CN118451138A - Non-stretch film, sealing film and multilayer sealing film - Google Patents
Non-stretch film, sealing film and multilayer sealing film Download PDFInfo
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- CN118451138A CN118451138A CN202280086122.XA CN202280086122A CN118451138A CN 118451138 A CN118451138 A CN 118451138A CN 202280086122 A CN202280086122 A CN 202280086122A CN 118451138 A CN118451138 A CN 118451138A
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- propylene
- propylene polymer
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- alpha
- film
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- 238000007789 sealing Methods 0.000 title claims abstract description 62
- 229920006302 stretch film Polymers 0.000 title description 5
- 229920001155 polypropylene Polymers 0.000 claims abstract description 142
- 239000004711 α-olefin Substances 0.000 claims abstract description 92
- 229920000089 Cyclic olefin copolymer Polymers 0.000 claims abstract description 60
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims abstract description 54
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims abstract description 53
- 239000000203 mixture Substances 0.000 claims abstract description 51
- CXWXQJXEFPUFDZ-UHFFFAOYSA-N tetralin Chemical compound C1=CC=C2CCCCC2=C1 CXWXQJXEFPUFDZ-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000010410 layer Substances 0.000 claims description 38
- 238000005259 measurement Methods 0.000 claims description 18
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- XYGKGASSKJWLTN-UHFFFAOYSA-N CCCCCCC.CCCCCCC Chemical compound CCCCCCC.CCCCCCC XYGKGASSKJWLTN-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
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- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 description 2
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 2
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- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 2
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- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 1
- LDTAOIUHUHHCMU-UHFFFAOYSA-N 3-methylpent-1-ene Chemical compound CCC(C)C=C LDTAOIUHUHHCMU-UHFFFAOYSA-N 0.000 description 1
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- Compositions Of Macromolecular Compounds (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
Abstract
The invention provides an unstretched polypropylene film which has good balance between rigidity and low-temperature heat sealing performance and is excellent in rigidity or an unstretched polypropylene film which has excellent rigidity and can realize heat sealing at low temperature. The non-stretched film of the present invention is formed from a propylene polymer composition containing, in a specific ratio: a specific propylene-based polymer (A); and an MFR of 0.1 to 30g/10 min, an intrinsic viscosity [ eta ] of more than 1.5dl/g and less than 5.0dl/g as measured in a tetralin solvent at 135 ℃, and a propylene-alpha-olefin copolymer (B) containing a specific amount of structural units derived from an alpha-olefin (excluding propylene).
Description
Technical Field
The present invention relates to a non-stretch film, a sealing film and a multilayer sealing film.
Background
Propylene polymers are widely used as materials for various molded articles (for example, refer to patent documents 1 to 4), and the required properties vary depending on the molding method and the use. For example, films made of propylene polymers are widely used as packaging films for foods and various goods, by utilizing excellent mechanical properties such as rigidity and optical properties such as gloss. It is known that a polypropylene film without stretching (for example, see patent documents 5 to 7) is excellent in balance between rigidity and heat resistance. Patent document 8 discloses a non-stretched polypropylene film which uses a specific propylene polymer and is particularly excellent in rigidity.
Prior art literature
Patent literature
Patent document 1: international publication No. 1999/007752
Patent document 2: international publication No. 2005/097842
Patent document 3: japanese patent laid-open No. 2001-302858
Patent document 4: japanese patent laid-open No. 2006-045446
Patent document 5: japanese patent laid-open No. 2002-265712
Patent document 6: japanese patent application laid-open No. 2005-320359
Patent document 7: japanese patent laid-open publication No. 2011-236357
Patent document 8: international publication No. 2021/025142
Disclosure of Invention
Technical problem to be solved by the invention
However, when the unstretched polypropylene film described in patent document 8 is used as a sealing film, the sealing performance is low (sealing temperature is high).
Accordingly, the first aspect of the present invention has an object (hereinafter referred to as "first object") of: provided is a non-stretched polypropylene film having a good balance of rigidity and low-temperature heat sealing properties.
In addition, the second aspect of the present invention has an object (hereinafter referred to as "second object") of: provided is a non-stretched polypropylene film which has excellent rigidity and can realize heat sealing at low temperatures.
Technical scheme for solving technical problems
After intensive studies conducted by the inventors of the present invention, it was found that: a non-stretched film formed from the propylene polymer composition described below can solve the first problem, and has completed the first aspect of the present invention. The first aspect of the present invention relates to, for example, the following [1].
[1] A non-stretched film comprising a propylene polymer composition (X1), wherein the propylene polymer composition (X1) comprises a propylene polymer (A) and a propylene-alpha-olefin copolymer (B1),
The propylene polymer (A) contains: 20 to 50% by mass of a propylene polymer (a 1) having an intrinsic viscosity [ eta ] in the range of 10 to 12dl/g measured in a tetralin solvent at 135 ℃; and 50 to 80 mass% of a propylene polymer (a 2) having an intrinsic viscosity [ eta ] in the range of 0.5 to 1.5dl/g measured in a tetralin solvent at 135 ℃, wherein the total amount of the propylene polymer (a 1) and the propylene polymer (a 2) is 100 mass%,
The propylene-alpha-olefin copolymer (B1) has a melt flow rate (230 ℃ C., 2.16kg load) of 0.1 to 30g/10 min, an intrinsic viscosity [ eta ] measured in a tetralin solvent at 135 ℃ C., of more than 1.5dl/g and 5.0dl/g or less, and the propylene-alpha-olefin copolymer (B1) contains 5.5 mol% or more of structural units derived from an alpha-olefin (excluding propylene),
The content of the propylene polymer (A) is 1 to 10 parts by mass and the content of the propylene-alpha-olefin copolymer (B1) is 90 to 99 parts by mass, based on 100 parts by mass of the total of the propylene polymer (A) and the propylene-alpha-olefin copolymer (B1).
After further intensive studies, the inventors of the present invention found that: a non-stretched film formed from the propylene polymer composition described below can solve the second problem, and thus the second aspect of the present invention has been completed. The second aspect of the present invention relates to, for example, the following [2].
[2] A non-stretched film comprising a propylene polymer composition (X2), wherein the propylene polymer composition (X2) comprises a propylene polymer (A) and a propylene-alpha-olefin copolymer (B2),
The propylene polymer (A) contains: 20 to 50% by mass of a propylene polymer (a 1) having an intrinsic viscosity [ eta ] in the range of 10 to 12dl/g measured in a tetralin solvent at 135 ℃; and 50 to 80 mass% of a propylene polymer (a 2) having an intrinsic viscosity [ eta ] in the range of 0.5 to 1.5dl/g measured in a tetralin solvent at 135 ℃, wherein the total amount of the propylene polymer (a 1) and the propylene polymer (a 2) is 100 mass%,
The propylene-alpha-olefin copolymer (B2) has a melt flow rate (230 ℃ C., 2.16kg load) of 0.1 to 30g/10 min, an intrinsic viscosity [ eta ] measured in a tetralin solvent at 135 ℃ C., of more than 1.5dl/g and 5.0dl/g or less, and the propylene-alpha-olefin copolymer (B2) contains 1 mol% or more and less than 5.5 mol% of structural units derived from an alpha-olefin (excluding propylene),
The content of the propylene polymer (A) is 1 to 18 parts by mass and the content of the propylene-alpha-olefin copolymer (B2) is 82 to 99 parts by mass, based on 100 parts by mass of the total of the propylene polymer (A) and the propylene-alpha-olefin copolymer (B2).
The first and second aspects of the present invention also relate to the following [3] to [6].
[3] The unstretched film according to the above [1] or [2], wherein the propylene polymer (A) has a Melt Flow Rate (MFR) of 0.01 to 5g/10 min as measured at 230℃under a load of 2.16 kg.
[4] The non-stretched film according to any one of the above [1] to [3], wherein the ratio of the area of the high molecular weight region having a molecular weight of 150 ten thousand or more to the total area of the region surrounded by the molecular weight distribution curve of the propylene polymer (A) as measured by Gel Permeation Chromatography (GPC) is 7% or more.
[5] The non-stretched film according to any one of the above [1] to [4], wherein the propylene polymer (A) has two peaks in a molecular weight distribution curve as measured by GPC, and a ratio (MH/ML) of a peak molecular weight MH on a high molecular weight side to a peak molecular weight ML on a low molecular weight side is 50 or more.
[6] The unstretched film according to any one of the above [1] to [5], wherein the PP (110) plane has an axial orientation degree of 0.85 or more as determined by wide-angle X-ray diffraction measurement.
The first aspect of the present invention also relates to the following [7].
[7] A sealing film comprising a laminate of a sealing film main body and a surface layer in this order, wherein the surface layer is the non-stretch film according to any one of [1] or [3] to [6] (wherein [1] is directly or indirectly referred to).
The second aspect of the present invention also relates to the following [8].
[8] A multilayer sealing film comprising a laminate of an outer layer, an intermediate layer and a sealing layer in this order, wherein the intermediate layer is the non-stretch film according to any one of [2] or [3] to [6] (wherein [2] is directly or indirectly referred to).
Effects of the invention
The unstretched film of the first aspect of the present invention has a well-balanced and excellent low-temperature heat sealing performance (i.e., a low seal initiation temperature described later).
The unstretched film according to the second aspect of the present invention is excellent in rigidity and also excellent in sealing performance (i.e., low sealing initiation temperature, which will be described later).
Detailed Description
Hereinafter, modes for carrying out the present invention will be described.
[ Unstretched film ]
The unstretched film according to the first aspect of the present invention is formed from a propylene polymer composition (X1) containing a propylene polymer (a) and a propylene- α -olefin copolymer (B1) described below.
The unstretched film according to the second aspect of the present invention is formed from a propylene polymer composition (X2) containing a propylene polymer (a) and a propylene- α -olefin copolymer (B2) described below.
Hereinafter, the propylene- α -olefin copolymer (B1) and the propylene- α -olefin copolymer (B2) are collectively referred to as "propylene- α -olefin copolymer (B)", unless otherwise specified.
In addition, the propylene polymer composition (X1) and the propylene polymer composition (X2) are collectively referred to as "propylene polymer composition (X)", unless otherwise specified.
Details of measurement conditions of each element are described in examples.
[ Propylene Polymer (A) ]
The propylene polymer (A) contains: 20 to 50% by mass of a propylene polymer (a 1) having an intrinsic viscosity [ eta ] in the range of 10 to 12dl/g measured in a tetralin solvent at 135 ℃; and 50 to 80 mass% of a propylene polymer (a 2) having an intrinsic viscosity [ eta ] in the range of 0.5 to 1.5dl/g measured in a tetralin solvent at 135 ℃, wherein the total amount of the propylene polymer (a 1) and the propylene polymer (a 2) is 100 mass%.
Hereinafter, the intrinsic viscosity [ eta ] measured in a tetrahydronaphthalene solvent at 135℃will also be referred to simply as "intrinsic viscosity [ eta ]". The mass fraction of each of the propylene-based polymer (a 1) and the propylene-based polymer (a 2) is based on the total amount of (a 1) and (a 2).
< Propylene Polymer (a 1) >)
The intrinsic viscosity [ eta ] of the propylene polymer (a 1) is in the range of 10 to 12dl/g, preferably 10.5 to 11.5 dl/g. The mass fraction of the propylene polymer (a 1) in the propylene polymer (a) is in the range of 20 to 50 mass%, preferably in the range of 20 to 45 mass%, more preferably in the range of 20 to 40 mass%, and still more preferably in the range of 22 to 40 mass%.
Examples of the propylene polymer (a 1) include homopolymers of propylene and copolymers of propylene and an α -olefin having 2 to 8 carbon atoms (excluding propylene). 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 preferred as these alpha-olefins. One or two or more kinds of alpha-olefins may be used.
In the copolymer of propylene and an α -olefin having 2 to 8 carbon atoms, the content of the structural unit derived from propylene is usually 90 mass% or more, preferably 95 mass% or more, more preferably 98 mass% or more, and the content of the structural unit derived from an α -olefin having 2 to 8 carbon atoms (excluding propylene) is usually 10 mass% or less, preferably 5 mass% or less, more preferably 2 mass% or less. The content ratio can be measured by 13 C-NMR.
From the viewpoint of suppressing the number of Fish Eyes (FE) of a film obtained from the polymer composition, the intrinsic viscosity [ eta ] of the propylene polymer (a 1) is preferably in the range of 10 to 12 dl/g.
On the other hand, when the intrinsic viscosity [ eta ] of the propylene-based polymer (a 1) exceeds 12dl/g, the film formability tends to be poor, and the film surface appearance tends to be poor. When the intrinsic viscosity [ η ] of the propylene polymer (a 1) is less than 10dl/g, the resulting film tends to be insufficient in rigidity, heat resistance and gas barrier properties.
When the mass fraction of the propylene-based polymer (a 1) is less than 20 mass%, the resulting polymer composition tends to have insufficient melt tension, and the resulting film tends to have insufficient rigidity, heat resistance and gas barrier properties; when the content exceeds 50% by mass, the appearance tends to be poor at the time of film formation.
One or two or more kinds of the propylene-based polymers (a 1) may be used.
< Propylene Polymer (a 2) >)
The intrinsic viscosity [ eta ] of the propylene polymer (a 2) is in the range of 0.5 to 1.5dl/g, preferably in the range of 0.6 to 1.5dl/g, more preferably in the range of 0.8 to 1.5 dl/g. The mass fraction of the propylene polymer (a 2) in the propylene polymer (a) is in the range of 50 to 80 mass%, preferably in the range of 55 to 80 mass%, more preferably in the range of 60 to 80 mass%, and still more preferably in the range of 60 to 78 mass%.
Examples of the propylene polymer (a 2) include homopolymers of propylene and copolymers of propylene and an α -olefin having 2 to 8 carbon atoms (excluding propylene). 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 preferred as these alpha-olefins. One or two or more kinds of alpha-olefins may be used.
In the copolymer of propylene and an α -olefin having 2 to 8 carbon atoms, the content of the structural unit derived from propylene is usually 90 mass% or more, preferably 93 mass% or more, more preferably 94 mass% or more, and the content of the structural unit derived from an α -olefin having 2 to 8 carbon atoms (excluding propylene) is usually 10 mass% or less, preferably 7 mass% or less, more preferably 6 mass% or less. The content ratio can be measured by 13 C-NMR.
When the intrinsic viscosity [ eta ] of the propylene polymer (a 2) is less than 0.5dl/g, the melt tension of the obtained polymer composition is insufficient, and the fish eye of the obtained film tends to be poor, and when the intrinsic viscosity [ eta ] exceeds 1.5dl/g, the viscosity is high, and the film formability tends to be poor.
When the mass fraction of the propylene-based polymer (a 2) is less than 50 mass%, the appearance tends to be poor at the time of film formation, and when it exceeds 80 mass%, the melt tension of the obtained polymer composition tends to be insufficient, and the rigidity, heat resistance and gas barrier properties of the obtained film tend to be insufficient.
One or two or more kinds of the propylene-based polymers (a 2) may be used.
< Additive >)
Additives such as antioxidants, neutralizing agents, flame retardants, and crystallization nucleating agents may be blended with the propylene polymer (a) as necessary. One or more additives may be used. The proportion of the additive is not particularly limited and may be appropriately adjusted.
Physical Properties of propylene Polymer (A)
The Melt Flow Rate (MFR) of the propylene-based polymer (A) measured at 230℃under a load of 2.16kg is preferably in the range of 0.01 to 5g/10 min, more preferably in the range of 0.05 to 4g/10 min, still more preferably in the range of 0.1 to 3g/10 min. When the MFR of the propylene polymer (a) is in the above range, the film formability is excellent.
The propylene polymer (A) preferably has a Melt Tension (MT) measured at 230℃in the range of 5 to 30g, more preferably 7 to 25g, still more preferably 10 to 20 g. When the MT of the propylene polymer (A) is in the above range, the film formability is excellent.
The Melt Tension (MT) can be measured by the following apparatus and conditions.
The device comprises: CAPILOGRAPH 1C (trade name) manufactured by Toyo Seiyaku Co., ltd;
Temperature: 230 ℃;
orifice (orifice): l=8 mm, d=2.095 mm;
extrusion speed: 15 mm/min;
pulling speed: 15 m/min.
The ratio of the area of the high molecular weight region having a molecular weight of 150 ten thousand or more (the mass ratio of the high molecular weight component having a molecular weight of 150 ten thousand or more) to the total area of the region surrounded by the molecular weight distribution curve as measured by Gel Permeation Chromatography (GPC) of the propylene polymer (a) is preferably 7% or more, more preferably 10% or more, and still more preferably 12% or more. The upper limit of the area ratio is, for example, 30%, preferably 25%. The above-mentioned area ratio of the high molecular weight region being a specific ratio or more means that the propylene-based polymer (a) contains a high molecular weight component having a molecular weight of 150 ten thousand or more. At least a part of the high molecular weight component is a high molecular weight component having an intrinsic viscosity [ eta ] of 10 to 12 dl/g. Therefore, when the ratio of the high molecular weight component is within the above range, the melt tension of the polymer composition becomes more excellent.
The propylene-based polymer (A) preferably has two peaks in a molecular weight distribution curve as measured by GPC. The ratio of the peak molecular weight MH on the high molecular weight side to the peak molecular weight ML on the low molecular weight side (MH/ML) 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 molecular weight distribution curve has two peaks and MH/ML is more than a specific value, which indicates that the content of high molecular weight components in the polymer is large, and the intrinsic viscosity [ eta ] is also high. Therefore, the propylene polymer (a) of this embodiment contributes to an improvement in melt tension, rigidity at the time of film formation, and heat resistance.
From the viewpoints of tackiness and film formability, the peak molecular weight ML of the propylene polymer (a) on the low molecular weight side of the molecular weight distribution curve measured by GPC is preferably 10 ten thousand or less, more preferably 8 ten thousand or less, and still more preferably 5 ten thousand or less.
< Method for producing propylene Polymer (A)
The production method of the propylene polymer (A) may be any of various known production methods, and examples thereof include the methods described in paragraphs [0038] to [0075] of International publication No. 2021/025142.
[ Propylene-alpha-olefin copolymer (B) ]
The propylene-alpha-olefin copolymer (B1) has a Melt Flow Rate (MFR) of 0.1 to 30g/10 min measured at 230 ℃ under a load of 2.16kg, an intrinsic viscosity [ eta ] of more than 1.5dl/g and 5.0dl/g or less measured in a tetralin solvent at 135 ℃, and contains 5.5 mol% or more of a structural unit derived from an alpha-olefin excluding propylene.
The propylene-alpha-olefin copolymer (B2) is a copolymer having a Melt Flow Rate (MFR) of 0.1 to 30g/10 minutes measured at 230 ℃ under a load of 2.16kg, an intrinsic viscosity [ eta ] of more than 1.5dl/g and 5.0dl/g or less measured in a tetralin solvent at 135 ℃, and containing 1 mol% or more and less than 5.5 mol% of structural units derived from an alpha-olefin excluding propylene.
The intrinsic viscosity [ eta ] of the propylene-alpha-olefin copolymer (B) is higher than 1.5dl/g and 5.0dl/g or less, preferably higher than 1.5dl/g and 4.5dl/g or less, more preferably higher than 1.5dl/g and 4.0dl/g or less, still more preferably higher than 1.5dl/g and 2.5dl/g or less. When the propylene- α -olefin copolymer (B) having the intrinsic viscosity [ η ] in the above range is used, the productivity at the time of film formation is good, and the impact resistance of the obtained film is good.
The propylene-alpha-olefin copolymer (B) has a Melt Flow Rate (MFR) of 0.1 to 30g/10 min, preferably 0.3 to 10g/10 min, more preferably 0.5 to 10g/10 min, as measured at 230℃under a load of 2.16 kg. When the propylene- α -olefin copolymer (B) having an MFR in the above range is used, the productivity in film formation is good and the impact resistance of the obtained film is good.
The melting point (Tm) of the propylene- α -olefin copolymer (B1), specifically, the melting point (Tm) measured using a Differential Scanning Calorimeter (DSC) under the conditions employed in examples described later, is preferably 120 to 170 ℃, more preferably 125 to 170 ℃, still more preferably 125 to 135 ℃. The melting point (Tm) is preferably within the above range from the viewpoint of moldability and heat resistance.
The melting point (Tm) of the propylene- α -olefin copolymer (B2), specifically, the melting point (Tm) measured using a Differential Scanning Calorimeter (DSC) under the conditions employed in examples described later, is preferably 120 to 170 ℃, more preferably 125 to 170 ℃, still more preferably 130 to 170 ℃, particularly preferably 130 to 155 ℃. The melting point (Tm) is preferably within the above range from the viewpoint of moldability and heat resistance.
The propylene- α -olefin copolymer (B) preferably has a molecular weight distribution (Mw/Mn) of 4.0 or more, more preferably 4.0 to 6.5, and still more preferably 4.0 to 6.0, as measured by Gel Permeation Chromatography (GPC). Wherein Mn is a number average molecular weight and Mw is a weight average molecular weight.
Examples of the propylene- α -olefin copolymer (B) include propylene- α -olefin random copolymers, block-type propylene copolymers (propylene homopolymers or mixtures of propylene- α -olefin random copolymers with amorphous or low-crystalline propylene- α -olefin random copolymers), and random-block polypropylene.
Examples of the α -olefin include α -olefins having 2 to 12 carbon atoms such as ethylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene, 4-methyl-1-pentene and 3-methyl-1-pentene. As these alpha-olefins, ethylene, 1-butene, 1-hexene, 1-octene, 4-methyl-1-pentene are preferred. One or two or more kinds of alpha-olefins may be used.
In the propylene- α -olefin copolymer (B1), the content of the structural unit derived from the α -olefin (excluding propylene) is 5.5 mol% or more, preferably 5.5 to 9.0 mol%, and more preferably 5.5 to 7.0 mol% based on 100 mol% of the total of the content of the structural unit derived from the propylene and the structural unit derived from the α -olefin.
In the propylene- α -olefin copolymer (B2), the content of the structural unit derived from the α -olefin (excluding propylene) is 1 mol% or more and less than 5.5 mol%, preferably 1.5 to 4.5 mol%, more preferably 2.0 to 4.0 mol% in the case of the propylene- α -olefin copolymer (B2).
The content ratio can be measured by 13 C-NMR.
The propylene- α -olefin copolymer (B) can be produced by copolymerizing propylene with other α -olefin using a catalyst, and a commercially available polypropylene resin can be used. Examples of the catalyst include catalysts comprising solid catalyst components containing magnesium, titanium and halogen as essential components, organometallic compound catalyst components such as organoaluminum compounds, and electron donating compound catalyst components such as organosilicon compounds described in paragraphs [0050] to [0075] of International publication No. 2021/025142; a metallocene catalyst using a metallocene compound as one of the components of the catalyst.
The propylene polymer (a) and the propylene- α -olefin copolymer (B) may each contain at least one or more structural units derived from a biomass-derived monomer (propylene). The same monomer constituting the polymer may be a biomass-derived monomer alone, a fossil fuel-derived monomer alone, or both a biomass-derived monomer and a fossil fuel-derived monomer. The biomass-derived monomer is a monomer obtained from all renewable natural materials including fungi, yeasts, algae, bacteria, plant sources, animal sources, and the like, and residues thereof, and contains a 14 C isotope in a ratio of about 1×10 -12 as carbon, and the biomass carbon concentration (pMC) measured according to ASTM D6866 is about 100 (pMC). The biomass-derived monomer (propylene) can be obtained by, for example, a method known in the art.
From the viewpoint of reducing the environmental load, it is preferable that the propylene-based polymer (a) or the propylene- α -olefin copolymer (B) contain a structural unit derived from a biomass-derived monomer. Even if the starting olefin is a propylene polymer or a propylene- α -olefin copolymer containing a biomass-derived olefin under the same polymer production conditions such as a polymerization catalyst and a polymerization temperature, the molecular structure of the starting olefin other than the 14 C isotope, which is contained in a ratio of about 1×10 ﹣12, is equivalent to that of a propylene polymer or a propylene- α -olefin copolymer composed of a fossil fuel-derived monomer. Thus, their performance does not change either.
The propylene-based polymer (A) and the propylene- α -olefin copolymer (B) may contain at least one or more structural units derived from a monomer (propylene) derived from a chemical recycling source. The same monomers that make up the polymer may be chemical recycle-derived monomers alone, or may comprise chemical recycle-derived monomers as well as fossil fuel-derived monomers and/or biomass-derived monomers. The monomer (propylene) of chemical recycling origin can be obtained, for example, by methods known in the art.
From the viewpoint of reducing environmental load (mainly reducing waste), it is preferable that the propylene-based polymer (a) and the propylene- α -olefin copolymer (B) contain structural units derived from monomers of chemical recycling sources. Even if the raw material monomer contains a monomer derived from chemical recycling, the monomer derived from chemical recycling is a monomer that returns a polymer such as waste plastics to a monomer unit such as ethylene by depolymerization, thermal cracking, or the like, and a monomer produced from the monomer, and therefore, the molecular structure is equivalent to that of a propylene-based polymer or a propylene- α -olefin copolymer composed of a fossil fuel-derived monomer, as long as the polymerization catalyst, polymerization process, polymerization temperature, and other polymer production conditions are equivalent. Thus, their performance does not change either.
[ Other Components (additives) ]
The propylene polymer composition (X) may contain additives such as weather resistance stabilizers, heat resistance stabilizers, antistatic agents, slip agents, antiblocking agents, antifogging agents, nucleating agents, decomposers, pigments, dyes, plasticizers, hydrochloric acid absorbents, antioxidants, crosslinking agents, crosslinking accelerators, reinforcing agents, fillers, softeners, processing aids, activators, moisture absorbents, adhesives, flame retardants, and mold release agents, within the range that the object of the present invention is not impaired. One or more additives may be used.
[ Preparation and physical Properties of propylene Polymer composition (X) ]
The propylene polymer composition (X) may be produced by any known method, and examples thereof include a method of mixing the propylene polymer (a) with the propylene- α -olefin copolymer (B) and, if necessary, other components by using a henschel mixer, a V-blender, a ribbon blender, a drum blender, or the like; or a method in which the above-mentioned materials are mixed and then melt-kneaded by means of a single screw extruder, a twin screw extruder, a kneader, a Banbury mixer, a roll or the like, and then pelletized or pulverized.
In the propylene polymer composition (X1), the content of the propylene polymer (a) is 1 to 10 parts by mass, preferably 3 to 10 parts by mass, more preferably 4 to 10 parts by mass, and the content of the propylene- α -olefin copolymer (B1) is 90 to 99 parts by mass, preferably 90 to 97 parts by mass, more preferably 90 to 96 parts by mass, relative to 100 parts by mass of the total of the propylene polymer (a) and the propylene- α -olefin copolymer (B1).
The non-stretched film of the present invention having the content of the propylene polymer (a) and the propylene- α -olefin copolymer (B) in the above-mentioned range is excellent in balance between rigidity and heat sealing properties and also excellent in appearance after heat sealing.
On the other hand, when the content of the propylene- α -olefin copolymer (B1) is less than 90 parts by mass, the sealing property of the film tends to be deteriorated, that is, the heat sealing temperature tends to be high, and the appearance of the film after heat sealing may be deteriorated. When the content of the propylene- α -olefin copolymer (B1) is more than 99 parts by mass, the film rigidity tends to be poor, that is, the tensile elastic modulus tends to be low.
In the propylene polymer composition (X2), the content of the propylene polymer (a) is 1 to 18 parts by mass, preferably 3 to 10 parts by mass, more preferably 4 to 10 parts by mass, and the content of the propylene- α -olefin copolymer (B2) is 82 to 99 parts by mass, preferably 90 to 97 parts by mass, more preferably 90 to 96 parts by mass, relative to 100 parts by mass of the total of the propylene polymer (a) and the propylene- α -olefin copolymer (B2).
When the content of the propylene- α -olefin copolymer (B2) is less than 82 parts by mass, the sealing property of the film tends to be deteriorated, that is, the heat sealing temperature tends to be high. When the content of the propylene- α -olefin copolymer (B2) is more than 99 parts by mass, the film rigidity tends to be poor, that is, the tensile elastic modulus tends to be low.
In the present invention, the propylene polymer composition (X) is preferably produced by mixing the propylene polymer (a) comprising the propylene polymer (a 1) and the propylene polymer (a 2) obtained by batch multistage polymerization with the propylene- α -olefin copolymer (B) from the viewpoints of rigidity and heat resistance and the viewpoint of reducing fish eyes.
The molecular weight distribution (Mw/Mn) of the propylene polymer composition (X) as measured by Gel Permeation Chromatography (GPC) is preferably 5.0 or more, more preferably 5.5 or more, still more preferably 6.0 or more, and the upper limit is not particularly limited, for example, 25.
In the present invention, since the propylene polymer (a 2) and the propylene- α -olefin copolymer (B) and the propylene polymer (a 1) having a molecular weight higher than those of both are used, the molecular weight distribution of the propylene polymer composition (X) is increased. Therefore, it is estimated that when the film of the propylene polymer composition (X) is molded, the degree of orientation in the MD direction of the molding increases, and the propylene polymer is highly crystallized by the orientation, so that it is considered that a film excellent in rigidity, heat resistance and gas barrier properties can be obtained.
The Melt Flow Rate (MFR) of the propylene-based polymer composition (X) is usually 1 to 20g/10 minutes, preferably 2 to 15g/10 minutes, more preferably 3 to 10g/10 minutes, as measured at 230℃under a load of 2.16 kg.
[ Unstretched film ]
The unstretched film of the present invention is formed from the propylene polymer composition (X). The non-stretched film of the present invention exhibits high rigidity, heat resistance and gas barrier properties relative to the existing non-stretched polypropylene films. The unstretched film can be used as a packaging material for foods, beverages, industrial parts, sundries, toys, daily necessities, office goods, medical supplies, and the like.
The unstretched film of the present invention has a thickness of usually less than 200. Mu.m, preferably 10 to 150. Mu.m, more preferably 15 to 100. Mu.m. The unstretched film of the present invention is excellent in rigidity and thus can be easily formed into a film.
The degree of axial orientation of the PP (110) surface of the unstretched film of the present invention (details of the measurement method will be described later) determined by wide-angle X-ray diffraction measurement is preferably 0.85 or more, more preferably 0.88 or more. When the degree of the axis orientation is within this range, the molecules are sufficiently oriented, and the tensile elastic modulus of the film is improved. The upper limit of the degree of axial orientation may be, for example, 0.91. The value of the degree of the axis orientation may be increased or decreased by, for example, changing the film forming speed or changing the intrinsic viscosity [ η ] of the propylene polymer (a 1).
Examples of the method for producing the film include extrusion molding, compression molding, calender molding, and casting methods such as T-die method and inflation method.
The film formation may be performed, for example, as follows. The components constituting the propylene polymer composition (X) may be directly fed into a hopper or the like of a film forming machine, or the components may be previously mixed by a ribbon blender, a banbury mixer, a henschel mixer, a high-speed mixer or the like, or further melt-kneaded by a single screw extruder, a twin screw extruder, a roll or the like to obtain the propylene polymer composition (X), and then formed into a film.
When a specific production example of a film is described by the T-die method, the above components are fed into an extruder, melt-kneaded at a temperature of usually 180 to 280 ℃, preferably 200 to 270 ℃, and then extruded into a film shape from the die lip of the T-die, and the molten film is cooled and pulled by a pulling machine such as a pulling roll to obtain a film.
Examples of the cooling method of the molten film include a cooling method using a roll and air cooling by an air knife method or an air chamber method; extrusion cooling methods such as a polishing roller method, a swinging roller method, a belt casting method and the like are adopted; a contact cooling method using a refrigerant such as a water cooling method is used.
The obtained unstretched film may be subjected to a film treatment method used for general film formation, for example, corona discharge treatment or liquid coating treatment.
[ Sealing film and multilayer sealing film ]
The sealing film of the present invention has the unstretched film of the first aspect of the present invention as a surface layer.
The sealing film of the present invention is formed of a laminate having a sealing film main body and a surface layer in this order. Examples of the method for producing the sealing film include a coextrusion method and an extrusion coating method.
The sealing film body and the surface layer may be single-layered or multi-layered, respectively.
The multilayer sealing film of the present invention has the unstretched film of the second aspect of the present invention as an intermediate layer.
The multilayer sealing film of the present invention is formed of a laminate having an outer layer, an intermediate layer, and a sealing layer in this order. Examples of the method for producing the multilayer sealing film include a coextrusion method and an extrusion coating method.
The outer layer, the middle layer and the sealing layer can be single-layer or multi-layer respectively.
Examples of the material of the sealing layer include materials used for the sealing layer, such as vinyl resins.
As the sealing film body and the outer layer, a base material layer is exemplified.
The substrate layer is formed of a material having greater rigidity and strength. Examples of the above-mentioned materials include those selected from the group consisting of: a film (may be a stretched film) comprising at least one thermoplastic resin selected from polyamide resins such as nylon 11 and nylon 12, polyester resins such as polyethylene terephthalate and polybutylene terephthalate, polyolefin resins such as polyethylene resins and polypropylene resins, polyvinylidene chloride resins, saponified ethylene-vinyl acetate copolymers, polycarbonate resins, polystyrene resins, and acrylic resins; a metal foil; a metal vapor plating film; ceramic vapor-deposited films such as inorganic oxide vapor-deposited films; paper; a nonwoven fabric; and at least one of the above-mentioned laminated bodies of materials.
The thickness of the base layer is usually about 5 to 50. Mu.m.
Examples of the sealing film body and the outer layer include a barrier layer against a gas such as water vapor or oxygen, a sound absorbing layer, a light shielding layer, an adhesive layer, a coloring layer, a conductive layer, and a layer containing a recycled resin (these layers other than the base layer are also collectively referred to as "other layers").
Examples of the materials for forming the other layers in the sealing film include olefin polymer compositions other than the propylene polymer composition (X1), gas barrier resin compositions, and adhesive resin compositions.
Examples of the materials for forming the other layers in the multilayer sealing film include olefin polymer compositions other than the propylene polymer composition (X2), gas barrier resin compositions, and adhesive resin compositions.
Since the sealing film of the present invention has the non-stretched film of the first aspect of the present invention as a surface layer, heat sealing at low temperature, specifically sealing at a seal initiation temperature lower than 140 ℃, preferably 135 ℃ or lower, can be achieved, and has a high tensile elastic modulus. In addition, the appearance after heat sealing was also excellent.
The multilayer sealing film of the present invention has the unstretched film of the second aspect of the present invention as an intermediate layer. Thus, the intermediate layer facilitates heat sealing at a lower temperature than when propylene homopolymer is used for the intermediate layer. In addition, the multilayer sealing film of the present invention has a higher tensile modulus of elasticity than when using existing propylene- α -olefin copolymers.
The non-stretched film, the sealing film and the multilayer sealing film of the present invention can be used in various fields for packaging foods such as raw foods such as vegetables and fish, dried foods such as snack foods and noodles, aqueous foods such as soup and pickled products; a field for packaging medical-related articles used for various forms of medical articles such as tablets, powders, liquids, and the like, medical peripheral materials, and the like; a packaging film in a wide range of packaging fields such as various electrical equipment packaging fields for magnetic cassettes, electrical components and the like.
Examples
The present invention will be described in further detail based on examples, but the present invention is not limited to these examples. The polymer, polymer composition and unstretched film obtained in each example were measured and evaluated for various properties as follows.
(1) Mass fraction
In production example 1, the mass fractions of the propylene-based polymer obtained in the first stage (corresponding to the propylene-based polymer (a 1)) and the propylene-based polymer obtained in the second stage (corresponding to the propylene-based polymer (a 2)) were obtained from the amount of heat released from the reaction heat generated during the polymerization.
(2) Intrinsic viscosity [ eta ]
The intrinsic viscosity [ eta ] (dl/g) was measured in a tetralin solvent at 135 ℃. The intrinsic viscosity [ η 2 ] of the propylene polymer (corresponding to the propylene polymer (a 2)) obtained in the second stage is a value calculated from the following formula.
[η]2＝([η]total×100－[η]1×W1)/W2
[ Eta ] total: intrinsic viscosity of propylene polymer as a whole
[ Eta ] 1: intrinsic viscosity of propylene-based Polymer obtained in the first stage
W 1: mass fraction (%)
W 2: mass fraction (%)
(3) Comonomer content
The comonomer content was calculated by measuring 1 H-NMR spectrum at a measurement temperature of 120℃under a measurement condition (400 MHz, japanese electron ECX 400P) of 20ppm in spectral width, 7.0 seconds in pulse repetition time and 6.15 μsec (450 pulses) using o-dichlorobenzene-d 4 as a measurement solvent.
(4) Melt Flow Rate (MFR)
The Melt Flow Rate (MFR) (g/10 min) was measured in accordance with JIS-K7210 under conditions of a measurement temperature of 230℃and a load of 2.16kgf (21.2N).
(5) Ratio of high molecular weight region with molecular weight of 150 ten thousand or more, ML, MH/ML
The ratio of the high molecular weight region having a molecular weight of 150 ten thousand or more is a ratio of the area of the high molecular weight region having a molecular weight of 150 ten thousand or more to the total area of the region surrounded by a molecular weight distribution curve (specifically, a molecular weight distribution curve and a horizontal axis) measured by Gel Permeation Chromatography (GPC) under the following apparatus and conditions. Wherein, the horizontal axis is the molecular weight (logarithmic value) and the vertical axis is dw/dLog (M) [ w: accumulated 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 above molecular weight distribution curve were obtained, and MH/ML was calculated.
GPC measurement device
Gel permeation chromatograph: HLC-8321GPC/HT type (manufactured by Tosoh Co., ltd.) analyzer
Data processing software: empower 3 (Waters Co., ltd.)
Measurement conditions:
Column: TSKGEL GMH6-HT×2+TSKgel GMH6-HTL×2
(7.5 MM I.D..times.30 cm, manufactured by Tosoh Co., ltd.)
Column temperature: 140 DEG C
Mobile phase: o-dichlorobenzene (0.025% BHT)
A detector: differential refractometer
Flow rate: 1.0mL/min
Sample concentration: 0.1% (w/v)
Injection amount: 0.4mL
Sampling time interval: 1s
Column correction: monodisperse polystyrene (manufactured by Tosoh Co., ltd.)
Molecular weight conversion: PP conversion/general correction method (viscosity conversion coefficient K PS＝0.000138dl/g,αPS of PS (polystyrene) =0.700, viscosity conversion coefficient K PP＝0.000242dl/g,αPP of PP (polypropylene) =0.707)
(6) Melting point
The crystallization melting point was determined by measurement under the following measurement conditions using a differential scanning calorimeter (DSC, manufactured by Perkin Elmer Co., ltd. (Diamond DSC)) in accordance with JIS-K7121. The peak of the endothermic peak in the fourth step when the measurement is performed under the following measurement conditions is defined as the crystal melting point (Tm). When a plurality of endothermic peaks exist, the peak top of the endothermic peak having the largest peak height is defined as the crystalline melting point (Tm).
(Measurement conditions)
Measurement environment: nitrogen atmosphere
Sample amount: 5mg of
Sample shape: pressed film (230 ℃ C. Molding, thickness 400 μm)
Sample tray: aluminum sample tray with flat bottom
The first step: the temperature was raised from 30℃to 200℃at 320℃per minute and maintained for 10 minutes.
And a second step of: the temperature was reduced to 30℃at 20℃per minute.
And a third step of: hold at 30℃for 10 minutes.
Fourth step: the temperature was raised to 200℃at 20℃per minute.
(7) Modulus of elasticity of film
The tensile elastic modulus (MPa) was measured according to JIS K7161. The measurement was performed at 23℃with respect to the extrusion direction (MD) of the molding. The higher the tensile elastic modulus, the higher the rigidity is considered.
(8) Seal initiation temperature
A test piece having a width of 100mm and a length of 150mm was cut from the film produced in examples and the like using a heat seal tester of the Toyo Seisakusho machine, folding in half, heat-sealing at a predetermined heater temperature under a pressure of 0.2MPa for a sealing time of 1.0 second, the sealed test piece was cut into a test piece having a width of 15mm, and the peel strength (N/15 mm) was measured at a test speed of 300 mm/min using model TENSILON RT1225 manufactured by ORIENTEC CORPORATION. The measurement was repeated by changing the heater temperature at 1℃and the minimum value of the heater temperature (hereinafter referred to as "seal initiation temperature") for achieving a peel strength of 2.94N/15mm or more was determined.
(9) Degree of axial orientation
A wide-angle X-ray diffraction apparatus (RINT 2550, accessory apparatus: rotating sample table, X-ray source: cuK. Alpha., output: 40kV, 370mA, detector: scintillation counter) was used, and the samples were stacked on a sample holder with MD direction as a reference axis, and the azimuth distribution intensity of the crystal face peak (110) face was measured. In the obtained azimuth distribution curve (X-ray interference pattern), the degree of orientation F (degree of axial orientation) was calculated from the following equation based on the degree of crystallinity and the half width (α) of the peak, and evaluated.
Degree of orientation (F) = (180 ° - α)/180 °
(Alpha is the half-value width of the peak from orientation)
Production example 1
(1) Preparation of magnesium compounds
A reaction vessel (500 liter of internal volume) equipped with a stirrer was sufficiently replaced with nitrogen, 97.2kg of ethanol, 640g of iodine and 6.4kg of magnesium metal were charged, and the reaction was carried out under reflux while stirring until no more hydrogen was produced in the system, to obtain a solid reaction product. The reaction solution containing the solid reaction product was dried under reduced pressure, whereby the target magnesium compound (carrier of the solid catalyst) was obtained.
(2) Preparation of solid titanium catalyst component
30Kg of the above magnesium compound (pulverized product), 150 liters of purified heptane (n-heptane), 4.5 liters of silicon tetrachloride and 5.4 liters of di-n-butyl phthalate were added to a reaction vessel (500 liters of internal volume) equipped with a stirrer after sufficient replacement with nitrogen gas. The system was kept at 90℃and 144 liters of titanium tetrachloride was charged with stirring, and after reacting at 110℃for 2 hours, the solid content was separated and washed with 80℃purified heptane. 228 liters of titanium tetrachloride was further added, and after reacting at 110℃for 2 hours, the mixture was thoroughly washed with purified heptane to obtain a solid titanium catalyst component.
(3) Production of prepolymerized catalyst
To 200mL of heptane were added 10mmol of triethylaluminum, 2mmol of dicyclopentyldimethoxy silane and 1mmol of the solid titanium catalyst component obtained in the above (2) in terms of titanium atom. The internal temperature was kept at 20℃and propylene was continuously introduced while stirring. After 60 minutes, stirring was stopped, and as a result, a prepolymerized catalyst slurry in which 4.0g of propylene was polymerized per 1g of the solid titanium catalyst component was obtained.
(4) Main polymerization
Propylene 336 liters was charged into a 600 liter autoclave and heated to 60 ℃. Then, 8.7mL of triethylaluminum, 11.4mL of dicyclopentyldimethoxy silane and 2.9g of the prepolymerized catalyst slurry obtained in the above (3) as a solid titanium catalyst component were added to start polymerization. After 75 minutes from the start of polymerization, the temperature was lowered to 50℃over 10 minutes (end of the first stage polymerization).
The intrinsic viscosity [ eta ] of the propylene-based polymer (a 1-1) obtained by polymerization under the same conditions as those of the first stage was 11dl/g.
After the temperature was lowered, hydrogen was continuously introduced so that the pressure was kept constant at 3.3MPaG, and polymerization was carried out for 151 minutes. Then, the vent valve was opened to discharge the unreacted propylene through the cumulative flow meter (the second stage polymerization was completed).
Thus, 51.8kg of a powdery propylene polymer was obtained. The ratio of the propylene polymer (a 1-1) produced by the first stage polymerization to the propylene polymer (a 2-1) produced by the second stage polymerization was 25% by mass, and the ratio of the intrinsic viscosity [ eta ] was 0.99dl/g, respectively calculated from the mass balance.
To this propylene polymer, 2000ppm of IRGANOX1010 (manufactured by BASF corporation), 2000ppm of IRGAFOS168 (manufactured by BASF corporation) and 1000ppm of SANDSTAB P-EPQ (manufactured by Clariant Japan K.K.) were added, and 1000ppm of calcium stearate as a neutralizing agent was melt-kneaded by a twin-screw extruder to obtain a propylene polymer (A-1) in the form of pellets. The final propylene polymer (A-1) thus obtained had an MFR of 1.2g/10 min.
The physical properties of the polymer obtained in production example 1 are summarized in Table 1.
TABLE 1
TABLE 1
PREPARATION EXAMPLE 2
(1) Preparation of magnesium compounds
A reaction vessel (500 liter of internal volume) equipped with a stirrer was replaced sufficiently with nitrogen, 97.2kg of ethanol, 640g of iodine and 6.4kg of magnesium metal were charged, and the reaction was carried out under reflux while stirring until no more hydrogen was produced in the system, to obtain a solid reaction product. The reaction solution containing the solid reaction product was dried under reduced pressure, whereby the target magnesium compound (carrier of the solid catalyst) was obtained.
(2) Preparation of solid titanium catalyst component
30Kg of the above magnesium compound (pulverized product), 150 liters of purified heptane (n-heptane), 4.5 liters of silicon tetrachloride and 5.4 liters of di-n-butyl phthalate were added to a reaction vessel (500 liters of internal volume) equipped with a stirrer after sufficient replacement with nitrogen gas. The system was kept at 90℃and 144 liters of titanium tetrachloride was charged with stirring, and after reacting at 110℃for 2 hours, the solid content was separated and washed with 80℃purified heptane. 228 liters of titanium tetrachloride was further added, and after reacting at 110℃for 2 hours, the mixture was thoroughly washed with purified heptane to obtain a solid titanium catalyst component.
(3) Pretreatment of
230 Liters of purified heptane was charged into a reaction vessel having an internal volume of 500 liters and equipped with a stirrer, 25kg of the solid catalyst component was supplied, triethylaluminum was supplied in a proportion of 1.0mol/mol relative to the titanium atom in the solid catalyst component, and dicyclopentyldimethoxy silane was supplied in a proportion of 1.8mol/mol relative to the titanium atom in the solid catalyst component. Then, propylene was introduced until the partial pressure of propylene reached 0.3kgf/cm 2 G, and reacted at 25℃for 4 hours. After the completion of the reaction, the solid catalyst component was washed with purified heptane several times, carbon dioxide was further supplied thereto, and stirring was performed for 24 hours.
(4) Polymerization
In a polymerization apparatus with a stirrer having an internal volume of 200 liters, the solid catalyst component thus treated was supplied in an amount of 3mmol/hr in terms of titanium atom in the component, triethylaluminum was supplied in an amount of 4mmol/kg-PP, dicyclopentyldimethoxy silane was supplied in an amount of 1mmol/kg-PP, and propylene, ethylene, 1-butene and hydrogen were reacted at a polymerization temperature of 80℃and a polymerization pressure (total pressure) of 28kgf/cm 2 G. At this time, the supply amounts of ethylene, 1-butene and hydrogen were adjusted to achieve the desired ethylene, 1-butene content and MFR, respectively. The ethylene concentration of the composition analysis value (gas chromatography analysis) of the gas portion in the polymerization apparatus was 3.5mol%, the 1-butene concentration was 4.9mol%, and the hydrogen concentration was 2.5mol%.
To the propylene-ethylene-1-butene copolymer thus obtained, 2000ppm of IRGANOX1010 (manufactured by BASF corporation), 2000ppm of IRGAFOS168 (manufactured by BASF corporation), and 1000ppm of SANDSTAB P-EPQ (manufactured by Clariant Japan K.K.) were added, and 1000ppm of calcium stearate as a neutralizing agent was melt-kneaded by a twin-screw extruder to obtain a propylene-ethylene-1-butene random copolymer (B-1) in the form of pellets.
PREPARATION EXAMPLE 3
A propylene-ethylene random copolymer (B-2) was obtained in the same manner as in production example 2, except that the ethylene supply amount, the 1-butene supply amount and the hydrogen supply amount were adjusted so that the ethylene concentration in the composition analysis value (gas chromatography analysis) of the gas portion in the polymerization apparatus in "(4) polymerization" was 2.0mol%, the 1-butene concentration was 0mol% and the hydrogen concentration was 5.5 mol%.
PREPARATION EXAMPLE 4
A propylene-ethylene random copolymer (B-3) was obtained in the same manner as in production example 2 except that the ethylene supply amount, the 1-butene supply amount and the hydrogen supply amount were adjusted so that the ethylene concentration in the composition analysis value (gas chromatography analysis) of the gas portion in the polymerization apparatus in "(4) polymerization" was 1.6mol%, the 1-butene concentration was 0mol% and the hydrogen concentration was 4.2 mol%.
PREPARATION EXAMPLE 5
A propylene-ethylene-1-butene random copolymer (B-4) was obtained in the same manner as in production example 2 except that the ethylene supply amount, the 1-butene supply amount and the hydrogen supply amount were adjusted so that the ethylene concentration in the composition analysis value (gas chromatography analysis) of the gas portion in the polymerization apparatus in "(4) polymerization" was 1.7mol%, the 1-butene concentration was 4.0mol% and the hydrogen concentration was 2.3 mol%.
Production example 6
A propylene-ethylene random copolymer (B-5) was obtained in the same manner as in production example 2 except that the ethylene supply amount, the 1-butene supply amount and the hydrogen supply amount were adjusted so that the ethylene concentration in the composition analysis value (gas chromatography analysis) of the gas portion in the polymerization apparatus in "(4) polymerization" was 1.3mol%, the 1-butene concentration was 0mol% and the hydrogen concentration was 3.5 mol%.
Production example 7: f-704NP ]
Trade name "Prime Polypro F-704NP" manufactured by Presman Polymer Co., ltd. For convenience, the description will be made as a manufacturing example.
The physical properties of the polymers obtained in production examples 2 to 7 are summarized in Table 2.
TABLE 2
TABLE 2
Examples of the first aspect of the invention and comparative examples thereof
Examples 1 to1
From 5 parts by mass of the propylene-based polymer (A-1) obtained in production example 1 and 95 parts by mass of the propylene-ethylene-1-butene random copolymer (B-1) obtained in production example 2, a non-stretched film having a thickness of 25 μm was produced under the following molding conditions using a non-stretched film molding machine in which a single-layer die having a width of 600mm was connected to an extruder (1) having a screw diameter of 75 mm.
Resin temperature: 248 DEG C
Cooling roll temperature: 30 DEG C
Molding speed: 150 m/min
The physical properties of the film are shown in Table 3.
Examples 1 to 2 and comparative examples 1 to 6
A stretch-free film was produced in the same manner as in example 1-1, except that the blending composition was changed as shown in table 3.
TABLE 3
TABLE 3 Table 3
Examples of the second aspect of the present invention and comparative examples thereof
Examples 2 to1
From 5 parts by mass of the propylene-based polymer (A-1) obtained in production example 1 and 95 parts by mass of the propylene-ethylene random copolymer (B-3) obtained in production example 4, a non-stretched film having a thickness of 25 μm was produced under the following molding conditions by using a non-stretched film molding machine in which a single-layer die having a width of 600mm was connected to an extruder (1) having a screw diameter of 75 mm.
Resin temperature: 248 DEG C
Cooling roll temperature: 30 DEG C
Molding speed: 150 m/min
The physical properties of the film are shown in Table 4.
Examples 2-2 to 2-5 and comparative examples 2-1 to 2-8
A stretch-free film was produced in the same manner as in example 2-1, except that the blending composition was changed as shown in table 4.
The results are summarized in Table 4.
TABLE 4
Claims (8)
1. A stretch-free film characterized by:
is formed from a propylene polymer composition (X1),
The propylene polymer composition (X1) comprises a propylene polymer (A) and a propylene-alpha-olefin copolymer (B1),
The propylene polymer (A) contains: 20 to 50% by mass of a propylene polymer (a 1) having an intrinsic viscosity [ eta ] in the range of 10 to 12dl/g measured in a tetralin solvent at 135 ℃; and 50 to 80 mass% of a propylene polymer (a 2) having an intrinsic viscosity [ eta ] in the range of 0.5 to 1.5dl/g measured in a tetralin solvent at 135 ℃, wherein the total amount of the propylene polymer (a 1) and the propylene polymer (a 2) is 100 mass%,
The propylene-alpha-olefin copolymer (B1) has a melt flow rate of 0.1 to 30g/10 min measured at 230 ℃ under a load of 2.16kg, an intrinsic viscosity [ eta ] of more than 1.5dl/g and 5.0dl/g or less measured in a tetralin solvent at 135 ℃, and contains 5.5 mol% or more of structural units derived from an alpha-olefin, wherein the alpha-olefin does not include propylene,
The content of the propylene polymer (A) is 1 to 10 parts by mass and the content of the propylene-alpha-olefin copolymer (B1) is 90 to 99 parts by mass, based on 100 parts by mass of the total of the propylene polymer (A) and the propylene-alpha-olefin copolymer (B1).
2. A stretch-free film characterized by:
formed from the propylene polymer composition (X2),
The propylene polymer composition (X2) comprises a propylene polymer (A) and a propylene-alpha-olefin copolymer (B2),
The propylene polymer (A) contains: 20 to 50% by mass of a propylene polymer (a 1) having an intrinsic viscosity [ eta ] in the range of 10 to 12dl/g measured in a tetralin solvent at 135 ℃; and 50 to 80 mass% of a propylene polymer (a 2) having an intrinsic viscosity [ eta ] in the range of 0.5 to 1.5dl/g measured in a tetralin solvent at 135 ℃, wherein the total amount of the propylene polymer (a 1) and the propylene polymer (a 2) is 100 mass%,
The propylene-alpha-olefin copolymer (B2) having a melt flow rate of 0.1 to 30g/10 min measured at 230 ℃ under a load of 2.16kg, an intrinsic viscosity [ eta ] of more than 1.5dl/g and less than 5.0dl/g measured in a tetralin solvent at 135 ℃, the propylene-alpha-olefin copolymer (B2) containing 1 mol% or more and less than 5.5 mol% of structural units derived from an alpha-olefin, wherein the alpha-olefin does not include propylene,
The content of the propylene polymer (A) is 1 to 18 parts by mass and the content of the propylene-alpha-olefin copolymer (B2) is 82 to 99 parts by mass, relative to 100 parts by mass of the total of the propylene polymer (A) and the propylene-alpha-olefin copolymer (B2).
3. The unstretched film according to claim 1 or 2, characterized in that:
The propylene polymer (A) has a Melt Flow Rate (MFR) of 0.01 to 5g/10 min as measured at 230℃under a load of 2.16 kg.
4. The unstretched film according to claim 1 or 2, characterized in that:
The ratio of the area of the high molecular weight region having a molecular weight of 150 ten thousand or more to the total area of the region surrounded by the molecular weight distribution curve as measured by Gel Permeation Chromatography (GPC) of the propylene polymer (a) is 7% or more.
5. The unstretched film according to claim 1 or 2, characterized in that:
The propylene polymer (A) has two peaks in a molecular weight distribution curve measured by GPC, and the ratio (MH/ML) of the peak molecular weight MH on the high molecular weight side to the peak molecular weight ML on the low molecular weight side is 50 or more.
6. The unstretched film according to claim 1 or 2, characterized in that:
the PP (110) surface has an axial orientation degree of 0.85 or more, as determined by wide-angle X-ray diffraction measurement.
7. A sealing film, characterized in that:
The sealing film is a laminate having a sealing film main body and a surface layer in this order,
The skin layer is the unstretched film of claim 1.
8. A multilayer sealing film, characterized in that:
the multilayer sealing film is a laminate having an outer layer, an intermediate layer, and a sealing layer in this order,
The intermediate layer is the unstretched film of claim 2.
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| Application Number | Priority Date | Filing Date | Title |
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| JP2022-001081 | 2022-01-06 | ||
| JP2022001081 | 2022-01-06 | ||
| JP2022-001080 | 2022-01-06 | ||
| PCT/JP2022/048281 WO2023132306A1 (en) | 2022-01-06 | 2022-12-27 | Non-oriented film, sealant film, and multilayered sealant film |
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| CN118451138A true CN118451138A (en) | 2024-08-06 |
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| CN202280086122.XA Pending CN118451138A (en) | 2022-01-06 | 2022-12-27 | Non-stretch film, sealing film and multilayer sealing film |
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