KR20000018313A - Polypropylene film and producing of method - Google Patents
Polypropylene film and producing of method Download PDFInfo
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- KR20000018313A KR20000018313A KR1019980035850A KR19980035850A KR20000018313A KR 20000018313 A KR20000018313 A KR 20000018313A KR 1019980035850 A KR1019980035850 A KR 1019980035850A KR 19980035850 A KR19980035850 A KR 19980035850A KR 20000018313 A KR20000018313 A KR 20000018313A
- Authority
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- South Korea
- Prior art keywords
- polypropylene film
- vinyl acetate
- film
- weight
- resin
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- -1 Polypropylene Polymers 0.000 title claims abstract description 45
- 239000004743 Polypropylene Substances 0.000 title claims abstract description 37
- 229920001155 polypropylene Polymers 0.000 title claims abstract description 37
- 238000000034 method Methods 0.000 title abstract description 13
- 229920005989 resin Polymers 0.000 claims abstract description 30
- 239000011347 resin Substances 0.000 claims abstract description 30
- 239000005038 ethylene vinyl acetate Substances 0.000 claims abstract description 23
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 claims abstract description 22
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims abstract description 15
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 claims abstract description 14
- 238000002844 melting Methods 0.000 claims abstract description 12
- 230000008018 melting Effects 0.000 claims abstract description 12
- 239000010410 layer Substances 0.000 claims description 33
- 239000000155 melt Substances 0.000 claims description 12
- 238000001125 extrusion Methods 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 7
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 4
- JHWNWJKBPDFINM-UHFFFAOYSA-N Laurolactam Chemical compound O=C1CCCCCCCCCCCN1 JHWNWJKBPDFINM-UHFFFAOYSA-N 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 3
- 239000002344 surface layer Substances 0.000 claims description 3
- IMSODMZESSGVBE-UHFFFAOYSA-N 2-Oxazoline Chemical compound C1CN=CO1 IMSODMZESSGVBE-UHFFFAOYSA-N 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- 125000001033 ether group Chemical group 0.000 claims description 2
- 150000003951 lactams Chemical group 0.000 claims 1
- 238000002156 mixing Methods 0.000 abstract description 3
- 239000007789 gas Substances 0.000 description 17
- DQXBYHZEEUGOBF-UHFFFAOYSA-N but-3-enoic acid;ethene Chemical compound C=C.OC(=O)CC=C DQXBYHZEEUGOBF-UHFFFAOYSA-N 0.000 description 11
- 238000004898 kneading Methods 0.000 description 10
- 230000000704 physical effect Effects 0.000 description 8
- 238000001816 cooling Methods 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 229920001577 copolymer Polymers 0.000 description 4
- 230000009477 glass transition Effects 0.000 description 4
- 238000009998 heat setting Methods 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 239000012792 core layer Substances 0.000 description 3
- 229920001519 homopolymer Polymers 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- 238000004806 packaging method and process Methods 0.000 description 3
- 229920005604 random copolymer Polymers 0.000 description 3
- 238000007711 solidification Methods 0.000 description 3
- 230000008023 solidification Effects 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 229920006020 amorphous polyamide Polymers 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 210000002615 epidermis Anatomy 0.000 description 2
- 239000006260 foam Substances 0.000 description 2
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 229920002689 polyvinyl acetate Polymers 0.000 description 2
- 239000011118 polyvinyl acetate Substances 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 239000012963 UV stabilizer Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 229920006026 co-polymeric resin Polymers 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 229920006379 extruded polypropylene Polymers 0.000 description 1
- 239000005357 flat glass Substances 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 239000012943 hotmelt Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 230000009965 odorless effect Effects 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000012785 packaging film Substances 0.000 description 1
- 229920006280 packaging film Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920005672 polyolefin resin Polymers 0.000 description 1
- 229920005633 polypropylene homopolymer resin Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 239000003507 refrigerant Substances 0.000 description 1
- 238000007665 sagging Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 210000003491 skin Anatomy 0.000 description 1
- 239000012748 slip agent Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000005486 sulfidation Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/16—Articles comprising two or more components, e.g. co-extruded layers
- B29C48/18—Articles comprising two or more components, e.g. co-extruded layers the components being layers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/022—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the choice of material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/92—Measuring, controlling or regulating
-
- 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
- B32B27/08—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 of synthetic resin
-
- 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
- B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
- B32B27/306—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising vinyl acetate or vinyl alcohol (co)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
- 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
- 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
- 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
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/08—Copolymers of ethene
- C08L23/0846—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
- C08L23/0853—Vinylacetate
-
- 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
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2023/00—Use of polyalkenes or derivatives thereof as moulding material
- B29K2023/04—Polymers of ethylene
- B29K2023/08—Copolymers of ethylene
- B29K2023/083—EVA, i.e. ethylene vinyl acetate copolymer
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2023/00—Use of polyalkenes or derivatives thereof as moulding material
- B29K2023/10—Polymers of propylene
- B29K2023/12—PP, i.e. polypropylene
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Laminated Bodies (AREA)
- Extrusion Moulding Of Plastics Or The Like (AREA)
Abstract
Description
본 발명은 3층 공압출 폴리프로필렌 필름에 관한 것으로서, 보다 상세하게는 기체 차폐성이 우수하고 적어도 1축배향된 3층 공압출 폴리프로필렌 필름에 관한 것이다.The present invention relates to a three-layer coextruded polypropylene film, and more particularly to a three-layer coextruded polypropylene film excellent in gas shielding properties and at least uniaxially oriented.
폴리프로필렌과 폴리에틸렌 등의 폴리올레핀은 폴리에틸렌테레프탈레이트 등과 함께 가장 널리 사용되는 필름 소재이다. 이중, 폴리프로필렌은 밀도가 0.90 ~ 0.92g/㎤로서 범용 플라스틱중 가장 가볍고 투명하며, 내열강도, 전기절연성, 내약품성, 내굴곡성이 뛰어날 뿐만 아니라 인체에 무해하고 환경친화적인 소재로 알려져 있다.Polyolefins such as polypropylene and polyethylene are the most widely used film materials with polyethylene terephthalate and the like. Among them, polypropylene has a density of 0.90 to 0.92 g / cm 3, which is the lightest and most transparent plastic among general purpose plastics. It is known to be excellent in heat resistance, electrical insulation, chemical resistance, and bending resistance, and also harmless to the human body and environmentally friendly.
그러나, 내한 충격강도가 약하다는 결점도 지니고 있어 최근에는 이러한 결점을 보완하기 위하여 프로필렌 단량체에 에틸렌 및 기타 올레핀계의 공단량체를 첨가하여 공중합시키고 있는데, 이러한 공중합체의 유무 및 구조에 따라 호모 폴리머, 랜덤 코폴리머 및 임팩트 코폴리머로 대별된다.However, it also has the drawback that the cold shock strength is weak, and recently, in order to compensate for this drawback, copolymerization of ethylene and other olefin-based comonomers is added to propylene monomer, and homopolymers, And are classified into random copolymers and impact copolymers.
각각의 특성을 살펴보면, 호모 폴리머는 결정성 및 용융점이 높고 강성이 우수하며, 랜덤 코폴리머는 투명도는 좋으나 결정성과 용융점이 낮고 강성이 떨어진다는 단점이 있으며, 임팩트 코폴리머는 특히 내충격성이 뛰어나다는 장점을 지니고 있다.The characteristics of the homopolymers are high crystallinity, high melting point, and high rigidity, and random copolymers have good transparency, low crystallinity, low melting point, and low rigidity, and impact copolymers are particularly excellent in impact resistance. It has advantages.
한편, 폴리프로필렌 필름은 가격이 저렴하고, 인쇄 증착 또는 합지 등을 통하여 다양하게 가공될 수 있으며, 무색무취일 뿐 아니라 환경친화성이 우수하여 포장용으로도 널리 사용되고 있다. 그러나, 연신된 폴리프로필렌 필름은 결정화도가 낮아 기체 차폐성이 낮으므로 식품포장용으로 사용하는데 문제가 되고 있다. 특히 장기간 보관을 요구하는 최근의 식품시장의 동향을 고려할 때 이러한 문제는 반드시 해결되어야 할 과제이다.On the other hand, polypropylene film is inexpensive, and can be processed in various ways through printing deposition or lamination, it is not only colorless and odorless, but also has excellent environmental friendliness and is widely used for packaging. However, the stretched polypropylene film has a low crystallinity and a low gas barrier property, which causes a problem in using it for food packaging. This problem must be solved, especially when considering the recent trends in the food market that require long-term storage.
이러한 과제를 해결하기 위하여 폴리프로필렌 필름에 기체차폐성을 부여하는 연구가 진행되어 왔다. 일본 공개특허공보 소 53-71182, 소 55-91520호에서는 무결정 폴리아미드 수지를 혼합 사용하였고, 소 48-79078, 소 49-23703, 평 03-140457호 등에서는 무기 첨가제(filler)를 사용하였으며, 소 46-50721, 소 55-12338에서는 폴리비닐아세테이트 공중합체를 단독으로 사용하여 차폐성을 개선시켰다. 또한, 소 58-213037, 소 60-90734, 소 61-225049 에서는 폴리터벤 수지를 첨가하여 물성을 개선하였다.In order to solve this problem, studies have been conducted to impart gas shielding properties to polypropylene films. In Japanese Patent Application Laid-Open Nos. 53-71182 and 55-91520, amorphous polyamide resins were mixed, and inorganic fillers were used in So 48-79078, So 49-23703, and Pyeong 03-140457. , 46-50721, 55-12338, polyvinylacetate copolymer was used alone to improve the shielding. In addition, in 58-213037, 60-90734, and 61-225049, polyterbene resin was added to improve physical properties.
그러나, 상기 무정형 폴리아미드 수지를 혼용하는 경우에는 투명도를 해치고 압출시 미용융 현상이 발생하고, 무기 첨가제를 적용하는 경우에는 일정수준 까지는 기체 차폐성을 개선할 수는 있으나 한계가 있어 첨가량이 지나치게 많은 경우 필름이 경화되어 깨지기 쉬우며, 폴리터벤 수지를 사용하는 경우에는 필름이 지나치게 유연해져 후가공이 어려워진다는 문제점을 각각 안고 있다. 따라서, 폴리비닐아세테이트 공중합체를 사용하는 경우가 그나마 가장 좋은 결과를 얻을 수 있다고 할 수 있다.However, when the amorphous polyamide resin is mixed, unmelting occurs during extrusion, and when the inorganic additive is applied, gas shielding can be improved up to a certain level, but there is a limit. Films are hardened and fragile, and when a polyterbene resin is used, the films are too flexible to have post-processing problems. Therefore, it can be said that the best results can be obtained when the polyvinylacetate copolymer is used.
그러나, 이 경우에도 폴리프로필렌 수지와의 혼련성이 나쁘고 과량 사용하는 경우 연신 공정시 가열롤에 부착될 수 있다는 문제점이 있다.However, even in this case, there is a problem that the kneading with the polypropylene resin is bad and may be attached to the heating roll during the stretching process in case of excessive use.
본 발명이 이루고자하는 기술적 과제는, 기체 차폐성이 뛰어나면서도 상기 문제점이 없이 폴리프로필렌계 수지와의 혼련성이 우수한 3층 공압출 폴리프로필렌 필름을 제공하는데 있다.An object of the present invention is to provide a three-layer coextruded polypropylene film having excellent gas shielding properties and excellent kneading with a polypropylene resin without the above problems.
도 1은 본 발명의 일실시예에 따른 폴리프로필렌 필름의 단면도이다.1 is a cross-sectional view of a polypropylene film according to an embodiment of the present invention.
*도면 부호 ** Drawing code *
1 .................................... 중심층1 .....................
2 .................................... 표피층2 ..................... The epidermal layer
상기 기술적 과제를 달성하기 위하여 본 발명에서는, 표면층과 중심층이 동시에 공압출되어 형성되는 3층 공압출 폴리프로필렌 필름에 있어서, 상기 중심층이 용융지수가 1 ~ 20 g/10분이고 용융온도가 140 ~ 180℃인 프로필렌계 수지를 주성분으로 하고 비닐아세테이트를 5 내지 20몰% 포함하는 에틸렌비닐아세테이트 공중합체 및 중량평균분자량이 2,000 ~ 30,000인 메타크릴레이트계 수지를 포함하는 것을 특징으로 하는 3층 공압출 폴리프로필렌 필름을 제공한다.In order to achieve the above technical problem, in the present invention, in the three-layer coextrusion polypropylene film formed by co-extrusion of the surface layer and the center layer at the same time, the center layer has a melt index of 1 to 20 g / 10 minutes and a melting temperature of 140 A three-layer pore comprising a ethylene vinyl acetate copolymer containing propylene resin at a temperature of ˜180 ° C. as a main component and containing 5 to 20 mol% of vinyl acetate, and a methacrylate resin having a weight average molecular weight of 2,000 to 30,000. An extruded polypropylene film is provided.
상기 폴리프로필렌 필름의 두께와 중심층의 두께비는 1:0.5 내지 1:0.9인 것이 바람직하다.The thickness ratio of the thickness of the polypropylene film and the center layer is preferably 1: 0.5 to 1: 0.9.
상기 에틸렌비닐아세테이트 공중합체와 메타크릴레이트계 수지는 중심층의 중량에 대하여 각각 1 내지 10 중량%로 포함되는 것이 바람직하다.The ethylene vinyl acetate copolymer and methacrylate-based resin is preferably contained in 1 to 10% by weight based on the weight of the central layer.
상기 메타크릴레티트계 수지는 하기의 화학구조를 갖는 수지로서 구조중의 R은 크리시딜 에테르(clicydyl ether), 라우로락탐(laurolactam), 카파락탐(capalactam) 또는 옥사솔린(oxasolin)인 것이 바람직하다.The methacrylate resin is a resin having the following chemical structure, wherein R in the structure is preferably glycidyl ether, laurolactam, capalactam or oxasolin. .
구조식constitutional formula
이하, 본 발명에 따른 3층 공압출 폴리프로필렌 필름 및 그 구체적인 제조방법을 상세히 설명하기로 한다.Hereinafter, the three-layer coextruded polypropylene film and its specific manufacturing method according to the present invention will be described in detail.
본 발명의 표피층 및 중심층에 사용되는 프로필렌계 수지는, 호모폴리머, 랜덤 코폴리머 또는 임팩트 코폴리머중 어느 것을 사용하여도 무방하고 사용 목적에 따라 혼합하여 사용하는 것도 가능하다. 그러나, 연신된 폴리프로필렌 필름의 물성 및 요구 수준을 만족시키기 위하여는 용융지수가 1 내지 20 g/10분이고 용융점이 140 내지 180℃인 프로필렌공중합체 수지를 사용하는 것이 바람직하다.The propylene resin used for the epidermal layer and the center layer of the present invention may be any of a homopolymer, a random copolymer or an impact copolymer, and may be mixed and used according to the purpose of use. However, in order to satisfy the physical properties and the required level of the stretched polypropylene film, it is preferable to use a propylene copolymer resin having a melt index of 1 to 20 g / 10 minutes and a melting point of 140 to 180 ° C.
본 발명에서 사용되는 에틸렌비닐아세테이트 공중합체는, 에틸렌과 비닐아세테이트를 공중합시킨 폴리머로서, 공중합체의 분자량 및 비닐아세테이트의 함량에 따라 특성이 달라진다. 즉, 분자량이 커질수록 강인성, 가소성, 내스트레스크랙성, 내충격성이 향상되며 성형성 및 표면 광택은 저하되고, 비닐아세테이트의 함량이 증가하면 밀도, 고무탄성, 유연성 및 혼련성이 향상되고 연화온도는 저하된다.The ethylene vinyl acetate copolymer used in the present invention is a polymer obtained by copolymerizing ethylene and vinyl acetate, and its properties vary depending on the molecular weight of the copolymer and the content of vinyl acetate. In other words, as the molecular weight increases, toughness, plasticity, stress crack resistance, and impact resistance are improved, and moldability and surface gloss are decreased, and as the content of vinyl acetate is increased, density, rubber elasticity, flexibility and kneading property are improved, and softening temperature. Is degraded.
통상, 비닐아세테이트의 함량이 10% 이하로 적은 에틸렌비닐아세테이트는 통상적인 폴리에틸렌과 마찬가지로 가공할 수 있고 인쇄 적성도 좋아지므로 필름, 라미네이트, 발포제 폼 또는 포장용 주머니 등으로 이용되고, 비닐아세테이트가 10 내지 20% 정도인 에틸렌비닐아세테이트는 PVC나 기타 다른 것과 혼합하여 성형성 또는 저온에서의 유연성을 향상시킬 목적으로 이용되며, 비닐아세테이트가 20 내지 30% 정도인 에틸렌비닐아세테이트는 왁스에 첨가하여 실링특성을 개선할 목적으로 사용된다.In general, ethylene vinyl acetate having a low vinyl acetate content of 10% or less can be processed like conventional polyethylene and has good printability. Therefore, ethylene vinyl acetate is used as a film, a laminate, a foam foam or a packaging bag, and vinyl acetate is 10 to 20. Ethylene vinyl acetate, which is about%, is used for mixing with PVC or other materials to improve moldability or flexibility at low temperatures. Ethylene vinyl acetate, which has about 20 to 30% of vinyl acetate, is added to wax to improve sealing properties. Used for the purpose.
본 발명의 에틸렌비닐아세테이트는, 바람직하기로는 비닐아세테이트의 함량이 5 내지 20몰% 인데, 비닐아세테이트의 함량이 5몰% 미만이면 본 발명에서 목적하는 효과를 얻을 수 없으며, 20몰%를 초과하는 경우에는 폴리프로필렌 수지와의 혼련성이 불량하여 필름의 물성이 떨어진다.Ethylene vinyl acetate of the present invention, preferably, the content of vinyl acetate is 5 to 20 mol%, if the content of vinyl acetate is less than 5 mol% can not achieve the desired effect in the present invention, exceeding 20 mol% In this case, the kneading with the polypropylene resin is poor, and the physical properties of the film are inferior.
상기 범위의 비닐아세테이트를 함유하는 에틸렌비닐아세테이트의 첨가량은 본 발명의 폴리프로필렌 중심층 혼합물에 대하여 1 내지 10중량%인 것이 바람직하다. 첨가량이 1중량% 미만이면 본 발명의 목적을 달성하기 위한 기체 차폐성이 부족하며 10중량부를 초과하면 필름의 늘어짐 현상이 발생하여 치수안정성을 해치게 되고 강도와 같은 기계적 특성이 떨어진다.It is preferable that the addition amount of ethylene vinyl acetate containing the vinyl acetate of the said range is 1 to 10 weight% with respect to the polypropylene core layer mixture of this invention. If the amount is less than 1% by weight, the gas shielding property is insufficient to achieve the object of the present invention, and if it exceeds 10 parts by weight, the film sagging occurs, thereby impairing the dimensional stability and the mechanical properties such as strength is inferior.
상기한 바와 같이, 폴리프로필렌의 기체 차폐성을 개선시키기 위해서는 에틸렌비닐아세테이트 공중합체가 가장 바람직하다. 그러나, 에틸렌비닐아세테이트는 단독사용되는 경우 폴리프로필렌 수지와의 혼련성이 불량하고 특히 과량 사용하는 경우 이런 현상이 더욱 현저해지는 단점이 있다. 따라서 이러한 문제점을 개선하기 위해 하기의 메타크릴레이트계 수지를 혼합사용한다.As mentioned above, in order to improve the gas shielding property of polypropylene, ethylene vinyl acetate copolymer is most preferable. However, ethylene vinyl acetate has a disadvantage in that kneading with polypropylene resin is poor when used alone, and this phenomenon becomes more remarkable especially when used in excess. Therefore, in order to improve this problem, the following methacrylate-based resin is mixed and used.
본 발명에서 사용되는 메타크릴레이트계 수지는 하기의 화학구조를 갖는다.The methacrylate resin used in the present invention has the following chemical structure.
구조식constitutional formula
여기서, R은 탄소원자 1 내지 3의 에테르, 락탐 화합물 또는 옥사졸 화합물로서, 바람직하기로는 크리시딜 에테르, 라우로락탐, 카파락탐 또는 옥사졸린이다. 이러한 화합물들은 에틸렌비닐아세테이트와의 반응이 용이하여 표면 수지에 하이드록시기를 형성함으로써 라디칼 말단기를 가지는 폴리올레핀계 수지와의 상용성을 개선시켜 주는 역할을 한다.Wherein R is an ether, lactam compound or oxazole compound of 1 to 3 carbon atoms, preferably chrycidyl ether, laurolactam, carparactam or oxazoline. These compounds facilitate the reaction with ethylene vinyl acetate to form a hydroxyl group on the surface resin serves to improve the compatibility with the polyolefin resin having a radical end group.
메타크릴레이트의 첨가량은 폴리프로필렌 필름의 중심층 혼합물에 대하여 1 내지 10중량%인 것이 바람직하다. 첨가량이 1 중량% 미만이면 목적하는 효과를 기대할 수 없으며 10중량%를 초과하면 에틸렌비닐아세테이트와 폴리프로필렌 수지와의 혼련성이 오히려 떨어져 수지간의 뭉침 현상이 발생하기 때문이다.It is preferable that the addition amount of methacrylate is 1 to 10 weight% with respect to the center layer mixture of a polypropylene film. If the added amount is less than 1% by weight, the desired effect cannot be expected. If the amount is more than 10% by weight, the kneading property between ethylene vinyl acetate and polypropylene resin is rather poor, and agglomeration between resins occurs.
본 발명의 폴리프로필렌 필름의 중심층은, 프로필렌계 수지, 에틸렌비닐아세테이트 공중합체 및 메타크릴레이트외에도, 필름의 물성을 해치지 않는 범위내에서 예컨대 산화방지제, 대전방지제, 슬립제 및 UV 안정제 등 공지의 첨가제를 포함할 수 있다.In addition to propylene resin, ethylene vinyl acetate copolymer and methacrylate, the center layer of the polypropylene film of the present invention is known in the range of not impairing the physical properties of the film, for example, an antioxidant, an antistatic agent, a slip agent and a UV stabilizer. It may include an additive.
폴리프로필렌 필름의 두께와 중심층의 두께비는 1:0.5 내지 1:0.9인 것이 바람직하다. 중심층의 두께비가 0.5보다 낮으면 필름의 기체 차폐성이 떨어지므로 에틸렌비닐아세테이트 공중합체의 농도를 높여야 하고, 이 경우 필름의 물성이 떨어지게 된다. 한편, 중심층의 두께비가 0.9 보다 크면 필름을 연신할 때 파단이 발생하고 가열롤의 표면에 필름이 부착하는 문제가 발생한다.It is preferable that the thickness ratio of the thickness of a polypropylene film and a center layer is 1: 0.5-1: 0.9. If the thickness ratio of the center layer is lower than 0.5, the gas shielding property of the film is lowered, so that the concentration of the ethylene vinyl acetate copolymer should be increased, in which case the physical properties of the film are inferior. On the other hand, when the thickness ratio of the center layer is greater than 0.9, breakage occurs when the film is stretched and a problem occurs that the film adheres to the surface of the heating roll.
본 발명의 3층 공압출 폴림프로필렌 필름은 용융, 압출, 성형, 연신배향의 단계별 공정을 연속으로 거쳐 제조된다.The three-layer coextruded polypropylene film of the present invention is produced through a continuous step-by-step process of melting, extrusion, molding, stretching orientation.
먼저, 프로필렌계 수지, 에틸렌비닐아세테이트 및 메타크릴레이트로 이루어진 상기 중심층 혼합물을 잘 혼련시킨 다음, 압출하여 용융쉬트(sheet)를 만든다.First, the mixture of the core layer consisting of propylene resin, ethylene vinyl acetate and methacrylate is kneaded well, and then extruded to form a melt sheet.
상기 압출성형에 있어서, 상기 혼합물의 가열용융은 통상적으로는 압출성형기를 이용하지만, 경우에 따라서 수지를 가열용융하지 않고 연화시킨 상태로 성형을 실시해도 무방하다. 여기에 사용되는 압출성형기는 1축 압출성형기, 2축 동방향 또는 이방향 압출성형기 어느 것이나 가능하나, 물성의 균일성을 위해 혼련성이 우수한 1축 직렬 랜덤형 압출성형기를 사용하는 것이 바람직하다. 이러한 압출성형기에서 상기 혼합물을 용융ㆍ혼련하여 얻은 용융물을 다이를 통하여 압출시키면 용융쉬트가 얻어진다. 사용되는 다이로는 티다이, 원고리대 등이 있다.In the above extrusion molding, the hot melt of the mixture is usually an extrusion molding machine, but in some cases, the resin may be molded in a softened state without heating the melt. The extruder used herein may be a single screw extruder, a biaxial coaxial or two-way extruder, but it is preferable to use a single screw extruder having a high kneading property for uniformity of physical properties. In such an extruder, a melt sheet obtained by melting and kneading the mixture is extruded through a die to obtain a melt sheet. Examples of dies used are T-dies and circular rings.
본 발명의 바람직한 실시예에 따르면, 상기 압출기내에 필터를 구비할 수 있다. 이는 용융물을 일정한 크기의 메시를 갖는 필터를 거치게 함으로써 혼련효과 및 이물질 제거효과를 얻기 위해서이다. 이와 같은 용도로 사용되는 필터는 100메시 (mesh)이상이면 가능하나 바람직하기로는 400메시 이상이다. 필터는 내압성이나 강도를 고려하여 적합한 것을 선택하는 것이 좋은데, 평판형, 원통형 등 어느 것이나 사용가능하다.According to a preferred embodiment of the present invention, a filter may be provided in the extruder. This is to obtain a kneading effect and foreign matter removal effect by passing the melt through a filter having a constant size mesh. The filter used for this purpose may be 100 mesh or more, but preferably 400 mesh or more. It is preferable to select a suitable filter in consideration of pressure resistance and strength, and any one of flat type and cylindrical type can be used.
또한, 압출온도는 경우에 따라 달리 선택될 수 있는데, 220 ~ 280℃의 온도범위로 선택하는 것이 바람직하다. 220℃ 보다 낮으면 압출이 불량해지며 280℃보다 높으면 분해가 현저해져 황화현상이 발생하고 압출기내에서 열화, 발포등이 초래된다.In addition, the extrusion temperature may be differently selected depending on the case, it is preferable to select a temperature range of 220 ~ 280 ℃. If the temperature is lower than 220 ° C, the extrusion becomes poor. If the temperature is higher than 280 ° C, the decomposition is remarkable, resulting in sulfidation and deterioration and foaming in the extruder.
두번째 단계로서, 다이로부터 압출되는 용융쉬트를 급속냉각시킨다.As a second step, the melt sheet extruded from the die is rapidly cooled.
냉각ㆍ고화과정은 기체 또는 액체 등의 냉매를 이용하는 금속롤을 사용하여 실시하는 것이 바람직하다. 금속롤을 사용하는 경우 쉬트의 두께를 균일하게 하거나 표면특성을 개선시키는 효과를 얻을 수 있다. 냉각온도는 쉬트의 유리전이온도 범위내에서, 바람직하기로는 0 내지 30℃의 온도범위내에서 실시하며, 냉각속도는 3∼200℃/초의 범위에서 이루어지는 것이 바람직하다. 냉각온도가 0℃ 미만이면 냉각속도가 너무 빨라서 쉬트의 강성이 순간적으로 증가하여 고화도중에 용융물이 물결치므로 안정된 성형이 이루어지기 어렵다. 반면에, 냉각온도가 20℃를 초과하는 경우에는 고화된 성형물의 결정화도가 증가하여 연신적성이 저하되는 문제점이 있다.The cooling and solidification process is preferably performed using a metal roll using a refrigerant such as gas or liquid. In the case of using a metal roll, it is possible to obtain an effect of making the thickness of the sheet uniform or improving surface properties. The cooling temperature is within the glass transition temperature range of the sheet, preferably within the temperature range of 0 to 30 ° C, and the cooling rate is preferably made in the range of 3 to 200 ° C / sec. If the cooling temperature is less than 0 ℃, the cooling rate is too fast to increase the rigidity of the sheet instantaneously and the melt is rippled during the solidification is difficult to achieve a stable molding. On the other hand, when the cooling temperature exceeds 20 ℃, there is a problem that the crystallinity of the solidified molded article is increased to reduce the stretchability.
냉각고화는 비교적 배향이 적은 상태로 실시하는 것이 바람직하며, 이와 같은 조건하에서 쉬트의 밀도가 1.07g/㎤ 이하, 결정화도가 5 ~ 30% 정도가 되도록 하는 것이 바람직하다.Cooling solidification is preferably carried out in a relatively low orientation, and under such conditions, it is preferable that the sheet has a density of 1.07 g / cm 3 or less and a crystallinity of about 5 to 30%.
세 번째 단계로서, 냉각고화된 쉬트를 적어도 1축으로 동시 또는 축차 연신시키는데, 두께의 균일도를 높이기 위해서 축차연신을 하는 것이 더욱 바람직하다. 특히, 다단연신을 하면 필름의 기계적 특성을 더욱 향상시킬 수 있다.As a third step, the cold-solidified sheet is simultaneously or sequentially stretched on at least one axis, and it is more preferable to gradually stretch to increase the uniformity of the thickness. In particular, multistage stretching can further improve the mechanical properties of the film.
종방향의 연신, 즉 연속필름성형 라인방향으로의 1축연신을 하는 경우에는 쉬트의 표면을 가열하여야 한다. 연신온도는 특별히 제한되지 않으나, 쉬트의 유리전이온도 내지 냉결정화온도 범위, 즉 150 내지 180℃인 것이 바람직하다. 연신온도가 150℃ 미만이면 쉬트의 연화가 불충분하여 연신이 용이하게 이루어지지 않으며, 180℃를 초과하면 결정화가 지나치게 진행되어 균일한 기계적 물성을 얻을 수 없기 때문이다. 롤의 속도차를 이용하는 1축연신은 종연신방법중 가장 일반적으로 사용되고 있는데, 생산성이 우수하여 널리 사용되고 있다. 연신비는 특별히 제한되지 않으나, 통상적으로 2 ~ 5배가 바람직하다. 연신비가 2배 미만인 경우에는 연신효과를 얻을 수 없고 5배를 초과하면 이후에 실시하는 횡방향 연신이 어렵게 된다.In the case of longitudinal stretching, ie uniaxial stretching in the direction of a continuous film forming line, the surface of the sheet must be heated. The stretching temperature is not particularly limited, but is preferably in the range of glass transition temperature to cold crystallization temperature of the sheet, that is, 150 to 180 ° C. If the stretching temperature is less than 150 ℃ the sheet is insufficient softening is not easy to stretch, and if it exceeds 180 ℃ crystallization proceeds excessively to obtain a uniform mechanical properties. Uniaxial stretching using the speed difference between rolls is most commonly used among longitudinal stretching methods, and is widely used because of its excellent productivity. The draw ratio is not particularly limited, but is usually 2 to 5 times. If the stretching ratio is less than 2 times, the stretching effect is not obtained, and if the stretching ratio is more than 5 times, the laterally lateral stretching becomes difficult.
본 발명의 일실시예에 의하면, 종방향으로 1차 연신된 필름은 필요할 경우 횡방향, 즉 필름주행방향에 대하여 90°방향으로 연신한다. 연신방법은 당해 업계에서 통상적으로 사용되는 방법이라면 특별히 제한되지 않는다. 그 중에서도 텐터 횡연신은 가장 전형적인 연신방법인데, 구체적으로 살펴보면 주행중인 필름의 양끝을 연속적으로 주행하는 클립 등으로 고정하고 그 고정상태를 횡방향 연신공정 온도와 유사한 온도 또는 이보다 5 내지 10℃ 정도 높은 온도에서 양끝의 클립사이의 거리를 점차 넓혀감으로써 실시하는 연신방법이다. 연신온도는 쉬트의 유리전이온도보다 5℃ 높은 온도에서 융점보다 30℃ 낮은 온도범위로 유지하는 것이 적당하다. 연신온도가 상기 범위 미만이면 쉬트의 연화가 불충분하여 연신이 어렵고, 상기 범위를 초과하면 표면이 일부 용해되어 균일한 두께의 필름을 얻을 수 없게 된다.According to one embodiment of the present invention, the film primarily drawn in the longitudinal direction is stretched in the transverse direction, that is, in a 90 ° direction with respect to the film running direction, if necessary. The stretching method is not particularly limited as long as it is a method commonly used in the art. Among them, tenter lateral stretching is the most typical stretching method. Specifically, both ends of the film being driven are fixed with clips running continuously, and the fixed state is similar to the lateral stretching process temperature, or about 5 to 10 ° C. higher than this. The stretching method is performed by gradually increasing the distance between the clips at both ends in temperature. The stretching temperature is appropriately maintained at a temperature range of 5 ° C. above the sheet glass transition temperature and 30 ° C. below the melting point. If the stretching temperature is less than the above range, the sheet is insufficiently softened, and stretching is difficult. If the stretching temperature is exceeded, the surface is partially dissolved to obtain a film having a uniform thickness.
횡연신비는 특별히 제한되지는 않으나, 3 ~ 10배의 범위로 하는 것이 바람직하다. 횡연신비가 3배 미만이면 횡방향의 기계적 강도가 충분하지 않고, 10배를 초과하면 파단이 일어날 가능성이 커지기 때문이다. 연신속도는 통상적으로 1×10 ~ 1×105%/분이 바람직하다.The lateral stretch ratio is not particularly limited, but is preferably in the range of 3 to 10 times. This is because if the lateral stretch ratio is less than 3 times, the mechanical strength in the transverse direction is not sufficient, and if it exceeds 10 times, the possibility of breakage increases. The stretching speed is usually preferably 1 × 10 to 1 × 10 5 % / minute.
이와 같은 조건으로 연신하여 얻어진 필름에 대해 치수안정성, 내열성, 강도 균일성을 향상시키기 위하여 일정한 고온상태에서 열고정을 실시하는 것이 바람직하다. 열고정은 통상적으로 하는 방법이지만, 연신필름의 인장상태, 이완상태 또는 제한수축상태하에서 190 ~ 200℃에서 0.5 ~ 120초 동안 실시하는 것이 바람직하다. 또한, 이러한 열고정은 상기 범위내에서 조건을 변화시켜 2회 이상 실시할 수도 있으며, 일반공기 뿐만 아니라 아르곤가스나 질소가스 또는 이들의 혼합가스 분위기하에서 실시해도 무방하다.It is preferable to heat-set in a constant high temperature state in order to improve dimensional stability, heat resistance, and intensity uniformity with respect to the film obtained by extending | stretching on such conditions. The heat setting is a conventional method, but it is preferably carried out for 0.5 to 120 seconds at 190 ~ 200 ℃ under the tensile state, relaxed state or limited shrinkage state of the stretched film. In addition, such heat setting may be carried out two or more times by changing the conditions within the above-mentioned range, and may be carried out not only in general air but also in argon gas, nitrogen gas or a mixed gas atmosphere thereof.
열고정단계를 거치지 않으면, 특히 유리전이온도 부근에서 변형이 일어나기 쉬우며, 후가공성이나 사용성이 제한될 우려가 있다. 필름에 가장 적합한 열고정온도는 상기 분위기내를 통과하는 필름의 속도, 즉 처리시간에 따라 달라진다. 처리시간은 각종 조건에 따라 결정되나 통상적으로는 3분 이하로 하는 것이 바람직하다. 열처리시간이 길면 성형중 필름이 늘어나는 등의 변형이 나타나기 때문이다.If the heat setting step is not performed, deformation is particularly likely to occur in the vicinity of the glass transition temperature, and there is a concern that post-processability or usability may be limited. The heat setting temperature most suitable for the film depends on the speed of the film passing through the atmosphere, i.e. the treatment time. The treatment time is determined according to various conditions, but usually 3 minutes or less is preferable. If the heat treatment time is long, deformation such as stretching of the film during molding appears.
이하, 실시예 및 비교예를 통해 본 발명을 보다 상세히 설명하기로 한다. 다만, 본 발명의 범위가 하기 실시예로 한정되는 것이 아님은 물론이다.Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples. However, it is a matter of course that the scope of the present invention is not limited to the following examples.
실시예 1Example 1
용융지수가 6 g/10분이고 용융점이 160℃인 호모 폴리프로필렌 수지 96kg에, 비닐아세테이트 함량이 9몰%인 에틸렌비닐아세테이트를 4kg, 크리시딜메타크릴레이트(GMA)를 2kg 첨가하고, 길이/직경의 비가 40인 이축동방향컴파운더(ZSK 25)를 이용하여 고분자 혼련칩을 생산하여 중심층으로 하였다.To 96 kg of homopolypropylene resin having a melt index of 6 g / 10 min and a melting point of 160 ° C., 4 kg of ethylene vinyl acetate having 9 mol% of vinyl acetate and 2 kg of glycidyl methacrylate (GMA) were added. A polymer kneading chip was produced using a biaxial coaxial compounder (ZSK 25) with a ratio of 40 as the center layer.
다음, 용융지수가 10g/10분이고 용융점이 148℃인 랜덤 폴리프로필렌 수지를 표면층으로 하여 상기 중심층과 함께 세 층을 동시에 공출시켜 토출하였다. 이때 중심층과 전체 쉬트두께와의 비는 16/20으로 하였고, 컴파운더의 초기입구온도는 220℃, 최종출구온도는 279℃이며, 토출되는 혼합용융물의 온도는 260℃였다.Next, three layers were simultaneously ejected and discharged together with the center layer using a random polypropylene resin having a melt index of 10 g / 10 minutes and a melting point of 148 ° C. as a surface layer. At this time, the ratio between the center layer and the total sheet thickness was 16/20, the initial inlet temperature of the compounder was 220 ° C, the final outlet temperature was 279 ° C, and the temperature of the mixed melt discharged was 260 ° C.
이어서, 10℃의 캐스팅롤에서 급냉하여 쉬트를 만들고, 급냉된 쉬트를 이용하여 185℃의 온도에서 종방향으로 5배 일축연신하고 다시 190℃의 온도에서 횡방향으로 6배 연신하여 두께 20㎛의 필름을 제조하였다. 다음, 상기 필름을 최종적으로 200℃에서 열고정하였다.Subsequently, the sheet was formed by quenching in a casting roll at 10 ° C., uniaxially stretched 5 times in the longitudinal direction at a temperature of 185 ° C. using a quenched sheet, and stretched 6 times in the transverse direction at a temperature of 190 ° C., to a thickness of 20 μm. A film was prepared. Next, the film was finally heat set at 200 ° C.
실시예 2 ~ 5Examples 2-5
필름의 제조조건을 표 1에 나타낸 바와 같이 변화시킨 것을 제외하고는, 실시예 1과 동일한 방법으로 동일한 두께의 필름을 제조하였다.Except having changed the manufacturing conditions of a film as shown in Table 1, the film of the same thickness was produced by the same method as Example 1.
비교예 1 ~ 5Comparative Examples 1 to 5
필름의 제조조건을 표 1에 나타낸 바와 같이 변화시킨 것을 제외하고는, 실시예 1과 동일한 방법으로 동일한 두께의 필름을 제조하였다.Except having changed the manufacturing conditions of a film as shown in Table 1, the film of the same thickness was produced by the same method as Example 1.
상기 실시예 및 비교예에서 제조된 필름에 대하여 하기와 같은 방법으로 각종 성능 평가를 하였다. 그 결과가 표 1에 나타나 있다.Various performance evaluations were made of the films prepared in Examples and Comparative Examples as follows. The results are shown in Table 1.
(1) 기체차폐성(gas barrier property)(1) gas barrier property
미국 모콘(Mocon)사의 가스투과속도시험기(모델명;Oxtran Twin)를 이용하여 24시간 동안 25℃, 1기압하에서 필름의 단위 면적당(㎡) 통과되는 산소의 양(㏄)을 측정하여, 산소량이 적은 필름을 기체차폐성이 우수한 것으로 평가하였다.Mocon's gas permeation rate tester (model: Oxtran Twin) was used to measure the amount of oxygen passed per unit area (m²) of the film at 25 ° C and 1 atmosphere for 24 hours. The film was evaluated as having excellent gas shielding properties.
(2) 강도(2) strength
인스트론사의 강도측정기(UTM, 모델-4206)을 이용하여, 길이 50nm 폭 20mm 두께 20㎛의 필름을 실온, 상대습도 65%의 조건에서 200mm/㎝의 속도로 인장하여 하중-신도의 챠트를 작성함으로써 필름의 강도를 평가하였다.Using Instron's strength measuring device (UTM, Model-4206), a 50 nm long 20 mm thick 20 μm film was stretched at a rate of 200 mm / cm at room temperature and 65% relative humidity to prepare a load-elongation chart. The strength of the film was evaluated by doing this.
(3) 필름의 표면 상태(3) the surface state of the film
필름 10㎝ × 10㎝ 면적에 나타나는 반점(흐림 현상)의 비율에 따라 필름의 표면 상태를 하기와 같이 평가하였다.The surface state of the film was evaluated as follows according to the ratio of spots (cloudy phenomenon) appearing in the film 10 cm × 10 cm area.
◎ 반점이 전혀 없음.◎ No spots at all.
○ 5% 이내로 사용 가능.○ Can be used within 5%.
△ 5 내지 10%로 용도 변경 사용△ change of use to 5 to 10%
× 10%이상으로 사용 불가.X 10% or more can not be used.
하기 표 1에서 알 수 있는 바와 같이, 실시예 1의 필름의 경우, 기계적 특성 및 필름의 표면상태가 매우 양호하였으며 특히 기체 차폐성이 우수하다는 것이 입증되었다. 또한 실시예 2 내지 5의 필름의 경우에는 그 물성이 양호한 반면 비교예 1 내지 5의 필름의 경우에는 물성이 불량하였다.As can be seen in Table 1 below, for the film of Example 1, the mechanical properties and the surface state of the film were very good, and it was proved that the gas shielding property was particularly excellent. In addition, the physical properties of the films of Examples 2 to 5 were good, whereas the physical properties of the films of Comparative Examples 1 to 5 were poor.
상기한 바와 같이, 표피층과 중심층을 공압출 시켜 형성한 3층 공압출 폴리프로필렌 필름의 중심층에, 비닐아세테이트의 함량이 5 내지 20몰%인 에틸렌비닐아세테이트 공중합체 및 이들의 상용성을 증가시키기 위한 메타크릴레이트계 화합물을 혼합시켜 만든 본 발명의 폴리프로필렌 필름은, 기체차폐성이 우수할 뿐 아니라 중심층 조성물의 상호 혼련성이 우수하여, 포장용 필름을 비롯해 다양한 용도에 사용될 수 있다.As described above, the ethylene vinyl acetate copolymer having a vinyl acetate content of 5 to 20 mol% and the compatibility thereof are increased in the center layer of the three-layer coextruded polypropylene film formed by coextrusion of the skin layer and the center layer. The polypropylene film of the present invention made by mixing a methacrylate-based compound to be used is not only excellent in gas shielding properties but also excellent in intermixing of the core layer composition, and can be used in various applications including packaging films.
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