WO2012018238A2 - Film polyester orienté biodégradable et procédé de préparation dudit film - Google Patents

Film polyester orienté biodégradable et procédé de préparation dudit film Download PDF

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Publication number
WO2012018238A2
WO2012018238A2 PCT/KR2011/005743 KR2011005743W WO2012018238A2 WO 2012018238 A2 WO2012018238 A2 WO 2012018238A2 KR 2011005743 W KR2011005743 W KR 2011005743W WO 2012018238 A2 WO2012018238 A2 WO 2012018238A2
Authority
WO
WIPO (PCT)
Prior art keywords
polyester film
oriented polyester
film
biodegradable
weight
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.)
Ceased
Application number
PCT/KR2011/005743
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English (en)
Other versions
WO2012018238A3 (fr
Inventor
Sang Ii Kim
Kyung Youn Kim
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
SKC Co Ltd
Original Assignee
SKC Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by SKC Co Ltd filed Critical SKC Co Ltd
Publication of WO2012018238A2 publication Critical patent/WO2012018238A2/fr
Publication of WO2012018238A3 publication Critical patent/WO2012018238A3/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • 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
    • B29C55/00—Shaping by stretching, e.g. drawing through a die; Apparatus therefor
    • B29C55/02—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets
    • B29C55/10—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets multiaxial
    • B29C55/12—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets multiaxial biaxial
    • B29C55/14—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets multiaxial biaxial successively
    • B29C55/143—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets multiaxial biaxial successively firstly parallel to the direction of feed and then transversely thereto
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/06—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from hydroxycarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/06—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from hydroxycarboxylic acids
    • C08G63/08—Lactones or lactides
    • 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
    • B29K2067/00—Use of polyesters or derivatives thereof, as moulding material
    • 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
    • B29K2067/00—Use of polyesters or derivatives thereof, as moulding material
    • B29K2067/04—Polyesters derived from hydroxycarboxylic acids
    • B29K2067/046—PLA, i.e. polylactic acid or polylactide
    • 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
    • B29K2995/00—Properties of moulding materials, reinforcements, fillers, preformed parts or moulds
    • B29K2995/0037—Other properties
    • B29K2995/0059—Degradable
    • B29K2995/006—Bio-degradable, e.g. bioabsorbable, bioresorbable or bioerodible
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • C08J2367/04—Polyesters derived from hydroxy carboxylic acids, e.g. lactones

Definitions

  • the present invention relates to a biodegradable oriented polyester film, which is useful for packaging, and a method for the preparation thereof.
  • plastics such as polyvinyl chloride (PVC), polyethylene (PE) and polypropylene (PP) are not completely satisfactory in terms of their performance characteristics. For example, they generate toxic pollutants when incinerated, and emit large amounts of carbon dioxide contributing greenhouse effect. Further, such plastic films are not biodegradable and accumulate in the soil when disposed.
  • PVC polyvinyl chloride
  • PE polyethylene
  • PP polypropylene
  • Japanese Laid-open Patent Publication No. 2003-147098 discloses a biodegradable polylactic acid film excellent transparency and flexibility, and moldable with a T-die extruder. According to this patent publication, when the content of D-lactic acid in polylactic acid is more than 4 parts by weight, adhesion of the film to a casting roll occurs. Thus, a ternary system polylactic acid, poly(butylene adipate/terephtalate)(PBAT) and polycaprolactone has been used to form films. However, haze of the obtained film is too high due to poor miscibility of resins thereby opaque films are obtained despite excellent transparency.
  • Japanese Laid-open Patent Publication No. 2004-244553 discloses a flexible and biodegradable polyester laminated film comprising a terpolymer of butanediol/succinic acid/caprolactone and amorphous polylactic acid, as a low temperature heat-sealing film. Further, in order to improve tear strength and heat sealing strength of the film disclosed in the above patent publication, Japanese Laid-open Patent Publication No.
  • 2004-237473 discloses a biodegradable polyester laminated film which comprises an aromatic polyester copolymer of PBAT/l,4-butanediol and a copolymer of aliphatic polyester copolymer of succinic acid/l,4-butanediol/caprolactone.
  • the film does not have enough flexibility.
  • a biodegradable oriented polyester film having enough flexibility and high transparency and a preparation method thereof.
  • a biodegradable oriented polyester film comprising a random copolymer of i) a polycaprolactone having a number average molecular weight of 500 to 10,000 and/or a caprolactone monomer and ii) a lactide.
  • a process for preparing a biodegradable oriented polyester film comprising the steps of: (a) random copolymerizing i) a polycaprolactone having a number average molecular weight of 500 to 10,000 and/or a caprolactone monomer and ii) a lactide to obtain a copolymer resin; (b) melt- extruding the copolymer resin to obtain a non-oriented sheet; and (c) orienting the non-oriented sheet in at least one direction, and heat-setting the resulting sheet to obtain the biodegradable oriented polyester film.
  • the biodegradable oriented polyester film is formed by random copolymerization of i) a polycaprolactone having a number average molecular weight of 500 to 10,000 and/or a caprolactone monomer and ii) a lactide.
  • a polycaprolactone is prepared by a ring-opening reaction of caprolactone monomers having a long alkyl chain (5 CH 2 ), thereby giving enough flexibility to the inventive film. Accordingly, flexibility of the film can be maximized by using a caprolactone monomer and/or a polycaprolactone having a number average molecular weight of 500 to 10,000 as an ingredient of a copolymer.
  • ingredient i) is preferably a polycaprolactone having a number average molecular weight of 500 to 10,000.
  • the lactide of ingredient ii) is preferably L-lactide.
  • the film shows more improved physical properties when L-lactide of high purity is used.
  • the weight ratio of ingredients i) and ii) comprised in the film is preferably 80:20 to 5:95.
  • the heat shrinkage of the film in either the longitudinal or transverse direction after heat treatment in hot air at 100 ° C for 5 min is preferably 1 to 75%.
  • the film preferably exhibits an initial elastic modulus of 50 to 350 kgf/mm .
  • the film preferably exhibits a haze of 20% or less.
  • the film preferably has a thickness of 10 to 300 rn.
  • the biodegradable oriented polyester film of the present invention is prepared by a process comprising the steps of: (a) random copolymerizing i) a polycaprolactone having a number average molecular weight of 500 to 10,000 and/or a caprolactone monomer and ii) a lactide to obtain a copolymer resin; (b) melt-extruding the copolymer resin to obtain a non-oriented sheet; and (c) orienting the non-oriented sheet in at least one direction of the longitudinal and transverse directions, and heat-setting the resulting sheet to obtain the biodegradable oriented polyester film.
  • step (a) ingredients i) and ii) are reacted in a weight ratio ranging from
  • the random copolymerization is preferably carried out at a temperature of 170 ⁇ 190 ° C for 3-5 hours under inert atmosphere, e.g., under nitrogen atmosphere.
  • the random copolymer resin may be prepared by a process comprising the steps of mixing 5 ⁇ 80 parts by weight of ingredient i) and 20-95 parts by weight of ingredient ii), adding thereto 0.01-0.1 part by weight of tin catalyst(stannous octoate) and 0.1-0.2 part by weight of SiO 2 as an antiblocking agent, and reacting the mixture at a temperature of 170 ⁇ 190 ° C for 3-5 hours under nitrogen atmosphere, and then removing by-products or unreacted materials under reduced pressure.
  • a melt-extruding temperature in step (b) is preferably 180-280 ° C .
  • step (c) the longitudinal drawing and/or the transverse drawing are preferably performed at a draw ratio of 2.5 to 3.5 and 3.5 to 4.5, respectively, and the heat-setting temperature is preferably 80-170 ° C .
  • a packaging material comprising the biodegradable oriented polyester film of the present invention.
  • the inventive film is environmentally friendly with high biodegradability and exhibits excellent transparency (a light transmittance of at least 90% and a haze of 20% or less).
  • the inventive film is made of polylactic acid- caprolactone copolymer resin thereby secures enough flexibility. That is, flexibility of the film can be maximized by using a caprolactone monomer and/or a polycaprolactone having a number average molecular weight of 500 to 10,000 as ingredients of copolymerization, without bleed out problems related with liquid plasticizers.
  • the inventive film is produced via drawing (orientation), so it has excellent strength and elongation characteristics.
  • the inventive film can be used for various packaging and wrapping uses, e.g., as a general packaging film, a fancy packaging film, a general label, a heat- shrinkable label, an agricultural mulching film and an overwrapping film, and for laminating on a paper, laminating on non-woven fabric, preparing a disposable gown, laminating on wallpaper and laminating on flooring.
  • caprolactone monomer 15 parts by weight of caprolactone monomer, 85 parts by weight of L- lactide, 0.02 part by weight of tin catalyst, and 0.2 part by weight of SiO 2 as an antiblocking agent were mixed together.
  • the mixture was reacted at a temperature of 190 ° C for 5 hours under nitrogen atmosphere, and then byproducts or unreacted materials were removed under reduced pressure, to obtain a random copolymer resin (Mn 100,000).
  • the resulting copolymer resin was melt-extruded at 200 ° C and the resulting sheet was drawn on a casting roll kept at 10 ° C at a draw ratio of 3.0 in the longitudinal direction at 85 ° C and at a draw ratio of 4.0 in the transverse direction at 105 ° C , and then, heat set at 100 ° C to obtain an oriented polyester film having a thickness of 20 ⁇ .
  • Example 1 The procedure of Example 1 was repeated except for heat setting temperature of 160 ° C to obtain an oriented polyester film having a thickness of 20 ⁇ .
  • the resulting copolymer resin was melt-extruded at 210 ° C and the resulting sheet was drawn on a casting roll kept at 9 ° C at a draw ratio of 3.0 in the longitudinal direction at 80 ° C and at a draw ratio of 4.0 in the transverse direction at 100 ° C, and then, heat set at 105 ° C to obtain an oriented polyester film having a thickness of 20 ⁇ .
  • Example 4
  • Example 3 The procedure of Example 3 was repeated except for heat setting temperature of 150 ° C to obtain an oriented polyester film having a thickness of 20 ⁇ .
  • the resulting copolymer resin was melt-extruded at 200 ° C and the resulting sheet was drawn on a casting roll kept at 15 ° C at a draw ratio of 3.0 in the longitudinal direction at 77 ° C and at a draw ratio of 3.8 in the transverse direction at 100 ° C, and then, heat set at 95 ° C to obtain an oriented polyester film having a thickness of 20 ⁇ .
  • the resulting copolymer resin was melt-extruded at 180 ° C and the resulting sheet was drawn on a casting roll kept at 13 ° C at a draw ratio of 3.0 in the longitudinal direction at 77 ° C and at a draw ratio of 3.8 in the transverse direction at 100 ° C , and then, heat set at 95 ° C to obtain an oriented polyester film having a thickness of 20 ⁇ .
  • Example 7
  • caprolactone 7 parts by weight of caprolactone, 10 parts by weight of polycaprolactone (Mn 1,000), 83 parts by weight of L-lactide, 0.03 part by weight of tin catalyst, and 0.2 part by weight of SiO 2 as an antiblocking agent were mixed together.
  • the mixture was reacted at a temperature of 190 ° C for 5 hours under nitrogen atmosphere, and then by-products or unreacted materials were removed under reduced pressure to obtain a random copolymer resin (Mn 80,000).
  • the resulting copolymer resin was melt-extruded at 190 ° C and the resulting sheet was drawn on a casting roll kept at 12 ° C at a draw ratio of 3.0 in the longitudinal direction at 85 ° C and at a draw ratio of 4.0 in the transverse direction at 100 ° C, and then, heat set at 85 ° C to obtain an oriented polyester film having a thickness of 20 ⁇ .
  • the resulting copolymer resin was melt-extruded at 190 ° C and the resulting sheet was drawn on a casting roll kept at 15 ° C at a draw ratio of 3.0 in the longitudinal direction at 90 ° C and at a draw ratio of 4.0 in the transverse direction at 110 ° C , and then, heat set at 160 ° C to obtain an oriented polyester film having a thickness of 20 ⁇ .
  • Comparative Example 2 14 parts by weight of polyol having a trimethylene group in the repeating units, 86 parts by weight of L-lactide, 0.01 part by weight of tin catalyst, and 0.2 part by weight of SiO 2 as an antiblocking agent were mixed. The mixture was reacted at a temperature of 190 ° C for 7 hours under nitrogen atmosphere, and then by-products or unreacted materials were removed under reduced pressure to obtain a random copolymer resin of Mn 70,000.
  • the resulting copolymer resin was melt-extruded at 200 ° C and the resulting sheet was drawn on a casting roll kept at 12 ° C at a draw ratio of 3.0 in the longitudinal direction at 85 ° C and at a draw ratio of 4.0 in the transverse direction at 105 ° C , and then, heat set at 150 ° C to obtain an oriented polyester film having a thickness of 20 ⁇ .
  • a polylactic acid resin(Tm 170 ° C , Tg 65 ° C) was dried with a hot air drier at 100 ° C for 3 hours to remove moisture therefrom.
  • 90 parts by weight of the dried resin, 10 parts by weight of caprolactone, and 0.1 part by weight of SiO 2 as an antiblocking agent were uniformly compounded using a twin screw extruder at 200 ° C , to obtain a homogeneous compound.
  • the resulting compound was melt-extruded at 190 ° C and the resulting sheet was drawn on a casting roll kept at 13 ° C at a draw ratio of 3.0 in the longitudinal direction at 75 ° C and at a draw ratio of 4.0 in the transverse direction at 95 ° C , and then, heat set at 150 ° C to obtain an oriented polyester film having a thickness of 20 ⁇ .
  • Compositions and preparation processes of the films of the Examples and the Comparative Examples are shown in Table 1. Performance Test
  • 0.003 g of a copolymer resin was dissolved in tetrahydrofuran(THF) and the resulting solution was injected into a GPC with ELSD (Waters Ltd., USA) at room temperature, and the eluent rate was lmL/min.
  • a film sample was dissolved in a mixture of deuteriochloroform (CDC1 3 ) and trifluoroacetic acid (4: 1 by weight ratio) and then analyzed with H-NMR (JSM-LA300, JEOL Ltd., Japan).
  • a film sample having a size of 20 cm x 20 cm was kept in a hot air oven at 150 ° C for 2 hours, and evaluated as below. o : The film surface was not slippery, and causes blocking with each other, x : The film surface was slippery, and does not cause blocking with each other.
  • Flex tester (Gelbo Inc., USA) consisting of a 165 mm sample fixing plate, a 88 mm sample fixing diameter and a 125 mm traveling distance, at a twisting motion of 450 degrees for 450 cycles for about 10 minutes.
  • the tested sample film was placed on a white paper, whereon an oily nitroglycerin-based ink was applied with a doctor blade.
  • the number of ink dots appeared on the white paper was counted as the pin-hole number.
  • the results reported are the average of three repeats.
  • a film sample was cut into a 200 mm (length) ⁇ 15 mm (width) piece, maintained at 100 °C in a circulating air oven for 5 minutes, and the change in the film length was measured. Using the following equation, the degrees of shrinkage in each of the longitudinal and transverse directions were calculated:
  • Heat shrinkage (%) [ ( length before heat treatment - length after heat treatment ) / length before heat treatment ] ⁇ 100 Table 1
  • the inventive films of Examples 1 to 7 showed superior properties over those of the films of Comparative Examples 1 to 3 in terms of bleed out, haze, pin-hole resistance, initial elastic modulus, and heat- shrinkability.
  • polyester oriented films of Examples 3 to 7 employing a polycaprolactone having a number average molecular weight of 500-10,000 as the copolymer ingredient has maximized the film flexibility. More free volume between polylactic acid chains allows segments can move more easily.
  • the films of Examples 1, 3 and 5 to 7 had a high heat-shrinkability due to a low heat setting temperature. Accordingly, the films of Examples 1, 3 and 5 to 7 can be used as an overwrapping film, while the films of Examples 2 and 4 having a low heat-shrinkability are useful as a general packaging film.
  • the films of Comparative Examples 1 and 2 made of polyethylene glycol (PEG) having a dimethylene group and polyol having a trimethylene group have lower flexibily as compared with the inventive films of Examples using caprolactone having a pentamethylene group (5 CH 2 ).
  • PEG polyethylene glycol
  • the film of Comparative Example 3 was prepared by extruding a compound/blend of caprolactone monomer and polylactic acid.
  • the film exhibited bleed out problem, resulted from migration of caprolactone monomer having small molecular weight out to the film surface.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)
  • Shaping By String And By Release Of Stress In Plastics And The Like (AREA)
  • Biological Depolymerization Polymers (AREA)
  • Polyesters Or Polycarbonates (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

Le film polyester orienté biodégradable selon l'invention, comprenant un copolymère aléatoire contenant i) une polycaprolactone présentant un poids moléculaire moyen de 500 à 10 000 et/ou un monomère de caprolactone et (ii) un lactide, est écologique et présente une excellent transparence et une flexibilité maximisée sans problème d'exsudation, et peut donc être utilisé pour divers conditionnements et emballages.
PCT/KR2011/005743 2010-08-06 2011-08-05 Film polyester orienté biodégradable et procédé de préparation dudit film Ceased WO2012018238A2 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
KR1020100075946A KR101214473B1 (ko) 2010-08-06 2010-08-06 생분해성 폴리에스터 연신 필름 및 이의 제조방법
KR10-2010-0075946 2010-08-06

Publications (2)

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WO2012018238A2 true WO2012018238A2 (fr) 2012-02-09
WO2012018238A3 WO2012018238A3 (fr) 2012-04-26

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PCT/KR2011/005743 Ceased WO2012018238A2 (fr) 2010-08-06 2011-08-05 Film polyester orienté biodégradable et procédé de préparation dudit film

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KR (1) KR101214473B1 (fr)
WO (1) WO2012018238A2 (fr)

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP3373341B2 (ja) * 1995-08-24 2003-02-04 カネボウ株式会社 ポリ乳酸共重合物
JP2990277B2 (ja) 1998-03-19 1999-12-13 工業技術院長 脂肪族ポリエステルシ―トの延伸加工方法
KR100453130B1 (ko) * 2001-11-21 2004-10-15 한국과학기술연구원 구조적 배열이 일정한 생분해성 락타이드(글리콜라이드또는 락타이드/글리콜라이드)/ε-카프로락톤 멀티블록공중합체 및 이의 제조 방법
JP4246523B2 (ja) 2003-03-06 2009-04-02 三菱樹脂株式会社 乳酸系樹脂組成物

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Publication number Publication date
KR20120013749A (ko) 2012-02-15
WO2012018238A3 (fr) 2012-04-26
KR101214473B1 (ko) 2012-12-24

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