow rate (MFR) of the polymer obtained in the subsequent stage than the melt flow rate of the polymer obtained in the preceding stage. A thermoformed container is provided.

According to the fourth invention of the present invention, in the first to third inventions, the crystalline propylene polymer (A) is produced by multistage polymerization, and the MFR of the polymer produced in the first reaction vessel. A thermoformed container is provided in which the MFR difference between (MFR1) and the crystalline propylene polymer (MFR) obtained by multistage polymerization is a crystalline propylene polymer represented by the following formula.
MFR1 / MFR ≧ 4.0

  According to a fifth invention of the present invention, in the first to fourth inventions, the crystalline propylene polymer (A) contains a solid catalyst component (a) containing titanium, magnesium and halogen as essential components; There is provided a thermoformed container characterized by being a crystalline propylene polymer obtained by a propylene polymerization catalyst comprising an organoaluminum component (b).

According to the sixth invention of the present invention, in the fifth invention, the crystalline propylene polymer (A) is further subjected to Si—OR ¹ bond (wherein R ¹ has 1 to 8 carbon atoms) during polymerization. It is a crystalline propylene polymer produced by supplying an organosilicon compound containing two or more hydrocarbon groups (provided that R ¹ is a hydrocarbon group having 1 to 8 carbon atoms). A thermoformed container is provided.

Further, according to the seventh aspect of the present invention, in the fifth or sixth aspect, the solid catalyst component (a) contacts the following (i), (ii), (iii) and (iv): Thus, a thermoformed container characterized by being obtained is provided.
(I) Solid component containing titanium, magnesium and halogen as essential components (ii) Organosilicon compound containing two or more Si—OR ¹ bonds (where R ¹ is a hydrocarbon residue having 1 to 8 carbon atoms) is there.)
(Iii) Vinylsilane compounds (iv) Organometallic compounds of periodic group I-III metals are provided.

  The thermoformed container of the present invention is a food container as a deep-drawn thermoformed container having a high commercial value because a deep-drawn container having a large depth / caliber ratio can be solid-phase pressure-molded and can withstand high temperature retort processing. It can be widely used for containers in various fields such as detergent containers and medical containers.

It is explanatory drawing for demonstrating the frequency dependence curve G '((omega)) and frequency dependence curve G "((omega)) in the viscoelasticity of a general polypropylene.

[Crystalline Propylene Polymer (A)]
The present invention is a thermoformed container obtained by solid-phase pressure molding using a sheet of crystalline propylene polymer (A) that satisfies the following characteristics (a) to (c), and the ratio of the depth / caliber of the container Is a thermoformed container characterized by having a deep-drawn structure of 1 or more and having a thermal shrinkage rate of 3% or less at 125 ° C.
(A) In the measurement of temperature rising elution fractionation (TREF) using orthodichlorobenzene as a solvent, the temperature (Tp) when the component eluted at a temperature of 40 ° C. or less is 1% by weight or less and the amount of the eluted component is the largest (B) Storage of the intersection Gc between the frequency ω dependency curve G ′ (ω) of the storage elastic modulus and the frequency ω dependency curve G ″ (ω) of the loss elastic modulus by dynamic viscoelasticity measurement. the value of the elastic modulus (unit: Pa) when the ¹⁰⁵ times the reciprocal of the PI, melt flow rate PI of 4.0 or more (c) JIS K7210 (230 ℃ , 2.16kg load) was measured on the basis of (MFR) is 0.2-1 g / 10 min

  The crystalline propylene polymer (A) used in the present invention has 1% by weight or less of components eluted at a temperature of 40 ° C. or lower in the measurement of temperature rising elution fractionation (TREF) using orthodichlorobenzene as a solvent. 0.8 or less, and more preferably 0.5 or less. Furthermore, the temperature at which the amount of the eluted component is the largest is in the range of 113.0 ° C. to 125.0 ° C., preferably in the range of 115.0 to 120.0 ° C., more preferably 116.0 ° C. to 119.0 ° C. It is in the range of ° C. If the temperature of the component that elutes at a temperature of 40 ° C. or lower is 1% by weight or more and the amount of the eluted component is the largest, the temperature is less than 113.0 ° C., which is inconvenient because thermoformed product characteristics cannot be obtained.

In addition, the detail of the measuring method of the elution component by the temperature rising elution fractionation (TREF) used by this invention is as follows.
A sample is dissolved in orthodichlorobenzene at 140 ° C. to obtain a solution. This is introduced into a 140 ° C. TREF column, cooled to 100 ° C. at a rate of 8 ° C./min, and then cooled to 40 ° C. at a rate of 4 ° C./min, and held for 10 minutes. Thereafter, orthodichlorobenzene as a solvent is allowed to flow through the column at a flow rate of 1 ml / min, and then the column is linearly heated to 140 ° C. at a temperature rising rate of 100 ° C./hour to obtain an elution curve.
Column size: 4.3mmφ × 150mm
Column packing material: 100 μm surface inactive treated glass beads Solvent: Orthodichlorobenzene Sample concentration: 5 mg / ml
Sample injection volume: 0.1 ml
Solvent flow rate: 1 ml / min Detector: Fixed wavelength infrared detector, manufactured by FOXBORO, MIRAN, 1A
Measurement wavelength: 3.42 μm

The crystalline propylene polymer (A) has a melt flow rate (MFR) measured in accordance with JIS K7210 (230 ° C., 2.16 kg load) in the range of 0.2 to 1 g / 10 min. 0.3 to 0.9 g / 10 min is preferable, and 0.3 to 0.8 g / 10 min is more preferable.
If the melt flow rate is less than 0.2 g / 10 minutes, the decrease in flowability results in a decrease in moldability, and if it exceeds 1 g / 10 minutes, the thermoformed product characteristics cannot be obtained.

Further, the crystalline propylene polymer (A) is an intersection of the frequency ω-dependent curve G ′ (ω) of the storage elastic modulus measured by dynamic viscoelasticity and the frequency ω-dependent curve G ″ (ω) of the loss elastic modulus. the value of the storage modulus gc (unit: Pa) when the ¹⁰⁵ times the reciprocal of the PI, PI is not less than 4.0, preferably not less than 4.2, 4.3 or higher is more preferable.
Here, PI can obtain a larger PI value as the MFR difference between the polymer produced in the first reaction tank and the crystalline propylene polymer obtained by multistage polymerization is larger in two or more stages of multistage polymerization. .

  In the present invention, the dynamic viscoelasticity measurement refers to measuring the dynamic viscoelasticity of the polymer melt, and can be measured with an apparatus for measuring ordinary dynamic viscoelasticity. As an apparatus for measuring dynamic viscoelasticity, for example, a so-called mechanical spectrum meter manufactured by Rheometrix or Iwamoto Seisakusho may be mentioned, but it is not limited to these.

  The measurement of dynamic viscoelasticity is performed in a molten state and generally measures strain and stress called the gap load method. The gap includes a cylindrical type, a cone and disk type, a parallel disk type, etc., and is not particularly limited. Generally, polymer melts are treated as viscoelastic bodies. Can do. If the viscosity of the polymer melt is as low as that of a low molecule, it can be measured using a cylindrical shape, a cone and a disk shape, etc., so that the measurement sample will not be washed away.

  Regarding the process of finishing a polymer material into a product, that is, the molding process, the viscoelastic behavior of the polymer melt at the molding process temperature is important. For example, there are cases where a ballast effect in which the liquid is elongated in a streamline direction when pulled at a high speed and the liquid is contracted in the streamline direction when pushed out from a thin tube is observed as a defect such as silver or a flow mark in injection molding. Such a phenomenon is thought to originate from rheological properties, particularly elasticity, long relaxation times, and even significant non-Newtonian properties.

  In this viscoelastic phenomenology, a case where a liquid of a high-viscosity polymer melt is filled between two parallel plates and shifted (shear strain) is considered. After giving a constant strain: γ = γ0 at time t = 0, the stress G (t) that maintains this constant strain amount decreases exponentially with time. This time indicates the speed at which the stress inherent in the high-viscosity liquid relaxes, and is called the relaxation time and indicates a value specific to the substance. The ratio of the relaxing stress σ (t) to the constant strain γ0 applied at the beginning changes with time. The elastic modulus G (t) = σ (t) / γ0 is called the relaxation elastic modulus. When the constant strain is a strain that vibrates sinusoidally at an angular frequency ω, the elastic modulus G * (ω) defined as the ratio of the stress and the sinusoidal strain becomes a complex number, which is referred to as a complex elastic modulus. The real part is called the dynamic elastic modulus or storage elastic modulus G ′, and the imaginary part is called the loss elastic modulus G ″, so that the non-Newtonian property of the polymer melt can be evaluated. This means that the stress has the same frequency, but the phase changes. Tan δ = G ′ / G ″ = 1 / ωτ, and the stress phase is advanced by δ. .

Frequency dependence curve G ′ (ω) and frequency dependence curve in which the viscoelasticity of general polypropylene is taken with the frequency ω of sinusoidal strain on the horizontal axis and the measured storage elastic modulus and loss elastic modulus plotted on the vertical axis. G ″ (ω) is shown in FIG.
When the intersection of the frequency dependence curve G ′ (ω) of the dynamic elastic modulus and the frequency dependence curve G ″ (ω) of the loss elastic modulus measured at a frequency range of 0.01 rad / sec to 150 rad / sec is Gc. , The value obtained by multiplying the reciprocal of the value of storage elastic modulus in Gc (unit: Pa) by 10 ⁵ was defined as the index PI for viscoelasticity (reference: edited by Edward P. Moore, Jr., translated by Yasuda et al., “ Polypropylene Handbook, published in 1998, Industrial Research Committee). In the present invention, the frequency dependence curves of the storage elastic modulus and loss elastic modulus include straight lines.

  Depending on the measurement conditions, the curves of G ′ (ω) and G ″ (ω) may not have an intersection point, but can have the intersection point by appropriately selecting the measurement condition. Gc can be determined at 150 to 250 ° C. In the present invention, Gc is usually measured at 210 ° C., but a propylene-based resin sample having an MFR of 2 g / 10 min or less is measured at 230 ° C., and the MFR is 2 g / 10. It is preferable to measure a propylene-based resin sample exceeding 210 minutes at 210 ° C. Further, when the content of the low molecular weight substance is large and Newtonian viscosity is exhibited, or the melt flow rate of polypropylene (hereinafter also referred to as MFR) (temperature 230). C., a load of 2.16 kgf) having a low molecular weight exceeding 100 g / 10 min can be measured at a lower temperature, for example, 180.degree. When the range is 0.01 rad / sec to 150 rad / sec, each curve of G ′ (ω) and G ″ (ω) can have an intersection. Further, when the viscosity is low, the frequency dependence of the complex elastic modulus can be obtained by measuring using a conical type or a cylindrical type. Here, the Newtonian property indicates that it becomes a straight line when plotted as shown in FIG. 1 (reference: edited by Japanese Society of Rheology, Lecture / Rheology (1992); Nemoto et al., Journal of Rheology, Vol. 119, 181 (1991)).

  The index PI that defines the propylene polymer of the present invention is a useful index because it can easily represent polypropylene having a broader and more complicated form of molecular weight distribution. That is, when controlling the molecular weight distribution by combining polymers having different molecular weights, for example, a low molecular weight substance having a molecular weight of about 5,000 or less, which is difficult to measure by general gel permeation chromatography (hereinafter also referred to as GPC), and a column It is useful to use this index PI in place of the molecular weight distribution in the case of combining with an ultra-high molecular weight substance having a molecular weight of several million or more, which is not suitable for GPC measurement due to the limit from the exclusion limit volume. In addition, for example, in the molecular weight distribution curve of GPC and the like, it is ambiguous as represented by “becoming a double mountain”, “being bimodal”, “having a shoulder”, “drawing a hem”, “camel-type distribution”, etc. Useful because expressions can be avoided.

The value of PI of the crystalline propylene polymer (A) in the present invention is required to be 4.0 or more, preferably 4.2 or more, and more preferably 4.4 or more. If PI is less than 4.0, the thermoformed product characteristics cannot be obtained, which is disadvantageous.
As described above, in order to increase the PI value in this way, the MFR difference between the polymer produced in the first reaction tank and the crystalline propylene polymer obtained by the multistage polymerization in two or more stages of multistage polymerization is increased. It is possible by increasing it.

[Polypropylene composition]
In the present invention, it is preferable to add a nucleating agent to the crystalline propylene polymer (A), and the amount thereof is 0.01 nucleating agent relative to 100 parts by weight of the crystalline propylene polymer (A). -0.5 parts by weight. 0.02-0.4 weight part is more preferable, and 0.05-0.3 weight part is further more preferable. When the amount of the nucleating agent used is 0.5 parts by weight or more, the production cost increases, which is inconvenient.

  As the nucleating agent used in the present invention, aromatic carboxylic acid metal salts, aromatic phosphate metal salts, sorbitol derivatives, amine compounds, and the like are used. Among these nucleating agents, aluminum pt-butylbenzoate, sodium 2,2′-methylenebis (4,6-di-t-butylphenyl) phosphate, 2,2′-methylenebis (4,6) phosphate -Di-t-butylphenyl) aluminum, p-methyl-benzylidene sorbitol, p-ethyl-benzylidene sorbitol, 1,3,2,4-dibenzylidene sorbitol, 1,3,2,4-bis (p-methylbenzylidene) Sorbitol, 1,3-p-chlorobenzylidene-2,4-p-methylbenzylidene sorbitol, 1,3,2,4-bis (p-ethylbenzylidene) sorbitol, 1,3,2,4-bis Preferred examples include (3,4-dimethylbenzylidene) sorbitol and those represented by the following chemical formula [a], but are not limited thereto. No.

A commercially available nucleating agent can be used. For example, trade names Adeka Stub NA-11 and NA-21 manufactured by Adeka Company, trade name Gelall MD manufactured by Shin Nippon Rika Co., Ltd., and product names Milad NX3988 and Mirad NX8000 manufactured by Milliken are listed.
These may be used as a mixture of two or more.

The crystalline polypropylene polymer (A) used in the present invention has an MFR difference between the MFR (MFR1) of the polymer produced in the first reaction tank and the crystalline polypropylene polymer (MFR) obtained by multistage polymerization. The following formula is preferable.
MFR1 / MFR ≧ 4.0
MFR1 / MFR is preferably 4.0 or more, more preferably 4.2 or more, and even more preferably 4.5 or more. If MFR1 / MFR is less than 4.0, the properties of the thermoformed product cannot be obtained, which is inconvenient.
Here, the MFR of each reaction tank can be controlled by adjusting the hydrogen concentration in each reaction tank, as is well known.

[Method for producing crystalline propylene polymer]
The crystalline propylene polymer (A) used in the present invention is preferably obtained by two or more stages of multistage polymerization.
Examples of the catalyst used for the polymerization include a Ziegler-Natta catalyst formed from (a) a solid catalyst component containing magnesium, titanium, halogen, and an electron donor as necessary, and (b) an organoaluminum compound. It is preferable to be used.

Furthermore, it is preferable to use the solid catalyst component (a) obtained by contacting the following (i), (ii), (iii) and (iv).
(I) A solid component containing titanium, magnesium and halogen as essential components (ii) containing two or more Si—OR ¹ bonds (where R ¹ is a hydrocarbon residue having 1 to 8 carbon atoms). Organosilicon Compound (iii) Vinylsilane Compound (iv) Organometallic Compound of Periodic Group I-III Metal

<Component (i)>
Component (i) is a raw material solid component containing titanium, magnesium and halogen. These three elements (three components) of titanium (Ti) -magnesium (Mg) -halogen are contained as essential components. Here, “contained as an essential component” means that in addition to the listed three components, other suitable elements may be included, and each of these elements is present as an arbitrary desired compound. As well as the fact that these elements may exist as bonded to each other. The raw material solid components themselves containing titanium, magnesium and halogen are known. For example, JP-A-53-45688, 54-3894, 54-31092, 54-39483, 54-94591, 54-118484, 54-131589, 55-75411 55-90510, 55-90511, 55-90511, 55-127405, 55-147507, 55-155003, 56-18609, 56-70005, 56-72001, 56-86905, 56-90807, 56-155206, 57-92007, 57-12003, 58-5309, 58-5310, 58 -5311, 58-8706, 58-27732, 58-32604, 58-32605, 58-67 03, 58-117206, 58-127708, 58-183708, 58-183709, 59-149905, 59-149906, 60-130607, 61-55104 61-204204, 62-508, 62-15209, 62-20507, 62-184005, 62-236805, 63-199207, 63-264607, 63-264608, JP-A-1-79203, 1-139601, 1-215806, 7-258328, 7-269125, 11-21309, each publication, etc. used.

  Moreover, the thing etc. which processed these with tungsten and a molybdenum compound are mentioned.

  Examples of the magnesium compound serving as the magnesium source of component (i) include magnesium halide, dialkoxymagnesium, alkoxymagnesium halide, magnesium oxyhalide, dialkylmagnesium, magnesium oxide, magnesium hydroxide, magnesium carboxylate, and the like. Of these, preferred are magnesium halide, dialkoxymagnesium and alkoxymagnesium halide.

Further, the titanium compound serving as a titanium source component (i) has the general formula _{^{Ti (OR 2) 4-q}} X q ( where, ^{R 2} is a hydrocarbon group, preferably of the order of 1 to 10 carbon atoms Yes, X represents halogen, and q is 0 ≦ q ≦ 4.) Specific examples include TiCl ₄ , TiBr ₄ , Ti (OC ₂ H ₅ ) Cl ₃ , Ti (OC ₂ H ₅ ) ₂ Cl ₂ , Ti (OC ₂ H ₅ ) ₃ Cl, Ti (O-i-C _{3). H 7) Cl 3, Ti (} O-n-C 4 H 9) Cl 3, Ti (O-n-C 4 H 9) 2 Cl 2, Ti (OC 2 H 5) Br 3, Ti (OC 2 H _{5) (O-n-C} 4 H 9) 2 Cl, Ti (O-n-C 4 H 9) 3 Cl, Ti (OC 6 H 5) Cl 3, Ti (O-i-C 4 H 9) ₂ Cl ₂ , Ti (OC ₅ H ₁₁ ) Cl ₃ , Ti (OC ₆ H ₁₃ ) Cl ₃ , Ti (OC ₂ H ₅ ) ₄ , Ti (On-C ₃ H ₇ ) ₄ , Ti (O— _{n-C 4 H 9) 4} , Ti (O-i-C 4 H 9) 4, Ti (O-n-C 6 H 13) 4, Ti (O- _{-C 8 H 17) 4, Ti} (OCH 2 CH (C 2 H 5) C 4 H 9) 4 , and the like.

Further, a molecular compound obtained by reacting an electron donor described later with TiX ′ ₄ (where X ′ is a halogen) can also be used as a titanium source. Specific examples of such molecular compounds include TiCl ₄ · CH ₃ COC ₂ H ₅ , TiCl ₄ · CH ₃ CO ₂ C ₂ H ₅ , TiCl ₄ · C ₆ H ₅ NO ₂ , TiCl ₄ · CH ₃ COCl, TiCl ₄ · C ₆ H ₅ COCl, TiCl ₄ · C ₆ H ₅ CO ₂ C ₂ H ₅ , TiCl ₄ · ClCOC ₂ H ₅ , TiCl ₄ · C ₄ H ₄ O and the like can be mentioned.

In addition, TiCl ₃ (including TiCl ₄ reduced with hydrogen, aluminum metal reduced or organometallic compound reduced), TiBr ₃ , Ti (OC ₂ H ₅ ) Cl ₂ , TiCl ₂ , It is also possible to use titanium compounds such as dicyclopentadienyl titanium dichloride and cyclopentadienyl titanium trichloride.

Among these titanium compounds described above, TiCl ₄ , Ti (OC ₄ H ₉ ) ₄ , Ti (OC ₂ H ₅ ) Cl _{3 and the} like are particularly preferable.

The halogen of component (i) is usually supplied from the aforementioned magnesium and / or titanium halogen compounds, but other halogen sources, for example, aluminum halides such as AlCl ₃ , boron such as BCl _3, etc. Supplied from known halogenating agents such as halides of silicon, silicon halides such as SiCl ₄ , phosphorus halides such as PCl ₃ and PCl ₅ , tungsten halides such as WCl ₆ , molybdenum halides such as MoCl ₅ You can also The halogen contained in the solid catalyst component (a) may be fluorine, chlorine, bromine, iodine or a mixture thereof, and chlorine is particularly preferable.

  Examples of the electron donor (internal donor) that can be used for the production of the raw material solid component (i) include alcohols, phenols, ketones, aldehydes, carboxylic acids, esters of organic acids or inorganic acids, ethers, Examples include oxygen-containing electron donors such as acid amides and acid anhydrides, nitrogen-containing electron donors such as ammonia, amines, nitriles, and isocyanates, and sulfur-containing electron donors such as sulfonate esters. it can.

  More specifically, (i) alcohols having 1 to 18 carbon atoms such as methanol, ethanol, propanol, pentanol, hexanol, octanol, dodecanol, octadecyl alcohol, benzyl alcohol, phenylethyl alcohol, isopropylbenzyl alcohol, ) Phenols having 6 to 25 carbon atoms which may have alkyl groups such as phenol, cresol, xylenol, ethylphenol, propylphenol, isopropylphenol, nonylphenol, naphthol, (c) acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, C3-C15 ketones such as benzophenone, (d) acetaldehyde, propionaldehyde, octylaldehyde, benzaldehyde, tolualdehyde, Aldehydes of 2 to 15 carbon atoms such as naphthaldehyde,

(E) methyl formate, methyl acetate, ethyl acetate, vinyl acetate, propyl acetate, octyl acetate, cyclohexyl acetate, cellosolve acetate, ethyl propionate, methyl butyrate, ethyl valerate, ethyl stearate, methyl chloroacetate, ethyl dichloroacetate, Methyl methacrylate, ethyl crotonate, ethyl cyclohexanecarboxylate, methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, octyl benzoate, cyclohexyl benzoate, phenyl benzoate, benzyl benzoate, cellosolve benzoate , Organic acid monoesters such as methyl toluate, ethyl toluate, amyl toluate, ethyl ethyl benzoate, methyl anisate, ethyl anisate, ethyl ethoxybenzoate, γ-butyrolactone, α-valerolactone, coumarin, phthalide Or diethyl phthalate, dibutyl phthalate, diheptyl phthalate, diethyl succinate, dibutyl maleate, diethyl 1,2-cyclohexanecarboxylate, ethylene carbonate, norbornanedienyl-1,2-dimethylcarboxylate, cyclopropane C2-C20 organic acid esters of organic acid polyvalent esters such as -1,2-dicarboxylic acid-n-hexyl, diethyl 1,1-cyclobutanedicarboxylate,

(F) Carbon number of inorganic acid esters such as silicate esters such as ethyl silicate and butyl silicate, (to) acetyl chloride, benzoyl chloride, toluic acid chloride, anisic acid chloride, phthaloyl chloride, isophthaloyl chloride 2-15 acid halides, (thi) methyl ether, ethyl ether, isopropyl ether, butyl ether, amyl ether, tetrahydrofuran, anisole, diphenyl ether, 2,2-dimethyl-1,3-dimethoxypropane, 2,2-diisopropyl- 1,3-dimethoxypropane, 2,2-diisobutyl-1,3-dimethoxypropane, 2-isopropyl-2-isobutyl-1,3-dimethoxypropane, 2-isopropyl-2-s-butyl-1,3-dimethoxy Propane, 2-t-butyl-2- Til-1,3-dimethoxypropane, 2-t-butyl-2-isopropyl-1,3-dimethoxypropane, 2,2-dicyclopentyl-1,3-dimethoxypropane, 2,2-dicyclohexyl-1,3- 2-20 carbon atoms such as dimethoxypropane, 2,2-diphenyl-1,3-dimethoxypropane, 2,2-dimethyl-1,3-diethoxypropane, 2,2-diisopropyl-1,3-diethoxypropane Ethers of

(Li) Acid amides such as acetic acid amide, benzoic acid amide, toluic acid amide, (nu) amines such as methylamine, ethylamine, diethylamine, tributylamine, piperidine, tribenzylamine, aniline, pyridine, picoline, tetramethylethylenediamine , Nitriles such as (l) acetonitrile, benzonitrile, tolunitrile, (wo) 2- (ethoxymethyl) -ethyl benzoate, 2- (t-butoxymethyl) -ethyl benzoate, 3-ethoxy-2-phenylpropiyl Alkoxy ester compounds such as ethyl onate, ethyl 3-ethoxypropionate, ethyl 3-ethoxy-2-s-butylpropionate, ethyl 3-ethoxy-2-t-butylpropionate,

(Wa) Ketoester compounds such as ethyl 2-benzoylbenzoate, ethyl 2- (4′-methylbenzoyl) benzoate, ethyl 2-benzoyl-4,5-dimethylbenzoate, (f) methyl benzenesulfonate, benzene Examples thereof include sulfonic acid esters such as ethyl sulfonate, ethyl p-toluenesulfonate, isopropyl p-toluenesulfonate, n-butyl p-toluenesulfonate, and s-butyl p-toluenesulfonate.

Two or more kinds of these electron donors can be used.
Among these, organic acid ester compounds, acid halide compounds and ether compounds are more preferable, and particularly preferable are those selected from the group consisting of phthalic acid diester compounds and phthalic acid dihalide compounds.

The solid catalyst component (a) is produced, for example, by the following production method using other components as necessary.
(A) A method of contacting a magnesium halide with an electron donor and a titanium-containing compound.
(B) A method in which alumina or magnesia is treated with a halogenated phosphorus compound, and a magnesium halide, an electron donor, and a titanium halogen-containing compound are brought into contact therewith.

(C) Inert reaction products obtained by contacting a titanium halide compound and / or a silicon halogen compound and an electron donor with a solid component obtained by contacting magnesium halide with titanium tetraalkoxide and a specific polymer silicon compound. A method of washing with an organic solvent. In addition, as a polymer silicon compound used here, what is shown by a following formula is suitable.
-[Si (H) (R ³ ) -O-] _X-
Here, in the above formula, R ³ is a hydrocarbon group having about 1 to 10 carbon atoms, and x represents a degree of polymerization such that the viscosity of the polymer silicon compound is about 1 to 100 centistokes.
Specifically, methyl hydrogen polysiloxane, ethyl hydrogen polysiloxane, phenyl hydrogen polysiloxane, cyclohexyl hydrogen polysiloxane, 1,3,5,7-tetramethylcyclotetrasiloxane, 1,3,5,7 , 9-pentamethylcyclopentasiloxane is preferred.

(D) A magnesium compound is dissolved with a titanium tetraalkoxide and / or an electron donor, and the titanium compound and the electron donor are brought into contact with a solid component precipitated with a halogenating agent or a titanium halogen compound. How to contact.
(E) An organomagnesium compound such as a Grignard reagent is allowed to act on a halogenating agent, a reducing agent, etc., and then contacted with an electron donor as necessary, and then a titanium compound and an electron donor are contacted. , How to contact each one separately.
(F) A method in which an alkoxymagnesium compound is contacted with a halogenating agent and / or a titanium compound in the presence or absence of an electron donor, or each is contacted separately.

  Among these production methods, the above (a), (c), (d) and (f) are particularly preferable.

<Component (ii)>
The component (ii) preferably used for producing the solid catalyst component (a) of the present invention contains two or more Si—OR ¹ bonds (where R ¹ is a hydrocarbon group having 1 to 8 carbon atoms). It is an organosilicon compound.

As bond residues other than —OR ¹ group bonded to a silicon atom, a bond residue selected from hydrogen, halogen, a hydrocarbon group (for example, an alkyl group, a cycloalkyl group, an aryl group, etc.) and a siloxy group What you have is usually used.

  Preferred organosilicon compounds are those having at least one hydrocarbon group, more preferably a carbon atom adjacent to the silicon atom, that is, the α-position hydrocarbon atom is a secondary or tertiary carbon atom and has 3 carbon atoms. It has -20 branched chain hydrocarbon groups.

Specific examples of the organosilicon compound of component (ii) include (CH ₃ ) ₃ CSi (CH ₃ ) (OCH ₃ ) ₂ , (CH ₃ ) ₃ CSi (CH (CH ₃ ) ₂ ) (OCH ₃ ) ₂ , (CH ₃ ) ₃ CSi (CH ₃ ) (OC ₂ H ₅ ) ₂ , (CH ₃ ) ₃ CSi (C ₂ H ₅ ) (OCH ₃ ) ₂ , (CH ₃ ) ₃ CSi (n—C ₃ H ₇ ) (OCH ₃ ) ₂ , (CH ₃ ) ₃ CSi (n—C ₆ H ₁₃ ) (OCH ₃ ) ₂ , (C ₂ H ₅ ) ₃ CSi (CH ₃ ) (OCH ₃ ) ₂ , (CH ₃ ) (C _{2 H 5) CHSi (CH 3} ) (OCH 3) 2, ((CH 3) 2 CHCH 2) 2 Si (OCH 3) 2, (C 2 H 5) (CH 3) 2 CSi (CH 3) (OCH _{3) 2, (C 2 H} 5) (CH 3) 2 CSi (C _{3) (OC 2 H 5)} 2, (CH 3) 3 CSi (OCH 3) 3, (CH 3) 3 CSi (OC 2 H 5) 3, (CH 3) (C 2 H 5) CHSi (OCH 3 ) ₃ , (CH ₃ ) ₂ CH (CH ₃ ) ₂ CSi (CH ₃ ) (OCH ₃ ) ₂ , ((CH ₃ ) ₃ C) ₂ Si (OCH ₃ ) ₂ , (C ₂ H ₅ ) (CH ₃ ) ₂ CSi (OCH ₃ ) ₃ , (C ₂ H ₅ ) (CH ₃ ) ₂ CSi (OC ₂ H ₅ ) ₃ , (CH ₃ ) ₃ CSi (OC (CH ₃ ) ₃ ) (OCH ₃ ) ₂ , ( _{(CH3) 2 CH) 2 Si} (OCH 3) 2, ((CH 3) 2 CH) 2 Si (OC 2 H 5) 2, (C 5 H 9) 2 Si (OCH 3) 2, (C 5 H _{9) 2 Si (OC 2 H} 5) 2, (C 5 H 9) (CH 3) Si _{OCH 3) 2, (C 5} H 9) ((CH 3) 2 CHCH 2) Si (OCH 3) 2, (C 6 H 11) Si (CH 3) (OCH 3) 2, (C 6 H 11) ₂ Si (OCH ₃ ) ₂ , (C ₆ H ₁₁ ) ((CH ₃ ) ₂ CHCH ₂ ) Si (OCH ₃ ) ₂ , ((CH ₃ ) ₂ CHCH ₂ ) ((C ₂ H ₅ ) (CH ₃ ) CH) Si (OCH ₃ ) ₂ , ((CH ₃ ) ₂ CHCH ₂ ) ((CH ₃ ) ₂ CH) Si (OC ₅ H ₁₁ ) ₂ , HC (CH ₃ ) ₂ C (CH ₃ ) ₂ Si (CH ₃ ) (OCH ₃ ) ₂ , HC (CH ₃ ) ₂ C (CH ₃ ) ₂ Si (CH ₃ ) (OC ₂ H ₅ ) ₂ , HC (CH ₃ ) ₂ C (CH ₃ ) ₂ Si (OCH ₃ ) ₃ , (CH ₃ ) ₃ CSi (OCH (CH ₃ ) ₂ ) (OC H ₃ ) ₂ , (CH ₃ ) ₃ CSi (OC (CH ₃ ) ₃ ) (OCH ₃ ) _{2 and the} like.

Among these, preferred are (CH ₃ ) ₃ CSi (CH ₃ ) (OCH ₃ ) ₂ , (CH ₃ ) ₃ CSi (CH (CH ₃ ) ₂ ) (OCH ₃ ) ₂ , (CH ₃ ) ₃ CSi (CH ₃ ) (OC ₂ H ₅ ) ₂ , (CH ₃ ) ₃ CSi (C ₂ H ₅ ) (OCH ₃ ) ₂ , (CH ₃ ) ₃ CSi (n—C ₃ H ₇ ) (OCH _{3 ) 2, (CH 3) 3} CSi (n-C 6 H 13) (OCH 3) 2, (C 5 H 9) 2 Si (OCH 3) 2, (C 5 H 9) 2 Si (OC 2 H 5 ) ₂ , (C ₆ H ₁₁ ) Si (CH ₃ ) (OCH ₃ ) ₂ , (C ₆ H ₁₁ ) ₂ Si (OCH ₃ ) _{2 and the} like.

<Ingredient (iii)>
Component (iii) preferably used to form solid catalyst component (a) is a vinyl silane compound. As the vinylsilane compound, at least one hydrogen atom in monosilane (SiH ₄ ) is replaced with a vinyl group (CH ₂ ═CH—), and some of the remaining hydrogen atoms are halogen (preferably Cl), It shows a structure substituted with an alkyl group (preferably a hydrocarbon group having 1 to 12 carbon atoms), an aryl group (preferably a phenyl group), an alkoxy group (preferably an alkoxy group having 1 to 12 carbon atoms), or the like. is there.

More _{specifically, CH 2 = CH-SiH 3} , CH 2 = CH-SiH 2 (CH 3), CH 2 = CH-SiH (CH 3) 2, CH 2 = CH-Si (CH 3) 3, _{CH 2 = CH-SiCl 3,} CH 2 = CH-SiCl 2 (CH 3), CH 2 = CH-SiCl (CH 3) 2, CH 2 = CH-SiH (Cl) (CH 3), CH 2 = CH _{-Si (C 2 H 5) 3} , CH 2 = CH-SiCl (C 2 H 5) 2, CH 2 = CH-SiCl 2 (C 2 H 5), CH 2 = CH-Si (CH 3) 2 ( _{C 2 H 5), CH 2} = CH-Si (CH 3) (C 2 H 5), (CH 2 = CH) 2 -SiH 2, (CH 2 = CH) 2 -SiH (CH 3), (CH _{2 = CH) 2 -SiH (CH} 3), (CH 2 = CH) _{-Si (CH 3) 2, (} CH 2 = CH) 2 -SiCl 2, (CH 2 = CH) 2 -SiCl (CH 3), (CH 2 = CH) 2 -SiH (Cl), (CH 2 = _{CH) 2 -Si (C 2 H} 5) 2, (CH 2 = CH) 2 -SiCl (C 2 H 5), (CH 2 = CH) 2 -Si (CH 3) (C 2 H 5), ( _{CH 2 = CH) 3 -SiH,} (CH 2 = CH) 3 -Si (CH 3), (CH 2 = CH) 3 -SiCl, (CH 2 = CH) 3 -Si (C 2 H 5), ( CH ₂ ═CH) ₄ —Si and the like can be exemplified. Of these, CH ₂ ═CH—Si (CH ₃ ) ₃ and (CH ₂ ═CH) ₂ —Si (CH ₃ ) ₂ are particularly preferable.

<Component (iv)>
Component (iv) that is preferably used to form solid catalyst component (a) is an organometallic compound of Groups I-III of the periodic table. Since it is an organometallic compound, this compound has at least one organic group / metal bond. The organic group in that case is typically a hydrocarbon group having about 1 to 10 carbon atoms, preferably about 1 to 6 carbon atoms. Typical metals for this compound are lithium, magnesium, aluminum and zinc, especially aluminum.

The remaining valence (if any) of the metal of the organometallic compound in which at least one of the valences is filled with an organic group is a hydrogen atom, a halogen atom, a hydrocarbon group (the hydrocarbon group has 1 to About 10 and preferably about 1 to 6), or the metal via a carbon atom (specifically, —O—Al (CH ₃ ) — of methylalumoxane) and others.

Specific examples of such organometallic compounds include (a) organolithium compounds such as methyllithium, n-butyllithium and tert-butyllithium, (b) butylethylmagnesium, dibutylmagnesium, hexylethylmagnesium and butylmagnesium. Organic magnesium compounds such as chloride and tert-butylmagnesium bromide, (c) Organic zinc compounds such as diethylzinc and dibutylzinc, (d) Trimethylaluminum, triethylaluminum, triisobutylaluminum, tri-n-hexylaluminum, tri-n -Octyl aluminum, tri-n-decyl aluminum, diethyl aluminum monochloride, diisobutyl aluminum monochloride, ethyl aluminum sesquichloride, ethyl aluminum dichloride Diethylaluminum hydride, diisobutylaluminum hydride, diethylaluminum ethoxide, diethylaluminum phenoxide, and organic aluminum compounds such as methylaluminoxane.
Of these, organoaluminum compounds are particularly preferred.

<Production of solid catalyst component (a)>
The solid catalyst component (a) is obtained by bringing the components (i) to (iv) constituting the component (a) and optional components used as necessary into contact with each other stepwise or temporarily, And / or finally by washing with an organic solvent.
Specifically, (a): a method in which the component (i) and the component (iii) are contacted, then the component (ii) and the component (iv) are contacted, and finally washed (b): the component ( Method of contacting and washing component (iii) and component (iv) after contacting i) and component (ii), (c): contacting component (i), (ii), and (iii) simultaneously Later, a method of bringing component (iv) into contact and washing is employed.

  As a solvent used for organic solvent washing, an inert organic solvent, for example, an aliphatic or aromatic hydrocarbon solvent (for example, hexane, heptane, toluene, cyclohexane, etc.), or a halogenated hydrocarbon solvent (for example, chloride-n-) is used. Butyl, 1,2-dichloroethylene, carbon tetrachloride, chlorobenzene, etc.).

Although the contact conditions of each component constituting the solid catalyst component (a) need to be carried out in the absence of oxygen, it can be arbitrary as long as the effect of the present invention is recognized. The following conditions are preferred.
The contact temperature is about −50 to 200 ° C., more preferably 0 to 100 ° C. Examples of the contact method include a mechanical method using a rotating ball mill, a vibration mill, a jet mill, a medium stirring pulverizer, and the like, and a method of contacting by stirring in the presence of an inert diluent. Examples of the inert diluent used at this time include aliphatic or aromatic hydrocarbons and halohydrocarbons, polysiloxanes, and the like.

The amount ratio of the amount of each component constituting the solid catalyst component (a) can be any as long as the effect of the present invention is recognized, but generally it is preferably within the following range.
The usage-amount of the titanium compound of a component (i) is 0.0001-1,000 by mole ratio (Ti / Mg) with respect to the usage-amount of the magnesium compound to be used, More preferably, it is 0.01-10. When a compound therefor is used as the halogen source, the amount used is 0.01 by mole relative to the amount of magnesium used, regardless of whether the titanium compound and / or magnesium compound contains halogen. -1,000 is good, and more preferably is 0.1-100. The amount of the electron donor used is 0.001 to 10 in molar ratio (halogen / Mg) to the amount of magnesium compound used, and more preferably 0.01 to 5.

The quantity ratio of component (i) to component (ii) is 0.01 to 1,000, more preferably the atomic ratio (silicon / titanium) of silicon of component (ii) to the titanium component constituting component (i). 0.1-100. The quantity ratio of the component (iii) to the component (i) is 0.01 to 1,000 in terms of the atomic ratio (silicon / titanium) of the silicon atom in the component (iii) to the titanium atom in the component (i). Preferably it is 0.01-300. The amount ratio of component (iii) to component (i) is 0.01 to 1,000, more preferably 0.1 to 100, in terms of the atomic ratio of metal of the organometallic compound (metal / titanium). The amount of the organometallic compound of component (iv) used is 0.1 to 100, more preferably 1 to 50 in terms of the atomic ratio of metal to the titanium component constituting component (i) (metal atom / titanium).
In the middle and / or at the end of the production of the solid catalyst component (a), a washing step with an inert organic solvent similar to that used in the solvent washing may be added in addition to the solvent washing. it can.

  The (b) organoaluminum compound is used as a co-catalyst, for example, trialkylaluminum such as trimethylaluminum, triethylaluminum and triisobutylaluminum, alkylaluminum halide such as diethylaluminum chloride and diisobutylaluminum chloride, diethylaluminum hydride and the like Alkyl aluminum hydrides, alkyl aluminum alkoxides such as diethyl aluminum ethoxide, alumoxanes such as methylalumoxane and tetrabutylalumoxane, complex organoaluminum compounds such as dibutyl methylboronate, and lithium aluminum tetraethyl. It is also possible to use a mixture of two or more of these.

In producing the crystalline propylene polymer (A) of the present invention, it is preferable to further use an electron donating compound (external donor). As the electron donating compound (external donor), those exemplified as the electron donating compound (internal donor) in the case of the solid component (i), and containing two or more Si—OR ¹ bonds exemplified in the component (ii) An organosilicon compound etc. can be illustrated. Among these, in particular, when tert-butylmethyldimethoxysilane is used as an external donor during production, the isotactic pentad fraction (mmmm fraction) of the propylene-based polymer is further increased and the rigidity is improved.

  The catalyst systems from (a) and (b) above are characterized in that the melt flow rate varies greatly with the amount of hydrogen that is chain transfer.

The polymerization is preferably performed by multistage polymerization combining a bulk polymerization step using propylene itself as a polymerization solvent and a gas phase polymerization step of polymerizing raw material propylene in a gas phase.
Each step of the bulk polymerization step and the gas phase polymerization step may have any number of steps. Examples thereof include a method in which bulk polymerization is performed in two stages and subsequently gas phase polymerization is performed in one stage, and a method in which bulk polymerization is performed in one stage and gas phase polymerization is performed in one stage. However, it is preferable that each step of the bulk polymerization step and the gas phase polymerization step has two or more steps because the molecular weight distribution can be easily widened by the polymerization blend and more elastic properties can be imparted.

  Further, in the melt flow rate of the crystalline propylene polymer obtained from each stage of the multistage polymerization, the melt flow rate in the subsequent stage is lower than the melt flow rate in the previous stage, that is, the melt flow rate gradually becomes lower as the latter stage is reached. It is preferable. When the melt flow rate is higher than that in the previous stage, the melt elasticity of the crystalline propylene polymer is insufficient or the fish eyes are increased, which is disadvantageous.

  The crystalline propylene polymer of the present invention comprises a bulk polymerization step using the above catalyst systems (a) and (b) as a polymerization solvent, and a gas phase polymerization step for polymerizing propylene as a raw material in a gas phase state. Can be produced by multistage polymerization in combination. At that time, hydrogen, which is a chain transfer agent, is mainly charged into the bulk polymerization of the former stage to produce a high melt flow rate, and in the gas phase polymerization of the latter stage, further hydrogen is added to the hydrogen brought in from the previous stage according to the situation. Addition produces a low melt flow rate. Here, by using the catalysts (a) and (b), it becomes possible to easily make a difference in melt flow rate, and a crystalline propylene polymer having high melt elasticity can be obtained.

  The polymerization reactor is not particularly limited in shape and structure, but a tank with a stirrer generally used in bulk polymerization, a tube reactor, a fluidized bed reactor in gas phase polymerization, a horizontal reactor having a stirring blade, etc. Is mentioned.

  Two or more polymerization tanks connected in series are used. (A) The solid catalyst component is supplied only to the first polymerization tank, and (b) most of the organoaluminum is supplied to the first polymerization tank. It doesn't matter.

  In the first polymerization tank, a predetermined amount of propylene is continuously supplied at a constant polymerization pressure and temperature, and the catalyst and hydrogen are controlled so that the ratio of propylene to hydrogen is constant. The produced polymer is sequentially transferred to the next stage polymerization tank together with the unreacted raw material. No catalyst is supplied to the second and subsequent polymerization tanks, and polymerization is carried out with the catalyst contained in the polymer transferred from the preceding polymerization tank. Further, in the second and subsequent homopolymerization tanks, the supply of propylene is continued so that the polymerization pressure is maintained at a predetermined value. Hydrogen may or may not be supplied after the second polymerization tank. When not supplied, the hydrogen remaining as unreacted in the preceding polymerization tank is transferred to the next reactor and used. In order to give a broader molecular weight distribution and give elastic properties, it is better not to supply after the second polymerization tank.

Although it does not specifically limit regarding the polymerization pressure, Usually, 0.2-5 Mpa, Preferably it implements at about 0.3-2 Mpa. The polymerization pressure in each stage may be the same or different.
The polymerization temperature is not particularly limited, but is usually selected from the range of 20 to 100 ° C, preferably 40 to 80 ° C. The polymerization temperature at each stage may be the same or different.

  The polymerization time is not particularly limited, but is usually 10 minutes to 10 hours. Generally, 30 minutes to 2 hours are standard for bulk polymerization, gas phase polymerization step, each step, and bulk polymerization, and 2 to 5 hours are standard for gas phase polymerization. In addition, the polymerization time of each stage of the multistage is not particularly limited, but is set to 30 minutes for the first stage, 30 minutes for the second stage, and 1 hour for the third stage.

In addition, the crystalline propylene polymer (A) used in the present invention includes an antioxidant, a neutralizing agent, a light stabilizer, an ultraviolet absorber, an inorganic filler, an antiblocking agent, a lubricant, an antistatic agent, a metal-free agent. Various additives that can be usually used for polypropylene, such as an activator and a colorant, can be blended within a range that does not impair the object of the present invention.
Examples of antioxidants include phenolic antioxidants, phosphite antioxidants, and thio antioxidants, and examples of neutralizing agents include higher fatty acid salts such as calcium stearate, zinc stearate, and aluminum stearate. And hydrotalcites, and examples of light stabilizers and ultraviolet absorbers include hindered amines, nickel complex compounds, benzotriazoles, and benzophenones.
The crystalline propylene polymer (A) can be used as it is, or added with another polymer such as another polypropylene, polyethylene or various elastomers within the range not impairing the effects of the present invention. You can also do it.

[Sheet of crystalline propylene polymer]
The crystalline propylene polymer (A) sheet used in the present invention is a sheet composed of at least a main layer using the crystalline propylene polymer (A) of the present invention, and has a multilayer structure of two or more layers. There is no problem. For example, even if a barrier sheet in which a barrier resin layer such as ethylene-vinyl alcohol copolymer (EVOH) or polyamide resin and an adhesive layer are disposed between the main layers is provided, a high gloss layer or low gloss layer is provided as the outermost layer. It is also possible to arrange a layer having a design property such as a layer.

Particularly in medical containers and food containers that perform retort treatment, it is preferable to have a multilayer structure with a barrier resin in order to prevent oxidative deterioration of the contents. The crystalline propylene polymer (A) sheet is composed of a main layer constituting a container main body part, and a gas barrier resin such as ethylene-vinyl alcohol copolymer (EVOH), MXD6 polyamide, polyvinyl alcohol, polyvinylidene chloride (PVDC), etc. And a multilayer laminate of 5 or more layers in which various materials made of maleic anhydride-modified polypropylene for adhering the gas barrier resin and the polypropylene layer are laminated.
MXD6 polyamide is a polyamide obtained using metaxylylenediamine and adipic acid as main components. Of the above, the gas barrier layer is particularly preferably ethylene-vinyl alcohol copolymer (EVOH) or MXD6 polyamide.

The thickness of the polypropylene-based sheet used in the present invention is preferably 0.3 to 4 mm, more preferably 0.5 to 3.5 mm, and particularly preferably 0.8 to 3 mm. If the thickness is much less than 0.3 mm, the rigidity of the container is impaired, and if the thickness is much more than 4 mm, sheet molding may be difficult.
Further, in the crystalline propylene polymer sheet, the thickness ratio of the barrier layer to the main layer (barrier layer / main layer) is preferably 0.02 or more and 2 or less, more preferably 0.04 or more and 0.15 or less. Preferably, it is 0.06 or more and 0.12 or less. When the thickness ratio between the barrier layer and the main layer is less than 0.02, the barrier resin may absorb water during the retort treatment and the barrier performance may be deteriorated. When it exceeds 2, the elongation unevenness of the barrier layer at the time of container molding may occur, and the commercial value of the container may be reduced.

Such a sheet of crystalline propylene polymer can be formed into a multi-layer polypropylene sheet using a feed block or a multi-manifold using a plurality of extruders usually used for forming polypropylene.
As a specific method for producing a polypropylene-based sheet, a crystalline propylene polymer (A) blended with other components as necessary is passed through a known uniaxial or biaxial screw extruder to form a sheet from a coat solder die. After being extruded, the metal roll surface (in which cooling water or oil circulates) is pressed and solidified by cooling with an air knife, air chamber, hard rubber roll, steel belt, or metal roll. . It is also possible to cool and solidify both sides of the sheet with a steel belt.
Among such sheet cooling methods, a method using metal rolls and / or steel belts on both sides of the sheet is the most preferable method because a sheet surface with less surface irregularities, that is, a sheet having excellent transparency can be obtained. .

[Thermoforming container]
The thermoforming container of the present invention has a deep drawing structure having a depth / caliber ratio of 1 or more, which is obtained by solid-phase pressure forming using a polypropylene sheet.
The thermoformed container of the present invention has a drawing ratio that is a ratio of the (maximum) depth to the bottom surface of the container body and the (maximum) width (bore diameter) of the container body, regardless of whether the container shape is square or round. However, it is necessary that it is 1.0 or more, preferably 1.2 or more. A squeezing ratio of 1.0 or more is generally called a deep-drawn container and is obtained by plug-assisted solid-phase pressure molding, and has excellent container rigidity and impact strength. It is difficult to obtain a container with small deformation due to processing. However, according to the present invention, it is possible to easily obtain a container having a small deformation by retort processing.

Such a thermoforming container is obtained by using a crystalline propylene polymer sheet, softened at a temperature lower than the melting peak temperature of the crystalline propylene polymer, and preferably obtained by a solid-state pressure molding machine equipped with plug assist. Can do.
Examples of the heating method in such thermoforming include indirect heating, hot plate heating, and hot roll heating. If molding is performed at a temperature exceeding the melting peak temperature of the sheet, the transparency, gloss and thickness uniformity of the resulting thermoformed container are deteriorated, assist plugs are attached, and molding is likely to be impossible.
In the present invention, such solid-phase pressure molding is performed at a temperature lower than the melting peak temperature of the crystalline propylene polymer (A) constituting the polypropylene-based sheet, preferably plug-assist molding.

  When the plug-assisted thermoforming is performed at a temperature lower than the melting peak temperature of the crystalline propylene polymer, it is preferably softened by heating at a temperature within a melting peak temperature range of 5 to 30 ° C., By pushing down the assist plug, the polypropylene sheet is made into a container shape and pre-shaped into a container shape by solid-state pressure air forming, and subsequently, air pressure is applied to the pre-shaped part and the polypropylene sheet is By closely contacting the surface of the mold cavity, a deep-drawn container can be formed.

[Use of thermoformed container]
The thermoformed container of the present invention is excellent in design and can be retorted, so it can be used for containers in various fields such as food containers, detergent containers, and medical containers, and is widely used particularly in the beverage food field. be able to.

EXAMPLES Hereinafter, although this invention is demonstrated further more concretely based on an Example, this invention is not limited to these Examples.
Analysis and evaluation methods performed in Examples and Comparative Examples are as follows.

[1. Melt flow rate (MFR)]
MFR was measured according to JIS-K-6758 (conditions 230 ° C., load 2.16 kgf) (unit: g / 10 minutes).

[2. Flexural modulus]
The flexural modulus was determined by preparing a test piece according to the method described in JIS-K-6758 by injection molding using a polypropylene composition and conforming to JIS-K-7203 at a bending speed of 2 mm / min at 23 ° C. It was measured.

[3. Melting point (Tm)]
The melting point (Tm) was measured using a Seiko DSC. After taking 5.0 mg of sample and holding it at 200 ° C. for 5 minutes, it is crystallized at a rate of temperature decrease of 10 ° C./min to 40 ° C. to erase its thermal history, and further melted at a rate of temperature increase of 10 ° C./min. The melting point (Tm) was defined as the peak temperature of the melting curve.

[4. Measurement of dynamic viscoelasticity]
A propylene-based resin was compression-molded by a press at 230 ° C. for 5 minutes so as not to contain bubbles, and a disk-shaped measurement sample having a thickness of 1.5 mm and a diameter of 25 mm was obtained. The measurement was performed using a rheometer (RMS800) manufactured by Rheometrics. Using parallel disks with a diameter of 25 mm arranged with a gap of 1.4 mm, a sample with an MFR of 2 g / 10 min or less is 230 ° C., a sample with an MFR of over 2 g / 10 min is 210 ° C., In addition, the storage elastic modulus (G ′) and the loss elastic modulus (G ″) were measured at a frequency range of 0.01 rad / sec to 150 rad / sec. The curves G ′ (ω) and G ″ (ω) intersect. the storage modulus at the intersection Gc (unit: Pa) 10 ⁵ times the reciprocal of the PI.

[5. Thermoforming characteristics]
(1) Container drawing ratio:
The outer diameter and depth of the mouth of the deep-drawn molded product were measured with calipers, and the ratio (depth / outer diameter) was taken as the drawing ratio.
(2) Container molding temperature:
The sheet surface temperature immediately before molding in the container molding machine was measured with a non-contact type radiation thermometer.
(3) Plug adhesion:
Using the polypropylene sheet obtained in each example, the container was continuously formed for 30 minutes, and it was confirmed according to the following criteria whether or not deposits on the plug were generated.
○: No adhesion ×: Adhesion occurs and molding is impossible (4) Heat shrinkage:
The obtained thermoformed container was treated in an oven at 125 ° C. for 30 minutes, the volume before and after that was measured, and the volume shrinkage was measured.
(5) Appearance The appearance of the obtained thermoformed container was visually observed for abnormalities.

<Example 1>
(I) Production of catalyst a 20 liters of dehydrated and deoxygenated n-heptane was introduced into a tank equipped with a stirrer with an internal volume of 50 liters purged with nitrogen, and then 10 moles of magnesium chloride and 20 moles of tetrabutoxytitanium were introduced. After reacting at 95 ° C. for 2 hours, the temperature was lowered to 40 ° C., 12 liters of methylhydropolysiloxane (viscosity 20 centistokes) was introduced, and the reaction was further continued for 3 hours. The ingredients were washed with n-heptane.
Subsequently, 5 liters of dehydrated and deoxygenated n-heptane was introduced into the tank using the tank equipped with a stirrer, and then 3 mol of the solid component synthesized above was introduced in terms of magnesium atom. Next, 5 liters of silicon tetrachloride was mixed with 2.5 liters of n-heptane and introduced at 30 ° C. for 30 minutes. The temperature was raised to 70 ° C. and reacted for 3 hours. Then, the reaction solution was taken out, The resulting solid component was washed with n-heptane.
Subsequently, 2.5 liters of dehydrated and deoxygenated n-heptane was introduced into the tank using the tank with a stirrer, and 0.3 mol of phthalic acid chloride was mixed and introduced at 90 ° C. for 30 minutes. And reacted at 95 ° C. for 1 hour. After completion of the reaction, washing with n-heptane was performed. Next, 2 liters of titanium tetrachloride was added at room temperature, and the temperature was raised to 100 ° C., followed by reaction for 2 hours. After completion of the reaction, washing with n-heptane was performed. Further, 0.6 liters of silicon tetrachloride and 8 liters of n-heptane were introduced, reacted at 90 ° C. for 1 hour, and sufficiently washed with n-heptane to obtain a solid component. This solid component contained 1.30% by weight of titanium.

Next, 8 liters of n-heptane, 400 g of the solid component obtained above, 0.27 mol of t-butyl-methyl-dimethoxysilane and 0.27 mol of vinyltrimethylsilane were introduced into the tank equipped with a stirrer substituted with nitrogen. And contacted at 30 ° C. for 1 hour. Next, the mixture was cooled to 15 ° C., 1.5 mol of triethylaluminum diluted in n-heptane was introduced over 15 minutes under 15 ° C., and after the introduction, the temperature was raised to 30 ° C. and reacted for 2 hours. The solid catalyst component (a) (390 g) was obtained by washing with heptane.
The obtained solid catalyst component (a) contained 1.22% by weight of titanium.
Furthermore, 6 liters of n-heptane and 1 mol of triisobutylaluminum diluted in n-heptane were introduced over 30 minutes at 15 ° C., and then about 0.4 kg / kg of propylene was controlled so as not to exceed 20 ° C. Preliminarily polymerized by introducing for 1 hour. As a result, a polypropylene-containing preactivated catalyst (catalyst a) in which 0.9 g of propylene was polymerized per 1 g of solid was obtained.

(Ii) Production of crystalline propylene polymer 1 Crystalline propylene polymer 1 was obtained using a polymerization tank in which two stirred bulk polymerization tanks and two gas phase fluidized beds, a total of four, were connected.
The catalyst a as a polymerization catalyst is continuously supplied to the first reactor so as to achieve a target production amount, and triethylaluminum as a co-catalyst is also supplied to the first reactor only with respect to magnesium in the catalyst. It was continuously fed so that the molar ratio was 5 mol. Furthermore, as an electron donating compound, tert-butylmethyldimethoxysilane was added to 3.0 mol. ppm was fed continuously.
The operating conditions of each polymerization tank were as follows: the first reactor had a temperature of 70 ° C., a pressure of 2.8 MPaG, a hydrogen concentration of 2.5 mol%, an average residence time of 0.5 hours, the second reactor had a temperature of 67 ° C. and a pressure of 2 Bulk polymerization with 0.5 MPaG, hydrogen concentration of 1.3 mol%, average residence time of 0.4 hours, third reactor at 80 ° C., pressure of 1.7 MPaG, average residence time of 0.7 hours, hydrogen concentration of 4.0 × 10 ^-2 mol% gas phase polymerization, the fourth reactor was gas phase polymerization of 80 ° C., pressure 1.1 MPaG, hydrogen concentration 3.9 × 10 ⁻³ mol% average residence time 1.4 hours.
As a result of this polymerization, a crystalline propylene polymer 1 having a catalytic activity of 31,000 gPP / gcat and an MFR of 0.33 g / 10 min was obtained. The MFR obtained in each stage was 1.91 g / 10 minutes from the first reactor, 1.82 g / 10 minutes from the second reactor, 0.73 g / 10 minutes from the third reactor, and the fourth reaction. The discharge was 0.33 g / 10 min.

(Iii) Production of polypropylene composition 1 With respect to 100 parts by weight of crystalline propylene polymer 1, 0.05 part by weight of IRGANOX 1010 (trade name, manufactured by Ciba Specialty Chemicals) as a phenolic antioxidant is added. 0.1 parts by weight of IRGAFOS168 (trade name, Ciba Specialty Chemicals) as a system antioxidant, and 0.05 parts by weight of DHT4A (trade name, hydrotalcite manufactured by Kyowa Chemical Industry Co., Ltd.) as a neutralizing agent Then, 0.1 part by weight of Adeka Stub NA-11 (trade name, manufactured by ADEKA) as a nucleating agent was blended, and melt-kneaded and pelletized using an extruder to obtain a polypropylene composition 1.
Various physical properties measured for the obtained pellets are shown in Table 1.

(Iv) Production of polypropylene sheet and thermoformed container The polypropylene sheet obtained by putting the pellets obtained above into an extruder with a screw diameter of 50 mm, heat-melt plasticizing at a resin temperature of 230 ° C., and extruding from a T-die. Was taken up at a speed of 1 m / min while being cooled and solidified with a mirror-finished metal cast roll whose surface temperature was controlled at 60 ° C. to obtain a sheet having a width of 500 mm and an overall thickness of 2.0 mm. .
Next, using this sheet, a thermoformed container (drawing ratio 1.4) having a diameter of 75 mmφ and a depth of 105 mm was formed by a solid-state pressure forming machine RDM50K (manufactured by Erich). The sheet temperature immediately before molding was 155 ° C.
Various evaluations described above were performed on the sheet and the thermoformed container.
The results are shown in Table 1.

<Example 2>
(I) Production of crystalline propylene polymer 2 The hydrogen concentrations in the first, second, third and fourth reactors were 3.0 mol%, 1.5 mol% and 5.0 × 10 ⁻² mol, respectively. %, 4.7 × 10 ⁻³ mol%, and the same conditions as in Example 1 were used.
As a result of this polymerization, a crystalline propylene polymer 2 having a catalytic activity of 32,000 gPP / gcat and an MFR of 0.60 g / 10 min was obtained. In addition, the MFR obtained in each stage was 1.98 g / 10 minutes from the first reactor, 2.43 g / 10 minutes from the second reactor, 1.19 g / 10 minutes from the third reactor, and the fourth reaction. The discharge was 0.60 g / 10 min.

(Ii) Production of polypropylene composition 2 With respect to 100 parts by weight of crystalline propylene polymer 2, 0.05 part by weight of IRGANOX 1010, 0.1 part by weight of IRGAFOS 168, 0.05 part by weight of DHT4A, nucleating agent Polypropylene composition 2 was obtained by blending 0.1 part by weight of NA-11, and melt-kneading and pelletizing using an extruder.
Various physical properties measured for the obtained pellets are shown in Table 1.
Thereafter, sheet molding and evaluation were performed in the same manner as in Example 1. The results are shown in Table 1.

<Example 3>
With respect to 100 parts by weight of the crystalline propylene polymer 1, 0.05 part by weight of IRGANOX 1010, 0.1 part by weight of IRGAFOS 168, 0.1 part by weight of calcium stearate (manufactured by Nitto Kasei Kogyo Co., Ltd.) as a neutralizing agent, A polypropylene composition 3 was obtained by blending 0.3 part by weight of Mirad NX8000 (trade name, manufactured by Milliken) as a nucleating agent, and melt-kneading and pelletizing using an extruder.
About the obtained pellet, the sheet | seat and the thermoforming container were created similarly to Example 1. FIG.
Various evaluations described above were performed on the sheet and the thermoformed container. The results are shown in Table 1.

<Comparative Example 1>
(I) Production of catalyst b 6 liters of n-hexane, 5.0 mol of diethylaluminum monochloride (DEAC) and 12.0 mol of diisoamyl ether were mixed at 25 ° C. for 5 minutes and reacted at the same temperature for 5 minutes. Reaction liquid (I) (diisoamyl ether / DEAC molar ratio 2.4) was obtained. 40 moles of titanium tetrachloride was placed in a nitrogen-substituted reactor and heated to 35 ° C., and the entire amount of the reaction solution (I) was added dropwise to the reactor over 180 minutes, then kept at the same temperature for 30 minutes and heated to 75 ° C. The reaction was further continued for 1 hour, cooled to room temperature, the supernatant was removed, 30 liters of n-hexane was added, and decantation was repeated 4 times to obtain 1.9 kg of a solid product (II). With the total amount of this solid product (II) suspended in 30 liters of n-hexane, 1.6 kg of diisoamyl ether and 3.5 kg of titanium tetrachloride were added at 20 ° C. over about 5 minutes at room temperature. And reacted at 60 ° C. for 1 hour. After completion of the reaction, the mixture was cooled to room temperature (20 ° C.), the supernatant was removed by decantation, 30 liters of n-hexane was added, stirred for 15 minutes, and allowed to stand to remove the supernatant 5 times. After repeating, it was dried under reduced pressure to obtain a solid catalyst component (b).

Furthermore, after replacing the stainless steel reactor with an inclined blade having an internal volume of 200 liters with nitrogen gas, after adding 20 liters of n-hexane, 420 g of diethylaluminum monochloride and 30 g of the solid catalyst component (b) at room temperature, Reaction was performed at a pressure of 5 kg / cm ² G for 5 minutes, and unreacted propylene and n-hexane were removed under reduced pressure to obtain a pre-activated catalyst (catalyst b) granular material (per 1 g of solid product (b)) Propylene 30.0 g reaction).

(Ii) Production of crystalline propylene polymer 3 Crystalline propylene polymer 3 was obtained using one stirred bulk polymerization tank.
The catalyst b was continuously supplied as a catalyst so as to achieve the target production amount, diethylaluminum monochloride as a cocatalyst was 450 wtppm, and methyl methacrylate as an electron donating compound was continuously supplied as 7.0 wtppm.
Further, bulk polymerization was performed under the operating conditions of the polymerization tank at a temperature of 70 ° C., a pressure of 3.0 MPaG, a hydrogen concentration of 0.6 mol%, and an average residence time of 2.8 hours.
As a result of this polymerization, a crystalline propylene polymer 3 having a catalytic activity of 4,500 gPP / gcat and an MFR of 0.50 g / 10 min was obtained.

(Iii) Production of polypropylene composition 4 With respect to 100 parts by weight of crystalline propylene polymer 3, 0.1 parts by weight of IRGANOX1010, 0.1 part by weight of IRGAFOS168 and calcium stearate as a neutralizing agent (Nitto Kasei Kogyo Co., Ltd.) Manufactured) 0.1 parts by weight was blended, and melt-kneaded using an extruder and pelletized to obtain a polypropylene composition 4.
Various physical properties measured for the obtained pellets are shown in Table 1.
Thereafter, sheet molding and evaluation were performed in the same manner as in Example 1. The results are shown in Table 1.

<Comparative example 2>
(I) Production of crystalline propylene polymer 4 A crystalline propylene polymer 4 was prepared as follows using a polymerization tank in which two stirred bulk polymerization tanks and two gas phase fluidized beds, a total of four, were connected. Got.
The solid catalyst component (a) is continuously supplied as a catalyst to the first reactor so as to achieve a target production amount, and triethylaluminum as a co-catalyst is added to the first reactor only 5% of magnesium in the catalyst. It supplied continuously so that it might become a molar ratio. Furthermore, as an electron donating compound, tert-butylmethyldimethoxysilane was added to 3.0 mol. ppm was fed continuously.
The operating conditions of each polymerization tank were as follows: the first reactor had a temperature of 70 ° C., a pressure of 2.9 MPaG, a hydrogen concentration of 1.1 mol%, an average residence time of 0.6 hours, the second reactor had a temperature of 67 ° C. and a pressure of 2 Bulk polymerization with .6 MPaG, hydrogen concentration 0.6 mol%, average residence time 0.4 hours, third reactor 80 ° C., pressure 1.7 MPaG, average residence time 0.7 hours, hydrogen concentration 8.0 × 10 ^-2 mol% gas phase polymerization, the fourth reactor was vapor phase polymerization at 80 ° C, pressure 1.1 MPaG, hydrogen concentration 0.1 mol%, average residence time 1.4 hours.
As a result of this polymerization, a crystalline propylene polymer 4 having a catalytic activity of 35,000 gPP / gcat and an MFR of 0.47 g / 10 min was obtained. The MFR obtained in each stage was 0.50 g / 10 minutes from the first reactor, 0.55 g / 10 minutes from the second reactor, 0.55 g / 10 minutes from the third reactor, and from the fourth reactor. It was 0.47 g / 10 minutes.

(Ii) Production of polypropylene composition 5 With respect to 100 parts by weight of the crystalline propylene polymer 4, 0.1 part by weight of IRGANOX 1010, 0.2 part by weight of IRGAFOS 168 and 0.1 part by weight of calcium stearate are blended. The polypropylene composition 5 was obtained by melt-kneading and pelletizing using an extruder.
Various physical properties measured for the obtained pellets are shown in Table 1.
Thereafter, sheet molding and evaluation were performed in the same manner as in Example 1. The results are shown in Table 1.

<Comparative Example 3>
(I) Production of crystalline propylene polymer 5 The following polymerization was carried out using a continuous reaction apparatus in which two fluidized bed reactors having an internal volume of 230 liters were connected.
First, in a first reactor, a polymerization temperature of 75 ° C., a propylene partial pressure of 1.8 MPa, and hydrogen as a molecular weight control agent are continuously fed so that the molar ratio of hydrogen / propylene is 1.1 × 10 ^−3. At the same time, triethylaluminum was fed at 5.25 g / hr and the solid catalyst component (a) was fed so that the polymer polymerization rate was 20 kg / hr. The powder polymerized in the first reactor (crystalline propylene polymer) was continuously withdrawn so that the amount of powder held in the reactor was 60 kg and transferred continuously to the second reactor (pre-stage polymerization step). .
Propylene is continuously supplied at a polymerization temperature of 80 ° C. so that the pressure becomes 2.0 MPa, and hydrogen as a molecular weight control agent is adjusted to a hydrogen / propylene molar ratio of 1.0 × 10 ^−2. And ethyl alcohol as an active hydrogen compound was supplied in an amount of 1.0-fold mol with respect to triethylaluminum. The powder polymerized in the second reactor is continuously extracted into the vessel so that the amount of powder held in the reactor is 40 kg, and the reaction is stopped by supplying nitrogen gas containing moisture to obtain a polypropylene resin. (Post polymerization process).
As a result of this polymerization, a crystalline propylene polymer 5 having an MFR of 0.50 g / 10 min was obtained. The MFR obtained in each stage was 0.10 g / 10 minutes from the first reactor and 0.60 g / 10 minutes from the second reactor.

(Ii) Production of polypropylene composition 6 With respect to 100 parts by weight of the crystalline propylene polymer 5, 0.05 part by weight of IRGANOX 1010, 0.1 part by weight of IRGAFOS 168, 0.05 part by weight of DHT4A, NA-11 Was blended and melt-kneaded using an extruder and pelletized to obtain a polypropylene composition 5.
Various physical properties measured for the obtained pellets are shown in Table 1.
Thereafter, sheet molding and evaluation were performed in the same manner as in Example 1. The results are shown in Table 1.

<Comparative example 4>
(I) Production of crystalline propylene polymer 6 The hydrogen concentrations in the first, second, third, and fourth reactors were 6.0 mol%, 2.8 mol%, and 6.0 × 10 ⁻² mol, respectively. %, 1.7 × 10 ⁻² mol%, and the same conditions as in Example 1 were used.
As a result of this polymerization, a crystalline propylene polymer 6 having a catalytic activity of 34,000 gPP / gcat and an MFR of 1.50 g / 10 min was obtained.
The MFR obtained in each stage was 7.70 g / 10 minutes from the first reactor, 7.32 g / 10 minutes from the second reactor, 3.37 g / 10 minutes from the third reactor, and the fourth reaction. The discharge was 1.50 g / 10 min.
The measured physical properties of the obtained crystalline propylene polymer 6 are shown in Table 1.

(Ii) Production of polypropylene resin composition 7 With respect to 100 parts by weight of crystalline propylene polymer 6, 0.05 part by weight of IRGANOX 1010, 0.1 part by weight of IRGAFOS 168, 0.05 part by weight of DHT4A, nucleation Polypropylene resin composition 7 was obtained by blending 0.1 part by weight of NA-11 as an agent, and melt-kneading and pelletizing using an extruder.
Thereafter, sheet molding and evaluation were performed in the same manner as in Example 1. The results are shown in Table 1.

<Example 4>
The polypropylene composition 1 was introduced into an extruder with a screw diameter of 50 mm, and both surface layers were charged with EVOH pellets (trade name BX6804B, manufactured by Nippon Synthetic Chemical Industry) into an extruder with a screw diameter of 40 mm. Furthermore, the adhesive resin (trade name Modic P604V, manufactured by Mitsubishi Chemical Corporation) is put into another extruder with a screw diameter of 40 mm and extruded from a T-die through a feed block so as to come to both outer layers of the EVOH layer. The polypropylene sheet was continuously taken up at a speed of 1 m / min while being cooled and solidified by sandwiching it with a mirror-finished metal cast roll whose surface temperature was controlled at 60 ° C., and having a width of 500 mm and an EVOH layer thickness of 0. A three-kind five-layer sheet having a thickness of 1 mm, an adhesive resin thickness of 0.1 mm and an overall thickness of 2 mm was obtained.
A thermoformed container was molded using this sheet in the same manner as in Example 1.
Various evaluations described above were performed on this thermoformed container. The results are shown in Table 1.

<Comparative Example 5>
(I) Production of crystalline propylene polymer 7 A crystalline propylene polymer 7 was prepared as follows using a polymerization tank in which two stirred bulk polymerization tanks and two gas phase fluidized beds, a total of four, were connected. Got.
The solid catalyst component (catalyst a) after pre-polymerization is continuously supplied as a catalyst to the first reactor so as to achieve a target production amount, and triethylaluminum as a co-catalyst is also supplied to the first reactor. Only a 5 mole ratio with respect to magnesium in the catalyst was continuously fed. Further, tert-butylmethyldimethoxysilane as an electron donating compound was added to the first reactor only at 3.0 mol. ppm was fed continuously.
The operating conditions of each polymerization tank were as follows: the first reactor had a temperature of 70 ° C., a pressure of 2.9 MPaG, a hydrogen concentration of 2.4 mol%, an ethylene concentration of 0.3 mol%, and an average residence time of 0.5 hours. Polymerization, the second reactor is 67 ° C., the pressure is 2.6 MPaG, the hydrogen concentration is 1.4 mol%, the ethylene concentration is 0.2 mol%, the average residence time is 0.4 hour bulk polymerization, the third reactor is 80 C., pressure 1.7 MPaG, average residence time 0.7 hours, hydrogen concentration 2.1 × 10 ⁻² mol%, ethylene concentration 0.1 mol% gas phase polymerization, fourth reactor is 80 ° C., pressure 1 The gas phase polymerization was performed at a pressure of 0.1 MPaG, a hydrogen concentration of 2.8 × 10 ⁻³ mol%, an ethylene concentration of 5.0 × 10 ⁻³ mol%, and an average residence time of 1.4 hours.
As a result of this polymerization, a crystalline propylene polymer 7 having a catalytic activity of 35,000 gPP / gcat, an MFR of 0.61 g / 10 min, and an ethylene content of 0.35 wt% was obtained.
The MFR obtained in each stage was 3.40 g / 10 minutes from the first reactor, 2.90 g / 10 minutes from the second reactor, 1.40 g / 10 minutes from the third reactor, and the fourth reaction. The output was 0.61 g / 10 min [MFR ratio (MFR1 / MFR2) = 5.6].
The measured physical properties of the obtained crystalline propylene polymer 7 are shown in Table 1.

(Ii) Production of polypropylene resin composition 8 With respect to 100 parts by weight of crystalline propylene polymer 7, 0.05 part by weight of IRGANOX 1010 as a phenol-based antioxidant and 0.1 weight by weight of IRGAFOS 168 as a phosphorus-based antioxidant Part, 0.05 part by weight of DHT4A as a neutralizing agent and 0.1 part by weight of Adeka Stub NA11 as a nucleating agent were blended, melt-kneaded using an extruder, and pelletized to obtain a polypropylene composition 8. .
Various physical properties measured for the obtained pellets are shown in Table 1.
Thereafter, in the same manner as in Example 1, sheet forming and evaluation were performed. The results are shown in Table 1.

From the results of the above examples and comparative examples, the following can be understood.
(1) Examples 1, 2, and 3 are examples of crystalline propylene polymers having extremely high rigidity and low heat shrinkage.
(2) Comparative Example 1 is an example of a crystalline propylene polymer having low rigidity. From a comparison with Examples 1 and 2, the flexural modulus is also low. Furthermore, there is a difficulty in application to a field requiring a heat shrinkage rate.
(3) Comparative Example 2 is an example of a crystalline propylene polymer having high rigidity but low melt viscoelasticity. From a comparison with Examples 1 and 2, it is clear that the thermoforming properties are poor.
(4) Comparative Example 3 is an example of a crystalline propylene polymer having high melt viscoelasticity but slightly low rigidity. Despite the large amount of nucleating agent used, the flexural modulus is low and the thermoforming properties are poor, as compared with Examples 1 and 2. In addition, the production efficiency is low due to the method of producing the high molecular weight polypropylene in the former stage and the low molecular weight polypropylene in the latter stage, and further, fish eyes are easily generated.
(5) Comparative Example 4 is an example in which the rigidity is high but the MFR is high. From comparison with Examples 1 and 2, the thermoforming properties are poor.
(6) Comparative Example 5 is an example in which the rigidity (Tp) is low, but the temperature (Tp) when the amount of the eluted component is the largest is low in the measurement of temperature rising elution fractionation (TREF). From comparison with Examples 1 and 2, the thermoforming properties are poor.
(7) Example 4 is a thermoformed container made of a multilayer sheet with EVOH. This is an example in which a container having a low heat shrinkage is obtained even in a multilayer sheet.

  The thermoformed container of the present invention is a food container as a deep-drawn thermoformed container having a high commercial value because a deep-drawn container having a large depth / caliber ratio can be solid-phase pressure-molded and can withstand high temperature retort processing. Since it can be widely used for containers in various fields such as detergent containers and medical containers, its industrial applicability is very large.

Claims (7)

Thermoforming having a deep drawing structure in which the ratio of the depth / caliber of the container is 1 or more obtained by solid-state pressure forming a sheet of crystalline propylene polymer (A) satisfying the following (a) to (c) A thermoformed container having a thermal shrinkage at 125 ° C. of 3% or less.
(A) In the measurement of temperature rising elution fractionation (TREF) using orthodichlorobenzene as a solvent, the temperature (Tp) when the component eluted at a temperature of 40 ° C. or less is 1% by weight or less and the amount of the eluted component is the largest 113 ° C. or more and 125 ° C. or less (b) Storage at the intersection Gc between the frequency ω dependency curve G ′ (ω) of the storage elastic modulus and the frequency ω dependency curve G ″ (ω) of the loss elastic modulus by dynamic viscoelasticity measurement. the value of the elastic modulus (unit: Pa) when the ¹⁰⁵ times the reciprocal of the PI, melt flow rate PI of 4.0 or more (c) JIS K7210 (230 ℃ , 2.16kg load) was measured on the basis of (MFR) is 0.2-1 g / 10 min   The sheet of the crystalline propylene polymer (A) contains 0.01 to 0.5 parts by weight of the nucleating agent with respect to 100 parts by weight of the crystalline propylene polymer (A). 1. The thermoformed container according to 1.   A crystalline propylene polymer (A) is produced by a multistage polymerization of two or more stages comprising a bulk polymerization process of one or more stages and a gas phase polymerization process of one or more stages, and the melt flow rate ( The thermoformed container according to claim 1 or 2, which is a crystalline propylene polymer having a MFR) lower than the melt flow rate of the polymer obtained in the preceding stage. The crystalline propylene polymer (A) is produced by multistage polymerization, and the MFR difference between the MFR (MFR1) of the polymer produced in the first reactor and the crystalline propylene polymer (MFR) obtained by multistage polymerization Is a crystalline propylene polymer represented by the following formula.
MFR1 / MFR ≧ 4.0   The crystalline propylene polymer (A) is a crystalline propylene polymer obtained by a propylene polymerization catalyst comprising a solid catalyst component (a) containing titanium, magnesium and halogen as essential components, and an organoaluminum component (b). The thermoformed container according to claim 1, wherein the thermoformed container is provided. When the crystalline propylene polymer (A) is further polymerized, an organosilicon compound containing two or more Si—OR ¹ bonds (where R ¹ is a hydrocarbon group having 1 to 8 carbon atoms) (provided that The thermoforming container according to claim 5, wherein R ¹ is a crystalline propylene polymer produced by supplying R ¹ is a hydrocarbon group having 1 to 8 carbon atoms. The thermoforming container according to claim 5 or 6, wherein the solid catalyst component (a) is obtained by bringing the following (i), (ii), (iii) and (iv) into contact with each other.
(I) Solid component containing titanium, magnesium and halogen as essential components (ii) Organosilicon compound containing two or more Si—OR ¹ bonds (where R ¹ is a hydrocarbon residue having 1 to 8 carbon atoms) is there.)
(Iii) Vinylsilane compound (iv) Organometallic compound of periodic group I-III metal

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