Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
  • C08F10/04—Monomers containing three or four carbon atoms
  • C08F10/06—Propene
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
  • C08F110/04—Monomers containing three or four carbon atoms
  • C08F110/06—Propene
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
  • C08F210/04—Monomers containing three or four carbon atoms
  • C08F210/06—Propene
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
  • C08J5/18—Manufacture of films or sheets
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
  • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
  • C08L23/10—Homopolymers or copolymers of propene
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
  • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
  • C08L23/10—Homopolymers or copolymers of propene
  • C08L23/12—Polypropene
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
  • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
  • C08L23/16—Ethylene-propylene or ethylene-propylene-diene copolymers
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
  • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
  • C08J2323/10—Homopolymers or copolymers of propene

Definitions

• the present invention relates to an unstretched film made of a propylene polymer composition and a laminate containing the film.
• Polyolefins (olefin polymers) represented by polyethylene and polypropylene require little energy for production, are lightweight, and have excellent recyclability. Reuse, Recycle) is gaining more attention. Polyolefins are used in various fields such as daily necessities, kitchen utensils, packaging films, home electric appliances, machine parts, electric parts, and automobile parts.
• polypropylene has excellent rigidity and heat resistance, but is inferior to polyethylene in cold resistance and impact resistance. has been proposed (see, for example, Patent Documents 1 to 4).
• unstretched polypropylene film has an excellent balance of rigidity and heat resistance. In some cases, the rigidity may not be sufficient.
• An object of the present invention is to obtain an unstretched film with improved rigidity.
• the present invention relates to the following [1] to [10].
• a propylene-based polymer (a1) having a limiting viscosity [ ⁇ ] in the range of 10 to 12 dl/g measured in a tetralin solvent at 135°C was measured in a range of 20 to 50% by mass and in a tetralin solvent at 135°C.
• the propylene polymer (a2) having a limiting viscosity [ ⁇ ] in the range of 0.5 to 1.5 dl/g is added in the range of 50 to 80% by mass [however, the total amount of (a1) and (a2) is 100 % by mass.
• An unstretched film characterized by comprising a propylene polymer composition comprising:
• the propylene polymer composition is characterized by being a composition containing the propylene-based polymer (A) in the range of 1 to 20% by mass and the propylene homopolymer (B1) in the range of 80 to 99% by mass.
• the propylene polymer composition is characterized by being a composition containing the propylene-based polymer (A) in the range of 15 to 40% by mass and the propylene homopolymer (B2) in the range of 60 to 85% by mass.
• the propylene-based polymer (A) has a melt flow rate (MFR) measured at a measurement temperature of 230°C and a load of 2.16 kg in accordance with JIS K 7210 in the range of 0.01 to 5 g/10 minutes and 230°C.
• MFR melt flow rate
• the propylene-based polymer (A) has a high-molecular-weight region having a molecular weight of 1,500,000 or more, which accounts for 7% or more of the total area surrounded by the molecular weight distribution curve measured by gel permeation chromatography (GPC).
• GPC gel permeation chromatography
• the propylene-based polymer (A) has two peaks in the molecular weight distribution curve measured by GPC, and the ratio (MH/ The unstretched film according to item [1], which is a polymer having ML) of 50 or more.
• the propylene homopolymer (B1) is characterized by being a polymer having a weight average molecular weight (Mw) to number average molecular weight (Mn) ratio (Mw/Mn) in the range of 4.0 to 8.0.
• Mw weight average molecular weight
• Mn number average molecular weight
• the unstretched film according to any one of items [1] to [6].
• a laminate comprising the unstretched film according to any one of items [1] to [9].
• the unstretched film of the present invention has good transparency and rigidity, so it can be used as a packaging film in a wide range of packaging fields.
• the unstretched film of the present invention [hereinafter sometimes simply referred to as "film”. ] has an intrinsic viscosity [ ⁇ ] of 10 to 12 dl/g measured in a tetralin solvent at 135°C.
• the propylene-based polymer (a1) in the range of 20 to 50% by mass, and the propylene-based polymer ( a2) in the range of 50 to 80% by mass [where the total amount of (a1) and (a2) is 100% by mass. ].
• intrinsic viscosity [ ⁇ ] measured in a tetralin solvent at 135°C is also simply referred to as "intrinsic viscosity [ ⁇ ]".
• the intrinsic viscosity [ ⁇ ] of the propylene-based polymer (a1) which is one of the components contained in the propylene-based polymer (A) according to the present invention, is in the range of 10 to 12 dl/g, preferably 10.5. It is in the range of ⁇ 11.5 dl/g.
• the mass fraction of the propylene-based polymer (a1) in the propylene-based polymer (A) is in the range of 20 to 50% by mass, preferably 20 to 45% by mass, more preferably 20 to 40% by mass, More preferably, it is in the range of 22-40% by mass.
• Examples of the propylene-based polymer (a1) according to the present invention include propylene homopolymers and copolymers of propylene and ⁇ -olefins having 2 to 8 carbon atoms (excluding propylene).
• Examples of ⁇ -olefins having 2 to 8 carbon atoms include ethylene, 1-butene, 1-hexene, 1-octene and 4-methyl-1-pentene. Ethylene is preferred as these ⁇ -olefins.
• One or more ⁇ -olefins can be used.
• the content of structural units derived from propylene is usually 90% by mass or more, preferably 95% by mass or more, more preferably 98% by mass or more. and the content of structural units derived from ⁇ -olefins having 2 to 8 carbon atoms (excluding propylene) is usually 10% by mass or less, preferably 5% by mass or less, more preferably 2% by mass or less. is.
• the content ratio can be measured by 13 C-NMR.
• the film formability tends to deteriorate and the film surface appearance tends to deteriorate. Further, when the intrinsic viscosity [ ⁇ ] of the propylene-based polymer (a1) is less than 10 dl/g, the obtained film tends to have insufficient rigidity and heat resistance.
• the mass fraction of the propylene-based polymer (a1) is less than 20% by mass, the resulting polymer composition tends to have insufficient melt tension, and the resulting film tends to have insufficient rigidity and heat resistance. If it exceeds 50% by mass, it tends to cause poor appearance during film molding.
• the propylene-based polymer (a1) can be used alone or in combination of two or more.
• the intrinsic viscosity [ ⁇ ] of the propylene-based polymer (a2) which is one of the components contained in the propylene-based polymer (A) according to the present invention, is preferably in the range of 0.5 to 1.5 dl/g. is in the range 0.6-1.5 dl/g, more preferably 0.8-1.5 dl/g.
• the mass fraction of the propylene-based polymer (a2) in the propylene-based polymer (A) is in the range of 50 to 80% by mass, preferably 55 to 80% by mass, more preferably 60 to 80% by mass, More preferably, it is in the range of 60-78% by mass.
• Examples of the propylene-based polymer (a2) according to the present invention include propylene homopolymers and copolymers of propylene and ⁇ -olefins having 2 to 8 carbon atoms (excluding propylene).
• Examples of ⁇ -olefins having 2 to 8 carbon atoms include ethylene, 1-butene, 1-hexene, 1-octene and 4-methyl-1-pentene. Ethylene is preferred as these ⁇ -olefins.
• One or more ⁇ -olefins can be used.
• the content of structural units derived from propylene is usually 90% by mass or more, preferably 93% by mass or more, more preferably 94% by mass or more. and the content of structural units derived from ⁇ -olefins having 2 to 8 carbon atoms (excluding propylene) is usually 10% by mass or less, preferably 7% by mass or less, more preferably 6% by mass or less. is.
• the content ratio can be measured by 13 C-NMR.
• the melt tension of the propylene-based polymer (A) is insufficient, while the intrinsic viscosity [ ⁇ ] is 1.5 dl. /g, the viscosity tends to be high and the film formability tends to deteriorate.
• the mass fraction of the propylene-based polymer (a2) is less than 50% by mass, it tends to cause poor appearance during film molding, and when it exceeds 80% by mass, the melt tension of the propylene-based polymer (A) In addition, the rigidity and heat resistance of the resulting film tend to be insufficient.
• the propylene-based polymer (a2) can be used alone or in combination of two or more.
• Additives such as an antioxidant, a neutralizing agent, a flame retardant, and a crystal nucleating agent can be added to the propylene-based polymer (A) according to the present invention, if necessary. Additives can be used alone or in combination of two or more. The proportion of the additive is not particularly limited and can be adjusted as appropriate.
• the propylene-based polymer (A) according to the present invention has a melt flow rate (MFR) measured at 230° C. under a load of 2.16 kg, preferably from 0.01 to 5 g/10 minutes, more preferably from 0.05 to 4 g/10 min, more preferably in the range of 0.1 to 3 g/10 min.
• MFR melt flow rate
• the propylene-based polymer (A) according to the present invention preferably has a melt tension (MT) measured at 230°C in the range of 5 to 30 g, more preferably 7 to 25 g, and even more preferably 10 to 20 g.
• MT melt tension
• the melt tension (MT) of the propylene-based polymer (A) in the present invention can be measured using the following equipment and conditions.
• the propylene-based polymer (A) according to the present invention is the total area of the region surrounded by the molecular weight distribution curve measured by gel permeation chromatography (GPC).
• the area ratio of the high molecular weight region with a molecular weight of 1,500,000 or more (corresponding to the mass ratio of the high molecular weight component with a molecular weight of 1,500,000 or more) is preferably 7% or more, more preferably 10% or more, and still more preferably 12%. That's it.
• the upper limit of the area ratio is, for example, 30%, preferably 25%.
• the area ratio of the high-molecular-weight region occupies a specific ratio or more means that the propylene-based polymer (A) contains a high-molecular-weight component having a molecular weight of 1,500,000 or more. At least part of this high molecular weight component is a high molecular weight component having an intrinsic viscosity [ ⁇ ] of 10 to 12 dl/g. Therefore, if the proportion of the high molecular weight component is within the above range, the melt tension of the propylene-based polymer (A) will be more excellent.
• the propylene-based polymer (A) according to the present invention preferably has two peaks in the molecular weight distribution curve measured by GPC.
• the ratio (MH/ML) of the peak molecular weight (MH) on the high molecular weight side and the peak molecular weight (ML) on the low molecular weight side is preferably 50 or more, more preferably 70 or more, and still more preferably 90 or more.
• the upper limit of the ratio (MH/ML) is, for example, 500, preferably 300.
• the fact that the molecular weight distribution curve has two peaks and MH/ML is a specific value or more indicates that the polymer has a high content of high molecular weight components and a high intrinsic viscosity [ ⁇ ]. Therefore, the propylene-based polymer (A) having such an aspect contributes to improvement of melt tension and improvement of rigidity and heat resistance when formed into a film.
• the propylene-based polymer (A) according to the present invention has a peak molecular weight ML on the low molecular weight side of the molecular weight distribution curve measured by GPC, from the viewpoint of viscosity and film formability, preferably 100,000 or less, more preferably It is 80,000 or less, more preferably 50,000 or less.
• ⁇ Method for producing propylene-based polymer (A)>> As the method for producing the propylene-based polymer (A) according to the present invention, various known production methods can be mentioned. After that, the propylene-based polymer (a1) and the propylene-based polymer (a2) are mixed or melt-kneaded in the above range to obtain the propylene-based polymer (A) (1); A method (2) of obtaining the propylene-based polymer (A) by producing the coalescence (a1) and the propylene-based polymer (a2) in one polymerization system or two or more polymerization systems can be mentioned.
• the propylene-based polymer (a1), the propylene-based polymer (a2) and, if necessary, additives and the like are mixed using a Henschel mixer, a V-type blender, a tumbler blender, a ribbon blender, or the like. Then, by melt-kneading using a single-screw extruder, a multi-screw extruder, a kneader, a Banbury mixer, or the like, a high-quality propylene-based polymer (A) in which the above components are uniformly dispersed and mixed can be obtained. can.
• the resin temperature during melt-kneading is usually 180 to 280°C, preferably 200 to 260°C.
• a propylene-based polymer (A) containing a relatively high-molecular-weight propylene-based polymer (a1) and a relatively low-molecular-weight propylene-based polymer (a2) is produced by multistage polymerization of two or more stages. can be obtained. Additives may be added to the obtained propylene-based polymer (A) as necessary.
• a preferred method for producing the propylene-based polymer (A) includes the above-mentioned method (2). are used together, and a method of polymerizing in two or more stages of multi-stage polymerization can be mentioned.
• propylene or propylene and an ⁇ -olefin having 2 to 8 carbon atoms are polymerized substantially in the absence of hydrogen, and the intrinsic viscosity [ ⁇ ] is 10. to 12 dl/g, preferably 10.5 to 11.5 dl/g relatively high molecular weight propylene polymer (a1) in propylene polymer (A) 20 to 50 mass%, preferably 20 to 45% by mass, more preferably 20 to 40% by mass, to produce a relatively low-molecular-weight propylene-based polymer (a2) in the second and subsequent polymerizations.
• the intrinsic viscosity [ ⁇ ] of the relatively low-molecular-weight propylene-based polymer (a2) produced in the second and subsequent polymerizations is 0.5 to 1.5 dl/g, preferably 0.6 to 1 .5 dl/g, more preferably 0.8 to 1.5 dl/g.
• This intrinsic viscosity [ ⁇ ] is the intrinsic viscosity [ ⁇ ] of the propylene-based polymer produced in that stage alone, and the intrinsic viscosity [ ⁇ ] of the entire propylene-based polymer including the propylene-based polymer up to the previous stage of that stage is do not have.
• the MFR of the finally obtained propylene-based polymer (A) is preferably 0.01 to 5 g/10 min, more preferably 0.05 to 4 g/10 min, and further It is preferably adjusted to 0.1 to 3 g/10 minutes.
• the method for adjusting the intrinsic viscosity [ ⁇ ] of the propylene-based polymer produced in the second stage and thereafter is not particularly limited, but a method using hydrogen as a molecular weight modifier is preferred.
• the production order (polymerization order) of the propylene-based polymer (a1) and the propylene-based polymer (a2) in the first stage, the propylene-based polymer having a relatively high molecular weight is prepared substantially in the absence of hydrogen.
• a relatively low-molecular-weight propylene-based polymer (a2) for example, in the presence of hydrogen in the second step or later.
• the production order can be reversed, after producing a relatively low-molecular-weight propylene-based polymer (a2) in the first stage, a relatively high-molecular-weight propylene-based polymer is produced in the second and subsequent stages.
• Each stage of the multi-stage polymerization can be carried out continuously or batchwise, preferably batchwise.
• the propylene-based polymer (A) containing the propylene-based polymer (a1) and the propylene-based polymer (a2) obtained by multi-stage polymerization by a batch system contains the propylene-based polymer (a1), which is an ultra-high molecular weight component.
• a film is obtained which is well dispersed and thus has excellent stiffness and heat resistance.
• composition unevenness may occur between polymer particles due to residence time distribution, and fisheyes in the film may increase.
• a film with less fish eyes can be obtained. Therefore, by adopting the batch method, a film with few fish eyes can be obtained in spite of using the propylene-based polymer (a1) having a high molecular weight.
• the homopolymerization of propylene or the polymerization of propylene with an ⁇ -olefin having 2 to 8 carbon atoms can be carried out by known methods such as slurry polymerization and bulk polymerization. method can be done. In addition, it is preferable to use a polypropylene production catalyst, which will be described later.
• the conditions for producing the propylene-based polymer (a1) are as follows: in the absence of hydrogen, the starting monomers are polymerized at a temperature of preferably 20 to 80° C., more preferably 40 to 70° C., and the polymerization pressure is generally normal pressure. It is preferably produced by bulk polymerization under conditions of up to 9.8 MPa, preferably 0.2 to 4.9 MPa.
• the conditions for producing the propylene-based polymer (a2) include starting monomers at a polymerization temperature of preferably 20 to 80° C., more preferably 40 to 70° C., and a polymerization pressure of generally normal pressure to 9.8 MPa, preferably It is preferably produced by polymerization under conditions of 0.2 to 4.9 MPa and in the presence of hydrogen as a molecular weight modifier.
• Catalysts for producing polypropylene that can be used for producing the propylene-based polymer (a1), the propylene-based polymer (a2) and the propylene-based polymer (A) include, for example, It can be formed from a solid catalyst component containing magnesium, titanium and halogen as essential components, an organometallic compound catalyst component such as an organoaluminum compound, and an electron-donating compound catalyst component such as an organosilicon compound. As a thing, the following catalyst components can be used.
• Solid catalyst component As the carrier constituting the solid catalyst component, a carrier obtained from metallic magnesium, alcohol, and halogen and/or halogen-containing compound is preferable.
• metal magnesium granular, ribbon-shaped, powdered magnesium, etc. can be used.
• Metal magnesium is preferably not coated with magnesium oxide or the like on its surface.
• the alcohol it is preferable to use a lower alcohol having 1 to 6 carbon atoms.
• ethanol is used to obtain a carrier that significantly improves the expression of catalytic performance.
• the amount of alcohol to be used is preferably 2 to 100 mol, more preferably 5 to 50 mol, per 1 mol of metallic magnesium. 1 type(s) or 2 or more types can be used for alcohol.
• Halogen is preferably chlorine, bromine or iodine, preferably iodine.
• MgCl 2 and MgI 2 are preferable.
• the amount of the halogen or halogen-containing compound to be used is usually 0.0001 gram-atom or more, preferably 0.0005 gram-atom or more, and further It is preferably 0.001 gram-atom or greater. Halogens and halogen-containing compounds can be used singly or in combination of two or more.
• a method of obtaining a carrier by reacting metallic magnesium, an alcohol, and a halogen and/or a halogen-containing compound includes, for example, metallic magnesium, an alcohol, and a halogen and/or a halogen-containing compound, under reflux (e.g., about 79° C.) until generation of hydrogen gas is no longer observed (usually for 20 to 30 hours).
• the reaction is preferably carried out in an inert gas atmosphere such as nitrogen gas or argon gas.
• the obtained carrier When the obtained carrier is used for the synthesis of the solid catalyst component, it may be dried or washed with an inert solvent such as heptane after filtering.
• the obtained carrier is nearly granular and has a sharp particle size distribution. Furthermore, the variation in particle size is very small even for individual particles.
• the sphericity (S) represented by the following formula (I) is less than 1.60, particularly less than 1.40, and the particle size distribution index (P) represented by the following formula (II) is preferably less than 5.0, especially less than 4.0.
• E1 represents the projected contour length of the particle
• E2 represents the perimeter of a circle equal to the projected area of the particle.
• D90 refers to the particle diameter corresponding to a mass cumulative fraction of 90%. That is, it indicates that the sum of the mass of particles smaller than the particle diameter represented by D90 is 90% of the total mass of all particles.
• D10 refers to the particle diameter corresponding to a mass cumulative fraction of 10%.
• the solid catalyst component is usually obtained by bringing at least the titanium compound into contact with the carrier.
• the contact with the titanium compound may be performed in multiple steps.
• Titanium compounds include, for example, titanium compounds represented by general formula (III).
• X 1 is a halogen atom, particularly preferably a chlorine atom
• R 1 is a hydrocarbon group having 1 to 10 carbon atoms, preferably a linear or branched alkyl group, and R 1 is plural When present, they may be the same or different and n is an integer from 0-4.
• titanium compounds include Ti(Oi-C 3 H 7 ) 4 , Ti(O-C 4 H 9 ) 4 , TiCl(O-C 2 H 5 ) 3 , TiCl(Oi —C 3 H 7 ) 3 , TiCl(O—C 4 H 9 ) 3 , TiCl 2 (O—C 4 H 9 ) 2 , TiCl 2 (Oi-C 3 H 7 ) 2 , TiCl 4 . , TiCl 4 are preferred.
• One or two or more titanium compounds can be used.
• the solid catalyst component is usually obtained by further contacting the carrier with an electron-donating compound.
• Electron-donating compounds include, for example, di-n-butyl phthalate. 1 type(s) or 2 or more types can be used for an electron-donating compound.
• a halogen-containing silicon compound such as silicon tetrachloride can be brought into contact.
• a halogen-containing silicon compound such as silicon tetrachloride can be brought into contact.
• One or more halogen-containing silicon compounds can be used.
• the solid catalyst component can be prepared by a known method. For example, a method of using an inert hydrocarbon such as pentane, hexane, peptane, or octane as a solvent, adding the carrier, the electron-donating compound, and the halogen-containing silicon compound to the solvent, and then adding the titanium compound while stirring. is mentioned. Usually, 0.01 to 10 mol, preferably 0.05 to 5 mol, of the electron donating compound is added to 1 mol of the carrier in terms of magnesium atom, and titanium is added to 1 mol of the carrier in terms of magnesium atom. 1 to 50 mol, preferably 2 to 20 mol of the compound is added, and the contact reaction is carried out at 0 to 200° C.
• an inert hydrocarbon such as pentane, hexane, peptane, or octane
• the solid catalyst component may also be a component obtained by contacting a liquid magnesium compound and a liquid titanium compound in the presence of an electron donating compound.
• the contact with the liquid titanium compound may be carried out in multiple times.
• a liquid magnesium compound is obtained, for example, by contacting a known magnesium compound and an alcohol, preferably in the presence of a liquid hydrocarbon medium, to liquefy.
• magnesium compounds include magnesium halides such as magnesium chloride and magnesium bromide.
• Alcohols include, for example, aliphatic alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, 2-ethylhexyl alcohol.
• liquid hydrocarbon media include hydrocarbon compounds such as heptane, octane, and decane.
• the amount of alcohol used in preparing the liquid magnesium compound is generally 1.0 to 25 mol, preferably 1.5 to 10 mol, per 1 mol of the magnesium compound.
• One or more liquid magnesium compounds can be used.
• liquid titanium compound examples include the titanium compound represented by the general formula (III) described above.
• the amount of the liquid titanium compound to be used is usually 0.1 to 1000 mol, preferably 1 to 200 mol, per 1 mol of magnesium atoms (Mg) contained in the liquid magnesium compound.
• One or two or more liquid titanium compounds can be used.
• electron-donating compounds include dicarboxylic acid ester compounds such as phthalates, acid anhydrides such as phthalic anhydride, organosilicon compounds such as dicyclopentyldimethoxysilane, dicyclohexyldimethoxysilane, cyclohexylmethyldimethoxysilane, and polyethers. , acid halides, acid amides, nitriles, and organic acid esters.
• the amount of the electron-donating compound to be used is usually 0.01 to 5 mol, preferably 0.1 to 1 mol, per 1 mol of magnesium atoms (Mg) contained in the liquid magnesium compound. 1 type(s) or 2 or more types can be used for an electron-donating compound.
• the temperature during contact is usually -70 to 200°C, preferably 10 to 150°C.
• organoaluminum compound is preferable as the organometallic compound catalyst component.
• organoaluminum compounds include compounds represented by general formula (IV).
• R 2 is an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group or an aryl group
• X 2 is a halogen atom or an alkoxy group, preferably a chlorine atom or a bromine atom
• n is 1 to 3 integers.
• organoaluminum compounds include trialkylaluminum compounds such as trimethylaluminum, triethylaluminum and triisobutylaluminum, diethylaluminum monochloride, diisobutylaluminum monochloride, diethylaluminum monoethoxide, and ethylaluminum sesquichloride.
• One or two or more organoaluminum compounds can be used.
• the amount of the organometallic compound catalyst component used is usually 0.01 to 20 mol, preferably 0.05 to 10 mol, per 1 mol of titanium atom in the solid catalyst component.
• organosilicon compounds are preferred as electron-donating compound components to be used in the polymerization system.
• organosilicon compounds include dicyclopentyldimethoxysilane, cyclohexylmethyldimethoxysilane, diethylaminotriethoxysilane, diisopropyldimethoxysilane, and cyclohexylisobutyldimethoxysilane.
• One or two or more organosilicon compounds can be used.
• the amount of the electron donating compound component used is usually 0.01 to 20 mol, preferably 0.1 to 5 mol, per 1 mol of titanium atom in the solid catalyst component.
• the solid catalyst component is subjected to pretreatment such as prepolymerization before being used for polymerization.
• pretreatment such as prepolymerization before being used for polymerization.
• an inert hydrocarbon such as pentane, hexane, peptane, octane, etc.
• adding the solid catalyst component, the organometallic compound catalyst component, and, if necessary, the electron-donating compound component to the solvent Propylene is fed and reacted while stirring.
• Propylene is preferably fed under a partial pressure of propylene higher than atmospheric pressure and pretreated at 0-100° C. for 0.1-24 hours.
• the propylene homopolymer (B) which is one of the components of the propylene polymer composition forming the unstretched film of the present invention, is selected from the following propylene homopolymer (B1) or the following propylene homopolymer (B2).
• the propylene homopolymer (B1) which is one of the propylene homopolymers (B) according to the present invention, has a melt flow rate (MFR ) is more than 10 g/10 min and 40 g/10 min or less, preferably a propylene homopolymer having an MFR in the range of 15 to 40 g/10 min.
• MFR melt flow rate
• the propylene homopolymer (B1) according to the present invention preferably has a weight average molecular weight (Mw) to number average molecular weight (Mn) ratio (Mw/Mn) of 4.0 to 8.0, more preferably 4. It ranges from 0.5 to 6.0.
• the Mw/Mn of the propylene homopolymer (B1) was calculated by obtaining the average molecular weight (number average molecular weight Mn, weight average molecular weight Mw) from the molecular weight distribution curve measured by GPC.
• the propylene homopolymer (B2) which is another one of the propylene homopolymers (B) according to the present invention, has a weight average molecular weight (Mw) to number average molecular weight (Mn) ratio (Mw/Mn) of 4. less than .0, preferably in the range of 2.0 to 4.0.
• the Mw/Mn of the propylene homopolymer (B2) was calculated by obtaining the average molecular weight (number average molecular weight Mn, weight average molecular weight Mw) from the molecular weight distribution curve measured by GPC.
• the propylene homopolymer (B2) according to the present invention has a melt flow rate (MFR) of usually 1 to 40 g/10 minutes, preferably 1 to 40 g/10 minutes, measured at a measurement temperature of 230°C and a load of 2.16 kg in accordance with JIS K 7210. has an MFR in the range of 5-20 g/10 min.
• MFR melt flow rate
• the propylene homopolymer (B) according to the present invention can be produced by homopolymerizing propylene using a catalyst, and a commercially available propylene homopolymer (homo PP) can be used.
• the catalyst is formed from, for example, the aforementioned solid catalyst component containing magnesium, titanium and halogen as essential components, an organometallic compound catalyst component such as an organoaluminum compound, and an electron-donating compound catalyst component such as an organosilicon compound. metallocene catalysts using a metallocene compound as one component of the catalyst.
• the propylene-based polymer (A) and propylene homopolymer (B) according to the present invention may each contain at least one biomass-derived monomer (propylene).
• the same kind of monomers constituting the polymer may be only biomass-derived monomers, or may contain both biomass-derived monomers and fossil fuel-derived monomers.
• Biomass-derived monomers are monomers derived from any renewable natural sources and their residues, such as plant-derived or animal-derived, including fungi, yeast, algae and bacteria, and containing 14C isotope as carbon.
• the biomass carbon concentration (pMC) measured according to ASTM D 6866 is about 100 (pMC).
• a biomass-derived monomer (propylene) is obtained by a conventionally known method.
• the propylene-based polymer (A) or the propylene homopolymer (B) according to the present invention contains a biomass-derived monomer from the viewpoint of reducing environmental load. If the polymer production conditions such as the polymerization catalyst and polymerization temperature are the same, even if the raw material olefin contains biomass-derived olefin, the molecular structure other than containing the 14C isotope at a ratio of about 10 -12 is derived from fossil fuels. It is equivalent to a propylene-based polymer or a propylene homopolymer consisting of monomers. Therefore, the performance is assumed to be unchanged.
• the propylene-based polymer (A) or the propylene homopolymer (B) according to the present invention contains a chemically recycled propylene-derived monomer.
• the propylene constituting the polymer may be only propylene derived from chemical recycling, or may contain propylene derived from chemical recycling and propylene derived from fossil fuel and/or propylene derived from biomass. Chemically recycled propylene can be obtained by a conventionally known method.
• the propylene homopolymer (A) according to the present invention contains propylene derived from chemical recycling from the viewpoint of reducing the environmental load (mainly reducing waste).
• the monomer derived from chemical recycling is a monomer obtained by depolymerizing or thermally decomposing a polymer such as waste plastic into a monomer unit such as propylene, or using the monomer as a raw material. Since it is a produced monomer, its molecular structure is equivalent to that of a propylene homopolymer composed of a fossil fuel-derived monomer if polymer production conditions such as a polymerization catalyst, polymerization process and polymerization temperature are the same. Therefore, the performance is assumed to be unchanged.
• the propylene polymer composition for forming the unstretched film of the present invention contains the propylene polymer (A) in an amount of 1 to 40% by mass and the propylene homopolymer (B) in an amount of 60 to 99% by mass. Range [However, the total amount of (A) and (B) shall be 100% by mass. ].
• the propylene-based polymer (A) is preferably used. 1 to 20% by mass, more preferably 5 to 20% by mass, and 80 to 99% by mass, more preferably 80 to 97% by mass of the propylene homopolymer (B1) [where (A) and (B1) is 100% by mass. ].
• the propylene homopolymer (B2) is used as the propylene homopolymer (B) which is a component of the propylene polymer composition forming the unstretched film of the present invention
• the propylene-based polymer ( A) in the range of 15 to 40% by mass, more preferably 20 to 40% by mass
• the propylene homopolymer (B2) in the range of 65 to 85% by mass, more preferably 60 to 80% by mass [however, The total amount of (A) and (B2) is 100% by mass. ].
• the propylene polymer composition according to the present invention comprises the propylene-based polymer (A) and the propylene homopolymer (B), or the propylene homopolymer (B1) or the propylene homopolymer (B2). is contained in an amount within the above range, a non-stretched film having good transparency and rigidity (tensile modulus) can be obtained.
• the transparency of the resulting non-stretched film may be significantly deteriorated, and the appearance of the film may be poor.
• the amount of the propylene-based polymer (A) is less than the lower limit, the obtained unstretched film may not be improved in rigidity (tensile modulus).
• the propylene polymer composition according to the present invention preferably has a melt flow rate (MFR) of 1 to 20 g/10 minutes, preferably 2, measured at a measurement temperature of 230°C and a load of 2.16 kg in accordance with JIS K 7210. -15 g/10 min, more preferably in the range of 3-10 g/10 min.
• MFR melt flow rate
• the propylene-based polymer composition according to the present invention contains, in addition to the propylene-based polymer (A) and the propylene homopolymer (B), a weather resistance stabilizer and a heat stabilizer within a range not impairing the object of the present invention.
• agent anti-static agent, slip agent, anti-blocking agent, anti-fog agent, nucleating agent, decomposing agent, pigment, dye, plasticizer, hydrochloric acid absorber, antioxidant, cross-linking agent, cross-linking accelerator, reinforcing agent, filler
• Additives such as agents, softening agents, processing aids, activators, moisture absorbents, pressure-sensitive adhesives, flame retardants, mold release agents, etc. can be contained. Additives can be used alone or in combination of two or more.
• the propylene-based polymer composition according to the present invention may contain a nucleating agent in order to improve transparency and heat resistance.
• Nucleating agents include, for example, sorbitol compounds such as dibenzylidene sorbitol, organic phosphoric ester compounds, rosinate compounds, C4-C12 aliphatic dicarboxylic acids and metal salts thereof. Among these, organic phosphoric acid ester compounds are preferred.
• One or more nucleating agents can be used.
• the amount of the nucleating agent is preferably 0.05 to 0.5 parts by mass, more preferably 0.1 to 0.1 part by mass, per 100 parts by mass in total of the propylene-based polymer (A) and the propylene homopolymer (B). 3 parts by mass can be used.
• the propylene-based polymer composition according to the present invention can be produced by adopting any known method.
• melt-kneading A method of granulating or pulverizing may be mentioned.
• the unstretched film of the present invention is formed from the propylene-based polymer composition.
• the unstretched film of the present invention exhibits higher rigidity and heat resistance than conventional unstretched polypropylene films.
• the unstretched film is used, for example, as a packaging material for foods, beverages, industrial parts, miscellaneous goods, toys, daily necessities, office supplies, medical supplies, and the like.
• the thickness of the unstretched film of the present invention is usually less than 200 ⁇ m, preferably 10-150 ⁇ m, more preferably 15-100 ⁇ m. Since the unstretched film of the present invention is excellent in rigidity, it can be easily made into a thin film.
• the unstretched film of the present invention preferably has a longitudinal tensile modulus of 2500 MPa or more and a haze of 10% or less measured according to ASTM D-1003 (JIS K7105).
• Examples of methods for producing the non-stretched film of the present invention include extrusion molding methods such as the T-die method and inflation method, compression molding methods, calendar molding methods, and casting methods.
• a non-stretched film can be molded, for example, as follows.
• the above components constituting the propylene-based polymer composition may be directly added to a hopper or the like of a film forming machine, or the above components may be mixed in advance using a ribbon blender, a Banbury mixer, a Henschel mixer, a super mixer, or the like.
• the mixture may be melt-kneaded using a kneader such as a single-screw extruder, a twin-screw extruder, or a roll to obtain a propylene-based polymer composition, followed by film forming.
• a specific production example of a non-stretched film will be described in terms of the T-die method.
• a film is extruded through the die lip of a T-die, and the molten film is cooled and taken up by a take-up device such as nip rolls to obtain a non-stretched film.
• Cooling methods for molten films include, for example, air knife method or air chamber method using rolls and air cooling, polishing roll method, swing roll method, narrow pressure cooling method such as belt casting method, contact with refrigerant such as water cooling method, etc. cooling method.
• the obtained non-stretched film can be subjected to film treatment methods used for ordinary film molding, such as corona discharge treatment and liquid agent coating treatment.
• the laminate of the present invention has the unstretched film of the present invention.
• the laminate may be a laminate having two or more layers of the non-stretched film of the present invention, or may be a laminate having one or more layers of the non-stretched film of the present invention and one or more other layers.
• Various functions can be imparted to the film by forming a laminated structure. Methods used in that case include a co-extrusion method and an extrusion coating method.
• Other layers include, for example, a barrier layer for gases such as water vapor and oxygen, a sound absorbing layer, a light shielding layer, an adhesive layer, an adhesive layer, a colored layer, a conductive layer, and a recycled resin-containing layer.
• gases such as water vapor and oxygen
• a sound absorbing layer such as water vapor and oxygen
• the unstretched film and laminate of the present invention are suitable for various food packaging fields such as fresh foods such as vegetables and fish meat, dried foods such as snacks and noodles, water foods such as soups and pickles; tablets, powders, liquids, etc. It can be used as a packaging film in a wide range of packaging fields, such as medical products used for various forms of medical products and medical peripheral materials; .
• prepolymerization catalyst To 200 mL of heptane, 10 mmol of triethylaluminum, 2 mmol of dicyclopentyldimethoxysilane, and 1 mmol of the solid catalyst component obtained by the above adjustment were added in terms of titanium atoms. The internal temperature was kept at 20° C., and propylene was continuously introduced while stirring. After 60 minutes, the stirring was stopped, and as a result, a prepolymerized catalyst (prepolymerized catalyst) in which 4.0 g of propylene was polymerized per 1 g of the solid catalyst was obtained.
• the intrinsic viscosity [ ⁇ ] of the propylene-based polymer (a1-1) polymerized under the same conditions as in the first stage was 11 dl/g.
• composition, physical properties, etc. of the obtained propylene-based polymer (A-1) were measured by the methods described below.
• Table 1 shows the measurement results.
• the solid portion was collected by hot filtration, resuspended in 275 ml of titanium tetrachloride, and heated again at 110°C for 2 hours. After completion of the reaction, the solid portion was collected again by hot filtration and thoroughly washed with 110° C. decane and hexane until no free titanium compound was detected in the solution.
• the solid titanium catalyst component prepared as described above was stored as a hexane slurry, and part of it was dried to investigate the catalyst composition.
• the solid titanium catalyst component contained 2.3 wt% titanium, 61 wt% chlorine, 19 wt% magnesium and 12.5 wt% DIBP.
• prepolymerized catalyst (b-1) 100.0 g of the solid titanium catalyst component (a-1), 19.2 ml of cyclohexylmethyldimethoxysilane, 65.6 mL of triethylaluminum, and 10 L of heptane were placed in an autoclave with an internal volume of 20 L and equipped with a stirrer, and the internal temperature was maintained at 15 to 20°C. 600 g of propylene was added and reacted with stirring for 100 minutes. After the polymerization was completed, the solid components were allowed to settle, and the supernatant was removed and washed with heptane twice. The resulting prepolymerized catalyst was resuspended in purified heptane, and the concentration of the solid catalyst component was adjusted to 1.0 g/L with heptane.
• the obtained slurry was sent to a vessel polymerization vessel with an internal capacity of 70 L equipped with a stirrer, and polymerized further.
• a vessel polymerization vessel with an internal capacity of 70 L equipped with a stirrer, and polymerized further.
• 45 kg/hour of propylene and hydrogen were supplied so that the hydrogen concentration in the gas phase was 4.3 mol %.
• Polymerization was carried out at a polymerization temperature of 70°C and a pressure of 3.1 MPa/G.
• the obtained propylene homopolymer (B1-1) had an MFR of 15 g/10 min and an Mw/Mn of 5.0.
• the solid portion was collected by hot filtration, resuspended in 275 ml of titanium tetrachloride, and heated again at 110°C for 2 hours. After completion of the reaction, the solid portion was collected again by hot filtration and thoroughly washed with 110° C. decane and hexane until no free titanium compound was detected in the solution.
• the solid titanium catalyst component prepared as described above was stored as a hexane slurry, and part of it was dried to investigate the catalyst composition.
• the solid titanium catalyst component contained 2.3 wt% titanium, 61 wt% chlorine, 19 wt% magnesium and 12.5 wt% DIBP.
• prepolymerized catalyst (b-2) 100.0 g of the solid titanium catalyst component (a-1), 22.4 ml of dicyclopentyldimethoxysilane, 65.6 mL of triethylaluminum, and 10 L of heptane were placed in an autoclave with an internal volume of 20 L and equipped with a stirrer, and the internal temperature was maintained at 15 to 20°C. 600 g of propylene was added and reacted with stirring for 100 minutes. After the polymerization was completed, the solid components were allowed to settle, and the supernatant was removed and washed with heptane twice. The resulting prepolymerized catalyst was resuspended in purified heptane, and the concentration of the solid catalyst component was adjusted to 1.0 g/L with heptane.
• the obtained slurry was sent to a vessel polymerization vessel with an internal capacity of 70 L equipped with a stirrer, and polymerized further.
• a vessel polymerization vessel with an internal capacity of 70 L equipped with a stirrer, and polymerized further.
• 45 kg/hour of propylene and hydrogen were supplied so that the hydrogen concentration in the gas phase was 15.8 mol %.
• Polymerization was carried out at a polymerization temperature of 63° C. and a pressure of 3.2 MPa/G.
• the resulting propylene homopolymer (B1-2) had an MFR of 30 g/10 min and an Mw/Mn of 5.2.
• the solid portion was collected by hot filtration, resuspended in 275 ml of titanium tetrachloride, and heated again at 110°C for 2 hours. After completion of the reaction, the solid portion was collected again by hot filtration and thoroughly washed with 110° C. decane and hexane until no free titanium compound was detected in the solution.
• the solid titanium catalyst component prepared as described above was stored as a hexane slurry, and part of it was dried to investigate the catalyst composition.
• the solid titanium catalyst component contained 2.3 wt% titanium, 61 wt% chlorine, 19 wt% magnesium and 12.5 wt% DIBP.
• prepolymerized catalyst (b-1) 100.0 g of the solid titanium catalyst component (a-1), 19.2 ml of cyclohexylmethyldimethoxysilane, 65.6 mL of triethylaluminum, and 10 L of heptane were placed in an autoclave with an internal volume of 20 L and equipped with a stirrer, and the internal temperature was maintained at 15 to 20°C. 600 g of propylene was added and reacted with stirring for 100 minutes. After the polymerization was completed, the solid components were allowed to settle, and the supernatant was removed and washed with heptane twice. The resulting prepolymerized catalyst was resuspended in purified heptane, and the concentration of the solid catalyst component was adjusted to 1.0 g/L with heptane.
• the obtained slurry was sent to a vessel polymerization vessel with an internal capacity of 70 L equipped with a stirrer, and polymerized further.
• a vessel polymerization vessel with an internal capacity of 70 L equipped with a stirrer, and polymerized further.
• 45 kg/hour of propylene and hydrogen were supplied so that the hydrogen concentration in the gas phase was 2.9 mol %.
• Polymerization was carried out at a polymerization temperature of 70°C and a pressure of 3.1 MPa/G.
• the obtained propylene homopolymer (D-1) had an MFR of 9 g/10 min and an Mw/Mn of 5.0.
• Propylene homopolymer (D-2) As the propylene homopolymer (D-2), a propylene homopolymer having an MFR of 6.5 g/10 min and an Mw/Mn of 5.2 (trade name: Prime Polypro F-704NP, manufactured by Prime Polymer Co., Ltd.) was used.
• the intrinsic viscosity [ ⁇ ] (dl/g) was measured at 135°C in a tetralin solvent.
• the intrinsic viscosity [ ⁇ ] 2 of the propylene-based polymer (corresponding to the propylene-based polymer (a2)) obtained in the second stage is a value calculated from the following formula.
• [ ⁇ ] 2 ([ ⁇ ] total x 100 - [ ⁇ ] 1 x W 1 )/W 2 [ ⁇ ] total : Intrinsic viscosity of the entire propylene-based polymer [ ⁇ ] 1 : Intrinsic viscosity of the propylene-based polymer obtained in the first stage W 1 : Mass of the propylene-based polymer obtained in the first stage Fraction (%) W 2 : mass fraction (%) of the propylene-based polymer obtained in the second stage [Melt flow rate]
• MFR melt flow rate
• the ratio of the high molecular weight region having a molecular weight of 1,500,000 or more is the molecular weight of the total area surrounded by the molecular weight distribution curve (specifically, the molecular weight distribution curve and the horizontal axis) measured by GPC under the following equipment and conditions. It is the area ratio of the high molecular weight region of 1,500,000 or more.
• the horizontal axis is molecular weight (logarithmic value) and the vertical axis is dw/dLog(M) [w: integrated mass fraction, M: molecular weight].
• the peak molecular weight MH on the high molecular weight side and the peak molecular weight ML on the low molecular weight side of the molecular weight distribution curve were obtained to calculate MH/ML. Also, from the molecular weight distribution curve, the average molecular weight (number average molecular weight Mn, weight average molecular weight Mw) was obtained to calculate the molecular weight distribution (Mw/Mn).
• Tensile modulus was measured according to the method of JIS K7161. The measurement was performed at 23° C. in the direction of extrusion (MD) and the direction perpendicular to MD (TD). It can be said that the higher the tensile modulus, the higher the rigidity.
• the physical properties of the obtained unstretched film were measured by the methods described above.
• Example 1 instead of the propylene polymer composition used in Comparative Example 1, the propylene-based polymer (A-1) obtained in Production Example 1: 10 parts by mass, and the propylene homopolymer obtained in Production Example 2 ( B1-1): A non-stretched film was obtained in the same manner as in Comparative Example 1, except that a propylene polymer composition comprising 90 parts by mass was used.
• the physical properties of the obtained unstretched film were measured by the methods described above.
• Example 2 instead of the propylene polymer composition used in Example 2, a propylene polymer comprising 20 parts by mass of a propylene polymer (A-1) and 80 parts by mass of a propylene homopolymer (B1-1). A non-stretched film was obtained in the same manner as in Example 1 except that the composition was used.
• the physical properties of the obtained unstretched film were measured by the methods described above.
• the physical properties of the obtained unstretched film were measured by the methods described above.
• Example 3 A non-stretched film was obtained in the same manner as in Example 1, except that the propylene homopolymer (B1-2) was used in place of the propylene homopolymer (B1-1) used in Example 1.
• the physical properties of the obtained unstretched film were measured by the methods described above.
• Example 4 An unstretched film was obtained in the same manner as in Example 2, except that the propylene homopolymer (B1-2) was used in place of the propylene homopolymer (B1-1) used in Example 2.
• the physical properties of the obtained unstretched film were measured by the methods described above.
• the physical properties of the obtained unstretched film were measured by the methods described above.
• the physical properties of the obtained unstretched film were measured by the methods described above.
• the physical properties of the obtained unstretched film were measured by the methods described above.
• the solid portion was collected by hot filtration, resuspended in 275 ml of titanium tetrachloride, and heated again at 110°C for 2 hours. After completion of the reaction, the solid portion was collected again by hot filtration and thoroughly washed with 110° C. decane and hexane until no free titanium compound was detected in the solution.
• the solid titanium catalyst component prepared as described above was stored as a hexane slurry, and part of it was dried to investigate the catalyst composition.
• the solid titanium catalyst component contained 2.3 wt% titanium, 61 wt% chlorine, 19 wt% magnesium and 12.5 wt% DIBP.
• prepolymerized catalyst (b-2) 100.0 g of the solid titanium catalyst component (a-1), 22.4 ml of dicyclopentyldimethoxysilane, 65.6 mL of triethylaluminum, and 10 L of heptane were placed in an autoclave with an internal volume of 20 L and equipped with a stirrer, and the internal temperature was maintained at 15 to 20°C. 600 g of propylene was added and reacted with stirring for 100 minutes. After the polymerization was completed, the solid components were allowed to settle, and the supernatant was removed and washed with heptane twice. The resulting prepolymerized catalyst was resuspended in purified heptane, and the concentration of the solid catalyst component was adjusted to 1.0 g/L with heptane.
• the obtained slurry was sent to a vessel polymerization vessel with an internal capacity of 70 L equipped with a stirrer, and polymerized further.
• a vessel polymerization vessel with an internal capacity of 70 L equipped with a stirrer, and polymerized further.
• 45 kg/hour of propylene and hydrogen were supplied so that the hydrogen concentration in the gas phase was 2.4 mol %.
• Polymerization was carried out at a polymerization temperature of 70°C and a pressure of 2.9 MPa/G.
• the obtained propylene polymer had an MFR of 3.0 g/10 minutes.
• transition metal catalyst component (a-2) contained 2% by mass of titanium and 18% by mass of diisobutyl phthalate.
• prepolymerized catalyst (b-3) 100 g of the transition metal catalyst component (a-2), 15.4 mL of triethylaluminum, and 100 L of heptane are placed in an autoclave with an internal capacity of 200 L and equipped with a stirrer. rice field. After the polymerization was completed, 4.1 mL of titanium tetrachloride was charged to obtain a prepolymerized catalyst (b-3).
• This prepolymerized catalyst (b-3) contained 6 g of propylene homopolymer per 1 g of the transition metal catalyst component.
• the obtained propylene homopolymer had an MFR of 1.7 g/10 minutes.
• the obtained propylene homopolymer (B2-2) had an MFR of 9 g/10 minutes and an Mw/Mn of 3.7.
• the solid portion was collected by hot filtration, resuspended in 275 ml of titanium tetrachloride, and heated again at 110°C for 2 hours. After completion of the reaction, the solid portion was collected again by hot filtration and thoroughly washed with 110° C. decane and hexane until no free titanium compound was detected in the solution.
• the solid titanium catalyst component prepared as described above was stored as a hexane slurry, and part of it was dried to investigate the catalyst composition.
• the solid titanium catalyst component contained 2.3 wt% titanium, 61 wt% chlorine, 19 wt% magnesium and 12.5 wt% DIBP.
• prepolymerized catalyst (b-1) 100.0 g of the solid titanium catalyst component (a-1), 19.2 ml of cyclohexylmethyldimethoxysilane, 65.6 mL of triethylaluminum, and 10 L of heptane were placed in an autoclave with an internal volume of 20 L and equipped with a stirrer, and the internal temperature was maintained at 15 to 20°C. 600 g of propylene was added and reacted with stirring for 100 minutes. After the polymerization was completed, the solid components were allowed to settle, and the supernatant was removed and washed with heptane twice. The resulting prepolymerized catalyst was resuspended in purified heptane, and the concentration of the solid catalyst component was adjusted to 1.0 g/L with heptane.
• the obtained slurry was sent to a vessel polymerization vessel with an internal capacity of 70 L equipped with a stirrer, and polymerized further.
• a vessel polymerization vessel with an internal capacity of 70 L equipped with a stirrer, and polymerized further.
• 45 kg/hour of propylene and hydrogen were supplied so that the hydrogen concentration in the gas phase was 2.9 mol %.
• Polymerization was carried out at a polymerization temperature of 70°C and a pressure of 3.1 MPa/G.
• the obtained propylene homopolymer had an MFR of 9 g/10 minutes.
• the obtained propylene homopolymer (D2-1) had an MFR of 18 g/10 min and an Mw/Mn of 4.3.
• the physical properties of the obtained unstretched film were measured by the methods described above.
• Example 5 instead of the propylene polymer composition used in Comparative Example 10, the propylene-based polymer (A-1) obtained in Production Example 1: 10 parts by mass, and the propylene homopolymer obtained in Production Example 5 ( B2-1): A non-stretched film was obtained in the same manner as in Comparative Example 10 except that a propylene polymer composition consisting of 90 parts by mass was used.
• the physical properties of the obtained unstretched film were measured by the methods described above.
• Example 6 instead of the propylene polymer composition used in Example 5, a propylene polymer comprising 30 parts by mass of a propylene polymer (A-1) and 70 parts by mass of a propylene homopolymer (B2-1). A non-stretched film was obtained in the same manner as in Example 1 except that the composition was used.
• the physical properties of the obtained unstretched film were measured by the methods described above.
• the physical properties of the obtained unstretched film were measured by the methods described above.
• Example 7 A non-stretched film was obtained in the same manner as in Example 5 except that the propylene homopolymer (B2-2) was used instead of the propylene homopolymer (B2-1) used in Example 5.
• the physical properties of the obtained unstretched film were measured by the methods described above.
• Example 8 A non-stretched film was obtained in the same manner as in Example 6 except that the propylene homopolymer (B2-2) was used in place of the propylene homopolymer (B2-1) used in Example 6.
• the physical properties of the obtained unstretched film were measured by the methods described above.
• the physical properties of the obtained unstretched film were measured by the methods described above.
• the physical properties of the obtained unstretched film were measured by the methods described above.
• the physical properties of the obtained unstretched film were measured by the methods described above.

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