JP2003238786A - Polyester resin composition and film prepared therefrom - Google Patents
Polyester resin composition and film prepared therefromInfo
- Publication number
- JP2003238786A JP2003238786A JP2002045911A JP2002045911A JP2003238786A JP 2003238786 A JP2003238786 A JP 2003238786A JP 2002045911 A JP2002045911 A JP 2002045911A JP 2002045911 A JP2002045911 A JP 2002045911A JP 2003238786 A JP2003238786 A JP 2003238786A
- Authority
- JP
- Japan
- Prior art keywords
- polyester resin
- weight
- ethylene
- film
- polyethylene
- Prior art date
- Legal status (The legal status 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 status listed.)
- Pending
Links
- 239000004645 polyester resin Substances 0.000 title claims abstract description 79
- 229920001225 polyester resin Polymers 0.000 title claims abstract description 79
- 239000000203 mixture Substances 0.000 title claims abstract description 38
- -1 polyethylene Polymers 0.000 claims abstract description 50
- 239000004698 Polyethylene Substances 0.000 claims abstract description 33
- 229920000573 polyethylene Polymers 0.000 claims abstract description 33
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical group OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 28
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical group C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000005977 Ethylene Substances 0.000 claims abstract description 21
- 239000000155 melt Substances 0.000 claims abstract description 20
- KKEYFWRCBNTPAC-UHFFFAOYSA-N terephthalic acid group Chemical group C(C1=CC=C(C(=O)O)C=C1)(=O)O KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229920000642 polymer Polymers 0.000 claims abstract description 15
- 125000000524 functional group Chemical group 0.000 claims abstract description 13
- 238000001125 extrusion Methods 0.000 claims abstract description 12
- 150000002009 diols Chemical group 0.000 claims abstract description 9
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 6
- 125000001142 dicarboxylic acid group Chemical group 0.000 claims abstract description 6
- 125000003700 epoxy group Chemical group 0.000 claims abstract description 6
- 125000003277 amino group Chemical group 0.000 claims abstract description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 4
- 239000004615 ingredient Substances 0.000 abstract 2
- 239000004593 Epoxy Substances 0.000 abstract 1
- 125000004356 hydroxy functional group Chemical group O* 0.000 abstract 1
- 239000011342 resin composition Substances 0.000 abstract 1
- 238000000465 moulding Methods 0.000 description 35
- 238000000034 method Methods 0.000 description 25
- 229920001577 copolymer Polymers 0.000 description 18
- 238000012360 testing method Methods 0.000 description 16
- 239000003795 chemical substances by application Substances 0.000 description 9
- 229920000139 polyethylene terephthalate Polymers 0.000 description 9
- 239000005020 polyethylene terephthalate Substances 0.000 description 9
- 238000011156 evaluation Methods 0.000 description 8
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 238000002156 mixing Methods 0.000 description 7
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 6
- 238000012545 processing Methods 0.000 description 6
- 239000003607 modifier Substances 0.000 description 5
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 229920000728 polyester Polymers 0.000 description 4
- 238000004064 recycling Methods 0.000 description 4
- 238000007789 sealing Methods 0.000 description 4
- 239000004711 α-olefin Substances 0.000 description 4
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 3
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 239000012812 sealant material Substances 0.000 description 3
- 229920002725 thermoplastic elastomer Polymers 0.000 description 3
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 2
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 2
- RYPKRALMXUUNKS-UHFFFAOYSA-N 2-Hexene Natural products CCCC=CC RYPKRALMXUUNKS-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 230000001771 impaired effect Effects 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 229920001684 low density polyethylene Polymers 0.000 description 2
- 239000004702 low-density polyethylene Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000005022 packaging material Substances 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 239000013502 plastic waste Substances 0.000 description 2
- 229920013716 polyethylene resin Polymers 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 229920005672 polyolefin resin Polymers 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229920005992 thermoplastic resin Polymers 0.000 description 2
- PXGZQGDTEZPERC-UHFFFAOYSA-N 1,4-cyclohexanedicarboxylic acid Chemical compound OC(=O)C1CCC(C(O)=O)CC1 PXGZQGDTEZPERC-UHFFFAOYSA-N 0.000 description 1
- ISPYQTSUDJAMAB-UHFFFAOYSA-N 2-chlorophenol Chemical compound OC1=CC=CC=C1Cl ISPYQTSUDJAMAB-UHFFFAOYSA-N 0.000 description 1
- LLLVZDVNHNWSDS-UHFFFAOYSA-N 4-methylidene-3,5-dioxabicyclo[5.2.2]undeca-1(9),7,10-triene-2,6-dione Chemical compound C1(C2=CC=C(C(=O)OC(=C)O1)C=C2)=O LLLVZDVNHNWSDS-UHFFFAOYSA-N 0.000 description 1
- 229920001634 Copolyester Polymers 0.000 description 1
- 239000004278 EU approved seasoning Substances 0.000 description 1
- 229920000181 Ethylene propylene rubber Polymers 0.000 description 1
- 229920000219 Ethylene vinyl alcohol Polymers 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- ORLQHILJRHBSAY-UHFFFAOYSA-N [1-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1(CO)CCCCC1 ORLQHILJRHBSAY-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 235000013361 beverage Nutrition 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- 239000002981 blocking agent Substances 0.000 description 1
- GXSZVFYWAFOWJB-UHFFFAOYSA-N but-1-ene ethene styrene Chemical group C=C.C=CCC.C=C.C=CC1=CC=CC=C1 GXSZVFYWAFOWJB-UHFFFAOYSA-N 0.000 description 1
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical class C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000010101 extrusion blow moulding Methods 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000000796 flavoring agent Substances 0.000 description 1
- 235000019634 flavors Nutrition 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 235000011194 food seasoning agent Nutrition 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 229920001903 high density polyethylene Polymers 0.000 description 1
- 239000004700 high-density polyethylene Substances 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- ABMFBCRYHDZLRD-UHFFFAOYSA-N naphthalene-1,4-dicarboxylic acid Chemical compound C1=CC=C2C(C(=O)O)=CC=C(C(O)=O)C2=C1 ABMFBCRYHDZLRD-UHFFFAOYSA-N 0.000 description 1
- RXOHFPCZGPKIRD-UHFFFAOYSA-N naphthalene-2,6-dicarboxylic acid Chemical compound C1=C(C(O)=O)C=CC2=CC(C(=O)O)=CC=C21 RXOHFPCZGPKIRD-UHFFFAOYSA-N 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 description 1
- 229920006027 ternary co-polymer Polymers 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
Landscapes
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明はポリエステル樹脂と
ポリエチレン及び相溶化剤よりなるポリエステル樹脂組
成物及び該組成物から得られるフィルムに関する。さら
に詳しくは、ヒートシール性、耐引裂性、耐衝撃性など
の機械的特性に優れ、更には押出成形等の成形加工にお
ける成形性に優れるポリエステル樹脂組成物及び該ポリ
エステル樹脂組成物から得られるフィルムに関するもの
である。TECHNICAL FIELD The present invention relates to a polyester resin composition comprising a polyester resin, polyethylene and a compatibilizer, and a film obtained from the composition. More specifically, a polyester resin composition excellent in mechanical properties such as heat sealability, tear resistance, and impact resistance, and further excellent in moldability in a molding process such as extrusion molding, and a film obtained from the polyester resin composition. It is about.
【０００２】[0002]
【従来の技術】エチレングリコール単位を主体とするジ
オール単位およびテレフタル酸単位を主体とするジカル
ボン酸単位から主としてなるポリエステル樹脂（以下単
にポリエステル樹脂と称することがある）は、機械的特
性、耐熱性、剛性、ガスバリアー性、フレーバーバリア
ー性等に優れている事から、調味料、飲料類、化粧品等
の容器、或いは食品包装用フィルムの材料として広く用
いられている。その一方、ポリエステル樹脂は未延伸状
態では耐衝撃性に劣り、またそれ自身はヒートシールが
不可能な事から、ヒートシールをして形成される袋類、
或いはシーラント材には殆ど用いられていない。2. Description of the Related Art A polyester resin (hereinafter sometimes simply referred to as a polyester resin) mainly composed of a diol unit mainly composed of an ethylene glycol unit and a dicarboxylic acid unit mainly composed of a terephthalic acid unit has mechanical properties, heat resistance, Since it is excellent in rigidity, gas barrier property, flavor barrier property, etc., it is widely used as a material for containers for seasonings, beverages, cosmetics, etc., or a film for food packaging. On the other hand, polyester resin is inferior in impact resistance in the unstretched state, and since heat sealing itself is impossible, bags formed by heat sealing,
Alternatively, it is rarely used as a sealant material.
【０００３】一方で、ポリエステル樹脂は一般に溶融粘
度及び溶融張力が低いことから、押出成形、特にインフ
レーション成形、及び押出ブロー成形には適していな
い。これらの成形加工法においては、成形時、材料の溶
融張力が高いことが求められるが、大抵のポリエステル
樹脂はその加工温度において十分な溶融張力を有してい
ない。この問題を解決するために、固相重合等の手段を
用いて分子量を高めた高分子量ポリエステル樹脂、また
は分岐鎖状ポリエステル樹脂等が提示されているが、こ
れらの解決法は材料コストの上昇を招くのが一般的であ
る。On the other hand, since polyester resins generally have low melt viscosity and melt tension, they are not suitable for extrusion molding, particularly inflation molding, and extrusion blow molding. In these molding methods, it is required that the material has a high melt tension at the time of molding, but most polyester resins do not have a sufficient melt tension at the processing temperature. In order to solve this problem, a high molecular weight polyester resin whose molecular weight has been increased by means such as solid phase polymerization, or a branched polyester resin has been proposed, but these solutions increase the material cost. It is common to invite them.
【０００４】前記したポリエステル樹脂の有する問題の
うち、特に耐衝撃性及びヒートシール性を向上させるた
めに、ポリエステル樹脂に対しポリオレフィン樹脂或い
は熱可塑性エラストマー等の、耐衝撃性に優れ、またヒ
ートシールが可能な熱可塑性樹脂を改質剤としてブレン
ドする技術、更にはこれら改質剤にポリエステル樹脂と
反応性のある官能基を導入することにより変性してポリ
エステル樹脂との相溶性を高める技術、或いは第三成分
としてポリエステル樹脂と改質剤の両者に親和性のある
物質を相溶化剤として添加し、改質剤の効果を高める技
術が提示されている。これらの技術によっても、耐衝撃
性及びヒートシール性に関わる問題をある程度解消する
ことは可能である。しかしながら、これらの技術は、前
記したポリエステル樹脂の有する問題のうち、成形性、
とりわけ押出成形における成形性が不良であるという問
題を解消するという点では十分とは言い難い。Among the above-mentioned problems of the polyester resin, in order to improve impact resistance and heat sealability in particular, polyester resin is superior in impact resistance such as polyolefin resin or thermoplastic elastomer and heat sealable. A technique of blending possible thermoplastic resins as a modifier, further a technique of introducing functional groups reactive with the polyester resin into these modifiers to improve the compatibility with the polyester resin, or A technique has been proposed in which a substance having an affinity for both the polyester resin and the modifier is added as a three-component as a compatibilizer to enhance the effect of the modifier. Even with these techniques, it is possible to solve problems relating to impact resistance and heat sealability to some extent. However, these techniques, among the problems that the polyester resin has, moldability,
In particular, it cannot be said to be sufficient in terms of solving the problem of poor moldability in extrusion molding.
【０００５】すなわち、ポリエステル樹脂に対しポリオ
レフィン樹脂或いは熱可塑性エラストマー等の熱可塑性
樹脂を改質剤として配合しても、溶融粘度は高まるもの
の、溶融張力は殆ど変わらず、押出成形における成形性
の向上は果たせない。ポリエステル樹脂と反応性のある
官能基を有する重合体が組成物に含まれていれば、ポリ
エステル樹脂と官能基を有する重合体が反応することに
より、実質的にポリエステル樹脂の分子量が増し、溶融
粘度と溶融張力を高めることが可能である。しかし、押
出成形における成形性の不足を十分に解消する効果を得
るためには、多量の配合が必要な場合が多く、また概し
てこのような官能基を付加された重合体は高価なため、
材料コストを引き上げるという結果を招く。That is, when a thermoplastic resin such as a polyolefin resin or a thermoplastic elastomer is added to a polyester resin as a modifier, the melt viscosity is increased, but the melt tension is almost unchanged and the moldability in extrusion molding is improved. I can't. If the composition has a polymer having a functional group that is reactive with the polyester resin, the polyester resin reacts with the polymer having a functional group, thereby substantially increasing the molecular weight of the polyester resin and increasing the melt viscosity. It is possible to increase the melt tension. However, in order to obtain the effect of sufficiently eliminating the lack of moldability in extrusion molding, a large amount of compounding is often necessary, and, in general, such a functional group-added polymer is expensive,
This results in higher material costs.
【０００６】一方、近年、環境負荷の低減に対する意識
の高まりから、プラスチック廃棄物の回収及び再生量が
増してきている。プラスチック廃棄物の回収、再生を代
表するものとしてポリエステル樹脂製ボトルが挙げられ
るが、回収ボトルをマテリアルリサイクルにより再生す
る場合、分子量低下による、機械特性の劣化、加工性の
低下は避けられない問題であり、ポリエステル樹脂の特
性改良、成形性の向上は必要性を増している。On the other hand, in recent years, the amount of collection and recycling of plastic waste has been increasing due to the increased awareness of reduction of environmental load. Polyester resin bottles are a representative example of the collection and recycling of plastic waste.However, when the collection bottles are recycled by material recycling, deterioration of mechanical properties and processability due to a decrease in molecular weight is an unavoidable problem. Therefore, there is an increasing need to improve the properties of polyester resins and improve moldability.
【０００７】[0007]
【発明が解決しようとする課題】本発明はこのような状
況に鑑みなされたもので、ポリエステル樹脂が本来有す
る機械的特性、耐熱性、剛性等の優れた特徴は保持しつ
つ、耐衝撃性を改良し、またヒートシール性に優れてい
て製袋加工等の二次加工を容易ならしめ、且つ押出成形
等における成形加工性が改良されたポリエステル樹脂組
成物、並びに該ポリエステル樹脂組成物からなるフィル
ムを提供することを目的とする。SUMMARY OF THE INVENTION The present invention has been made in view of such a situation, and the polyester resin has excellent impact resistance while maintaining excellent characteristics such as mechanical properties, heat resistance, and rigidity. A polyester resin composition which is improved and has excellent heat sealability to facilitate secondary processing such as bag-making processing, and has improved moldability in extrusion molding, and a film made of the polyester resin composition The purpose is to provide.
【０００８】[0008]
【課題を解決するための手段】本発明者らは鋭意検討を
重ねた。この結果、ポリエステル樹脂とメルトフローレ
ートが特定の範囲にあるポリエチレンと特定の相溶化剤
を特定の割合で配合すると、ポリエステル樹脂が本来有
する機械的特性、耐熱性、剛性等の優れた特徴は保持し
つつ、耐衝撃性が改良され、且つ押出成形等の成形加工
における成形性が改良されたポリエステル樹脂組成物、
並びに該ポリエステル樹脂組成物からなるフィルムが得
られる事を見出し本発明に至ったものである。すなわち
本発明は、
エチレングリコール単位を主体とするジオール単位お
よびテレフタル酸単位を主体とするジカルボン酸単位か
ら主としてなる（Ａ）ポリエステル樹脂と、メルトフロ
ーレートが３（ｇ／１０ｍｉｎ）以下の（Ｂ）ポリエチ
レンと、エチレンの繰り返し単位を有する高分子であっ
て、かつカルボキシル基、またはその誘導体基、エポキ
シ基、ヒドロキシル基、アミノ基の群の中から選ばれた
少なくとも１種の官能基を有する（Ｃ）相溶化剤、の三
成分を必須成分として含み、且つ（Ａ）の割合が重量比
で９０〜６０％であり、（Ｂ）と（Ｃ）の合計の割合が
重量比で１０〜４０％であり、且つ（Ｂ）と（Ｃ）の割
合が重量比で１／１〜１０／１である事を特徴とするポ
リエステル樹脂組成物に関するものである。Means for Solving the Problems The present inventors have made extensive studies. As a result, when polyester resin and polyethylene having a melt flow rate in a specific range and a specific compatibilizer are blended in a specific ratio, excellent characteristics such as mechanical properties, heat resistance, and rigidity inherent in the polyester resin are retained. While having improved impact resistance, and a polyester resin composition having improved moldability in molding processing such as extrusion molding,
Moreover, they have found that a film made of the polyester resin composition can be obtained, and have reached the present invention. That is, the present invention comprises a polyester resin (A) mainly composed of a diol unit mainly composed of an ethylene glycol unit and a dicarboxylic acid unit mainly composed of a terephthalic acid unit, and a (B) having a melt flow rate of 3 (g / 10 min) or less. Polyethylene and a polymer having a repeating unit of ethylene and having at least one functional group selected from the group consisting of a carboxyl group or a derivative group thereof, an epoxy group, a hydroxyl group and an amino group (C ) Compatibilizer, which is an essential component, and the proportion of (A) is 90 to 60% by weight, and the total proportion of (B) and (C) is 10 to 40% by weight. And the ratio of (B) and (C) is 1/1 to 10/1 in terms of weight ratio.
【０００９】に記載のポリエステル樹脂組成物から
形成されたフィルムに関するものである。The present invention relates to a film formed from the polyester resin composition described in the above.
【００１０】[0010]
【発明の実施の形態】以下、本発明を詳細に説明する。
本発明で使用するエチレングリコール単位を主体とする
ジオール単位およびテレフタル酸単位を主体とするジカ
ルボン酸単位から主としてなる（Ａ）ポリエステル樹脂
とは、所謂ポリエチレンテレフタレートのみならず、ジ
カルボン酸成分、またはジオール成分のどちらか、また
は双方が、前記したテレフタル酸およびエチレングリコ
ール以外のものから選ばれて構成されたポリエステル単
位を含む共重合体であってもよい。テレフタル酸以外の
ジカルボン酸成分を具体的に挙げれば、例えばイソフタ
ル酸、ナフタリン−１，４−ジカルボン酸、ナフタリン
−２，６−ジカルボン酸等の芳香族ジカルボン酸、シュ
ウ酸、コハク酸、アジピン酸、セバシン酸、ウンデカジ
カルボン酸等の脂肪族ジカルボン酸、ヘキサヒドロテレ
フタル酸等の脂環族ジカルボン酸が挙げられる。エチレ
ングリコール以外のグリコール成分としては、具体的に
例えばジエチレングリコール、プロピレングリコ−ル、
１，４−ブタンジオール等の脂肪族グリコール、シクロ
ヘキサンジメタノール等の脂環族グリコールが挙げられ
る。また、共重合ポリエステルを用いる場合、その共重
合比等が特に制限されるものではない。さらにテレフタ
ル酸およびエチレングリコールからのみなるポリエチレ
ンテレフタレートと、テレフタル酸以外のジカルボン酸
単位やエチレングリコール以外のジオール単位を含む共
重合体ポリエステル樹脂、あるいは、テレフタル酸やエ
チレングリコールを構造単位に全く含まないポリエステ
ル樹脂の混合物を用いても良い。BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below.
The (A) polyester resin mainly composed of a diol unit mainly composed of an ethylene glycol unit and a dicarboxylic acid unit mainly composed of a terephthalic acid unit used in the present invention means not only a so-called polyethylene terephthalate but also a dicarboxylic acid component or a diol component. Either or both of the above may be a copolymer containing a polyester unit selected from those other than the above-mentioned terephthalic acid and ethylene glycol. Specific examples of the dicarboxylic acid component other than terephthalic acid include, for example, aromatic dicarboxylic acids such as isophthalic acid, naphthalene-1,4-dicarboxylic acid, naphthalene-2,6-dicarboxylic acid, oxalic acid, succinic acid, and adipic acid. , Aliphatic dicarboxylic acids such as sebacic acid and undecadicarboxylic acid, and alicyclic dicarboxylic acids such as hexahydroterephthalic acid. Specific examples of glycol components other than ethylene glycol include diethylene glycol, propylene glycol,
Examples thereof include aliphatic glycols such as 1,4-butanediol and alicyclic glycols such as cyclohexanedimethanol. In addition, when a copolyester is used, the copolymerization ratio and the like are not particularly limited. Further, a polyethylene polyester terephthalate consisting only of terephthalic acid and ethylene glycol, a copolymer polyester resin containing a dicarboxylic acid unit other than terephthalic acid and a diol unit other than ethylene glycol, or a polyester containing no terephthalic acid or ethylene glycol as a structural unit. A mixture of resins may be used.
【００１１】本発明で用いられるポリエステル樹脂の固
有粘度は特に制限を受けるものではないが、ｏ−クロロ
フェノール溶媒中において２５℃で測定した溶融粘度よ
り求めた固有粘度が０．３（ｄｌ／ｇ）以上、さらには
０．５（ｄｌ／ｇ）以上であるものが好ましい。使用す
るポリエステル樹脂の固有粘度が０．３（ｄｌ／ｇ）以
下である場合、溶融張力の低さにより成形性が悪化し、
またフィルム等の成形体の機械特性等が不満足なものと
なり好ましくない。The intrinsic viscosity of the polyester resin used in the present invention is not particularly limited, but the intrinsic viscosity determined from the melt viscosity measured at 25 ° C. in an o-chlorophenol solvent is 0.3 (dl / g). ) Or more, more preferably 0.5 (dl / g) or more. When the intrinsic viscosity of the polyester resin used is 0.3 (dl / g) or less, moldability deteriorates due to low melt tension,
Further, the mechanical properties of the molded product such as a film become unsatisfactory, which is not preferable.
【００１２】そして本発明においては、メルトフローレ
ートが３（ｇ／１０ｍｉｎ）以下の（Ｂ）ポリエチレン
が用いられる。なお、（Ｂ）ポリエチレンは０．０１
（ｇ／１０ｍｉｎ）以上のメルトフローレートを有して
いることが好ましい。このようなポリエチレンとして
は、エチレンの重合体である高密度ポリエチレン、及び
低密度ポリエチレン、及びエチレンとα−オレフィンの
共重合体などが挙げられる。尚、エチレンとα−オレフ
ィンの共重合体に関しては、主要量のエチレンと炭素数
３〜１２程度のα−オレフィン、具体的に例えばプロピ
レン、１−ブテン、１−ヘキセン、１−オクテン、４−
メチル−１−ペンテン、等との二元共重合体、或いは三
元共重合体等が挙げられる。そしてこれらは単独で用い
ても良いし、二種以上組み合わせて用いても良い。ただ
し、単独で用いるにしても、混合物を用いるにしても、
そのメルトフローレートは荷重２１６０ｇ、温度１９０
℃で測定した時に、３（ｇ／１０ｍｉｎ）以下でなけれ
ばならない。メルトフローレートが３（ｇ／１０ｍｉ
ｎ）を超えるポリエチレンをに用いた場合、組成物の溶
融張力が不十分であり、本発明の課題のひとつである押
出成形等の成形加工における成形性が改良されず好まし
くない。また、複数のポリエチレンを組み合わせて用い
る場合、それぞれのメルトフローレートが３（ｇ／１０
ｍｉｎ）以下である必要はなく、複数組み合わせられた
ポリエチレン組成物としてのメルトフローレートが３
（ｇ／１０ｍｉｎ）以下であればよい。なお、メルトフ
ローレートが３（ｇ／１０ｍｉｎ）以下のポリエチレン
を用いることにより本発明の目的を達成できるが、成形
性の更なる向上のため、また組成物を成形加工してなる
フィルム等の成形品の耐衝撃性等の物性を優れたものに
するためには、ポリエチレンのメルトフローレートは
１．５（ｇ／１０ｍｉｎ）以下が好ましく、更に好まし
くは１．０（ｇ／１０ｍｉｎ）以下である。In the present invention, polyethylene (B) having a melt flow rate of 3 (g / 10 min) or less is used. In addition, (B) polyethylene is 0.01
It is preferable to have a melt flow rate of (g / 10 min) or more. Examples of such polyethylene include high-density polyethylene, which is a polymer of ethylene, low-density polyethylene, and a copolymer of ethylene and α-olefin. Regarding the copolymer of ethylene and α-olefin, the main amount of ethylene and the α-olefin having about 3 to 12 carbon atoms, specifically, for example, propylene, 1-butene, 1-hexene, 1-octene, 4-
Examples thereof include binary copolymers with methyl-1-pentene, etc., and ternary copolymers. These may be used alone or in combination of two or more. However, whether used alone or in a mixture,
The melt flow rate is 2160 g load and 190 temperature.
It must be 3 (g / 10 min) or less when measured at ° C. Melt flow rate is 3 (g / 10mi
When polyethylene exceeding n) is used for the composition, the melt tension of the composition is insufficient, and the moldability in molding processing such as extrusion molding, which is one of the subjects of the present invention, is not improved, which is not preferable. When a plurality of polyethylenes are used in combination, each melt flow rate is 3 (g / 10
min) or less, and the melt flow rate as a polyethylene composition in which a plurality thereof are combined is 3 or less.
It may be (g / 10 min) or less. The object of the present invention can be achieved by using polyethylene having a melt flow rate of 3 (g / 10 min) or less, but for the purpose of further improving moldability, molding of a film or the like obtained by molding the composition. In order to improve the physical properties such as impact resistance of the product, the melt flow rate of polyethylene is preferably 1.5 (g / 10 min) or less, more preferably 1.0 (g / 10 min) or less. .
【００１３】さらに本発明においては、エチレンの繰り
返し単位を有する高分子であって、かつカルボキシル
基、またはその誘導体基、エポキシ基、ヒドロキシル
基、アミノ基の群の中から選ばれた少なくとも１種の官
能基を有する（Ｃ）相溶化剤が用いられる。すなわち相
溶化剤は、本来は非相溶系であるポリエステル樹脂とポ
リエチレンの混合物中において、ポリエステル樹脂相と
ポリエチレン樹脂相の界面に選択的に局在することによ
り、界面の自由エネルギーを減少させ、混合時の分散を
助長し、両界面の接着性を向上させる機能を果たす。ポ
リエステル樹脂とポリエチレン樹脂の混合系において相
溶化剤として機能する高分子物質は種々考えられるが、
本発明で用いる相溶化剤は、エチレンの繰り返し単位を
有する高分子であって、かつカルボキシル基、またはそ
の誘導体基、エポキシ基、ヒドロキシル基、アミノ基の
群の中から選ばれた少なくとも１種の官能基、より好ま
しくは、カルボキシル基、またはその誘導体基、エポキ
シ基の群の中から選ばれた少なくとも１種の官能基を有
する。このような相溶化剤は、分子構造中のエチレンの
繰り返し単位からなる部分が、ポリエチレンと親和性を
示す。また、官能基がポリエステル樹脂と親和性を示
す。さらにある割合で官能基がポリエステル樹脂と結合
してポリエステル樹脂の実質的な分子量を高めることか
ら、溶融張力を向上させ、その結果成形性を改良する効
果をもたらす。Further, in the present invention, a polymer having a repeating unit of ethylene and at least one kind selected from the group consisting of a carboxyl group or a derivative group thereof, an epoxy group, a hydroxyl group and an amino group is selected. A (C) compatibilizer having a functional group is used. That is, the compatibilizing agent selectively localizes at the interface between the polyester resin phase and the polyethylene resin phase in the mixture of the polyester resin and polyethylene, which is originally an incompatible system, thereby reducing the free energy of the interface and mixing. It has the function of promoting the dispersion of time and improving the adhesiveness of both interfaces. There are various possible polymeric substances that function as compatibilizers in a mixed system of polyester resin and polyethylene resin.
The compatibilizer used in the present invention is a polymer having an ethylene repeating unit, and is at least one selected from the group consisting of a carboxyl group or a derivative group thereof, an epoxy group, a hydroxyl group and an amino group. It has a functional group, more preferably at least one functional group selected from the group consisting of a carboxyl group, a derivative group thereof, and an epoxy group. In such a compatibilizing agent, the portion composed of the repeating unit of ethylene in the molecular structure exhibits affinity with polyethylene. Further, the functional group has an affinity with the polyester resin. Further, the functional group is bonded to the polyester resin at a certain ratio to increase the substantial molecular weight of the polyester resin, thereby improving melt tension and, as a result, improving moldability.
【００１４】このようなエチレンの繰り返し単位を有す
る高分子を例示すれば、前述の（Ｂ）の如きエチレンの
重合体、及びエチレンとα−オレフィンの共重合体、エ
チレン−（メタ）アクリル酸共重合体、エチレン−酢酸
ビニル共重合体、あるいは、スチレン−エチレンブテン
−エチレンブロック共重合体、エチレン−プロピレンラ
バー、エチレン−プロピレン−ジエン共重合体、水素添
加スチレン−ブタジエンラバー等の熱可塑性エラストマ
ー等が挙げられ、これら高分子に前記した官能基が導入
される。このような官能基を導入する手段としては公知
の方法が採用可能である。例えばエチレンの繰り返し単
位を有する高分子に無水マレイン酸等の酸無水物をグラ
フト重合する手法、或いはエチレンを必須成分とするモ
ノマーとグリシジルメタクリレートを共重合する手法等
が挙げられる。Examples of such a polymer having a repeating unit of ethylene include a polymer of ethylene as described in (B) above, a copolymer of ethylene and α-olefin, and a copolymer of ethylene- (meth) acrylic acid. Polymers, ethylene-vinyl acetate copolymers, styrene-ethylene butene-ethylene block copolymers, ethylene-propylene rubbers, ethylene-propylene-diene copolymers, hydrogenated styrene-butadiene rubbers and other thermoplastic elastomers, etc. And the functional groups described above are introduced into these polymers. A known method can be employed as a means for introducing such a functional group. For example, a method of graft-polymerizing an acid anhydride such as maleic anhydride onto a polymer having a repeating unit of ethylene, or a method of copolymerizing a monomer having ethylene as an essential component with glycidyl methacrylate is used.
【００１５】そして、本発明のポリエステル樹脂組成物
は上記した（Ａ）ポリエステル樹脂、（Ｂ）ポリエチレ
ン、及び（Ｃ）相溶化剤を、（Ａ）の割合が重量割合で
９０〜６０％であり、（Ｂ）と（Ｃ）の合計の割合が重
量比で１０〜４０％であり、且つ（Ｂ）と（Ｃ）の割合
が重量比で１／１〜１０／１の範囲で含有することが必
要である。The polyester resin composition of the present invention contains the above-mentioned (A) polyester resin, (B) polyethylene, and (C) compatibilizer in a proportion of (A) of 90 to 60% by weight. , The total proportion of (B) and (C) is 10 to 40% by weight, and the proportion of (B) and (C) is in the range of 1/1 to 10/1 by weight. is necessary.
【００１６】（Ａ）ポリエステル樹脂の割合が重量比で
６０％未満であって、（Ｂ）ポリエチレンと（Ｃ）相溶
化剤の合計の割合が重量比で４０％以上である場合は、
ポリエステル樹脂が本来有する機械的特性、耐熱性、剛
性等の優れた特徴が損なわれる。一方、（Ａ）ポリエス
テル樹脂の割合が重量比で９０％を超え、（Ｂ）ポリエ
チレンと（Ｃ）相溶化剤の合計の割合が重量比で１０％
未満ある場合は、成形品の耐衝撃性及びヒートシール性
の改良効果が十分でなく、また溶融張力の向上による成
形性の向上も不十分となる。When the ratio of the (A) polyester resin is less than 60% by weight and the total ratio of the (B) polyethylene and the (C) compatibilizer is 40% or more by weight,
The excellent characteristics such as mechanical properties, heat resistance and rigidity inherent in the polyester resin are impaired. On the other hand, the ratio of (A) polyester resin exceeds 90% by weight, and the total ratio of (B) polyethylene and (C) compatibilizer is 10% by weight.
If it is less than the range, the effect of improving the impact resistance and heat sealability of the molded product is not sufficient, and the improvement of the moldability due to the improvement of the melt tension is also insufficient.
【００１７】また、（Ｂ）ポリエチレンと（Ｃ）相溶化
剤の割合が重量比で１／１〜１０／１の範囲を外れ、
（Ｃ）相溶化剤の割合が少ない場合は、本発明の目的が
達成されず、混合時の分散不良による成形性の悪化はも
ちろん、機械的特性等の製品物性の不良を生じるように
なる。上記範囲を超えて（Ｃ）相溶化剤の混合割合が多
い場合は、ゲル状物の発生を生じやすく、製品外観の不
良を生じやすい。また一般に相溶化剤はポリエステル樹
脂、やポリエチレンと比較して遥かに高価なため原料コ
ストの上昇を招く。Further, the proportions of (B) polyethylene and (C) compatibilizer are out of the range of 1/1 to 10/1 by weight,
When the proportion of the compatibilizing agent (C) is small, the object of the present invention is not achieved, resulting in poor moldability due to poor dispersion during mixing and poor product properties such as mechanical properties. When the mixing ratio of the compatibilizing agent (C) exceeds the above range, a gelled product is liable to be generated and a defective product appearance is liable to be generated. Further, since the compatibilizer is generally much more expensive than polyester resin or polyethylene, the cost of raw materials is increased.
【００１８】なお、本発明のポリエステル樹脂組成物
は、発明の目的を損なわない範囲で、その用途に応じて
公知の添加剤を添加する事ができる。例えば酸化防止
剤、滑剤、アンチブロッキング剤、難燃剤、紫外線吸収
剤、光安定剤、帯電防止剤、着色剤等が挙げられる。The polyester resin composition of the present invention may be added with known additives depending on the intended use, as long as the object of the invention is not impaired. Examples thereof include antioxidants, lubricants, anti-blocking agents, flame retardants, ultraviolet absorbers, light stabilizers, antistatic agents, colorants and the like.
【００１９】本発明のポリエステル樹脂組成物の製造方
法は特に制限を受けるものはない。例えば、予め、ニー
ダー、バンバリーミキサー、二軸混錬押出機等の混錬機
を用いて各成分を所定の割合で含有する混合組成物を溶
融混合してから造粒する方法が挙げられる。また、成形
法によっては、所定の割合の成分をドライブレンドし、
直接成形機に供給して成形を行うようにしても良い。The method for producing the polyester resin composition of the present invention is not particularly limited. For example, a method in which a kneader, a Banbury mixer, a twin-screw kneading extruder or the like is used in advance to melt-mix a mixed composition containing each component in a predetermined ratio, and then granulation is performed. Also, depending on the molding method, dry blending a predetermined proportion of components,
The molding may be performed by directly supplying the molding machine.
【００２０】さらに本発明は、上記したポリエステル樹
脂組成物から形成されたフィルムも提供するものであ
る。本発明によって提供されるフィルムはヒートシール
性、耐引裂性、耐衝撃性などの機械的特性に優れたもの
であり、この特性を生かして袋類、シーラント材、各種
包材にとりわけ好適なものである。上記したポリエステ
ル樹脂組成物からフィルムを製造する方法も特に制限を
受けるものはなく、インフレーション成形法、Ｔダイ式
押出成形法、カレンダー成形法、プレス成形法が採用で
きる。なお、本発明のポリエステル樹脂組成物は成形加
工性に優れるという特長を有しているため、従来、ポリ
エステル系組成物に対して採用が困難であったインフレ
ーション成形法を採用できる。従って、同成形法に用い
られる装置の設備コストが比較的低廉であるという点、
チューブ状のフィルムが得られるという点も参酌する
と、インフレーション成形法を採用するのが最も有利で
あると言える。Further, the present invention also provides a film formed from the above polyester resin composition. The film provided by the present invention has excellent mechanical properties such as heat sealability, tear resistance, and impact resistance, and is particularly suitable for bags, sealant materials, and various packaging materials by making use of these characteristics. Is. The method for producing a film from the above polyester resin composition is not particularly limited, and an inflation molding method, a T-die type extrusion molding method, a calender molding method, and a press molding method can be adopted. Since the polyester resin composition of the present invention has a feature of being excellent in molding processability, it is possible to adopt an inflation molding method which has hitherto been difficult to adopt for a polyester composition. Therefore, the equipment cost of the device used in the molding method is relatively low,
Taking into consideration that a tubular film can be obtained, it can be said that the inflation molding method is most advantageous.
【００２１】本発明のポリエステル樹脂組成物から得ら
れるフィルムは用途に応じて、ポリエチレン或いはポリ
プロピレンなどのポリオレフィン類、ポリ塩化ビニル、
ポリアミド、エチレン−ビニルアルコール共重合体、ア
ルミ箔、紙、など他の基材と二種或いはそれ以上に積層
してもよい。The film obtained from the polyester resin composition of the present invention is a polyolefin such as polyethylene or polypropylene, polyvinyl chloride,
You may laminate | stack with 2 or more types with other base materials, such as polyamide, ethylene-vinyl alcohol copolymer, aluminum foil, and paper.
【００２２】[0022]
【実施例】以下に、本発明を実施例及び比較例によって
さらに詳細に説明するが、本発明はその要旨を超えない
限りこれらの例により何ら限定されるものではない。な
お、本実施例で用いた種々の試験法を以下に記す。EXAMPLES The present invention will be described in more detail below with reference to examples and comparative examples, but the present invention is not limited to these examples as long as the gist thereof is not exceeded. The various test methods used in this example are described below.
【００２３】＜振子式衝撃強度＞供試フィルムの振子式
衝撃強度をＡＳＴＭ−Ｄ７８１の方法により測定した。<Pendulum Impact Strength> The pendulum impact strength of the test film was measured by the method of ASTM-D781.
【００２４】＜引裂き強度＞供試フィルムの引裂き強度
をＪＩＳ Ｋ７１２８−２（エルメンドルフ引裂法）の
方法により測定した。なお、測定はフィルムの縦方向に
ついて行った。<Tear Strength> The tear strength of the test film was measured by the method of JIS K7128-2 (Elmendorf tear method). The measurement was carried out in the longitudinal direction of the film.
【００２５】＜ヒートシール試験＞供試フィルムを温度
２３℃、相対湿度５０％の雰囲気中で４８時間放置した
後、フィルムを２つ折りにし、バーシーラーにてシール
バー温度２２０℃、シールバー圧力０．３２ＭＰａ、シ
ール時間１秒の条件でヒートシールした。なお、シール
バーには厚み１００μｍのテフロン（登録商標）製シー
トを巻きつけ、試料フィルムの融着を防いだ。次に、ヒ
ートシール部分の幅が１０ｍｍになるように短冊状のＴ
字型剥離強度測定用試験片を切り出し、破壊伸び測定用
の標線をヒートシール部を挟んで４０ｍｍの間隔で付加
した。作製した試験片を、温度２３℃、相対湿度５０％
の雰囲気下で、引張試験機を用いてチャック間距離５０
ｍｍ、引張速度５００ｍｍ／分の条件で引張り、試験片
が破壊されるときの応力と標線間の距離を測定し、シー
ル強度とシール破断伸度を求めた。なお、測定はフィル
ムの縦方向について７点を測定し、その平均値をシール
強度及びシール破壊伸度とした。<Heat Seal Test> The test film was left in an atmosphere of a temperature of 23 ° C. and a relative humidity of 50% for 48 hours, then the film was folded in two and a seal bar temperature of 220 ° C. and a seal bar pressure of 0 were used. Heat sealing was performed under the conditions of 0.32 MPa and a sealing time of 1 second. A Teflon (registered trademark) sheet having a thickness of 100 μm was wrapped around the seal bar to prevent fusion of the sample film. Next, make a strip-shaped T so that the width of the heat-sealed part is 10 mm.
A test piece for measuring the P-shaped peel strength was cut out, and marked lines for measuring the breaking elongation were added at intervals of 40 mm with the heat-sealed portion sandwiched therebetween. The prepared test piece is at a temperature of 23 ° C. and a relative humidity of 50%.
In the atmosphere of, using a tensile tester, distance between chucks 50
The tensile strength was 500 mm / min and the tensile strength was 500 mm / min. The stress when the test piece was broken and the distance between the marked lines were measured to obtain the seal strength and the seal breaking elongation. The measurement was carried out at 7 points in the longitudinal direction of the film, and the average value was taken as the seal strength and the seal breaking elongation.
【００２６】［実施例１］
（Ａ）ポリエステル樹脂として、テレフタル酸をジカル
ボン酸成分、エチレングリコールをジオール成分として
重合してなり、固有粘度が０．７５（ｄｌ／ｇ）のポリ
エチレンテレフタレートを８０重量％と、（Ｂ）ポリエ
チレンとしてメルトフローレートが０．５０（ｇ／１０
ｍｉｎ）、密度が０．９２０（ｇ／ｃｍ ３）である高圧
重合法低密度ポリエチレンを１５重量％と、（Ｃ）相溶
化剤として無水マレイン酸０．４重量％でグラフト変性
された、エチレン−１−ブテン共重合体を５重量％を用
いた。（Ａ）ポリエステル樹脂は除湿乾燥機を用い、１
４０℃で５時間以上乾燥してから使用した。上記３成分
のペレットをブレンドし、φ５０ｍｍの押出し機を有す
る空冷インフレーション成形機にて、樹脂温度２７５℃
で成形することにより、厚み２５μｍのフィルムを得
た。使用した空冷インフレーション成形機は、通常ポリ
エチレンの成形に用いられる一般的な仕様の成形機であ
るが、何ら問題なく成形ができた。得られたフィルムに
関して、引張破壊強度及び引張破壊伸度、及び振子式衝
撃強度を測定した。その結果を下記表１に示す。また、
ヒートシール試験の結果を下記表２に示す。[Example 1]
(A) As a polyester resin, terephthalic acid
Boronic acid component, ethylene glycol as diol component
Polymerized polymer with an intrinsic viscosity of 0.75 (dl / g)
80% by weight of ethylene terephthalate and (B) polyethylene
Melt flow rate of 0.50 (g / 10
min) and the density is 0.920 (g / cm Three) Is high pressure
Polymerization method 15% by weight of low density polyethylene and (C) compatible
Graft modification with 0.4% by weight of maleic anhydride as an agent
5% by weight of ethylene-1-butene copolymer
I was there. For (A) polyester resin, a dehumidifying dryer is used.
It was used after drying at 40 ° C. for 5 hours or more. Above 3 components
Blended pellets and has an extruder of φ50mm
Air-cooled inflation molding machine
A film with a thickness of 25 μm is obtained by molding with
It was The air-cooled inflation molding machine used is
A general-purpose molding machine used for molding ethylene.
However, molding was possible without any problems. On the obtained film
Regarding tensile fracture strength and tensile fracture elongation, and pendulum impact
The strike strength was measured. The results are shown in Table 1 below. Also,
The results of the heat seal test are shown in Table 2 below.
【００２７】［実施例２］
（Ａ）ポリエステル樹脂として、テレフタル酸が９０モ
ル％とイソフタル酸が１０モル％からなるジカルボン酸
成分と、エチレングリコールが９７モル％とジエチレン
グリコールが３モル％からなるジオール成分を重合して
なり、固有粘度が０．８０（ｄｌ／ｇ）である共重合ポ
リエチレンテレフタレートを８０重量％と、実施例１で
用いた（Ｂ）ポリエチレンを１５重量％と、同じく実施
例１で用いた（Ｃ）相溶化剤を５重量％用い、実施例１
と同様にして成形を行い、厚み２５μｍのフィルムを得
た。フィルムの成形は実施例１と同じく、何ら問題なく
行えた。実施例１と同様にして行ったフィルムの評価試
験の結果を表１及び２に示す。Example 2 As the polyester resin (A), a dicarboxylic acid component containing 90 mol% of terephthalic acid and 10 mol% of isophthalic acid, and a diol containing 97 mol% of ethylene glycol and 3 mol% of diethylene glycol. 80% by weight of copolymerized polyethylene terephthalate having an intrinsic viscosity of 0.80 (dl / g) and 15% by weight of polyethylene (B) used in Example 1, and the same as in Example 1 The compatibilizing agent (C) used in Example 1 was used in an amount of 5% by weight.
A film having a thickness of 25 μm was obtained by molding in the same manner as in (1). As in Example 1, the film was formed without any problem. The results of the film evaluation test conducted in the same manner as in Example 1 are shown in Tables 1 and 2.
【００２８】［実施例３］実施例１で用いた（Ａ）ポリ
エステル樹脂であるポリエチレンテレフタレートを８０
重量％と、同じく実施例１で用いた（Ｂ）ポリエチレン
を１５重量％と、（Ｃ）相溶化剤としてメチルアクリレ
ートを２５重量％、グリシジルメタクリレートを８重量
％含有するエチレン／メタアクリレート／グリシジルメ
タクリレート共重合体を５重量％用い、実施例１と同様
にして成形を行い、厚み２５μｍのフィルムを得た。フ
ィルムの成形は実施例１と同じく、何ら問題なく行え
た。実施例１と同様にして行ったフィルムの評価試験の
結果を表１及び２に示す。[Example 3] Polyethylene terephthalate, which is the polyester resin (A) used in Example 1, was added to 80%.
% Ethylene, 15% by weight of polyethylene (B) used in Example 1, 25% by weight of methyl acrylate (C) as a compatibilizer, and 8% by weight of glycidyl methacrylate, ethylene / methacrylate / glycidyl methacrylate. Using 5% by weight of the copolymer, molding was carried out in the same manner as in Example 1 to obtain a film having a thickness of 25 μm. As in Example 1, the film was formed without any problem. The results of the film evaluation test conducted in the same manner as in Example 1 are shown in Tables 1 and 2.
【００２９】［実施例４］実施例１で用いた（Ａ）ポリ
エステル樹脂であるポリエチレンテレフタレートを８０
重量％と、（Ｂ）ポリエチレンとしてメルトフローレー
トが２．０（ｇ／１０ｍｉｎ）、密度が０．９２１（ｇ
／ｃｍ３）であるエチレン−１−ヘキセン共重合体を１
５重量％と、実施例１で用いた（Ｃ）相溶化剤である無
水マレイン酸でグラフト変性された、エチレン−１−ブ
テン共重合体を５重量％用い、実施例１と同様にして成
形を行い、厚み２５μｍのフィルムを得た。フィルムの
成形は実施例１と同じく、何ら問題なく行えた。実施例
１と同様にして行ったフィルムの評価試験の結果を表１
及び２に示す。[Embodiment 4] Polyethylene terephthalate, which is the polyester resin (A) used in Embodiment 1, is 80
% By weight, the melt flow rate as polyethylene (B) is 2.0 (g / 10 min), and the density is 0.921 (g
/ Cm 3 ), the ethylene-1-hexene copolymer is 1
5% by weight and 5% by weight of the ethylene-1-butene copolymer graft-modified with (C) the compatibilizing agent used in Example 1, maleic anhydride, were molded in the same manner as in Example 1. Then, a film having a thickness of 25 μm was obtained. As in Example 1, the film was formed without any problem. The results of the evaluation test of the film conducted in the same manner as in Example 1 are shown in Table 1.
And 2 are shown.
【００３０】［実施例５］実施例１で用いた（Ａ）ポリ
エステル樹脂であるポリエチレンテレフタレートを６５
重量％と、同じく実施例１で用いた（Ｂ）ポリエチレン
を２５重量％と、同じく実施例１で用いた（Ｃ）相溶化
剤である無水マレイン酸でグラフト変性された、エチレ
ン−１−ブテン共重合体を１０重量％用い、実施例１と
同様にして成形を行い、厚み２５μｍのフィルムを得
た。フィルムの成形は実施例１と同じく、何ら問題なく
行えた。実施例１と同様にして行ったフィルムの評価試
験の結果を表１及び２に示す。[Example 5] Polyethylene terephthalate, which is the polyester resin (A) used in Example 1, was 65%.
% Ethylene, and 25% by weight of polyethylene (B) used in Example 1 and ethylene-1-butene graft-modified with maleic anhydride (C) used in Example 1 which is also a compatibilizer. Using 10% by weight of the copolymer, molding was performed in the same manner as in Example 1 to obtain a film having a thickness of 25 μm. As in Example 1, the film was formed without any problem. The results of the film evaluation test conducted in the same manner as in Example 1 are shown in Tables 1 and 2.
【００３１】［実施例６］実施例１で用いた（Ａ）ポリ
エステル樹脂であるポリエチレンテレフタレートを８０
重量％と、同じく実施例１で用いた（Ｂ）ポリエチレン
を１５重量％と、同じく実施例１で用いた（Ｃ）相溶化
剤である無水マレイン酸でグラフト変性された、エチレ
ン−１−ブテン共重合体を５重量％用いた。（Ａ）ポリ
エステル樹脂は除湿乾燥機を用い、１４０℃で５時間以
上乾燥してから使用した。上記３成分をペレットブレン
ドして、φ５０ｍｍの押出し機を有するＴダイキャスト
フィルム成形機にて、樹脂温度２８０℃、チルロール表
面温度４５℃で成形し、厚み２５μｍのフィルムを得
た。成形は何等問題なく行えた。実施例１と同様にして
行ったフィルムの評価試験の結果を表１及び２に示す。[Embodiment 6] Polyethylene terephthalate, which is the polyester resin (A) used in Embodiment 1, is 80
Ethylene-1-butene graft-modified with 15% by weight of (B) polyethylene used in Example 1 and 15% by weight of (C) compatibilizer used in Example 1, maleic anhydride. 5% by weight of copolymer was used. The polyester resin (A) was dried with a dehumidifying dryer at 140 ° C. for 5 hours or more before use. The above three components were pellet-blended and molded with a T die-cast film molding machine having a φ50 mm extruder at a resin temperature of 280 ° C. and a chill roll surface temperature of 45 ° C. to obtain a film having a thickness of 25 μm. The molding could be done without any problems. The results of the film evaluation test conducted in the same manner as in Example 1 are shown in Tables 1 and 2.
【００３２】［比較例１］実施例１で用いた（Ａ）ポリ
エステル樹脂であるポリエチレンテレフタレートを８０
重量％と、メルトフローレートが６．０（ｇ／１０ｍｉ
ｎ）、密度が０．９１８（ｇ／ｃｍ３）であるエチレン
／１−ヘキセン共重合体を１５重量％と、実施例１で用
いた（Ｃ）相溶化剤である無水マレイン酸でグラフト変
性された、エチレン−１−ブテン共重合体を５重量％用
い、実施例１と同様にして成形を行い、厚み２５μｍの
フィルムを得た。しかしながら、空冷インフレーション
成形におけるバブルの引き上げ作業が非常に困難であ
り、またようやく引き上げることができたバブルの安定
性も実施例に比べ劣るものであり、安定な生産には程遠
い状況であった。実施例１と同様にして行ったフィルム
の評価試験の結果を表１及び２に示す。Comparative Example 1 Polyethylene terephthalate, which is the polyester resin (A) used in Example 1, is 80
% By weight and melt flow rate of 6.0 (g / 10 mi
n), 15% by weight of ethylene / 1-hexene copolymer having a density of 0.918 (g / cm 3 ), and graft modification with maleic anhydride which is the (C) compatibilizer used in Example 1. 5% by weight of the obtained ethylene-1-butene copolymer was used and molded in the same manner as in Example 1 to obtain a film having a thickness of 25 μm. However, the work of pulling up the bubbles in the air-cooled inflation molding was extremely difficult, and the stability of the bubbles that could be finally pulled up was inferior to that in the examples, and the situation was far from stable production. The results of the film evaluation test conducted in the same manner as in Example 1 are shown in Tables 1 and 2.
【００３３】［比較例２］実施例１で用いた（Ａ）ポリ
エステル樹脂であるポリエチレンテレフタレートを８０
重量％と、同じく実施例１で用いた（Ｂ）ポリエチレン
を１９重量％と、同じく実施例１で用いた（Ｃ）相溶化
剤である無水マレイン酸でグラフト変性された、エチレ
ン−１−ブテン共重合体を１重量％用い、実施例１と同
様にして成形を行い、厚み２５μｍのフィルムを得た。
しかしながら、空冷インフレーション成形におけるバブ
ルの引き上げ作業が非常に困難であり、またようやく引
き上げることができたバブルの安定性も実施例に比べ劣
るものであり、安定な生産には程遠い状況であった。実
施例１と同様にして行ったフィルムの評価試験の結果を
表１及び２に示す。[Comparative Example 2] Polyethylene terephthalate, which is the polyester resin (A) used in Example 1, is 80%.
% Ethylene, 19% by weight polyethylene (B) used in Example 1 and ethylene-1-butene graft-modified with maleic anhydride (C) compatibilizer used in Example 1 Using 1% by weight of the copolymer, molding was performed in the same manner as in Example 1 to obtain a film having a thickness of 25 μm.
However, the work of pulling up the bubbles in the air-cooled inflation molding was extremely difficult, and the stability of the bubbles that could be finally pulled up was inferior to that in the examples, and the situation was far from stable production. The results of the film evaluation test conducted in the same manner as in Example 1 are shown in Tables 1 and 2.
【００３４】［比較例３］実施例１で用いた（Ａ）ポリ
エステル樹脂であるポリエチレンテレフタレートを９５
重量％と、同じく実施例１で用いた（Ｂ）ポリエチレン
を３．７５重量％と、同じく実施例１で用いた（Ｃ）相
溶化剤である無水マレイン酸でグラフト変性された、エ
チレン−１−ブテン共重合体を１．２５重量％用い、実
施例１と同様にしてフィルムの成形を試みた。しかしな
がら、バブルの引き上げ作業が非常に困難なものであ
り、目的とするフィルムを得ることができなかった。[Comparative Example 3] Polyethylene terephthalate, which is the polyester resin (A) used in Example 1, is 95%.
Ethylene-1 graft-modified with maleic anhydride, which is the compatibilizing agent (C) used in Example 1, and (B) polyethylene used in Example 1 (3.75% by weight). An attempt was made to form a film in the same manner as in Example 1 using 1.25% by weight of butene copolymer. However, the work of pulling up the bubbles was very difficult, and the intended film could not be obtained.
【００３５】［比較例４］比較例３で用いたのと全く同
じ組成物を用い、実施例６と同様にＴダイキャストフィ
ルム成形機にて、樹脂温度２８０℃、チルロール表面温
度４５℃で製膜し、厚み２５μｍのフィルムを得た。こ
の原料配合でも、Ｔダイキャストフィルム成形法では問
題なく成形が可能であった。実施例１と同様にして行っ
たフィルムの評価試験の結果を表１及び２に示す。[Comparative Example 4] Using the same composition as used in Comparative Example 3, the same process as in Example 6 was carried out using a T die cast film molding machine at a resin temperature of 280 ° C and a chill roll surface temperature of 45 ° C. A film having a thickness of 25 μm was obtained. Even with this raw material formulation, molding was possible without problems by the T die cast film molding method. The results of the film evaluation test conducted in the same manner as in Example 1 are shown in Tables 1 and 2.
【００３６】[0036]
【表１】 [Table 1]
【００３７】[0037]
【表２】 [Table 2]
【００３８】上記の表１及び表２の結果から明らかなよ
うに、（Ａ）ポリエステル樹脂と、メルトフローレート
が特定の範囲にある（Ｂ）ポリエチレンと、（Ｂ）相溶
化剤を特定の割合で混合してなる、本発明のポリエステ
ル樹脂組成物より成形された実施例１〜６のフィルム
は、良好な引裂き強度、及び衝撃強度を示し、またヒー
トシール性にも優れていることがわかる。加えて、良好
な成形性を示すことは各実施例に記載したとおりであ
る。As is clear from the results shown in Tables 1 and 2, (A) polyester resin, (B) polyethylene having a melt flow rate within a specific range, and (B) a compatibilizing agent in a specific ratio. It can be seen that the films of Examples 1 to 6 formed from the polyester resin composition of the present invention obtained by mixing in Table 1 show good tear strength and impact strength, and also have excellent heat sealability. In addition, good moldability is shown as described in each example.
【００３９】これに対して、実施例１〜６と同じく、ポ
リエステル樹脂、ポリエチレンと、相溶化剤から成るも
のの、ポリエチレンのメルトフローレート、及び三成分
の混合割合が本発明の範囲外である比較例１〜４の組成
物は、成形性に劣り、また得られたフィルムの引裂き強
度、衝撃強度、及びヒートシール性も不満足なものであ
った。特に、比較例１〜２、及び４の組成物から得られ
たフィルムのシール破壊伸度は何れも著しく小さい値を
示し、ヒートシール性が求められる用途に関しては、実
用的な価値がないことがわかる。On the other hand, as in Examples 1 to 6, a comparison was made in which the polyester resin, polyethylene and the compatibilizer were used, but the melt flow rate of polyethylene and the mixing ratio of the three components were outside the scope of the present invention. The compositions of Examples 1 to 4 were inferior in moldability, and the resulting films had unsatisfactory tear strength, impact strength, and heat sealability. In particular, the films obtained from the compositions of Comparative Examples 1 to 2 and 4 all have extremely small values of the seal breaking elongation, and may have no practical value in applications requiring heat sealability. Recognize.
【００４０】[0040]
【発明の効果】以上説明したように本発明のポリエステ
ル樹脂組成物は、押出し加工等の成形性に優れる。また
該ポリエステル樹脂組成物より成形されてなるフィルム
は、ヒートシール性、袋引裂性、耐衝撃性などの機械的
特性に優れる。そしてこのフィルムは前記特性を生かし
て各種袋類、シーラント材等の各種包材に好適に用いら
れるものである。そして、近年話題になっているポリエ
ステル樹脂製ボトル等のポリエステル樹脂のマテリアル
リサイクルによって得られる再生ポリエステル樹脂の有
効な活用にも道を提供するものであり有用であると言え
る。As described above, the polyester resin composition of the present invention is excellent in moldability such as extrusion processing. A film formed from the polyester resin composition has excellent mechanical properties such as heat sealability, bag tearability, and impact resistance. Further, this film is preferably used for various packaging materials such as various bags and sealant materials by utilizing the above characteristics. It can be said that it is also useful because it provides a way for effective utilization of recycled polyester resin obtained by material recycling of polyester resin such as bottles made of polyester resin, which has become a hot topic in recent years.
───────────────────────────────────────────────────── フロントページの続き Ｆターム(参考） 4F071 AA15 AA15X AA21X AA33X AA44 AA78 BA01 BB06 BB09 BC01 4J002 BB032 BB043 BB063 BB103 BB153 BB213 BP013 CF031 CF051 CF081 GG02 ─────────────────────────────────────────────────── ─── Continued front page F-term (reference) 4F071 AA15 AA15X AA21X AA33X AA44 AA78 BA01 BB06 BB09 BC01 4J002 BB032 BB043 BB063 BB103 BB153 BB213 BP013 CF031 CF051 CF081 GG02
Claims (2)
オール単位およびテレフタル酸単位を主体とするジカル
ボン酸単位から主としてなる（Ａ）ポリエステル樹脂
と、メルトフローレートが３（ｇ／１０ｍｉｎ）以下の
（Ｂ）ポリエチレンと、エチレンの繰り返し単位を有す
る高分子であって、かつカルボキシル基、またはその誘
導体基、エポキシ基、ヒドロキシル基、アミノ基の群の
中から選ばれた少なくとも１種の官能基を有する（Ｃ）
相溶化剤、の三成分を必須成分として含み、且つ（Ａ）
の割合が重量比で９０〜６０％であり、（Ｂ）と（Ｃ）
の合計の割合が重量比で１０〜４０％であり、且つ
（Ｂ）と（Ｃ）の割合が重量比で１／１〜１０／１であ
る事を特徴とするポリエステル樹脂組成物。1. A (A) polyester resin mainly composed of a diol unit mainly composed of an ethylene glycol unit and a dicarboxylic acid unit mainly composed of a terephthalic acid unit, and a (B) having a melt flow rate of 3 (g / 10 min) or less. Polyethylene and a polymer having a repeating unit of ethylene and having at least one functional group selected from the group consisting of a carboxyl group or a derivative group thereof, an epoxy group, a hydroxyl group and an amino group (C )
Compatibilizer, which contains three components as essential components, and (A)
Is 90 to 60% by weight and (B) and (C)
The polyester resin composition is characterized in that the total ratio is 10 to 40% by weight, and the ratios of (B) and (C) are 1/1 to 10/1 by weight.
物を押出成形して得られたフィルム。2. A film obtained by extrusion-molding the polyester resin composition according to claim 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2002045911A JP2003238786A (en) | 2002-02-22 | 2002-02-22 | Polyester resin composition and film prepared therefrom |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2002045911A JP2003238786A (en) | 2002-02-22 | 2002-02-22 | Polyester resin composition and film prepared therefrom |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2003238786A true JP2003238786A (en) | 2003-08-27 |
Family
ID=27784432
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2002045911A Pending JP2003238786A (en) | 2002-02-22 | 2002-02-22 | Polyester resin composition and film prepared therefrom |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2003238786A (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2005040257A1 (en) * | 2003-10-21 | 2005-05-06 | E.I. Dupont De Nemours And Company | Ethylene copolymer modified oriented polyester films, tapes, fibers and nonwoven textiles |
| JP2007070522A (en) * | 2005-09-08 | 2007-03-22 | Mitsui Chemicals Inc | Polyester composition and film |
| JP2007262183A (en) * | 2006-03-28 | 2007-10-11 | Mitsui Chemicals Inc | Polyester-based heat shrinkable film |
| WO2009069742A1 (en) * | 2007-11-30 | 2009-06-04 | Toray Industries, Inc. | Polyester film, method for production of the same, and area light source, solar battery back-sheet and solar battery each comprising the same |
| JP2010188613A (en) * | 2009-02-18 | 2010-09-02 | Fujimori Kogyo Co Ltd | Laminated film and packaging bag |
| WO2023092685A1 (en) * | 2021-11-25 | 2023-06-01 | 周菊青 | Thermal shrinkage heavy-duty packaging composite plastic film and preparation method therefor |
-
2002
- 2002-02-22 JP JP2002045911A patent/JP2003238786A/en active Pending
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2005040257A1 (en) * | 2003-10-21 | 2005-05-06 | E.I. Dupont De Nemours And Company | Ethylene copolymer modified oriented polyester films, tapes, fibers and nonwoven textiles |
| US7943699B2 (en) | 2003-10-21 | 2011-05-17 | E. I. Du Pont De Nemours And Company | Ethylene copolymer modified oriented polyester films, tapes, fibers and nonwoven textiles |
| JP2007070522A (en) * | 2005-09-08 | 2007-03-22 | Mitsui Chemicals Inc | Polyester composition and film |
| JP2007262183A (en) * | 2006-03-28 | 2007-10-11 | Mitsui Chemicals Inc | Polyester-based heat shrinkable film |
| WO2009069742A1 (en) * | 2007-11-30 | 2009-06-04 | Toray Industries, Inc. | Polyester film, method for production of the same, and area light source, solar battery back-sheet and solar battery each comprising the same |
| US8680206B2 (en) | 2007-11-30 | 2014-03-25 | Toray Industries, Inc. | Polyester film and a production process thereof, and a surface light source, solar battery backsheet and solar battery respectively obtained by using the same |
| JP2010188613A (en) * | 2009-02-18 | 2010-09-02 | Fujimori Kogyo Co Ltd | Laminated film and packaging bag |
| WO2023092685A1 (en) * | 2021-11-25 | 2023-06-01 | 周菊青 | Thermal shrinkage heavy-duty packaging composite plastic film and preparation method therefor |
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