WO1998040208A1 - Matiere d'emballage - Google Patents

Matiere d'emballage Download PDF

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Publication number
WO1998040208A1
WO1998040208A1 PCT/JP1998/001013 JP9801013W WO9840208A1 WO 1998040208 A1 WO1998040208 A1 WO 1998040208A1 JP 9801013 W JP9801013 W JP 9801013W WO 9840208 A1 WO9840208 A1 WO 9840208A1
Authority
WO
WIPO (PCT)
Prior art keywords
inorganic oxide
packaging material
film
oxide film
wettability
Prior art date
Application number
PCT/JP1998/001013
Other languages
English (en)
Japanese (ja)
Inventor
Shigeki Yamaguchi
Original Assignee
Idemitsu Petrochemical 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 Idemitsu Petrochemical Co., Ltd. filed Critical Idemitsu Petrochemical Co., Ltd.
Publication of WO1998040208A1 publication Critical patent/WO1998040208A1/fr

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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
    • 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

Definitions

  • the present invention relates to a packaging material for articles that require high gas barrier properties and strength.
  • packaging materials composed of a plastic film on which an inorganic oxide film has been adhered have been widely used in view of their high gas barrier properties, non-polluting properties, convenience, and cost reduction.
  • Conventional film materials are usually polyester-based resins.
  • the deposition of the inorganic oxide film is performed by vacuum evaporation.
  • polyester resin films have insufficient strength in some cases, and as a packaging material for heavy objects such as liquids, there are problems with the pinhole resistance and the performance required as a packaging material such as. Therefore, it has been proposed to use a polyamide film such as Nylon 6 which is excellent in strength.
  • the strength can be improved by using a polyamide resin film
  • the adhesive strength between the inorganic oxide film and the film can be improved.
  • the inorganic oxide film was peeled off because of its weakness.
  • the polyamide resin film itself undergoes relatively large dimensional changes due to moisture absorption, if the film absorbs moisture, the inorganic oxide film is liable to peel off, which is a major problem in durability as a packaging material. was there.
  • an object of the present invention is to provide a packaging material having an inorganic oxide film having high gas barrier properties and high adhesive strength. Disclosure of the invention
  • the packaging material according to the first invention of the present invention is characterized by having a polyamide-based film and an inorganic oxide film formed by plasma CVD and containing silicon, oxygen and carbon as main components. .
  • nylon 6 nylon 66
  • aromatic nylon for example, MX6
  • MX6 aromatic nylon
  • the plasma CVD method is a technique in which a high-frequency electric field is applied to a reaction gas, the gas is activated using the electric energy, and a thin film is formed under low-temperature plasma conditions.
  • an organic silane-based compound having a Si—O—C bond as a reaction gas raw material for example, 1,1,3,3-tetramethyldisiloxane, hexamethyldisiloxane, Tetraethoxysilane, tetramethoxysilane, vinyltrimethoxysilane, hexamethyldisilazane, and the like can be used.
  • an inorganic oxide film formed by the covalent bonding of the three elements of silicon (Si), oxygen (0), and carbon (C) adheres to the surface of the polyamide-based film. .
  • the packaging material contains a polyamide film and an inorganic oxide film, and the film may have a multilayer structure having the polyamide film.
  • the inorganic oxide film formed by the present invention is excellent in transparency and has an oxygen permeability of 2 cc / m3 / 24 hr or less.
  • a packaging material according to a second aspect of the present invention is the packaging material according to the first aspect, wherein an elemental composition ratio of carbon in the inorganic oxide film is 2 to 35 wt%. If the composition ratio of the carbon is less than 2 wt%, the film may absorb moisture. Due to dimensional changes and mechanical stress during actual use, a marked decrease in gas barrier properties is observed. On the other hand, when the content exceeds 35 wt%, the yellowing of the inorganic oxide film becomes severe and the transparency is impaired, and at the same time the gas barrier property of the film is lowered.
  • the composition ratio of carbon is 10 to 30 wt%.
  • the elemental composition ratio of carbon can be adjusted by changing the mixing ratio of the raw material gas supplied to the plasma CVD device.
  • the packaging material according to a third aspect of the present invention is the packaging material according to the first or second aspect, wherein the surface of the polyamide-based film on which the inorganic oxide film is adhered has a wettability of 42 to 56 mN / m2. There is a feature.
  • the wettability of the polyamide-based film surface is less than 42 mN / m2, the adhesion of the inorganic oxide film to the polyamide-based film surface is reduced, and the durability is deteriorated. Below, sufficient gas barrier properties cannot be obtained. On the other hand, if it exceeds 56 mN / m2, peeling of the inorganic oxide film under high humidity conditions tends to occur, and the gas barrier performance is reduced.
  • the wettability is between 44 and 54 mN / m2.
  • a packaging material according to a fourth invention of the present invention is the packaging material according to any of the first to third inventions, wherein the surface of the inorganic oxide film has a wettability of 45 to 70 mN / m2.
  • the wettability of the inorganic oxide film surface is less than 45 mN / m2, sufficient adhesive strength cannot be obtained at the time of lamination during printing and lamination, and the practicability as a packaging material is low. Become. On the other hand, if it exceeds 70 mN / m2, structural defects such as cracks will occur in the inorganic oxide film during processing, and the gas barrier properties will be significantly reduced.
  • the wettability is 50 to 70 mN / m2.
  • a packaging material according to a fifth invention of the present invention is characterized in that the packaging material according to any one of the first to fourth inventions is included as at least one layer in a laminated structure.
  • the film laminated on the inorganic oxide film of the layer made of the packaging material according to any one of the first to fourth inventions has an improved durability of the inorganic oxide film and a moisture-proof property of the laminate. The purpose is to improve heat resistance and heat resistance.
  • the laminated film may be a polyester film, a polyolefin film, a metal foil, or the like.
  • the adhesive strength between the film to be laminated and the inorganic oxide film is preferably 4 N / 15 mm or more, more preferably 7 N / 15 mm or more from the viewpoint of the adhesive strength.
  • FIG. 1 is a sectional view of a packaging material according to an embodiment of the present invention.
  • FIG. 2 is a sectional view of a packaging material having a laminated structure according to one embodiment of the present invention.
  • FIG. 3 is a graph showing the measured oxygen permeability versus elongation for the packaging materials of Example 2 and Comparative Example 9.
  • FIG. 4 is a graph showing the oxygen permeability of the packaging materials of Example 2 and Comparative Example 9 as a function of the number of times of the gelbo test.
  • FIG. 5 is a graph of the oxygen permeability of the packaging materials of Example 2 and Comparative Example 9 as a function of the number of times of falling impact.
  • FIGS. 1-10 A packaging material according to an embodiment of the present invention will be described with reference to FIGS.
  • one side 11 A of the polyamide-based film 11 is subjected to edge treatment to adjust the wettability of the surface to 42 to 56 mN / m 2.
  • the polyamide-based film 11 is put into a plasma CVD device,
  • the inorganic oxide film 12 composed of silicon (Si), oxygen (0) and carbon (C) is subjected to corona treatment by plasma CVD while supplying an organic silane-based compound, oxygen and an inert gas as a reaction gas raw material. Is attached to the surface 11A where When the inorganic oxide film 12 is formed, the gas flow ratio is controlled so that the elemental composition ratio of carbon becomes 2 to 35 wt%.
  • the wettability of the surface 12A of the inorganic oxide film 12 is adjusted to 45 to 70 mN / m2 by oxygen plasma treatment.
  • a packaging material according to the present embodiment is formed.
  • Prepare 15 The adhesive strength between the polyamide film 11 and the polyolefin film 14 is 4 N / 15 mni or more.
  • the resin types of the polyolefin-based film and the polyamide (PA) -based film are as follows, the content of carbon in the inorganic oxide film, the wettability of the surface of the polyamide-based film, and the The packaging materials of the examples were prepared with the surface wettability of the oxide film as shown in Table 1.
  • Polyolefin film L-LDPE film (LS-711C, manufactured by Idemitsu Petrochemical Co., Ltd., thickness: 60 ⁇ ).
  • Polyamide film Biaxially stretched Nylon Nylon 6 film (UNILON G-100, manufactured by Idemitsu Petrochemical Co., Ltd., 15 ⁇ thick).
  • the resin types of the polyolefin-based film and the polyamide-based film were the same as those in the examples, but the content of carbon in the inorganic oxide film, the wettability of the surface of the polyamide-based film, and the inorganic oxide film Table 2 shows the surface wettability of the samples, and packaging materials of the respective examples were produced.
  • the elemental composition ratio of carbon in the inorganic oxide film was measured using an XPS apparatus manufactured by ULVAC FAI.
  • the surface wettability was measured using a surface wetting index standard reagent manufactured by Wako Pure Chemical Industries, Ltd. or a contact angle measuring device.
  • the adhesive strength of the inorganic oxide film was measured by a tape peeling method.
  • the oxygen transmission rate during the elongation of the packaging material was measured using a tensile tester.
  • Example 3 As shown in Table 3, according to the packaging materials of Examples 1 to 3, each of which has a polyamide-based film and an inorganic oxide film formed by a plasma CVD method, and has a carbon element composition ratio in the inorganic oxide film. Since the wettability of the surface of the polyamide-based film on which the inorganic oxide film is adhered is within a predetermined range according to the present invention, the oxygen permeability, the adhesive strength of the inorganic oxide film, and the elongation of the packaging material during elongation. It can be seen that the oxygen permeability was all good.
  • the packaging materials of Comparative Examples 1 and 2 have the same composition as those of Examples 1 and 2, but the inorganic oxide film of the polyamide-based film is adhered. Since the wettability of the surface outside the predetermined range according to the present invention, There was a problem in the oxygen permeability and the oxygen permeability during elongation of the packaging material.
  • the yellowness was measured with a YI measuring instrument.
  • Example 2 the packaging material of Example 2 according to the above embodiment and Comparative Example 9 produced by using a vacuum deposition method was measured for distortion resistance (suitability for lamination processing) and compared. This strain resistance is measured with respect to the oxygen permeability relative to the elongation of the packaging material.
  • Figure 3 shows the results.
  • Example 2 is a packaging material having an inorganic oxide film formed by a plasma CVD method
  • Comparative Example 9 is a packaging material having a silicide film formed by vacuum evaporation.
  • Table 6 shows the characteristics. [Table 6]
  • the packaging material of Example 2 has an inorganic oxide film formed by the plasma CVD method, and therefore has a higher gas barrier performance due to the elongation of the packaging material than the packaging material of Comparative Example 9. Is small.
  • Example 2 and Comparative Example 9 were measured for practical barrier performance (stability of gas barrier performance against external force during lamination, bag making, filling, and transportation) and compared.
  • the practical barrier performance was measured with respect to oxygen permeability with respect to the number of times of the gelbo test.
  • Figure 4 shows the results.
  • the packaging material of Example 6 has an inorganic oxide film formed by the plasma CVD method, and thus has a more practical barrier due to the elongation of the packaging material than the packaging material of Comparative Example 9. It can be seen that there is little change in performance.
  • the bag making conditions for this bag are as follows.
  • Adhesive aliphatic polyester adhesive
  • Bag form 130 X 150mm (inside dimensions 1 10 X 1 10mm), 3-side seal: Seal width 10mm. Sealing temperature: 130 ° C / 130 ° C / 140 ° C.
  • the bag product made of the packaging material of the second embodiment was Because of the presence of the formed inorganic oxide film, the change in oxygen permeability after the drop impact test is smaller and superior impact resistance compared to the bag product made of the packaging material of Comparative Example 9. You can see that it is doing.
  • the present invention can be used as a packaging material for articles requiring high gas barrier properties and strength, such as foods and industrial parts. More specifically, it is useful as a packaging material such as a bag-in box (BIB), a standing bouch, a packaging material for letnoret, a container lid, a pillow bag, a gazette bag, a three-sided bag, a four-sided bag, and the like. Can be used.
  • a bag-in box BBIB
  • a standing bouch a packaging material for letnoret
  • a container lid such as a container lid, a pillow bag, a gazette bag, a three-sided bag, a four-sided bag, and the like.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Wrappers (AREA)
  • Laminated Bodies (AREA)

Abstract

La présente invention concerne une matière d'emballage constituée d'une couche d'oxyde inorganique présentant des propriétés élevées de barrière au gaz et de résistance des liaisons et moins susceptible de provoquer une détérioration des propriétés de barrière au gaz lors d'une utilisation pratique. La matière d'emballage (14) comprend une couche d'oxyde inorganique (12) constituée essentiellement de silicium, d'oxygène et de carbone, sa surface étant constituée d'une couche mince de polyamide (11) par dépôt chimique en phase gazeuse (CVD) au plasma. La teneur de l'élément carbone de la couche d'oxyde inorganique (12) est de 2 à 35 % en poids. La mouillabilité d'une surface (11a) de la couche mince (11) de polyamide sur laquelle on doit appliquer la couche d'oxyde inorganique (12) est de 42 à 56 mN/m2. La surface (12A) de la couche d'oxyde inorganique (12) présente une mouillabilité de 45 à 70 mN/m2.
PCT/JP1998/001013 1997-03-12 1998-03-11 Matiere d'emballage WO1998040208A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP9/57706 1997-03-12
JP05770697A JP3974215B2 (ja) 1997-03-12 1997-03-12 包装材料

Publications (1)

Publication Number Publication Date
WO1998040208A1 true WO1998040208A1 (fr) 1998-09-17

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ID=13063398

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PCT/JP1998/001013 WO1998040208A1 (fr) 1997-03-12 1998-03-11 Matiere d'emballage

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WO (1) WO1998040208A1 (fr)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4885340B2 (ja) * 1998-10-27 2012-02-29 大日本印刷株式会社 バリア性フィルムおよびそれを使用した積層材
JP4949542B2 (ja) * 1998-12-07 2012-06-13 大日本印刷株式会社 透明バリアフィルム、それを使用した積層材および包装用容器
JP4879377B2 (ja) * 1998-12-08 2012-02-22 大日本印刷株式会社 透明バリアフィルム、それを使用した積層材および包装用容器
SE520491C2 (sv) * 1999-04-07 2003-07-15 Tetra Laval Holdings & Finance Förpackningslaminat med barriäregenskaper mot gas och aromämnen

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH06305068A (ja) * 1993-04-21 1994-11-01 Idemitsu Petrochem Co Ltd 包装材料
JPH0872193A (ja) * 1994-09-08 1996-03-19 Toppan Printing Co Ltd 透明性を有するガスバリア性積層フィルム

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH06305068A (ja) * 1993-04-21 1994-11-01 Idemitsu Petrochem Co Ltd 包装材料
JPH0872193A (ja) * 1994-09-08 1996-03-19 Toppan Printing Co Ltd 透明性を有するガスバリア性積層フィルム

Also Published As

Publication number Publication date
JPH10249976A (ja) 1998-09-22
JP3974215B2 (ja) 2007-09-12

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