WO2021025142A1 - Composition de polymère à base de propylène, film non étiré et stratifié - Google Patents

Composition de polymère à base de propylène, film non étiré et stratifié Download PDF

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Publication number
WO2021025142A1
WO2021025142A1 PCT/JP2020/030325 JP2020030325W WO2021025142A1 WO 2021025142 A1 WO2021025142 A1 WO 2021025142A1 JP 2020030325 W JP2020030325 W JP 2020030325W WO 2021025142 A1 WO2021025142 A1 WO 2021025142A1
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WO
WIPO (PCT)
Prior art keywords
propylene
based polymer
molecular weight
mass
measured
Prior art date
Application number
PCT/JP2020/030325
Other languages
English (en)
Japanese (ja)
Inventor
篤太郎 木村
博貴 志水
知也 村上
Original Assignee
株式会社プライムポリマー
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 株式会社プライムポリマー filed Critical 株式会社プライムポリマー
Priority to JP2021537399A priority Critical patent/JP7308954B2/ja
Priority to CN202080055065.XA priority patent/CN114207012B/zh
Priority to KR1020227003127A priority patent/KR20220079514A/ko
Publication of WO2021025142A1 publication Critical patent/WO2021025142A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/10—Homopolymers or copolymers of propene
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/14—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers
    • B32B37/15—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers with at least one layer being manufactured and immediately laminated before reaching its stable state, e.g. in which a layer is extruded and laminated while in semi-molten state
    • B32B37/153—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers with at least one layer being manufactured and immediately laminated before reaching its stable state, e.g. in which a layer is extruded and laminated while in semi-molten state at least one layer is extruded and immediately laminated while in semi-molten state
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/10—Homopolymers or copolymers of propene
    • C08L23/12—Polypropene
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2270/00—Resin or rubber layer containing a blend of at least two different polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2439/00—Containers; Receptacles
    • B32B2439/70—Food packaging
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2439/00—Containers; Receptacles
    • B32B2439/80—Medical packaging
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2323/10—Homopolymers or copolymers of propene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2423/10—Homopolymers or copolymers of propene

Definitions

  • Examples of the propylene-based polymer (a2) include a homopolymer of propylene and a copolymer of propylene and an ⁇ -olefin having 2 to 8 carbon atoms (excluding propylene).
  • Examples of the ⁇ -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.
  • One kind or two or more kinds of ⁇ -olefins can be used.
  • the melt tension of the obtained polymer composition becomes insufficient, and the fish eye of the obtained film tends to deteriorate. If the ultimate viscosity [ ⁇ ] exceeds 1.5 dl / g, the viscosity tends to be high and the film formability tends to deteriorate.
  • this high molecular weight component is a high molecular weight component having an ultimate viscosity [ ⁇ ] of 10 to 12 dl / g. Therefore, when the ratio of the high molecular weight component is in the above range, the melt tension of the polymer composition becomes more excellent.
  • Additives may be added to the obtained propylene-based polymer (A), if necessary.
  • metallic magnesium, alcohol, and a halogen and / or a halogen-containing compound for example, metallic magnesium, alcohol, and a halogen and / or a halogen-containing compound are refluxed (eg, about).
  • a method of reacting at 79 ° C.) until no hydrogen gas generation is observed (usually 20 to 30 hours) can be mentioned.
  • the reaction is preferably carried out in an atmosphere of an inert gas such as nitrogen gas or argon gas.
  • the solid catalyst component is usually obtained by contacting the carrier with at least a titanium compound.
  • the contact with the titanium compound may be divided into a plurality of times.
  • the titanium compound include a titanium compound represented by the general formula (III).
  • the molecular weight distribution (Mw / Mn) of the propylene-based polymer (B) measured by gel permeation chromatography (GPC) is preferably 4.0 or more, more preferably 4.0 to 6.5. More preferably, it is 4.0 to 6.0.
  • the structure of the propylene-based polymer (B) is not particularly limited, and examples thereof include a propylene homopolymer and a copolymer of propylene and ⁇ -olefin (excluding propylene).
  • examples of the copolymer include a propylene / ⁇ -olefin random copolymer and a block-type propylene copolymer (a propylene homopolymer or a propylene / ⁇ -olefin random copolymer and an amorphous or low crystalline copolymer. (Mixed with propylene / ⁇ -olefin random copolymer), random block polypropylene and the like.
  • the content ratio of the structural unit derived from propylene is usually 90 to 99.9% by mass, preferably 92 to 99.5% by mass, and more preferably 94 to 99% by mass.
  • the content of the structural unit derived from ⁇ -olefin (excluding propylene) is usually 0.1 to 10% by mass, preferably 0.5 to 8% by mass, and more preferably 1 to 6%. It is mass%.
  • the content ratio can be measured by 13 C-NMR.
  • the propylene-based polymer composition contains a weather-resistant stabilizer, a heat-resistant stabilizer, an antistatic agent, a slip agent, an antiblocking agent, an antifogging agent, a nucleating agent, and a decomposition agent, as long as the object of the present invention is not impaired.
  • Pigments, dyes, plasticizers, hydrochloric acid absorbers, antioxidants, cross-linking agents, cross-linking accelerators, reinforcing agents, fillers, softeners, processing aids, activators, hygroscopic agents, adhesives, flame retardants, mold release agents Etc. can be contained.
  • One kind or two or more kinds of additives can be used.
  • the content of the propylene-based polymer (A) is less than 2 parts by mass, the rigidity, heat resistance and gas barrier property tend to be insufficient. If the content of the propylene-based polymer (A) exceeds 30 parts by mass, the transparency of the film deteriorates and the appearance tends to be poor.
  • the propylene-based weight containing the propylene-based polymer (a1) and the propylene-based polymer (a2) obtained by the multi-stage polymerization by the batch method is obtained from the viewpoint of rigidity and heat resistance and the reduction of fish eyes. It is preferable to prepare a propylene-based polymer composition by mixing the coalescence (A) and the propylene-based polymer (B).
  • the propylene-based polymer (a1) having a high molecular weight 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. Therefore, it is presumed that during film molding of the propylene-based polymer composition, the degree of orientation of the molding in the MD direction increases, and the orientation causes the propylene-based polymer to become highly crystallized. Therefore, rigidity, heat resistance, and gas barrier properties It is considered that an excellent film was obtained.
  • the melt flow rate (MFR) of the propylene-based polymer composition measured at 230 ° C. and a load of 2.16 kg is usually 1 to 20 g / 10 minutes, preferably 2 to 15 g / 10 minutes, more preferably 3 ⁇ 10 g / 10 minutes.
  • Examples of the film manufacturing method include an extrusion molding method such as a T-die method and an inflation method, a compression molding method, a calender molding method, and a casting method.
  • Film molding can be performed, for example, as follows.
  • the above components constituting the propylene-based polymer composition may be directly charged into a hopper or the like of a film molding machine, or the above components may be mixed in advance using a ribbon blender, a Bambari mixer, a Henschel mixer, a super mixer or the like. Alternatively, it may be melt-kneaded using a kneader such as a single-screw or twin-screw extruder or a roll to obtain a propylene-based polymer composition, and then film-molded.
  • a kneader such as a single-screw or twin-screw extruder or a roll to obtain a propylene-based polymer composition, and then film-molded.
  • Examples of the cooling method for the molten film include a roll and air cooling cooling method using an air knife method or an air chamber method, a narrow pressure cooling method using a polishing roll method, a swing roll method, a belt casting method, and a water cooling method. Cooling method can be mentioned.
  • Measurement condition Measurement environment: Nitrogen gas atmosphere Sample amount: 5 mg Sample shape: Press film (molded at 230 ° C, thickness 400 ⁇ m) Sample pan: Aluminum sample pan with a flat bottom First step: Raise the temperature from 30 ° C to 200 ° C at 320 ° C / min. Hold for 10 minutes. Second step: The temperature is lowered to 30 ° C. at 20 ° C./min. Third step: Hold at 30 ° C. for 10 minutes. Fourth step: The temperature is raised to 200 ° C. at 20 ° C./min.
  • the ultimate viscosity [ ⁇ ] of the propylene-based polymer (ca1-1) polymerized under the same conditions as in the first stage was 9 dl / g.
  • hydrogen was continuously added so that the pressure became constant at 3.3 MPaG, and polymerization was carried out for 95 minutes.
  • the vent valve was opened, and unreacted propylene was purged via an integrated flow meter (completion of polymerization in the second stage).

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Laminated Bodies (AREA)

Abstract

Le problème décrit par la présente invention est de fournir une composition de polymère à base de propylène permettant de former un film non étiré ayant une rigidité supérieure par comparaison à des films non étirés classiques. La solution selon l'invention porte sur une composition de polymère à base de propylène qui est caractérisée en ce qu'elle contient un polymère à base de propylène spécifique (A) et un polymère à base de propylène (B) ayant un point de fusion s'inscrivant dans la plage de 120 à 170 °C et une viscosité limite [η] supérieure à 1,5 dl/g mais inférieure ou égale à 5,0 dl/g mesurée dans un solvant Tétraline à 135 °C, par rapport au total de 100 parties en masse du polymère à base de propylène (A) et du polymère à base de propylène (B), la quantité contenue du polymère à base de propylène (A) étant de 2 à 30 parties en masse et la quantité contenue du polymère à base de propylène (B) étant de 70 à 98 parties en masse.
PCT/JP2020/030325 2019-08-08 2020-08-07 Composition de polymère à base de propylène, film non étiré et stratifié WO2021025142A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
JP2021537399A JP7308954B2 (ja) 2019-08-08 2020-08-07 プロピレン系重合体組成物、無延伸フィルムおよび積層体
CN202080055065.XA CN114207012B (zh) 2019-08-08 2020-08-07 丙烯系聚合物组合物、无拉伸膜和叠层体
KR1020227003127A KR20220079514A (ko) 2019-08-08 2020-08-07 프로필렌계 중합체 조성물, 무연신 필름 및 적층체

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2019146846 2019-08-08
JP2019-146846 2019-08-08

Publications (1)

Publication Number Publication Date
WO2021025142A1 true WO2021025142A1 (fr) 2021-02-11

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Country Link
JP (1) JP7308954B2 (fr)
KR (1) KR20220079514A (fr)
CN (1) CN114207012B (fr)
WO (1) WO2021025142A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2023090201A1 (fr) * 2021-11-17 2023-05-25 株式会社プライムポリマー Film non étiré comprenant une composition polymère de propylène
WO2023132306A1 (fr) * 2022-01-06 2023-07-13 株式会社プライムポリマー Film non orienté, film d'étanchéité et film d'étanchéité multicouche

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH10168251A (ja) * 1996-12-12 1998-06-23 Grand Polymer:Kk プロピレン系重合体組成物およびその成形品
JP2000159949A (ja) * 1998-11-27 2000-06-13 Grand Polymer:Kk ポリプロピレン樹脂組成物およびその製造方法
JP2006143975A (ja) * 2004-11-25 2006-06-08 Prime Polymer:Kk ポリプロピレン及び該ポリプロピレンの電気材料への応用

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WO1999007752A1 (fr) 1997-08-05 1999-02-18 Grand Polymer Co., Ltd. Composition de resine de polypropylene et utilisation de celle-ci
JP3721936B2 (ja) 2000-04-21 2005-11-30 住友化学株式会社 ポリプロピレン系樹脂組成物及びそれからなる成形体
JP2002265712A (ja) 2001-03-14 2002-09-18 Sumitomo Chem Co Ltd 易引裂きフィルム
CA2559429A1 (fr) 2004-03-31 2005-10-20 Prime Polymer Co., Ltd. Polymere de propylene multi-phases, processus de production de celui-ci et composition de resine de propylene
JP4815755B2 (ja) 2004-05-06 2011-11-16 住友化学株式会社 フィルム成形用樹脂組成物およびそれからなるフィルム
JP5010802B2 (ja) 2004-08-09 2012-08-29 日本ポリプロ株式会社 高剛性ポリプロピレン系組成物及び製造法
CN101319070B (zh) * 2007-06-06 2012-10-03 住友化学株式会社 聚丙烯树脂组合物及其拉伸膜
JP5124517B2 (ja) * 2008-05-16 2013-01-23 日本ポリプロ株式会社 ポリプロピレン系ブロー成形体
JP2011057852A (ja) * 2009-09-10 2011-03-24 Sumitomo Chemical Co Ltd ポリプロピレン系樹脂組成物およびそのフィルム
JP5742113B2 (ja) 2010-05-12 2015-07-01 住友化学株式会社 ポリプロピレン未延伸フィルム
JP2017165027A (ja) * 2016-03-17 2017-09-21 出光興産株式会社 一軸延伸物

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH10168251A (ja) * 1996-12-12 1998-06-23 Grand Polymer:Kk プロピレン系重合体組成物およびその成形品
JP2000159949A (ja) * 1998-11-27 2000-06-13 Grand Polymer:Kk ポリプロピレン樹脂組成物およびその製造方法
JP2006143975A (ja) * 2004-11-25 2006-06-08 Prime Polymer:Kk ポリプロピレン及び該ポリプロピレンの電気材料への応用

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2023090201A1 (fr) * 2021-11-17 2023-05-25 株式会社プライムポリマー Film non étiré comprenant une composition polymère de propylène
WO2023132306A1 (fr) * 2022-01-06 2023-07-13 株式会社プライムポリマー Film non orienté, film d'étanchéité et film d'étanchéité multicouche
KR20240090923A (ko) 2022-01-06 2024-06-21 가부시키가이샤 프라임 폴리머 무연신 필름, 실런트 필름 및 다층 실런트 필름

Also Published As

Publication number Publication date
JP7308954B2 (ja) 2023-07-14
JPWO2021025142A1 (fr) 2021-02-11
CN114207012A (zh) 2022-03-18
KR20220079514A (ko) 2022-06-13
CN114207012B (zh) 2023-09-15

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