KR20220012901A - Non-foaming sheets and containers - Google Patents

Abstract

An object of the present invention is to provide a polypropylene sheet having excellent rigidity and heat resistance. The present invention is a non-foaming sheet having a layer formed of a propylene-based polymer composition, wherein the composition has a specific propylene-based polymer (A) and a melting point of 120 to 170°C, 135°C, the limit measured in a tetralin solvent Viscosity [η] contains a propylene-based polymer (B) having a viscosity of more than 1.5 dl/g and 5.0 dl/g or less, with respect to a total of 100 parts by mass of the propylene-based polymer (A) and the propylene-based polymer (B), the propylene The content of the polymer (A) is 2 to 30 parts by mass, and the content of the propylene polymer (B) is 70 to 98 parts by mass.

Description

Non-foaming sheets and containers

The present invention relates to non-foaming sheets and containers.

Propylene-based polymers are widely used as a material for various molded articles (for example, refer to Patent Documents 1 and 2), and the properties required vary depending on the molding method and use. For example, a propylene polymer is a material excellent in impact resistance, hygiene, and environmental compatibility, and is used as a sheet|seat and a sheet-molding container (refer patent documents 3 - 4, for example).

International Publication No. 1999/007752 International Publication No. 2005/097842 Japanese Patent Laid-Open No. 2010-159320 Japanese Patent Laid-Open No. 2015-010105

From an environmental problem, thinning of a sheet|seat is calculated|required, and for this reason, the improvement of rigidity is required. In addition, depending on the use of the sheet, it may be heated by, for example, a microwave oven, and high heat resistance is required. An object of the present invention is to provide a polypropylene sheet excellent in rigidity and heat resistance, and a container obtained from the sheet.

MEANS TO SOLVE THE PROBLEM As a result of repeating earnest examination, the present inventors discovered that the polypropylene-type sheet|seat described below can solve the said subject, and completed this invention.

propylene 20 to 50 mass % of the polymer (a1), and 50 to 80 mass of the propylene polymer (a2) having an intrinsic viscosity [η] in the range of 0.5 to 1.5 dl/g measured in a tetralin solvent at 135° C. % [However, the total amount of the propylene-based polymer (a1) and the propylene-based polymer (a2) is 100% by mass.] The contained propylene-based polymer (A) has a melting point of 120 to 170°C, 135°C, tetral A propylene-based polymer (B) having an intrinsic viscosity [η] measured in a lean solvent of greater than 1.5 dl/g and 5.0 dl/g or less is contained, and a total of 100 masses of the propylene-based polymer (A) and the propylene-based polymer (B) A non-foaming sheet characterized in that the content of the propylene-based polymer (A) is 2 to 30 parts by mass relative to the part, and the content of the propylene-based polymer (B) is 70 to 98 parts by mass.

[2] The non-foaming sheet according to the above [1], wherein the propylene-based polymer composition has a molecular weight distribution (Mw/Mn) measured by gel permeation chromatography (GPC) of 6.0 or more.

[3] The non-foaming sheet according to the above [1] or [2], wherein the propylene-based polymer (B) has a melt flow rate (MFR) measured at 230°C and a load of 2.16 kg of 0.1 to 10 g/10 min.

[4] The ratio according to any one of [1] to [3], wherein the molecular weight distribution (Mw/Mn) measured by gel permeation chromatography (GPC) of the propylene-based polymer (B) exceeds 5 foam sheet.

[5] The non-foaming sheet according to any one of [1] to [4], wherein the thickness is 200 µm or more.

[6] The non-foaming sheet according to any one of [1] to [5], which is a single-layer sheet comprising a layer formed of the propylene-based polymer composition.

[7] The non-foaming sheet according to any one of [1] to [5], which is a laminated sheet having a layer formed of the propylene-based polymer composition.

[8] A container formed of the non-foaming sheet according to any one of [1] to [7].

ADVANTAGE OF THE INVENTION According to this invention, the polypropylene-type sheet|seat excellent in rigidity and heat resistance, and the container obtained from this sheet|seat can be provided.

The non-foaming sheet of the present invention has a layer formed of a propylene-based polymer composition containing a propylene-based polymer (A) and a propylene-based polymer (B), which will be described below, respectively.

In addition, the detail of the measurement condition of each requirement is described in the column of an Example.

[Propylene-based polymer (A)]

The propylene-based polymer (A) contains 20 to 50% by mass of the propylene-based polymer (a1) having an intrinsic viscosity [η] in the range of 10 to 12 dl/g measured in a tetralin solvent at 135°C, and 135°C; 50 to 80 mass % of the propylene polymer (a2) having an intrinsic viscosity [η] in the range of 0.5 to 1.5 dl/g measured in a tetralin solvent [provided that the propylene polymer (a1) and the propylene polymer (a2) ) is 100% by mass.] Included.

Hereinafter, the intrinsic viscosity [η] measured at 135°C in a tetralin solvent is also simply referred to as "intrinsic viscosity [η]". Each mass fraction of the propylene-based polymer (a1) and the propylene-based polymer (a2) is based on the total amount of (a1) and (a2).

<Propylene-based polymer (a1)>

The intrinsic viscosity [η] of the propylene-based polymer (a1) is in the range of 10 to 12 dl/g, preferably 10.5 to 11.5 dl/g. Moreover, the mass fraction of the propylene-type polymer (a1) in a propylene-type polymer (A) exists in the range of 20-50 mass %, Preferably it is 20-45 mass %, More preferably, it is 20-40 mass %. , more preferably in the range of 22 to 40 mass %.

Examples of the propylene-based polymer (a1) include a homopolymer of propylene and a copolymer of propylene and an α-olefin having 2 to 8 carbon atoms (however, excluding propylene), and a homopolymer of propylene is preferable. . Examples of the α-olefin having 2 to 8 carbon atoms include ethylene, 1-butene, 1-hexene, 1-octene, and 4-methyl-1-pentene. Ethylene is preferable as these ?-olefins. The α-olefin may be used alone or in combination of two or more.

When the intrinsic viscosity [η] of the propylene polymer (a1) exceeds 12 dl/g, the sheet formability tends to be poor. In addition, when the intrinsic viscosity [η] of the propylene-based polymer (a1) is less than 10 dl/g, the rigidity tends not to be sufficiently improved.

When the mass fraction of the propylene-based polymer (a1) is less than 20% by mass, the resulting sheet tends to lack rigidity and heat resistance, and when it exceeds 50% by mass, it tends to cause poor appearance during sheet molding.

The propylene polymer (a1) can be used 1 type or 2 or more types.

<Propylene-based polymer (a2)>

The intrinsic viscosity [η] of the propylene polymer (a2) is in the range of 0.5 to 1.5 dl/g, preferably in the range of 0.6 to 1.5 dl/g, and more preferably in the range of 0.8 to 1.5 dl/g. The mass fraction of the propylene polymer (a2) in the propylene polymer (A) is in the range of 50 to 80 mass%, preferably 55 to 80 mass%, more preferably 60 to 80 mass% , more preferably in the range of 60 to 78 mass%.

Examples of the propylene-based polymer (a2) include a homopolymer of propylene and a copolymer of propylene and an α-olefin having 2 to 8 carbon atoms (except propylene), and a homopolymer of propylene is preferable. . Examples of the α-olefin having 2 to 8 carbon atoms include ethylene, 1-butene, 1-hexene, 1-octene, and 4-methyl-1-pentene. Ethylene is preferable as these ?-olefins. The α-olefin may be used alone or in combination of two or more.

When the intrinsic viscosity [η] of the propylene-based polymer (a2) is less than 0.5 dl/g, the improvement in rigidity of the obtained polymer composition tends to be insufficient. When the intrinsic viscosity [η] exceeds 1.5 dl/g, the viscosity is high , the sheet formability tends to deteriorate.

When the mass fraction of the propylene-based polymer (a2) is less than 50 mass %, it causes poor appearance at the time of sheet forming, and when it exceeds 80 mass %, the improvement in rigidity tends to be insufficient.

The propylene polymer (a2) can be used 1 type or 2 or more types.

<Additives>

Additives, such as antioxidant, a neutralizing agent, a flame retardant, and a crystal nucleating agent, can be mix|blended with a propylene-type polymer (A) as needed. An additive can be used 1 type or 2 or more types. The ratio in particular of an additive is not restrict|limited, It is possible to adjust suitably.

<Physical properties of propylene-based polymer (A)>

The propylene-based polymer (A) has a melt flow rate (MFR) measured at 230°C and a load of 2.16 kg, preferably 0.01 to 5 g/10 min, more preferably 0.05 to 4 g/10 min, still more preferably 0.1 to 3 g/10 min. When the MFR of the propylene-based polymer (A) is within the above range, the sheet formability is excellent.

<Method for producing propylene-based polymer (A)>

As a manufacturing method of a propylene-type polymer (A), various well-known manufacturing methods are mentioned, For example, after manufacturing a propylene-type polymer (a1) and a propylene-type polymer (a2) which satisfy the said physical properties, respectively, Method (1) of obtaining a propylene-based polymer (A) by mixing or melt-kneading the propylene-based polymer (a1) and the propylene-based polymer (a2) within the above range; A method (2) of obtaining the propylene-based polymer (A) by preparing the propylene-based polymer (a1) and the propylene-based polymer (a2) satisfying the above physical properties in one polymerization system or two or more polymerization systems is exemplified.

In method (1), for example, the propylene-based polymer (a1), the propylene-based polymer (a2) and, if necessary, additives, etc. are mixed using a Henschel mixer, a V-type blender, a tumbler blender, a ribbon blender, etc. By melt-kneading using a single screw extruder, a multi-screw extruder, a kneader, or a Banbury mixer, the high-quality propylene polymer (A) in which each of the above components is uniformly dispersed and mixed can be obtained. The resin temperature at the time of melt-kneading is usually 180 to 280°C, and preferably 200 to 260°C.

In method (2), a propylene-based polymer (A) comprising a propylene-based polymer (a1) having a relatively high molecular weight and a propylene-based polymer (a2) having a relatively low molecular weight can be obtained by multistage polymerization of two or more stages. . You may add an additive to the obtained propylene-type polymer (A) as needed.

Preferred methods for producing the propylene-based polymer (A) include the above method (2). For example, propylene alone or propylene and other monomers are used in combination in the presence of a catalyst for producing highly stereoregular polypropylene. Thus, a method of polymerization in two or more stages of multistage polymerization is exemplified.

Specifically, in the polymerization in the first stage, propylene or propylene is polymerized with an α-olefin having 2 to 8 carbon atoms in substantially the absence of hydrogen, and the intrinsic viscosity [η] is 10 to 12 dl/g, preferably Preferably, the propylene-based polymer (a1) having a relatively high molecular weight of 10.5 to 11.5 dl/g is contained in the propylene-based polymer (A) in an amount of from 20 to 50% by mass, preferably from 20 to 45% by mass, more preferably from 20 to 40% by mass. % by mass, and in polymerization after the second stage, a propylene-based polymer (a2) having a relatively low molecular weight is prepared.

The intrinsic viscosity [η] of the propylene-based polymer (a2) having a relatively low molecular weight produced in the polymerization after the second stage is 0.5 to 1.5 dl/g, preferably 0.6 to 1.5 dl/g, more preferably is 0.8 to 1.5 dl/g. On the other hand, this intrinsic viscosity [η] is the intrinsic viscosity [η] of the propylene-based polymer produced alone at that stage, and the total intrinsic viscosity [η] including the propylene-based polymer up to the preceding stage of that stage is no.

Moreover, in the polymerization after the second stage, the MFR of the propylene-based polymer (A) finally obtained is preferably 0.01 to 5 g/10 min, more preferably 0.05 to 4 g/10 min, still more preferably 0.1 to Adjust to 3g/10min.

The method for adjusting the intrinsic viscosity [η] of the propylene polymer produced in the second stage and thereafter is not particularly limited, but a method using hydrogen as a molecular weight modifier is preferred.

As the production sequence (polymerization sequence) of the propylene-based polymer (a1) and the propylene-based polymer (a2), in the first step, a propylene-based polymer (a1) having a relatively high molecular weight is prepared in substantially the absence of hydrogen, After the second stage, for example, it is preferable to prepare the propylene-based polymer (a2) having a relatively low molecular weight in the presence of hydrogen. Although the production order can be reversed, in order to prepare the propylene-based polymer (a2) having a relatively low molecular weight in the first stage, and then to prepare the propylene-based polymer having a relatively high molecular weight in the second stage and thereafter, the first step Since it is necessary to infinitely remove molecular weight modifiers such as hydrogen contained in the reaction product in the first stage before the start of polymerization in the second stage and thereafter, the polymerization apparatus becomes complicated, and the intrinsic viscosity [η] after the second stage rises it's difficult.

Although superposition|polymerization of each stage in multistage superposition|polymerization may be performed continuously or it may be performed batchwise, it is preferable to perform batchwise. In the propylene-based polymer (A) comprising the propylene-based polymer (a1) and the propylene-based polymer (a2) obtained by batch polymerization multistage polymerization, the propylene-based polymer (a1) as an ultra-high molecular weight component is well dispersed, Accordingly, a sheet having excellent rigidity and heat resistance is obtained. In addition, when the propylene-based polymer (A) is produced by a continuous multistage polymerization method, compositional non-uniformity between the polymerized particles may occur due to the residence time distribution, and the fish eye of the sheet may increase. , a sheet with few fish eyes can be obtained. Therefore, by employing the batch method, it is possible to obtain a sheet with few fish eyes in spite of using the high molecular weight propylene polymer (a1).

≪Manufacturing conditions≫

In the production of the propylene-based polymer (a1) and the propylene-based polymer (a2), homopolymerization of propylene or polymerization of propylene and α-olefin having 2 to 8 carbon atoms can be carried out by known methods such as slurry polymerization and bulk polymerization. can Moreover, it is preferable to use the catalyst for polypropylene production mentioned later.

As the production conditions for the propylene-based polymer (a1), in the absence of hydrogen, the raw material monomer is subjected to polymerization temperature, preferably 20 to 80° C., more preferably 40 to 70° C., polymerization pressure, generally atmospheric pressure to It is preferable to prepare by bulk polymerization under the conditions of 9.8 MPa, preferably 0.2 to 4.9 MPa.

As the conditions for producing the propylene-based polymer (a2), the raw material monomer is used as a polymerization temperature, preferably 20 to 80° C., more preferably 40 to 70° C., and polymerization pressure, generally atmospheric pressure to 9.8 MPa, preferably It is preferable to prepare by polymerization under the conditions of 0.2 to 4.9 MPa and hydrogen as a molecular weight regulator.

≪Catalyst for polypropylene production≫

Catalysts for polypropylene production (hereinafter also simply referred to as “catalysts”) that can be used for production of the propylene-based polymer (a1), the propylene-based polymer (a2) and the propylene-based polymer (A) include, for example, magnesium and titanium. and a solid catalyst component containing halogen as an essential component, an organometallic compound catalyst component such as an organoaluminum compound, and an electron-donating compound catalyst component such as an organosilicon compound. can be used

(solid catalyst component)

As the carrier constituting the solid catalyst component, a carrier obtained from magnesium metal, an alcohol, and a halogen and/or a halogen-containing compound is preferable.

As metallic magnesium, magnesium, such as granular form, ribbon form, and powder form, can be used. Moreover, it is preferable that the coating|cover of magnesium oxide etc. is not produced|generated on the surface of metallic magnesium.

As the alcohol, it is preferable to use a lower alcohol having 1 to 6 carbon atoms. In particular, when ethanol is used, a carrier capable of remarkably improving the expression of the catalyst performance is obtained. To [ the usage-amount of alcohol / 1 mol of metallic magnesium ], Preferably it is 2-100 mol, More preferably, it is 5-50 mol. Alcohol can be used 1 type or 2 or more types.

As halogen, chlorine, bromine, and iodine are preferable and iodine is more preferable. Moreover, as a halogen-containing compound, MgCl2 _{and MgI2} are preferable. The amount of the halogen or halogen-containing compound to be used is, with respect to 1 gram atom of metallic magnesium, the halogen atom or halogen atom in the halogen-containing compound is usually 0.0001 gram atom or more, preferably 0.0005 gram atom or more, more preferably is greater than 0.001 gram atom. One type or two or more types of halogen and halogen-containing compounds can be used, respectively.

As a method for obtaining a carrier by reacting metallic magnesium, alcohol, and halogen and/or a halogen-containing compound, for example, metallic magnesium, an alcohol, and a halogen and/or a halogen-containing compound are refluxed (e.g. : about 79°C) until the generation of hydrogen gas is no longer confirmed (usually 20 to 30 hours). It is preferable to carry out the said reaction in inert gas atmosphere, such as nitrogen gas and argon gas.

When the obtained carrier is used for the synthesis of the solid catalyst component, a dried one may be used, or one washed with an inert solvent such as heptane after filtration may be used.

The obtained carrier is close to granular and has a sharp particle size distribution. Moreover, even when each particle is taken, the difference in particle size is very small. In this case, 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 less than 5.0, particularly less than 4.0 desirable.

S=(E1/E2) ² ...(I)

In Equation (I), E1 represents the projected contour length of the particle, and E2 represents the perimeter of the circle equal to the projected area of the particle.

P=D90/D10...(II)

In formula (II), D90 means the particle diameter corresponding to 90% of a mass accumulation fraction. That is, it has shown that the mass sum of the particle group smaller than the particle diameter represented by D90 is 90% of the total mass of all particles. D10 refers to a particle diameter corresponding to 10% of the cumulative mass fraction.

A solid catalyst component is normally obtained by making the said support|carrier contact at least a titanium compound. You may divide and perform the contact by a titanium compound into multiple times. As a titanium compound, the titanium compound represented by General formula (III) is mentioned, for example.

TiX ¹ _n (OR ¹ ) _{4 -n} ...(III)

In 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, a linear or branched alkyl group is preferable, and when there are two or more R ¹ They may be the same or different from each other, and n is an integer of 0-4.

Specifically, as a titanium compound, Ti(OiC ₃ H ₇ ) ₄ , Ti(OC ₄ H ₉ ) ₄ , TiCl(OC ₂ H ₅ ) ₃ , TiCl(OiC ₃ H ₇ ) ₃ , TiCl(OC ₄ H ₉ ) ) ₃ , TiCl ₂ (OC ₄ H ₉ ) ₂ , TiCl ₂ (OiC ₃ H ₇ ) ₂ , TiCl ₄ , and TiCl ₄ is preferable.

The titanium compound can be used 1 type or 2 or more types.

The solid catalyst component is usually obtained by further contacting the carrier with an electron-donating compound. Examples of the electron-donating compound include di-n-butyl phthalate. The electron-donating compound can be used 1 type or 2 or more types.

When the titanium compound and the electron-donating compound are brought into contact with the carrier, a halogen-containing silicon compound such as silicon tetrachloride may be brought into contact with the carrier. The halogen-containing silicon compound can be used 1 type or 2 or more types.

A solid catalyst component can be prepared by a well-known method. For example, using an inert hydrocarbon such as pentane, hexane, heptane or octane as a solvent, the carrier, electron donating compound and halogen-containing silicon compound are added to the solvent, and titanium is stirred while stirring. The method of injecting|throwing-in a compound is mentioned. Usually, 0.01 to 10 moles, preferably 0.05 to 5 moles of the electron-donating compound are added with respect to 1 mole of the carrier in terms of magnesium atoms, and the amount of the titanium compound is 1 to 50 moles of the support in terms of magnesium atoms. mol, preferably 2 to 20 moles are added, and the catalytic reaction may be carried out at 0 to 200°C for 5 minutes to 10 hours, preferably at 30 to 150°C for 30 minutes to 5 hours. After completion of the reaction, it is preferable to wash the generated solid catalyst component using an inert hydrocarbon such as n-hexane or n-heptane.

The solid catalyst component may be a component obtained by bringing a liquid magnesium compound and a liquid titanium compound into contact in the presence of an electron-donating compound. The contact with the liquid titanium compound may be divided into a plurality of times.

The liquid magnesium compound is obtained, for example, by bringing a known magnesium compound and alcohol into contact, preferably in the presence of a liquid hydrocarbon medium, to form a liquid phase. As a magnesium compound, magnesium halide, such as magnesium chloride and magnesium bromide, is mentioned, for example. Examples of the alcohol include aliphatic alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol and 2-ethylhexyl alcohol. As a liquid hydrocarbon medium, hydrocarbon compounds, such as heptane, octane, and decane, are mentioned, for example. The amount of alcohol to be used in preparing the liquid magnesium compound is usually 1.0 to 25 moles, preferably 1.5 to 10 moles, per 1 mole of the magnesium compound. One type or two or more types of liquid magnesium compounds can be used.

As a liquid titanium compound, the titanium compound represented by the above-mentioned general formula (III) is mentioned. The usage-amount of a liquid titanium compound is 0.1-1000 mol normally with respect to 1 mol of magnesium atoms (Mg) contained in a liquid magnesium compound, Preferably it is 1-200 mol. The liquid titanium compound can be used 1 type or 2 or more types.

Examples of the electron-donating compound include dicarboxylic acid ester compounds such as phthalic esters, acid anhydrides such as phthalic anhydride, dicyclopentyldimethoxysilane, dicyclohexyldimethoxysilane, cyclohexylmethyldime Organosilicon compounds, such as oxysilane, polyethers, acid halides, acid amides, nitriles, and organic acid esters are mentioned. The amount of the electron-donating compound to be used is usually 0.01 to 5 mol, preferably 0.1 to 1 mol with respect to 1 mol of the magnesium atom (Mg) contained in the liquid magnesium compound. The electron-donating compound can be used 1 type or 2 or more types.

The temperature at the time of making it contact is -70-200 degreeC normally, Preferably it is 10-150 degreeC.

(organometallic compound catalyst component)

In the catalyst component, as the organometallic compound catalyst component, an organoaluminum compound is preferable. As an organoaluminum compound, the compound represented by general formula (IV) is mentioned, for example.

AlR ² _n X ² _{3 -n} ...(IV)

In formula (IV), R ² is an alkyl group, cycloalkyl group or aryl group having 1 to 10 carbon atoms, X ² is a halogen atom, preferably a chlorine atom or a bromine atom, and n is an integer of 1 to 3.

Specific examples of the organoaluminum compound include trialkylaluminum compounds such as trimethylaluminum, triethylaluminum and triisobutylaluminum, diethylaluminum monochloride, diisobutylaluminum monochloride, diethylaluminum monoethoxide, and ethyl aluminum sesquichloride.

The organoaluminum compound can be used 1 type or 2 or more types.

The usage-amount of an organometallic compound catalyst component is 0.01-20 mol normally with respect to 1 mol of titanium atoms in a solid catalyst component, Preferably it is 0.05-10 mol.

(electron donating compound catalyst component)

An organosilicon compound is preferable as an electron-donating compound component provided to the polymerization system in the catalyst component. Examples of the organosilicon compound include dicyclopentyldimethoxysilane, cyclohexylmethyldimethoxysilane, diethylaminotriethoxysilane, diisopropyldimethoxysilane, cyclohexylisobutyldi and methoxysilane.

The organosilicon compound can be used 1 type or 2 or more types.

The amount of the electron-donating compound component to be used is usually 0.01 to 20 moles, preferably 0.1 to 5 moles, with respect to 1 mole of titanium atoms in the solid catalyst component.

(Pretreatment)

It is preferable to use the said solid catalyst component for superposition|polymerization, after pre-processing, such as prepolymerization. For example, using an inert hydrocarbon such as pentane, hexane, heptane, or octane as a solvent, to the solvent, the solid catalyst component, the organometallic compound catalyst component, and, if necessary, the electron donating compound component is added, and while stirring, propylene is supplied and reacted. It is preferable to supply propylene under the partial pressure of propylene higher than atmospheric pressure, and to pretreat at 0-100 degreeC for 0.1-24 hours. After completion of the reaction, it is preferable to wash the pretreated product using an inert hydrocarbon such as n-hexane or n-heptane.

[Propylene-based polymer (B)]

The propylene-based polymer (B) is a propylene-based polymer having a melting point of 120 to 170°C and an intrinsic viscosity [η] of more than 1.5 dl/g and 5.0 dl/g or less as measured in a tetralin solvent at 135°C.

Melting|fusing point (Tm) of a propylene-type polymer (B) is 120-170 degreeC, Preferably it is 130-170 degreeC, More preferably, it is 140-170 degreeC. From the viewpoints of moldability and heat resistance, the above range is preferable. The melting point is measured using a differential scanning calorimeter (DSC).

The intrinsic viscosity [η] of the propylene polymer (B) is more than 1.5 dl/g and 5.0 dl/g or less, preferably 1.6 to 4.0 dl/g, more preferably 1.7 to 3.5 dl/g. When the propylene-based polymer (B) having an intrinsic viscosity [η] in the above range is used, productivity at the time of sheet forming is good, and the resulting sheet has good impact resistance.

The propylene polymer (B) has a melt flow rate (MFR) measured at 230°C and a load of 2.16 kg, preferably 0.1 to 10 g/10 min, more preferably 0.2 to 5.0 g/10 min, still more preferably is 0.3 to 3.0 g/10 min. When the propylene-based polymer (B) having an MFR within the above range is used, the productivity at the time of sheet forming is good, and the resulting sheet has good impact resistance.

The molecular weight distribution (Mw/Mn) of the propylene-based polymer (B) measured by gel permeation chromatography (GPC) preferably exceeds 5, more preferably 5.5 to 10, still more preferably 5.5 -9. Here, Mn is a number average molecular weight, and Mw is a weight average molecular weight. When the molecular weight distribution (Mw/Mn) of the propylene-based polymer (B) is within the above range, a sheet more excellent in rigidity and heat resistance can be obtained.

The structure is not particularly limited as the propylene-based polymer (B), and examples thereof include a homopolymer of propylene and a copolymer of propylene and α-olefin (except for propylene). Examples of the copolymer include a propylene/α-olefin random copolymer, a block-type propylene copolymer (a propylene homopolymer or a propylene/α-olefin random copolymer, and amorphous or low-crystalline propylene/α-olefin) mixture of random copolymers) and random block polypropylene.

As α-olefin, for example, ethylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene, 4-methyl-1-pentene, 3-methyl-1-pentene ?-olefins having 2 to 12 carbon atoms, such as those, are mentioned. As these ?-olefins, ethylene, 1-butene, 1-hexene, 1-octene, and 4-methyl-1-pentene are preferable. The α-olefin may be used alone or in combination of two or more.

As the propylene-based polymer (B), a homopolymer of propylene is preferable from the viewpoints of rigidity and impact strength.

The propylene-based polymer (B) can be produced by polymerizing propylene or copolymerizing propylene with another α-olefin using a catalyst, and a commercially available polypropylene-based resin can be used. As the catalyst, for example, the above-mentioned 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. catalysts formed; and a metallocene catalyst using a metallocene compound as one component of the catalyst.

[Other ingredients (additives)]

The propylene-based polymer composition may contain a weathering stabilizer, a heat-resistant stabilizer, an antistatic agent, a slip agent, an anti-blocking agent, an antifogging agent, a nucleating agent, a decomposing agent, a pigment, a dye, a plasticizer, and a hydrochloric acid absorbent, within the scope not impairing the object of the present invention. , antioxidants, crosslinking agents, crosslinking accelerators, reinforcing agents, fillers, softeners, processing aids, activators, moisture absorbents, adhesives, flame retardants, mold release agents, and the like. An additive can be used 1 type or 2 or more types.

The said propylene-type polymer composition may contain a nucleating agent for improvement, such as transparency and heat resistance. Examples of the nucleating agent include sorbitol compounds such as dibenzylidene sorbitol, organophosphate ester compounds, rosinate compounds, C4-C12 aliphatic dicarboxylic acids, and metal salts thereof. Among these, organic phosphoric acid ester compounds are preferable.

One type or two or more types of nucleating agents can be used.

The nucleating agent is preferably 0.05 to 0.5 parts by mass, more preferably 0.1 to 0.3 parts by mass relative to 100 parts by mass in total of the propylene polymer (A) and the propylene polymer (B).

[Preparation of propylene-based polymer composition, physical properties]

The propylene-based polymer composition can be produced by employing any known method, for example, the propylene-based polymer (A) and the propylene-based polymer (B) and, if necessary, other components are mixed with a Henschel mixer, V - A method of mixing with a blender, ribbon blender, tumbler blender, etc., or after the above mixing, melt-kneading with a single screw extruder, twin screw extruder, kneader, Banbury mixer, roll, etc., and then granulation or pulverization method can be heard

In the propylene polymer composition, the content of the propylene polymer (A) is 2 to 30 parts by mass, preferably 3 to 100 parts by mass of the total of the propylene polymer (A) and the propylene polymer (B). It is 20 mass parts, More preferably, it is 5-15 mass parts, Content of a propylene-type polymer (B) is 70-98 mass parts, Preferably it is 80-97 mass parts, More preferably, it is 85-95 mass parts. .

When content of a propylene-type polymer (A) is less than 2 mass parts, there exists a tendency for rigidity or heat resistance to become inadequate. When the content of the propylene-based polymer (A) exceeds 30 parts by mass, transparency of the sheet tends to deteriorate and poor appearance tends to occur.

In the present invention, from the viewpoint of rigidity and heat resistance and from the viewpoint of reduction of fish eyes, a propylene-based polymer (A) comprising a propylene-based polymer (a1) and a propylene-based polymer (a2) obtained by batch polymerization multistage polymerization (A) and the propylene-based polymer (B) are preferably mixed to prepare a propylene-based polymer composition.

The molecular weight distribution (Mw/Mn) of the propylene-based polymer composition measured by gel permeation chromatography (GPC) is preferably 6.0 or more, more preferably 6.2 or more, still more preferably 6.4 or more, and the upper limit Although it does not specifically limit, For example, it is 15 or less. The molecular weight distribution (Mz/Mw) of the propylene-based polymer composition measured by GPC is preferably 3.0 or more, more preferably 3.2 or more, and still more preferably 3.5 or more, and the upper limit is not particularly limited, but For example, 8 or less. Here, Mn is a number average molecular weight, Mw is a weight average molecular weight, and Mz is a z average molecular weight.

In the present invention, since the propylene-based polymer (a1) having a high molecular weight is used, the molecular weight distribution of the propylene-based polymer composition is large. Accordingly, when the propylene-based polymer composition is formed into a sheet, the degree of orientation in the MD direction of the molding is increased, and it is assumed that the propylene polymer composition is highly crystallized due to the orientation, and a sheet excellent in rigidity and heat resistance is obtained.

The relaxation time (strain rate ω=1.0 radian/sec) of the propylene-based polymer composition obtained under the conditions of a temperature of 175° C., a strain of 5%, and a measurement angular frequency of 10 ⁻² to 10 ² s ⁻¹ using a viscoelasticity measuring device was 1.0 It is more than second, and it is preferable that molecular weight distribution index (PDI) is 10 or more, and it is more preferable that PDI is 12 or more.

Here, when the angular frequency at which the storage modulus G' becomes 2×10 ² Pa is ω1 and the angular frequency at which 2×10 ⁴ Pa is ω2, the index expressed by ω2/10ω1 is used as the molecular weight distribution index (PDI). do.

The relaxation time is obtained from the ratio of the storage elastic modulus to the loss elastic modulus at a specific angular frequency, and is an index (influenced by both MFR and molecular weight distribution) of the ease of relaxation of the molecular chain. PDI becomes a large value, so that non-Newtonian property is large, and becomes an index|index of molecular weight distribution.

When the relaxation time is 1.0 second or more and the molecular weight distribution index is 10 or more, the orientation in the MD direction due to the high molecular weight component is large at the time of sheet molding of the propylene-based polymer composition, and high rigidity and high heat resistance by orientation crystallization. The improvement effect tends to be large.

[Sheet Composition]

The non-foamed sheet of the present invention may be a single-layer sheet composed of a layer formed of the propylene-based polymer composition, or a laminated sheet having a layer formed of the propylene-based polymer composition. The non-foaming sheet is used, for example, as a packaging material for food, beverage, industrial parts, miscellaneous goods, toys, daily necessities, office supplies, medical supplies, and the like.

In the case of a laminated sheet, it may be a laminated sheet having two or more layers formed of the propylene-based polymer composition, or a laminated sheet having one or more layers formed of the propylene-based polymer composition and one or more other layers. By setting it as a laminated structure, various functions can further be provided to a sheet|seat. As a method used in that case, the co-extrusion method and the extrusion coating method are mentioned. As another layer, a barrier layer of gas, such as oxygen, and water vapor|steam, a sound absorption layer, a light-shielding layer, an adhesive layer, an adhesive layer, a colored layer, a conductive layer, and a regenerated resin containing layer are mentioned, for example. Specific examples of the material for forming the other layer include olefin-based polymer compositions other than the propylene-based polymer composition, gas barrier resin composition, and adhesive resin composition.

The thickness of the non-foaming sheet of the present invention is usually 200 µm or more, preferably 200 µm to 5.0 mm, and more preferably 300 µm to 3.0 mm.

The non-foaming sheet of the present invention is excellent in rigidity and heat resistance. Specifically, the non-foamed sheet of the present invention has a high tensile modulus of elasticity at normal temperature and a high tensile modulus of elasticity at high temperature. Moreover, since the said non-foaming sheet|seat has high melting|fusing point and melting enthalpy of a sheet, it is excellent in heat resistance. Moreover, the said non-foaming sheet|seat has little generation|occurrence|production of a fish eye in one Embodiment.

As a manufacturing method of a sheet|seat, extrusion molding methods, such as a T-die method and an inflation method, a compression molding method, a calendering method, and a casting|flow_spreading method are mentioned, for example.

Sheet shaping|molding can be performed as follows, for example. Each of the components constituting the propylene-based polymer composition may be directly introduced into the hopper of a sheet forming machine, or each of the components is mixed in advance using a ribbon blender, Banbury mixer, Henschel mixer, super mixer, or the like, or additionally, shortened Alternatively, the propylene-based polymer composition may be obtained by melt-kneading using a kneader such as a twin screw extruder or roll, and then sheet-molded.

If a specific example of manufacturing the sheet is described by the T-die method, each of the above components is put into an extruder and melt-kneaded at a temperature of usually 180 to 280°C, preferably 200 to 270°C, and then from the die lip of the T-die. It extrudes into a sheet form, this molten sheet|seat is cooled, it takes up with the take-up machine with a nip roll etc., and obtains a sheet|seat.

As a cooling method of the molten sheet, for example, a cooling method by roll and air cooling by an air knife method or an air chamber method, a pressure cooling method by a polishing roll method, a swing roll method, a belt casting method, etc., a contact cooling method using a refrigerant by a water cooling method, etc. can be heard

In this invention, a molded object can be obtained by processing the said non-foaming sheet|seat. For example, the non-foaming sheet is molded into a shape such as a container (eg, bottle, cup, tray, bowl) or lid by a conventionally known molding method such as vacuum molding, air pressure molding, ejection molding, or plug-assisted molding. By doing it, a molded object can be obtained. As molding conditions, conventionally well-known molding conditions are employable. The molded article is also excellent in rigidity and heat resistance.

Example

Hereinafter, the present invention will be described in more detail based on Examples, but the present invention is not limited to these Examples. In addition, the measurement and evaluation of the various characteristics of the polymer obtained in each example, a polymer composition, a sheet|seat, and a container were performed as follows.

(1) In Production Example, the mass fractions of the propylene-based polymer (corresponding to the propylene-based polymer (a1)) obtained in the first stage and the propylene-based polymer (corresponding to the propylene-based polymer (a2)) obtained in the second stage are, It was calculated|required from the sequence amount of the reaction heat generated at the time of polymerization.

(2) Intrinsic viscosity [η] (dl/g) was measured at 135°C in a tetralin solvent. On the other hand, the intrinsic viscosity [η] 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.

[η] ₂ =([η] _total ×100-[η] ₁ ×W ₁ )/W ₂

[η] _total : intrinsic viscosity of the entire propylene-based polymer

[η] ₁ : Intrinsic viscosity of the propylene-based polymer obtained in the first stage

W ₁ : Mass fraction (%) of the propylene-based polymer obtained in the first stage

W ₂ : Mass fraction (%) of the propylene-based polymer obtained in the second stage

(3) Melt flow rate (MFR) (g/10 min) was measured in accordance with JIS-K7210 at a measurement temperature of 230°C and a load of 2.16 kgf (21.2 N).

(4) melting point

The melting point of the propylene polymer (B) was measured using a differential scanning calorimeter (DSC, manufactured by Perkin Elmer). Here, the endothermic peak in the 3rd step was defined as melting|fusing point.

<Sample creation conditions>

Forming method: press forming

Mold: thickness 0.2mm

(The sample is clamped with aluminum foil and press-molded using a mold)

Molding temperature: 240℃

Press pressure: 300 kg/cm ² , Press time: 1 minute

After press molding, the sheet is cooled with ice water, and about 0.4 g of the sheet is sealed in the following measuring container.

Measuring vessel: DSC PANS 10μl BO-14-3015

DSC COVER BO14-3003

<Measurement conditions>

1st step: Raise the temperature from 30 ℃ to 230 ℃ at 10 ℃ / min, and hold for 10 min.

2nd step: Lower the temperature to 30°C at 10°C/min.

Third step: Raise the temperature to 230°C at 10°C/min.

(5) The average molecular weight (number average molecular weight Mn, weight average molecular weight Mw, z average molecular weight Mz) is obtained by gel permeation chromatography (GPC) under the following apparatus and conditions, and molecular weight distribution (Mw/Mn, Mz/ Mw) was obtained.

GPC measuring device

Gel permeation chromatograph HLC-8321 GPC/HT type (manufactured by Tosoh Corporation)

analysis device

Data processing software Empower 3 (manufactured by Waters)

Measuring conditions

Column: TSKgel GMH6-HT×2 + TSKgel GMH6-HTL×2

(All 7.5mmI.D.x30cm, manufactured by Tosoh Corporation)

Column temperature: 140°C

Mobile phase: o-dichlorobenzene (containing 0.025% BHT)

Detector: Differential Refractometer

Flow rate: 1.0 mL/min

Sample concentration: 0.1% (w/v)

Injection volume: 0.4mL

Sampling time interval: 1s

Column calibration: monodisperse polystyrene (manufactured by Tosoh Corporation)

Molecular weight conversion: PP conversion/universal calibration method (PS (polystyrene) viscosity conversion coefficient K _PS =0.000138dl/g,

α _PS =0.700, viscosity conversion factor of PP (polypropylene) K _PP =0.000242dl/g, α _PP =0.707)

(6) relaxation time (G'/G"/ω(τ))

It measured on condition of the following using the viscoelasticity measuring apparatus (made by Antonpa).

Sample: A φ25mm, 1mm thick disk was produced by a press molding machine.

(After pressurized at 230℃, 981N (100kgf) for 3 minutes, cooled at 30℃, 981N (100kgf) for 3 minutes)

Measurement conditions: temperature 175°C, strain 5%, measurement angular frequency 10 ^-2 ∼10 ² s ^-1 .

(7) Molecular Weight Distribution Index (PDI)

When measured under the same conditions using the viscoelasticity measuring device, when the angular frequency at which the storage elastic modulus G' is 2×10 ² Pa is ω1, and the angular frequency at which 2×10 ⁴ Pa is ω2, ω2/10ω1 The index represented by was taken as the molecular weight distribution index PDI.

(8) the modulus of elasticity of the container

The tensile modulus (MPa) was measured according to the method of JIS K7113. In addition, the measurement was performed on condition of 23 degreeC with respect to the depth direction of a container.

(9) vessel deformation load

The maximum load (g) when the side of the container was pushed in by 5 mm was measured.

(10) sheet DSC measurement

The melting point (Tm) of the sheet was measured using a differential scanning calorimeter (DSC, manufactured by Perkin Elmer). Here, the endothermic peak in the first step was defined as the melting point (Tm), and the area obtained from the endothermic peak curve was defined as the enthalpy of melting (ΔHm).

<Sample creation conditions>

sheet was used.

<Measurement conditions>

1st step: Raise the temperature from 30 ℃ to 230 ℃ at 10 ℃ / min, and hold for 10 min.

(11) sheet elastic modulus

The tensile modulus (MPa) was measured according to the method of JIS K7113. In addition, the measurement was performed on the conditions of 23 degreeC and 60 degreeC about the extrusion direction (MD) of shaping|molding, and the perpendicular|vertical direction (TD) of MD.

[Production Example 1]

(1) Preparation of magnesium compound

When the reactor with a stirrer (volume of 500 liters) is sufficiently replaced with nitrogen gas, ethanol 97.2 kg, iodine 640 g, and metal magnesium 6.4 kg are added, and hydrogen gas is not generated from the system under reflux conditions while stirring to obtain a solid reaction product. The target magnesium compound (solid catalyst carrier) was obtained by drying the reaction liquid containing the solid reaction product under reduced pressure.

(2) Preparation of solid titanium catalyst components

In a reactor equipped with a stirrer (volume of 500 liters) sufficiently purged with nitrogen gas, 30 kg of the above magnesium compound (unpulverized), 150 liters of purified heptane (n-heptane), 4.5 liters of silicon tetrachloride, and di-phthalate 5.4 liters of n-butyl were added. The inside of the system was maintained at 90°C, and 144 liters of titanium tetrachloride was added while stirring and reacted at 110°C for 2 hours, after which the solid component was separated and washed with purified heptane at 80°C. Furthermore, after adding 228 liters of titanium tetrachloride and making it react at 110 degreeC for 2 hours, it wash|cleaned enough with purified heptane, and the solid titanium catalyst component was obtained.

(3) Preparation of pre-polymerization catalyst

In 200 mL of heptane, 10 mmol of triethylaluminum, 2 mmol of dicyclopentyldimethoxysilane, and 1 mmol of the solid titanium catalyst component obtained in (2) above were added in terms of titanium atoms. The internal temperature was maintained at 20°C, and propylene was continuously introduced while stirring. After 60 minutes, stirring was stopped, and as a result, a prepolymerization catalyst slurry in which 4.0 g of propylene per 1 g of solid titanium catalyst component was polymerized was obtained.

(4) main polymerization

In a 600-liter autoclave, 336 liters of propylene was charged, and it heated up at 60 degreeC. Thereafter, 8.7 mL of triethylaluminum, 11.4 mL of dicyclopentyldimethoxysilane, and 2.9 g of the prepolymerization catalyst slurry obtained in (3) above were charged as a solid titanium catalyst component, and polymerization was initiated. After 75 minutes from the start of polymerization, the temperature was decreased to 50° C. over 10 minutes (end of polymerization in the first stage).

The intrinsic viscosity [η] of the propylene-based polymer (a1-1) polymerized under the same conditions as in the first stage was 11 dl/g.

After the temperature was lowered, hydrogen was continuously introduced so that the pressure became constant at 3.3 MPaG, and polymerization was performed for 151 minutes. Next, the vent valve was opened, and unreacted propylene was purged via an integrating flow meter (end of polymerization in the second stage).

In this way, 51.8 kg of a powdery propylene polymer was obtained. The ratio of the propylene-based polymer (a1-1) produced by polymerization in the first stage to the propylene-based polymer, calculated from the material balance, is 25% by mass, and the propylene-based polymer produced by polymerization in the second stage (a2-) The ratio of 1) was 75 mass %, and the intrinsic viscosity [η] was 0.99 dl/g.

To this propylene polymer, 2000 ppm of Irganox 1010 (manufactured by BASF), 2000 ppm of Irgafos 168 (manufactured by BASF), 1000 ppm of Sandostab P-EPQ (manufactured by Clariant Japan) as an antioxidant, and 1000 ppm of calcium stearate as a neutralizing agent It was added and melt-kneaded with a twin-screw extruder to obtain a pellet-form propylene-based polymer (A-1). The propylene polymer (A-1) finally obtained in this way had an MFR of 1.2 g/10 min.

[Example 1]

The propylene-based polymer (A-1) obtained in Production Example 1 and E-203GV (Prime Polymer Co., Ltd., Prime Polypro E-203GV) as the propylene-based polymer (B) were mixed in a mass ratio of 5:95, and these resins A total of 100 parts by mass of was melt-extruded with an extruder (TEM-41SS manufactured by Toshiba Machinery Co., Ltd.) at a resin temperature of 260°C to obtain a sheet-like resin composition. This sheet-like resin composition is sandwiched between a first cooling roll and a second cooling roll (each roll set temperature of 35°C and 75°C) and cooled, taken up at a speed of 0.8 m/min, and a sheet having a thickness of 1.5 mm is obtained got it Using the sheet, FK-0431-10 manufactured by Asano Laboratories Co., Ltd. was used and heated at an upper and lower heater set temperature of 450°C to prepare a cup container, and various evaluations were performed.

[Examples 2-3]

It carried out similarly to Example 1 except having changed the compounding composition as it described in Table 1.

[Example 4]

It carried out similarly to Example 2 except having used E-200GV (The Prime Polymer company make, Prime Polypro E-200GV) instead of E-203GV as a propylene-type polymer (B).

[Comparative Examples 1-2]

In Comparative Example 1, E-203GV (Prime Polymers, Prime Polypro E-203GV), Comparative Example 2, E-200GV (Prime Polymers, Prime Polypro E-200GV), in Example 1 A sheet and a cup container were created under the indicated molding conditions, and various evaluations were performed.

Various physical properties of E-203GV and E-200GV are as described in Table 1.

Claims (8)

It is a non-foaming sheet having a layer formed of a propylene-based polymer composition,
The propylene-based polymer composition,
20-50 mass % of the propylene-based polymer (a1) having an intrinsic viscosity [η] in the range of 10 to 12 dl/g at 135°C in a tetralin solvent, and an intrinsic viscosity measured in a tetralin solvent at 135°C The viscosity [η] is 50 to 80 mass % of the propylene polymer (a2) in the range of 0.5 to 1.5 dl/g [provided that the total amount of the propylene polymer (a1) and the propylene polymer (a2) is 100 mass % The propylene-based polymer (A) contained therein, and a propylene-based polymer having a melting point of 120 to 170°C and an intrinsic viscosity [η] of more than 1.5 dl/g and not more than 5.0 dl/g measured in a tetralin solvent at 135°C (B) containing;
With respect to a total of 100 parts by mass of the propylene-based polymer (A) and the propylene-based polymer (B), the content of the propylene-based polymer (A) is 2 to 30 parts by mass, and the content of the propylene-based polymer (B) is A non-foaming sheet, characterized in that it is 70 to 98 parts by mass. The method of claim 1,
A non-foaming sheet having a molecular weight distribution (Mw/Mn) of 6.0 or more as measured by gel permeation chromatography (GPC) of the propylene-based polymer composition. 3. The method of claim 1 or 2,
A non-foaming sheet having a melt flow rate (MFR) of 0.1 to 10 g/10 min of the propylene-based polymer (B) measured at 230°C and a load of 2.16 kg. 4. The method according to any one of claims 1 to 3,
A non-foaming sheet in which the molecular weight distribution (Mw/Mn) measured by gel permeation chromatography (GPC) of the propylene polymer (B) exceeds 5. 5. The method according to any one of claims 1 to 4,
Non-foaming sheet with a thickness of 200 μm or more. 6. The method according to any one of claims 1 to 5,
A non-foaming sheet, which is a single-layer sheet comprising a layer formed of the propylene-based polymer composition. 6. The method according to any one of claims 1 to 5,
A non-foaming sheet, which is a laminated sheet having a layer formed of the propylene-based polymer composition. A container formed of the non-foaming sheet according to any one of claims 1 to 7.