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WO2007036980A1 - Film lamine de permeabilite au gaz - Google Patents

Film lamine de permeabilite au gaz Download PDF

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Publication number
WO2007036980A1
WO2007036980A1 PCT/JP2005/017706 JP2005017706W WO2007036980A1 WO 2007036980 A1 WO2007036980 A1 WO 2007036980A1 JP 2005017706 W JP2005017706 W JP 2005017706W WO 2007036980 A1 WO2007036980 A1 WO 2007036980A1
Authority
WO
WIPO (PCT)
Prior art keywords
gas
gas barrier
film
laminated film
coating layer
Prior art date
Application number
PCT/JP2005/017706
Other languages
English (en)
Japanese (ja)
Inventor
Hiroshi Suzuki
Ryukichi Matsuo
Noboru Sasaki
Original Assignee
Toppan Printing 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 Toppan Printing Co., Ltd. filed Critical Toppan Printing Co., Ltd.
Priority to CN2005800405986A priority Critical patent/CN101065240B/zh
Priority to PCT/JP2005/017706 priority patent/WO2007036980A1/fr
Priority to JP2007537481A priority patent/JPWO2007036980A1/ja
Publication of WO2007036980A1 publication Critical patent/WO2007036980A1/fr

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
    • C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
    • C23C16/40—Oxides
    • C23C16/401—Oxides containing silicon
    • 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
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/042—Coating with two or more layers, where at least one layer of a composition contains a polymer binder
    • C08J7/0423—Coating with two or more layers, where at least one layer of a composition contains a polymer binder with at least one layer of inorganic material and at least one layer of a composition containing a polymer binder
    • 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
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/043—Improving the adhesiveness of the coatings per se, e.g. forming primers
    • 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
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/048—Forming gas barrier coatings
    • 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
    • C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds

Definitions

  • the present invention relates to a gas noreia laminated film used in the packaging field of foods, pharmaceuticals and the like.
  • packaging materials used for packaging foods, pharmaceuticals, etc. have been used to suppress the alteration of the contents and to maintain the efficacy of oxygen, water vapor, and other gases that alter the contents of the packaging material. It is necessary to prevent the influence of the gas, and it is required to have gas noria properties that block the permeation of these gases.
  • polybulal alcohol PVA
  • ethylenebulualcohol copolymer EVOH
  • PVDC polysalt vinylidene resin
  • a gas-nolia laminated film obtained by laminating or coating a polymer resin composition is generally used as a packaging film.
  • Metal vapor deposition films obtained by depositing metal or metal compounds such as aluminum (A1) on polymer resin compositions, and recently, silicon oxide (SiO 2) thin films such as silicon monoxide (SiO), ⁇ Magnesium (MgO) thin film with high transparency
  • Vapor-deposited films deposited on substrates that also have molecular material strength have been developed. These have superior gas noreia properties than gas noble materials made from a high molecular weight resin composition alone, and are less susceptible to deterioration under high humidity. Has begun to be used.
  • gas- noria laminated films using the above-described PVA and EVOH polymer resin compositions have a large temperature dependency and humidity dependency. Deterioration of the subbarrier property is observed, in particular, the water vapor nore property is lowered, and depending on the packaging application, the gas nore property may be remarkably lowered by boiling or retort treatment.
  • a gas noreia laminated film using a PVDC-based polymer resin composition has a low humidity dependency but a high gas noreia material having an oxygen noreer property of lcm 3 / m 2 .day 'atm or less. It is difficult to realize (high gas nolia material).
  • PVDC-based polymer resin compositions contain a large amount of chlorine, which causes problems in waste disposal such as incineration and recycling.
  • the above-mentioned metal vapor-deposited film on which a metal or a metal compound is vapor-deposited, a silicon oxide thin film such as silicon monoxide (Si 2 O), or a vapor-deposited film on which a magnesium oxide (MgO) thin film is vapor-deposited are used as a gas nore layer.
  • the thin film of inorganic compound is inflexible, weak against stagnation and bending, and has poor adhesion to the substrate, so it needs to be handled with care, especially after packaging materials such as printing, laminating and bag making. If a crack is generated during processing and the gas noria property is significantly lowered, there is a problem.
  • gas noria material has a certain degree of improvement in gas noria properties compared to the case of a single substrate, it cannot be said that the gas noria properties are still sufficient. Disclosure of the invention
  • the present invention is a gas-nore laminate film that is excellent in gas-nore property, has excellent flexibility, and can suppress degradation of gas-no-reality even when the film is stretched.
  • the purpose is to provide a program.
  • a polymer film substrate, a gas barrier inorganic vapor deposition layer formed on one surface of the polymer film substrate, and the gas barrier inorganic vapor deposition layer are formed.
  • the oxygen permeability when the laminate film is stretched 5% is not more than 1.5 times the oxygen permeability before stretch.
  • a gas-noria laminated film characterized by having noria properties.
  • the gas-nolia laminated film according to one embodiment of the present invention has a water vapor permeability such that the water vapor permeability when the laminated film is stretched by 2% is not more than 1.5 times the water vapor permeability before stretching. Has barrier properties.
  • polyethylene terephthalate film As the polymer film substrate, a polyethylene terephthalate film can be used.
  • the gas barrier coating layer a layer mainly composed of an aqueous polymer having a hydroxyl group can be used.
  • the water-based polymer polybulal alcohol, ethylenebulal alcohol copolymer, and those containing at least one selected from the group strength of cellulose strength can be used.
  • a layer mainly composed of a composite material composed of a metal alkoxide and Z or a hydrolyzate thereof and an aqueous polymer having a hydroxyl group can be used.
  • a metal alkoxide a silicon alkoxide can be used.
  • the gas noriotic coating layer may contain a silane coupling agent.
  • FIG. 1 is a cross-sectional view showing a configuration of a gas barrier laminate film according to an embodiment of the present invention.
  • FIG. 2 is a graph showing the relationship between the degree of elongation and the oxygen permeability of the gas barrier laminate films of Example 1 and Comparative Example 1.
  • FIG. 3 is a graph showing the relationship between the degree of elongation and the water vapor transmission rate of the gas barrier laminate films of Example 1 and Comparative Example 1.
  • FIG. 1 is a schematic view illustrating the configuration of a gas noreia laminated film according to an embodiment of the present invention.
  • a gas barrier laminate film 1 is formed by sequentially laminating a gas norelic inorganic vapor deposition layer 3 as a first layer and a gas nore coat layer 4 as a second layer on a substrate 2. Has been.
  • the substrate 2 is in the form of a sheet or a film, and is a polyolefin such as polyethylene or polypropylene, a polyester such as polyethylene terephthalate, polybutylene terephthalate or polyethylene naphthalate, a polyamide such as nylon 6 or nylon 66, a poly What is normally used as a packaging material, such as butyl chloride, polyimide, or a copolymer of these polymers, can be appropriately selected depending on the application.
  • a polyolefin such as polyethylene or polypropylene
  • a polyester such as polyethylene terephthalate, polybutylene terephthalate or polyethylene naphthalate
  • a polyamide such as nylon 6 or nylon 66
  • a poly What is normally used as a packaging material such as butyl chloride, polyimide, or a copolymer of these polymers, can be appropriately selected depending on the application.
  • the substrate 2 for example, known additives such as an antistatic agent, an ultraviolet absorber, a plasticizer, a lubricant, and a colorant are appropriately added as necessary. I can do it. Further, the surface of the substrate 2 can be subjected to surface modification such as corona treatment or anchor coating treatment to improve the adhesion of the coating.
  • known additives such as an antistatic agent, an ultraviolet absorber, a plasticizer, a lubricant, and a colorant are appropriately added as necessary. I can do it.
  • the surface of the substrate 2 can be subjected to surface modification such as corona treatment or anchor coating treatment to improve the adhesion of the coating.
  • the first gas noble inorganic deposition layer 3 formed on the substrate 2 is made of an oxide, nitride, or fluoride of silicon, aluminum, titanium, zirconium, tin, magnesium, or the like. These are formed by a vacuum process such as a vacuum deposition method, a sputtering method, or a plasma vapor deposition method (CVD method).
  • a vacuum process such as a vacuum deposition method, a sputtering method, or a plasma vapor deposition method (CVD method).
  • acid-aluminum is colorless and transparent, has excellent characteristics such as boil and retort resistance, and can be used in a wide range of applications.
  • the thickness of the gas barrier inorganic vapor-deposited layer 3 varies depending on the application and the thickness of the second layer, but it is desirable that the force of several nm is in the range of 500 nm. If the thickness is less than 5 nm, there is a problem in the continuity of the thin film, and if it exceeds 300 nm, cracks occur and the flexibility decreases immediately, so 5 ⁇ ! ⁇ 30 Onm.
  • the second gas noble coating layer 4 formed on the gas barrier inorganic vapor deposition layer 3 is formed by using a coating agent mainly composed of an aqueous solution containing an aqueous polymer or a water Z alcohol mixed solution.
  • the aqueous polymer used as a coating agent for forming the gas nore coating layer 4 is a polymer having a hydroxyl group in the molecule, and is not necessarily limited to a water-soluble polymer. For example, those having an affinity for water, such as Emulsion.
  • aqueous polymer examples include polybulal alcohol, polybulurpyrrolidone, denpene, methylcellulose, carboxymethylcellulose, sodium alginate, an ethylenebulalcohol copolymer, acrylic resin such as polyacrylic acid and polymethacrylic acid, These acrylic resin resins can be mentioned, and particularly, when a polyvinyl alcohol (hereinafter referred to as PVA) is used as a coating agent, the gas nooricity is most excellent.
  • PVA polyvinyl alcohol
  • the PVA here is generally obtained by saponifying polyvinyl acetate, and several tens of percent of acetate groups remain.
  • V a partly partially saponified PVA.
  • V Completely saponified, including up to PVA, not particularly limited! /.
  • the metal alkoxide includes tetraethoxysilane [Si (OCH)], triisopropoxyaluminum.
  • M (OR) (wherein M represents a metal such as Si, Ti, Ai or Zr, and R represents an n 3 2 5 alkyl group such as CH or CH)
  • tetraethoxysilane and triisopropoxyaluminum are preferable because they are relatively stable in an aqueous solvent after hydrolysis.
  • the gas barrier coating layer 4 contains a composite material of an aqueous polymer and a metal alkoxide or a hydrolyzate thereof.
  • the water resistance of the gas barrier coating layer 4 can be improved by using a metal alkoxide.
  • a silane coupling agent can be added to the coating agent. Thereby, the heat resistance of the formed gas barrier coating layer 4 is increased, and even when the gas barrier laminated film is used for packaging of a boiled product or a retort product, it is possible to suppress a decrease in the barrier property.
  • the coating agent has a range that does not impair the barrier property of the gas barrier coating layer 4, and is usually a filler, a lubricant that imparts slipperiness to the film, a colorant, a leveling agent, a purple color.
  • Known additives such as external line absorbers, antioxidants, dispersants, stabilizers, viscosity modifiers, and colorants can be added.
  • an inorganic layered compound such as montmorillonite or smectite can be added to the coating agent in order to give the gas nore coating layer 4 itself nore nature.
  • the film thickness varies depending on the type of coating agent.
  • the thickness after drying may be in the range of about 0.01 to LOO / z m. If it is 50 / z m or more, cracks are likely to occur in the film, so 0.01 to 50 m is desirable.
  • reaction layer is formed between the gas noble inorganic vapor deposition layer 3 and the coating formed by application of the coating agent, or a pinhole in which this coating is formed in the gas barrier inorganic vapor deposition layer 3.
  • a dense structure is formed by filling and reinforcing defects such as cracks and grain boundaries, or micropores, which serve as a protective layer for improving the gas barrier property and for the gas barrier inorganic vapor deposition layer.
  • the gas nooriety can be improved by the following mechanism. That is, the inorganic component composed of metal alkoxide undergoes hydrolysis and polycondensation reaction in solution to form a chain or three-dimensional toothpick polymer, and the polymerization proceeds further by evaporation of the solvent upon drying and heating. It is considered to form a complex at the molecular level with aqueous polymers. Therefore, silica sol (silica silicate (water glass) with fine particles such as silica (SiO 2) with a specific particle size can be obtained.
  • silica sol sica silicate (water glass) with fine particles such as silica (SiO 2) with a specific particle size
  • thermoplastic resin layer and a print layer that can be heat-sealed as necessary are provided on the gas nore coating layer 4 or the substrate 2.
  • processing such as printing and laminating on a packaging material is performed by unwinding the film on a machine, so that tensile stress is applied, and cracks are easily generated in the gas barrier vapor deposition layer.
  • the gas-nootropic laminated film according to one embodiment of the present invention described above is Since the decrease in barrier properties when stretched is small, the barrier properties that were initially retained are almost maintained even when printing on films or processing such as pasting with other films, resulting in high barrier properties. Certain packaging materials can be provided.
  • the gas barrier vapor deposition layer 3 with the inorganic compound strength is used as the first layer on the base material 2 with the polymer resin composition strength, and the aqueous polymer (or the composite of the aqueous polymer and the metal alkoxide).
  • the gas noble laminate film according to the present embodiment obtained by laminating the gas nore coating layer 4 containing the union) as the second layer has high gas nooriness and is flexible, laminate strength, and water resistance. Excellent in heat resistance, moisture resistance, and boil-retort resistance, and even when laminated with other resins, its strength is sufficient for practical use.
  • the oxygen permeability when the laminated film is stretched by 5% is 1.5 times or less of the oxygen permeability before stretching, it can be used as a packaging material in post-processing such as laminating and bag making. It has an excellent effect that it does not impair the gas properties.
  • Aluminum oxide was deposited on the top surface of a 12 m-thick polyethylene terephthalate substrate to a thickness of 15 nm. Further, tetraethoxysilane [Si (OC H):
  • TEOS TEOS
  • a coating agent containing poly bull alcohol
  • Aluminum oxide was deposited on the upper surface of a 12 m-thick polyethylene terephthalate substrate to a thickness of 15 nm to obtain a gas nore laminate film.
  • Example 1 and Comparative Example 1 were stretched in the longitudinal direction, and the gas barrier properties after stretching were determined and compared. That is, the gas nootropic laminated film was stored under constant temperature and humidity of 40 ° C.-90% RH for 4 weeks, and the gas barrier properties before and after that were evaluated by measuring oxygen permeability and water vapor permeability.
  • Oxygen barrier properties at 25 ° C—100% RH atmosphere Measured using a permeability measurement device (MOCON OXTRAN 10Z40A manufactured by Modern Control), and measured the water vapor barrier property using a water vapor permeability measurement device (PERMATRAN W6 manufactured by Modern Control) in an atmosphere of 40 ° C-90RH. .
  • the results are shown in Table 1 and Table 2 below.
  • Table 1 shows the oxygen barrier properties after elongation
  • Table 2 shows the water vapor permeability barrier properties after elongation.
  • 2 and 3 plot Table 1 and Table 2 with the degree of elongation on the horizontal axis and the degree of transmission on the vertical axis.
  • the laminated film according to Example 1 has almost no increase in oxygen permeability even at 5% elongation, whereas the laminated film according to Comparative Example 1 has 5 It can be seen that the oxygen permeability rapidly increased 20 times and the oxygen norality decreased at the elongation of%.
  • the laminated film according to Example 1 hardly increased the water vapor permeability even at an elongation of 2%, whereas the laminated film according to Comparative Example 1 At 2% elongation, the water vapor permeability increases abruptly 10 times, indicating that the water vapor barrier properties are reduced.
  • the gas barrier laminate film of the present invention maintains excellent gas permeability even after stretching due to the formation of a gas nore coating layer on the gas noble vapor deposition layer, so printing, laminating, It can be applied as a packaging material for foods, pharmaceuticals, etc., whose gas barrier properties do not deteriorate even when processing bags, etc., and its range of use is wide.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • General Chemical & Material Sciences (AREA)
  • Laminated Bodies (AREA)

Abstract

La présente invention a trait à un film laminé de perméabilité au gaz comportant un substrat de film polymère, une couche de dépôt en phase vapeur de perméabilité au gaz d'un composé inorganique formée à la surface du substrat de film polymère, et une couche de revêtement de perméabilité au gaz formée sur la couche de dépôt en phase vapeur de perméabilité au gaz, caractérisé en ce que le film présente une telle propriété de perméabilité au gaz qu'une perméabilité à l'oxygène du film après extension par 5 % est d'une grandeur égale ou inférieure par 1,5 fois que celle d'avant l'extension.
PCT/JP2005/017706 2005-09-27 2005-09-27 Film lamine de permeabilite au gaz WO2007036980A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
CN2005800405986A CN101065240B (zh) 2005-09-27 2005-09-27 气体阻挡性层叠薄膜
PCT/JP2005/017706 WO2007036980A1 (fr) 2005-09-27 2005-09-27 Film lamine de permeabilite au gaz
JP2007537481A JPWO2007036980A1 (ja) 2005-09-27 2005-09-27 ガスバリア性積層フィルム

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/JP2005/017706 WO2007036980A1 (fr) 2005-09-27 2005-09-27 Film lamine de permeabilite au gaz

Publications (1)

Publication Number Publication Date
WO2007036980A1 true WO2007036980A1 (fr) 2007-04-05

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Application Number Title Priority Date Filing Date
PCT/JP2005/017706 WO2007036980A1 (fr) 2005-09-27 2005-09-27 Film lamine de permeabilite au gaz

Country Status (3)

Country Link
JP (1) JPWO2007036980A1 (fr)
CN (1) CN101065240B (fr)
WO (1) WO2007036980A1 (fr)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2010082867A (ja) * 2008-09-30 2010-04-15 Dainippon Printing Co Ltd 選択ガス透過性フィルムおよびその製造方法
CN113507840A (zh) * 2019-03-01 2021-10-15 悠亚布莱德公司 冷冻食品包装产品的制造方法、食品包装用膜以及冷冻食品包装产品
CN114264595A (zh) * 2021-12-07 2022-04-01 江苏沃源包装制品有限公司 一种食品包装膜生产线的输送检验设备
US11473190B2 (en) 2017-06-22 2022-10-18 The Procter & Gamble Company Films including a water-soluble layer and a vapor-deposited inorganic coating
US11738367B2 (en) 2017-06-22 2023-08-29 The Procter & Gamble Company Films including a water-soluble layer and a vapor-deposited organic coating

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DE102009009876B4 (de) * 2009-02-20 2012-05-16 Kuhne Anlagenbau Gmbh Ein- oder mehrschichtige, räucherbare, lufttrockenbare, schlauchförmige Nahrungsmittelfolie für Lebensmittelverpackungen sowie Verfahren zu deren Herstellung
TWI590951B (zh) * 2011-07-28 2017-07-11 凸版印刷股份有限公司 積層體、阻氣薄膜、積層體之製造方法及積層體製造裝置
JP6304745B2 (ja) * 2013-01-31 2018-04-04 国立研究開発法人産業技術総合研究所 ガスバリア性評価装置および評価方法
CN114096406A (zh) * 2019-05-08 2022-02-25 昭和电工材料株式会社 阻隔材料及具备该阻隔材料的产品
CN114539916A (zh) * 2022-02-23 2022-05-27 浙江弘康半导体技术股份有限公司 一种降低水汽透过率的有机/无机杂化聚合物

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JPS62103139A (ja) * 1985-10-31 1987-05-13 東洋インキ製造株式会社 レトルトパウチ用包装材
JPH11300875A (ja) * 1998-04-23 1999-11-02 Toppan Printing Co Ltd 高バリアポリマー複合フィルムおよび包装体

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2010082867A (ja) * 2008-09-30 2010-04-15 Dainippon Printing Co Ltd 選択ガス透過性フィルムおよびその製造方法
US11473190B2 (en) 2017-06-22 2022-10-18 The Procter & Gamble Company Films including a water-soluble layer and a vapor-deposited inorganic coating
EP3642383B1 (fr) * 2017-06-22 2022-12-21 The Procter & Gamble Company Films comprenant une couche hydrosoluble et un revêtement inorganique déposé en phase vapeur
US11738367B2 (en) 2017-06-22 2023-08-29 The Procter & Gamble Company Films including a water-soluble layer and a vapor-deposited organic coating
CN113507840A (zh) * 2019-03-01 2021-10-15 悠亚布莱德公司 冷冻食品包装产品的制造方法、食品包装用膜以及冷冻食品包装产品
CN114264595A (zh) * 2021-12-07 2022-04-01 江苏沃源包装制品有限公司 一种食品包装膜生产线的输送检验设备

Also Published As

Publication number Publication date
CN101065240B (zh) 2011-12-14
CN101065240A (zh) 2007-10-31
JPWO2007036980A1 (ja) 2009-04-02

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