WO2006001659A1 - Films polyester a orientation biaxiale et procede de traitement de ces films - Google Patents

Films polyester a orientation biaxiale et procede de traitement de ces films Download PDF

Info

Publication number
WO2006001659A1
WO2006001659A1 PCT/KR2005/001978 KR2005001978W WO2006001659A1 WO 2006001659 A1 WO2006001659 A1 WO 2006001659A1 KR 2005001978 W KR2005001978 W KR 2005001978W WO 2006001659 A1 WO2006001659 A1 WO 2006001659A1
Authority
WO
WIPO (PCT)
Prior art keywords
film
temperature
equation
directional orientation
biaxially oriented
Prior art date
Application number
PCT/KR2005/001978
Other languages
English (en)
Inventor
Sang-Hyun Baek
Do-Hyun Kim
Original Assignee
Kolon Industries Inc.
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 Kolon Industries Inc. filed Critical Kolon Industries Inc.
Publication of WO2006001659A1 publication Critical patent/WO2006001659A1/fr

Links

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
    • 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
    • C08G63/91—Polymers modified by chemical after-treatment
    • C08G63/914—Polymers modified by chemical after-treatment derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/916—Dicarboxylic acids and dihydroxy compounds
    • 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
    • C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/16—Dicarboxylic acids and dihydroxy compounds
    • C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
    • C08G63/181—Acids containing aromatic rings
    • C08G63/183—Terephthalic 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
    • C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/16—Dicarboxylic acids and dihydroxy compounds
    • C08G63/20—Polyesters having been prepared in the presence of compounds having one reactive group or more than two reactive groups
    • 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
    • C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/46—Polyesters chemically modified by esterification
    • 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
    • C08G63/66—Polyesters containing oxygen in the form of ether groups
    • C08G63/668—Polyesters containing oxygen in the form of ether groups derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/672—Dicarboxylic acids and dihydroxy compounds

Definitions

  • the present invention relates to a biaxially oriented polyester film having excellent twisting properties, and processing method thereof, and more particularly, to a biaxially oriented polyester film that is useful for packaging materials for candies, chocolates, caramels and the like by imparting twisting properties to a biaxially oriented polyester film having inherently excellent mechanical properties, printabilities, transparencies, thickness uniformities, cutting properties, innoxious properties and the like and processing method thereof.
  • PET polyethyleneterephthalate
  • the polyethyleneterephthalate films prepared from aromatic dicarboxylic acid and ethyleneglycol have excellent mechanical properties including heat resistance, tensile strength, elongation ratio, Young's modulus, elastic recovery, impact resistance and the like, dimensional stability, electric insulation properties, it can be used as industrial materials and agricultural materials, such as magnetic recording tapes, photographic films, insulating materials, vapor depositing films(films to be vapor deposited) and the like.
  • an industrial method of PET films comprises melt-extruding PET polymers and cooling a melt-extrudates in cooling drum to form an amorphous sheet; and then annealing the amorphous sheet to form biaxially oriented films.
  • PET polymers are prepared by direct esterification reaction of dicarboxylic acid such as terephthalic acid and ethyleneglycol as major components at 200 to 280 ° C and an ambient pressure or under pressurized conditions, or trans esterification reaction of dimethylcarboxylate such as dimethylterephthalate and ethyleneglycol as major components in the presence of catalysts at 140 to 240 ° C, to obtain bis(j3 -hydroxyethyl)terephthalates and low molecular weight condensates thereof as major components, and successively heating it in combination with polycondensation catalysts at 260 to 300 ° C to carry out polycondensation.
  • dicarboxylic acid such as terephthalic acid and ethyleneglycol
  • an ambient pressure or under pressurized conditions or trans esterification reaction of dimethylcarboxylate such as dimethylterephthalate and ethyleneglycol as major components in the presence of catalysts at 140 to 240 ° C, to obtain bis(j3 -hydroxyethy
  • PET films have great industrial values due to their excellent physical properties as described above. However, their utilization is limited in some applications. Particularly, the films that are used as packaging materials for packaging candies, caramels, chocolates and the like should have excellent twisting properties, high stiffness, printabilities, innoxious properties to human body, cutting properties and the like, but PET films have very weak twisting properties due to their high recovery. Additionally, cellophanes, OPS, PVC films and the like have been used as packaging materials for candies, caramels, chocolates and the like in the past, since their twisting properties are excellent.
  • the PET films have also the twisting properties, the films can meet various physical properties including other mechanical properties, printabilities, transparencies, thickness uniformities, cutting properties, innoxious properties and the like that are necessary for packaging materials.
  • the PET films having twisting properties have not been developed due to high resiliency (elastic recovery properties) of the PET films.
  • an object of the present invention is to solve the problems involved in the prior art, and to provide a innoxious to human body and environment-friendly biaxially oriented polyester film that is useful for packaging materials for candies, chocolates, caramels and the like by imparting twisting properties to a biaxially oriented polyester film having inherently excellent mechanical properties, printabilities, transparencies, thickness uniformities, cutting properties, innoxious properties and the like and processing method thereof.
  • the present invention provides a biaxially oriented polyester film having 70 degrees or less of foldability ( ⁇ ), wherein the foldability is obtained by folding a film in half by using Heat Gradient under conditions of 0.2 MPa of pressure, 1 sec and an ambient temperature, and after 30 mins, calculating the degree of the folded portion by using the following equation 1.
  • Equation 1 ⁇ 2sin "1 (F/2L) wherein, F is a distance of an imaginary line connecting both end points of film folded in half, and 2L is total distance of the folded film.
  • the present invention provides a process for preparing a biaxially oriented polyester film having 70 degrees or less of foldability ( ⁇ ), wherein the foldability is obtained by folding a film in half by using Heat Gradient under conditions of 0.2 MPa of pressure, 1 sec and an ambient temperature and after 30 mins, calculating the degree of the folded portion by using the following equation 1,
  • Equation 1 ⁇ - 2sin "1 (F/2L) wherein, F is a distance of an imaginary line connecting both end points of film folded in half, and 2L is total distance of the folded film, comprising melting a polymer obtained from polyethyleneterephthalate alone or mixtures in combination with at least one copolymerization components at temperature of melting point or more, and then rapid cooling the molten polymer at temperature of glass transition temperature or less to prepare an amorphous sheet; biaxially orienting the amorphous sheet with larger machine directional(MD) orientation ratio than transverse directional(TD) orientation ratio under conditions of a machine directional orientation temperature that satisfies the following equation 2 and a transverse directional orientation temperature that satisfies the following equation 3;
  • Tg machine directional orientation temperature (Tsm) ⁇ Tg + 30 ° C
  • Tg is glass transition temperature
  • Tsm transversal orientation temperature (Tst) ⁇ Tsm + 30 ° C
  • Tsm is machine directional orientation temperature
  • Equation 4 Tg ⁇ annealing temperature ⁇ Tst + 30 ° C wherein, Tg is glass transition temperature, and Tst is transverse directional orientation temperature. relaxing the annealed film under relaxing condition that satisfies the following equation 5. Equation 5 -3% ⁇ relaxation ⁇ 3%
  • Fig. 1 is a scheme for illustrating calculating method of foldability.
  • W a width of film
  • L a distance of film folded in half
  • F a distance of an imaginary line connecting both end points of film folded in half
  • ⁇ a degree of portion folded in half, foldability
  • the polyester film according to the present invention has 70° or less of foldability as defined following to increase twisting properties.
  • the "foldability" of the present invention means degree ( ⁇ ) obtained by folding a film in half by using Heat Gradient under conditions of 0.2 MPa of pressure, 1 sec and an ambient temperature, and after 30 mins, calculating the degree of the folded portion by using the following equation 1. Equation 1 wherein, F is a distance of an imaginary line connecting both end points of film folded in half, and 2L is total distance of the folded film.
  • the polyester film of the present invention has 70 degrees or less of a foldability, and so when candies and the like are packaged with the polyester film used as packaging materials, the packages won't be disintegrated even after lapsing a long time. If the foldability is 70 degree or more, after somewhat lapsing time, the packages can be disintegrated and the content can be exserted. Therefore, the polyethylene film having 70 degrees of foldability cannot be suitable for packaging materials. Further, the polyester film of the present invention can be obtained from polyethyleneterephthalate alone, or mixtures in combination with at least one copolymerization components.
  • At least one copolymerization components is preferably selected from acids, esters or alcohols, more preferably is selected from acids including isophthalic acid and adipic acid; esters including naphtalenecarboxylicmethylester; alcohols including diethyleneglycol, polyethyleneglycol, polypropyleneglycol and polytetramethyleneglycol.
  • the polyester film of the present invention can be obtained from polyethyleneterephthalate alone, or mixtures in combination with at least one copolymerization components, therefore an addition of the copolymerization components can be carried out by any method including polymerizing method or blending method.
  • " " / ⁇ w J y ⁇ ft Preparation conditions of the polyester film can be set depending on thermaf ' o behaviors of respective compositions.
  • the first operation is melting a polymer obtained from polyethyleneterephthalate alone, or mixtures in combination with at least one copolymerization components at temperature of melting point or more, and then rapid cooling the molten polymer at temperature of glass transition temperature or less to prepare an amorphous sheet.
  • the second operation is biaxially orienting the amorphous sheet with larger machine directional orientation ratio than transverse directional orientation ratio under conditions of a machine directional orientation temperature that satisfies the above equation 2 and a transverse directional orientation temperature that satisfies the above equation 3.
  • a machine directional(MD) orientation temperature can be in the range of glass transition temperature of the composition to above 30 "C higher temperature than glass transition temperature.
  • the orientation can be carried out at temperature closing to glass transition temperature.
  • a transverse directional(TD) orientation can be also carried out in the range of machine directional orientation temperature to higher temperature above 30 ° C than machine directional orientation temperature.
  • the orientation is carried out in machine direction from 3 to 5 times, and then in transverse direction from 3 to 5 times.
  • a machine directional orientation ratio can be larger than transverse orientation ratio.
  • the biaxially oriented film is annealing at the temperature that satisfies the above equation 4, and then the annealed film is relaxed under conditions that satisfy the above equation 5.
  • the annealing temperature in the annealing operation is in a range from glass transition temperature to above 30O higher temperature than transverse direction orientation temperature, preferably transverse direction orientation temperature or less.
  • the heat treatment should be carried out at least at glass transition temperature or more to minimize shrinkage when heat is applied to the film.
  • a relaxation (%) can be 3% or less, preferably 0%. Rather, it is also possible in even case that an orientation is carried out in heat fixation zone (relaxation (%): -3%). However, in case of orientation, crimples in appearance can be occurred.
  • the present invention will be described in greater detail with reference to the following examples. The following examples are for illustrative purposes and are not intended to limit the scope of the invention.
  • Examples 1, 2 and comparative examples 1 to 4 An amorphous sheet was prepared by extruding polyethyleneterephthalate, and then rapid cooling extruded polyethyleneterephthalate. A film was prepared by biaxially orienting the amorphous sheet successively under conditions described in the following Table 1. A glass transition temperature of the rapid cooled non-oriented polyethyleneterephthalate was 68 ° C according to the result as analyzed with differential scanning calorimetry (DSC). Table 1
  • a folability measurement of the film was carried out as follows. It can be referred that the more a modified body by external force can not return to the original state, the more twisting properties is excellent. Therefore, we evaluated the foldability by folding a film with identical pressure for identical time period, releasing pressure, and then comparing folding degree of the film.
  • the foldability of the polyester film prepared according to the present invention was 70° or less, and the polyester film exhibited excellent folding properties.
  • Examples 3 to 7 and Comparative example 5 relate to the biaxially oriented polyester film prepared in combination with copolymerization components.
  • An amorphous sheet was prepared by extruding copolymerization polyester in combination with copolymerization components described in the following Table 3 and then rapid cooling it.
  • the glass transition temperature of the amorphous polyester copolymer sheet was measured by DSC. The results were shown in the Table 3.
  • the conditions for preparing the film are as follows, which are included in the scope of examples.
  • - machine directional orientation ratio 4.0 times
  • - transverse directional orientation ratio 3.5 times
  • - machine directional orientation temperature Tg + 25 " C
  • - transverse directional orientation temperature machine directional orientation temperature + 10 ° C
  • - relaxation (%) 0%
  • - annealing temperature transverse directional orientation temperature + 10 ° C .
  • the amorphous polyester copolymer sheet was prepared in a identical method to examples 3 to 7, except that heat treating temperature was transverse directional elongation temperature + 50 ° C .
  • the foldability of the polyester film prepared according to the present invention was 70° or less, and the polyester film exhibited excellent folding properties.
  • the polyester film can be used usefully as a packaging materials for packaging candies, caramels or chocolates since the polyester film has inherently mechanical properties, printabilities, transparencies, thickness uniformities, cutting properties, innoxious properties and the like as well as twisting properties.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Organic Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Shaping By String And By Release Of Stress In Plastics And The Like (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)
  • Wrappers (AREA)

Abstract

L'invention concerne un film de polyester à orientation biaxiale présentant une pliabilité (?) égale ou inférieure à 70 degrés, la pliabilité étant mesurée par pliage du film en deux au moyen d'un dispositif [gradient thermique] à une pression de 0,2 MPa, pendant 1 seconde, à température ambiante, et calcul du degré de pliure de la partie pliée au moyen de l'équation (1) suivante: 1. Equation 1 ? = 2sin-1(F/2L) dans laquelle F représente la longueur d'une ligne imaginaire reliant les deux extrémités du film plié en deux, et 2L représente la longueur totale du film plié. Ce film de polyester à orientation biaxiale peut servir de matériau d'emballage pour bonbons, caramels ou chocolats, du fait de ses qualités inhérentes en matière de propriétés mécaniques, d'aptitude à l'impression, de transparence, d'uniformité d'épaisseur, d'aptitude au découpage, d'absence de toxicité, et d'aptitude à la torsion.
PCT/KR2005/001978 2004-06-25 2005-06-24 Films polyester a orientation biaxiale et procede de traitement de ces films WO2006001659A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
KR10-2004-0048216 2004-06-25
KR1020040048216A KR100893721B1 (ko) 2004-06-25 2004-06-25 꼬임성이 우수한 이축연신 폴리에스테르 필름 및 그제조방법

Publications (1)

Publication Number Publication Date
WO2006001659A1 true WO2006001659A1 (fr) 2006-01-05

Family

ID=35782034

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/KR2005/001978 WO2006001659A1 (fr) 2004-06-25 2005-06-24 Films polyester a orientation biaxiale et procede de traitement de ces films

Country Status (3)

Country Link
KR (1) KR100893721B1 (fr)
TW (1) TWI292409B (fr)
WO (1) WO2006001659A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2009083771A1 (fr) 2007-12-27 2009-07-09 Polyplex Corporation Limited Film de polyester à orientation biaxiale et procédé pour le préparer
WO2012045801A1 (fr) 2010-10-07 2012-04-12 Nestec S.A. Coacervats complexes à base de lactoferrine et leurs utilisations

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR100873387B1 (ko) * 2005-12-12 2008-12-10 주식회사 코오롱 꼬임성을 갖는 폴리에스테르 필름의 제조방법
KR100932289B1 (ko) * 2008-07-30 2009-12-16 주식회사 코오롱 꼬임성을 갖는 폴리에스테르 필름
KR101511761B1 (ko) 2013-10-04 2015-04-14 도레이첨단소재 주식회사 이축연신 폴리에스테르 필름과 이의 제조방법 및 이의 단부 펄럭임 제어방법

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1999054529A1 (fr) * 1998-04-23 1999-10-28 E.I Dupont De Nemours And Company Film de polyester et ses procedes de fabrication
JP2001200073A (ja) * 2000-01-20 2001-07-24 Toray Ind Inc 貼り合わせ用ポリエステルフィルム

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR100541230B1 (ko) * 2001-12-11 2006-01-10 에스케이씨 주식회사 이축연신 폴리에스테르 필름

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1999054529A1 (fr) * 1998-04-23 1999-10-28 E.I Dupont De Nemours And Company Film de polyester et ses procedes de fabrication
JP2001200073A (ja) * 2000-01-20 2001-07-24 Toray Ind Inc 貼り合わせ用ポリエステルフィルム

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2009083771A1 (fr) 2007-12-27 2009-07-09 Polyplex Corporation Limited Film de polyester à orientation biaxiale et procédé pour le préparer
US8465842B2 (en) 2007-12-27 2013-06-18 Polyplex Corporation Limited Biaxial oriented polyester film and a process for preparing the same
WO2012045801A1 (fr) 2010-10-07 2012-04-12 Nestec S.A. Coacervats complexes à base de lactoferrine et leurs utilisations
EP2441443A1 (fr) 2010-10-07 2012-04-18 Nestec S.A. Coacervats complexes à base de lactoferrine et leurs utilisations

Also Published As

Publication number Publication date
TWI292409B (en) 2008-01-11
TW200606193A (en) 2006-02-16
KR100893721B1 (ko) 2009-04-17
KR20050122621A (ko) 2005-12-29

Similar Documents

Publication Publication Date Title
JP3258302B2 (ja) 生分解性２軸延伸フィルム
EP1449867B1 (fr) Fenetres de films de resine a base d'acide polylactique orientes biaxialement
TWI429691B (zh) 熱可收縮性聚酯膜
KR100675606B1 (ko) 생분해성 백
KR100845401B1 (ko) 폴리에스테르 블렌드 및 이로부터 제조된 열 수축성 필름
KR100816768B1 (ko) 열수축성 폴리에스테르계 필름
EP2217643A2 (fr) Film polyester thermorétractable
JP4243926B2 (ja) 生分解性熱収縮性フィルム及びそれを用いたシュリンク包装体
WO2006001659A1 (fr) Films polyester a orientation biaxiale et procede de traitement de ces films
JP3328418B2 (ja) 熱収縮性ポリ乳酸系フイルム
KR101695926B1 (ko) 폴리에스터 필름 및 이의 제조방법
JP4535553B2 (ja) 熱収縮性ポリエステルフィルム
JP4802371B2 (ja) 熱収縮性ポリエステル系フィルムの製造方法
US20050112346A1 (en) Method for the production of PET sheets
JP3662141B2 (ja) ポリ乳酸系収縮シート状物、及びこれを用いた包装材又は収縮ラベル材
JP3664969B2 (ja) 熱収縮性ポリ乳酸系重合体フィルム状物
KR20050117240A (ko) 폴리에스터 수축 필름
JP4543743B2 (ja) 成形用二軸延伸ポリ乳酸フィルムおよび容器
JP2004034451A (ja) 熱収縮性ポリエステル系フィルムの製造方法
JP2000280342A (ja) ポリ乳酸系収縮シート状物、及びこれを用いた包装材又は収縮ラベル材
JPH05305666A (ja) 形状記憶ポリエステル成形物
KR100888779B1 (ko) 꼬임성이 우수한 폴리에스터 필름
JP4502091B2 (ja) 熱収縮性ポリエステル系フィルム
JP2000198913A (ja) 易引裂性ポリ乳酸系二軸延伸フィルム
JPH093177A (ja) 乳酸系ポリマーから成るシュリンクフィルム

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): AE AG AL AM AT AU AZ BA BB BG BR BW BY BZ CA CH CN CO CR CU CZ DE DK DM DZ EC EE EG ES FI GB GD GE GH GM HR HU ID IL IN IS JP KE KG KM KP KZ LC LK LR LS LT LU LV MA MD MG MK MN MW MX MZ NA NG NI NO NZ OM PG PH PL PT RO RU SC SD SE SG SK SL SM SY TJ TM TN TR TT TZ UA UG US UZ VC VN YU ZA ZM ZW

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): GM KE LS MW MZ NA SD SL SZ TZ UG ZM ZW AM AZ BY KG KZ MD RU TJ TM AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IS IT LT LU MC NL PL PT RO SE SI SK TR BF BJ CF CG CI CM GA GN GQ GW ML MR NE SN TD TG

121 Ep: the epo has been informed by wipo that ep was designated in this application
NENP Non-entry into the national phase

Ref country code: DE

WWW Wipo information: withdrawn in national office

Country of ref document: DE

122 Ep: pct application non-entry in european phase