JP5835643B2 - Laminated body and method for producing the same - Google Patents

Laminated body and method for producing the same Download PDF

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Publication number
JP5835643B2
JP5835643B2 JP2011129494A JP2011129494A JP5835643B2 JP 5835643 B2 JP5835643 B2 JP 5835643B2 JP 2011129494 A JP2011129494 A JP 2011129494A JP 2011129494 A JP2011129494 A JP 2011129494A JP 5835643 B2 JP5835643 B2 JP 5835643B2
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Prior art keywords
nonwoven fabric
film
protective layer
gas barrier
polyester nonwoven
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JP2011129494A
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Japanese (ja)
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JP2012254591A (en
Inventor
木 泉 八
木 泉 八
木 貴 之 植
木 貴 之 植
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Dai Nippon Printing Co Ltd
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Dai Nippon Printing Co Ltd
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Priority to JP2011129494A priority Critical patent/JP5835643B2/en
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    • 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
    • B29C65/00—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor
    • B29C65/02—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor by heating, with or without pressure
    • B29C65/14—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor by heating, with or without pressure using wave energy, i.e. electromagnetic radiation, or particle radiation
    • B29C65/1429—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor by heating, with or without pressure using wave energy, i.e. electromagnetic radiation, or particle radiation characterised by the way of heating the interface
    • B29C65/1432—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor by heating, with or without pressure using wave energy, i.e. electromagnetic radiation, or particle radiation characterised by the way of heating the interface direct heating of the surfaces to be joined
    • 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
    • B29C65/00—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor
    • B29C65/02—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor by heating, with or without pressure
    • B29C65/14—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor by heating, with or without pressure using wave energy, i.e. electromagnetic radiation, or particle radiation
    • B29C65/1429—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor by heating, with or without pressure using wave energy, i.e. electromagnetic radiation, or particle radiation characterised by the way of heating the interface
    • B29C65/1435—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor by heating, with or without pressure using wave energy, i.e. electromagnetic radiation, or particle radiation characterised by the way of heating the interface at least passing through one of the parts to be joined, i.e. transmission welding
    • 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
    • B29C65/00—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor
    • B29C65/02—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor by heating, with or without pressure
    • B29C65/14—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor by heating, with or without pressure using wave energy, i.e. electromagnetic radiation, or particle radiation
    • B29C65/1429—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor by heating, with or without pressure using wave energy, i.e. electromagnetic radiation, or particle radiation characterised by the way of heating the interface
    • B29C65/1445—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor by heating, with or without pressure using wave energy, i.e. electromagnetic radiation, or particle radiation characterised by the way of heating the interface heating both sides of the joint
    • 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
    • B29C65/00—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor
    • B29C65/02—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor by heating, with or without pressure
    • B29C65/14—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor by heating, with or without pressure using wave energy, i.e. electromagnetic radiation, or particle radiation
    • B29C65/1429—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor by heating, with or without pressure using wave energy, i.e. electromagnetic radiation, or particle radiation characterised by the way of heating the interface
    • B29C65/1454—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor by heating, with or without pressure using wave energy, i.e. electromagnetic radiation, or particle radiation characterised by the way of heating the interface scanning at least one of the parts to be joined
    • B29C65/1458—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor by heating, with or without pressure using wave energy, i.e. electromagnetic radiation, or particle radiation characterised by the way of heating the interface scanning at least one of the parts to be joined once, i.e. contour welding
    • 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
    • B29C65/00—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor
    • B29C65/02—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor by heating, with or without pressure
    • B29C65/14—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor by heating, with or without pressure using wave energy, i.e. electromagnetic radiation, or particle radiation
    • B29C65/1429—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor by heating, with or without pressure using wave energy, i.e. electromagnetic radiation, or particle radiation characterised by the way of heating the interface
    • B29C65/1464—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor by heating, with or without pressure using wave energy, i.e. electromagnetic radiation, or particle radiation characterised by the way of heating the interface making use of several radiators
    • 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
    • B29C65/00—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor
    • B29C65/02—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor by heating, with or without pressure
    • B29C65/14—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor by heating, with or without pressure using wave energy, i.e. electromagnetic radiation, or particle radiation
    • B29C65/1429—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor by heating, with or without pressure using wave energy, i.e. electromagnetic radiation, or particle radiation characterised by the way of heating the interface
    • B29C65/1464—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor by heating, with or without pressure using wave energy, i.e. electromagnetic radiation, or particle radiation characterised by the way of heating the interface making use of several radiators
    • B29C65/1467—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor by heating, with or without pressure using wave energy, i.e. electromagnetic radiation, or particle radiation characterised by the way of heating the interface making use of several radiators at the same time, i.e. simultaneous welding
    • 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
    • B29C66/00—General aspects of processes or apparatus for joining preformed parts
    • B29C66/01—General aspects dealing with the joint area or with the area to be joined
    • B29C66/05—Particular design of joint configurations
    • B29C66/10—Particular design of joint configurations particular design of the joint cross-sections
    • B29C66/11—Joint cross-sections comprising a single joint-segment, i.e. one of the parts to be joined comprising a single joint-segment in the joint cross-section
    • B29C66/112—Single lapped joints
    • B29C66/1122—Single lap to lap joints, i.e. overlap joints
    • 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
    • B29C66/00—General aspects of processes or apparatus for joining preformed parts
    • B29C66/40—General aspects of joining substantially flat articles, e.g. plates, sheets or web-like materials; Making flat seams in tubular or hollow articles; Joining single elements to substantially flat surfaces
    • B29C66/41—Joining substantially flat articles ; Making flat seams in tubular or hollow articles
    • B29C66/45—Joining of substantially the whole surface of the articles
    • 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
    • B29C66/00—General aspects of processes or apparatus for joining preformed parts
    • B29C66/70—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material
    • B29C66/71—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material characterised by the composition of the plastics material of the parts to be joined
    • B29C66/712—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material characterised by the composition of the plastics material of the parts to be joined the composition of one of the parts to be joined being different from the composition of the other part
    • 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
    • B29C66/00—General aspects of processes or apparatus for joining preformed parts
    • B29C66/70—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material
    • B29C66/72—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material characterised by the structure of the material of the parts to be joined
    • B29C66/723—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material characterised by the structure of the material of the parts to be joined being multi-layered
    • B29C66/7234—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material characterised by the structure of the material of the parts to be joined being multi-layered comprising a barrier layer
    • B29C66/72341—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material characterised by the structure of the material of the parts to be joined being multi-layered comprising a barrier layer for gases
    • 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
    • B29C66/00—General aspects of processes or apparatus for joining preformed parts
    • B29C66/70—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material
    • B29C66/73—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material characterised by the intensive physical properties of the material of the parts to be joined, by the optical properties of the material of the parts to be joined, by the extensive physical properties of the parts to be joined, by the state of the material of the parts to be joined or by the material of the parts to be joined being a thermoplastic or a thermoset
    • B29C66/735—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material characterised by the intensive physical properties of the material of the parts to be joined, by the optical properties of the material of the parts to be joined, by the extensive physical properties of the parts to be joined, by the state of the material of the parts to be joined or by the material of the parts to be joined being a thermoplastic or a thermoset characterised by the extensive physical properties of the parts to be joined
    • B29C66/7352—Thickness, e.g. very thin
    • B29C66/73521—Thickness, e.g. very thin of different thickness, i.e. the thickness of one of the parts to be joined being different from the thickness of the other part
    • 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
    • B29C66/00—General aspects of processes or apparatus for joining preformed parts
    • B29C66/70—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material
    • B29C66/73—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material characterised by the intensive physical properties of the material of the parts to be joined, by the optical properties of the material of the parts to be joined, by the extensive physical properties of the parts to be joined, by the state of the material of the parts to be joined or by the material of the parts to be joined being a thermoplastic or a thermoset
    • B29C66/739—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material characterised by the intensive physical properties of the material of the parts to be joined, by the optical properties of the material of the parts to be joined, by the extensive physical properties of the parts to be joined, by the state of the material of the parts to be joined or by the material of the parts to be joined being a thermoplastic or a thermoset characterised by the material of the parts to be joined being a thermoplastic or a thermoset
    • B29C66/7392—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material characterised by the intensive physical properties of the material of the parts to be joined, by the optical properties of the material of the parts to be joined, by the extensive physical properties of the parts to be joined, by the state of the material of the parts to be joined or by the material of the parts to be joined being a thermoplastic or a thermoset characterised by the material of the parts to be joined being a thermoplastic or a thermoset characterised by the material of at least one of the parts being a thermoplastic
    • 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
    • B29C66/00—General aspects of processes or apparatus for joining preformed parts
    • B29C66/80—General aspects of machine operations or constructions and parts thereof
    • B29C66/83—General aspects of machine operations or constructions and parts thereof characterised by the movement of the joining or pressing tools
    • B29C66/834—General aspects of machine operations or constructions and parts thereof characterised by the movement of the joining or pressing tools moving with the parts to be joined
    • B29C66/8341—Roller, cylinder or drum types; Band or belt types; Ball types
    • B29C66/83411—Roller, cylinder or drum types
    • B29C66/83413—Roller, cylinder or drum types cooperating rollers, cylinders or drums
    • 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
    • B29C66/00—General aspects of processes or apparatus for joining preformed parts
    • B29C66/80—General aspects of machine operations or constructions and parts thereof
    • B29C66/83—General aspects of machine operations or constructions and parts thereof characterised by the movement of the joining or pressing tools
    • B29C66/836—Moving relative to and tangentially to the parts to be joined, e.g. transversely to the displacement of the parts to be joined, e.g. using a X-Y table
    • 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
    • B29C66/00—General aspects of processes or apparatus for joining preformed parts
    • B29C66/001—Joining in special atmospheres
    • B29C66/0012—Joining in special atmospheres characterised by the type of environment
    • B29C66/0014—Gaseous environments
    • B29C66/00141—Protective gases
    • 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
    • B29C66/00—General aspects of processes or apparatus for joining preformed parts
    • B29C66/70—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material
    • B29C66/71—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material characterised by the composition of the plastics material of the parts to be joined
    • 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
    • B29C66/00—General aspects of processes or apparatus for joining preformed parts
    • B29C66/70—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material
    • B29C66/73—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material characterised by the intensive physical properties of the material of the parts to be joined, by the optical properties of the material of the parts to be joined, by the extensive physical properties of the parts to be joined, by the state of the material of the parts to be joined or by the material of the parts to be joined being a thermoplastic or a thermoset
    • B29C66/737—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material characterised by the intensive physical properties of the material of the parts to be joined, by the optical properties of the material of the parts to be joined, by the extensive physical properties of the parts to be joined, by the state of the material of the parts to be joined or by the material of the parts to be joined being a thermoplastic or a thermoset characterised by the state of the material of the parts to be joined
    • B29C66/7371—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material characterised by the intensive physical properties of the material of the parts to be joined, by the optical properties of the material of the parts to be joined, by the extensive physical properties of the parts to be joined, by the state of the material of the parts to be joined or by the material of the parts to be joined being a thermoplastic or a thermoset characterised by the state of the material of the parts to be joined oriented or heat-shrinkable
    • B29C66/73711—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material characterised by the intensive physical properties of the material of the parts to be joined, by the optical properties of the material of the parts to be joined, by the extensive physical properties of the parts to be joined, by the state of the material of the parts to be joined or by the material of the parts to be joined being a thermoplastic or a thermoset characterised by the state of the material of the parts to be joined oriented or heat-shrinkable oriented
    • B29C66/73713—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material characterised by the intensive physical properties of the material of the parts to be joined, by the optical properties of the material of the parts to be joined, by the extensive physical properties of the parts to be joined, by the state of the material of the parts to be joined or by the material of the parts to be joined being a thermoplastic or a thermoset characterised by the state of the material of the parts to be joined oriented or heat-shrinkable oriented bi-axially or multi-axially

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  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Physics & Mathematics (AREA)
  • Health & Medical Sciences (AREA)
  • Electromagnetism (AREA)
  • Toxicology (AREA)
  • Laminated Bodies (AREA)
  • Lining Or Joining Of Plastics Or The Like (AREA)

Description

本発明は、積層体に関し、さらに詳細には、熱可塑性樹脂フィルム上に、薄膜層およびガスバリア性保護層を設けたバリア性フィルムと、ポリエステル不織布とを、バリア性フィルムのガスバリア性保護層がポリエステル不織布に対向するように、接着剤を介さずに接着した積層体およびその製造方法に関する。   The present invention relates to a laminate, and more specifically, a barrier film in which a thin film layer and a gas barrier protective layer are provided on a thermoplastic resin film, and a polyester nonwoven fabric, and the gas barrier protective layer of the barrier film is a polyester. The present invention relates to a laminate bonded to a non-woven fabric without using an adhesive and a method for producing the same.

ポリオレフィン系樹脂、ポリエステル系樹脂、ポリアミド系樹脂等の種々の高分子材料を繊維化したものウェッブ状に形成した不織布が広く使用されている。これら不織布は、使用する高分子材料の特性や繊維の特性に応じてさまざまな機能を発現し、その機能が発揮できるような用途に使用される。   Nonwoven fabrics that have been formed into a web-like shape obtained by fiberizing various polymer materials such as polyolefin resins, polyester resins, and polyamide resins are widely used. These non-woven fabrics are used for applications that exhibit various functions depending on the characteristics of the polymer material used and the characteristics of the fibers, and can exhibit these functions.

また、各種不織布はそのまま単独で使用されることもあるが、異なる高分子材料からなる不織布どうしを重ね合わせて不織布の積層体としたり、不織布とフィルムとを貼り合わせて、より高機能を発現できるような形態に加工することも行われている。このような積層体を形成する場合、接着剤（ラミネート樹脂）を用いて、二種の不織布を重ね合わせたり、不織布とフィルムとを重ね合わせて接着することが行われている。また、不織布やフィルムの材料によっては、ヒートシール加工、すなわち、熱を加えて、一方または両方の繊維ないしフィルムを軟化、溶融させて、互いの材料を接着することが行われている。   In addition, various non-woven fabrics may be used alone, but non-woven fabrics made of different polymer materials can be layered to form a laminate of non-woven fabrics, or non-woven fabrics and films can be bonded together to express higher functionality. Processing into such a form is also performed. When forming such a laminated body, two types of non-woven fabrics are superposed using an adhesive (laminate resin), or a non-woven fabric and a film are superposed and bonded. Further, depending on the material of the nonwoven fabric or the film, heat sealing, that is, applying heat, softening and melting one or both fibers or films and bonding the materials to each other is performed.

また、機能性フィルムとして、ポリエステル樹脂フィルム上に金属蒸着膜を形成したり、ガスバリア性保護層を設けたバリア性の積層フィルムが知られている。バリア性積層フィルムは、飲食品や医薬品、電子部材等のパッケージ材料として使用されているが、上記したような不織布と積層することも行われている。   Further, as a functional film, a barrier laminated film in which a metal vapor deposition film is formed on a polyester resin film or a gas barrier protective layer is provided is known. The barrier laminated film is used as a packaging material for foods and drinks, pharmaceuticals, electronic members, and the like, but is also laminated with a nonwoven fabric as described above.

しかしながら、異種材料からなる不織布ないしフィルムをラミネート樹脂を介して接着して積層体とした場合、ラミネート樹脂が不織布の開口部分を塞いでしまい、不織布本来の性能が低下してしまうことがあった。また、ラミネート樹脂成分が徐々に積層体から外部に溶出または揮発する場合があり、特に、安全性やクリーン性が重視される医療用分野においては、使用するラミネート樹脂によっては、不織布積層体に包装された内容物等を汚染してしまうことがあった。さらに、不織布積層体の使用分野によっては、長期使用によりラミネート樹脂自体が劣化することもあり、特に屋外等で使用される外装用途においては、ラミネート加工した積層体の耐候性が問題となることもあった。一方、不織布どうし、または不織布とフィルムとを貼り合わせてヒートシールして積層体を形成する場合には、ラミネート樹脂を使用しないため、上記のような問題は生じないものの、使用する材料によってはヒートシールできなかったり、接着強度が弱く実用に耐えないといった場合があった。   However, when a nonwoven fabric or film made of different materials is bonded via a laminate resin to form a laminate, the laminate resin may block the opening of the nonwoven fabric, and the inherent performance of the nonwoven fabric may deteriorate. In addition, the laminate resin component may gradually elute or volatilize from the laminate to the outside. Especially in the medical field where safety and cleanliness are important, depending on the laminate resin used, the laminate resin component may be packaged in a nonwoven fabric laminate. In some cases, the contents may be contaminated. Furthermore, depending on the field of use of the nonwoven fabric laminate, the laminate resin itself may deteriorate due to long-term use, and particularly in exterior applications used outdoors, the weather resistance of the laminated laminate may become a problem. there were. On the other hand, when a laminated body is formed by bonding non-woven fabrics or a non-woven fabric and a film to form a laminate, the above-mentioned problems do not occur because the laminate resin is not used. In some cases, it could not be sealed, or the adhesive strength was weak and it could not withstand practical use.

ところで、放射線や電子線を用いて材料の表面改質を行うことが従来から行われている。例えば、特開２００３−１１９２９３号公報（特許文献１）には、フッ素系樹脂に放射線を照射することにより架橋複合フッ素系樹脂が得られることが提案されている。また、Journal of Photopolymer Science and Technology Vol.19, No. 1 (2006), pp123-127（非特許文献１）には、ポリテトラフルオロエチレンフィルムとポリイミドフィルムとを積層させて高温下で電子線（以下、ＥＢと略す場合もある）を照射することにより、互いを接着することが提案されている。また、Material Transactions Vol.50, No.7 (2009), pp1859-1863（非特許文献２）には、ポリカーボネート樹脂の表面をナイロンフィルムで覆い、その上から電子線（以下、ＥＢと略す場合もある）を照射することにより、ポリカーボネート樹脂表面にナイロンフィルムを接着する技術が提案されている。さらに、日本金属学会誌第７２巻第７号（２００８）、ｐｐ５２６−５３１（非特許文献３）には、シリコーンゴム上に置いたナイロンフィルムの上からＥＢを照射することにより、互いを接着できることが記載されている。   By the way, surface modification of a material using radiation or an electron beam has been conventionally performed. For example, Japanese Patent Application Laid-Open No. 2003-119293 (Patent Document 1) proposes that a crosslinked composite fluororesin can be obtained by irradiating the fluororesin with radiation. In Journal of Photopolymer Science and Technology Vol.19, No. 1 (2006), pp123-127 (Non-patent Document 1), a polytetrafluoroethylene film and a polyimide film are laminated and an electron beam ( In the following, it has been proposed to bond each other by irradiating EB. In Material Transactions Vol.50, No.7 (2009), pp1859-1863 (Non-patent Document 2), the surface of the polycarbonate resin is covered with a nylon film, and an electron beam (hereinafter abbreviated as EB) may be applied from above. A technique for adhering a nylon film to a polycarbonate resin surface has been proposed. Furthermore, the Journal of the Japan Institute of Metals, Vol. 72, No. 7 (2008), pp 526-531 (Non-patent Document 3) can be bonded to each other by irradiating EB from a nylon film placed on silicone rubber. Is described.

特開２００３−１１９２９３号公報JP 2003-119293 A

Journal of Photopolymer Science and Technology Vol.19, No. 1 (2006), pp123-127Journal of Photopolymer Science and Technology Vol.19, No. 1 (2006), pp123-127 Material Transactions Vol.50, No. 7(2009), pp1859-1863Material Transactions Vol.50, No. 7 (2009), pp1859-1863 日本金属学会誌第７２巻第７号（２００８）、ｐｐ５２６−５３１Journal of the Japan Institute of Metals, Vol. 72, No. 7 (2008), pp 526-531

本発明者らは、今般、ガスバリア性フィルムとして知られる熱可塑性樹脂フィルム上に、薄膜層およびガスバリア性保護層を設けたバリア性フィルムと、ポリエステル不織布とを積層した積層体の製造において、ガスバリア性フィルムおよび／またはポリエステル不織布に電子線を照射することにより、ラミネート樹脂等を用いることなく、バリア性フィルムとポリエステル不織布とを強固に接着できることを見いだした。そして、ガスバリア性保護層を含むバリア性フィルムとポリエステル不織布とを重ね合わせた積層体のように、従来、接着剤により互いを接着していた積層体であっても、電子線照射によれば、接着剤を使用しなくても、バリア性フィルム側の原子とポリエステル不織布側の原子との間に結合が形成されて、互いが強固に接着できる、との知見を得た。本発明はかかる知見によるものである。   In the production of a laminate in which a thin film layer and a gas barrier protective layer are laminated on a thermoplastic resin film known as a gas barrier film, and a polyester nonwoven fabric, the present inventors have now made gas barrier properties. It has been found that by irradiating the film and / or polyester nonwoven fabric with an electron beam, the barrier film and the polyester nonwoven fabric can be firmly bonded without using a laminate resin or the like. And, like a laminate in which a barrier film containing a gas barrier protective layer and a polyester nonwoven fabric are stacked, conventionally, even a laminate that has been bonded to each other with an adhesive, according to electron beam irradiation, Even without the use of an adhesive, it was found that a bond was formed between the atoms on the barrier film side and the atoms on the polyester nonwoven fabric side so that they could be firmly bonded to each other. The present invention is based on this finding.

したがって、本発明の目的は、ガスバリア性フィルムとポリエステル不織布とを接着剤を使用せずに接着した積層体であって、積層体を使用する際にも異物や残留溶剤等が滲出することがなく、かつ、不織布の本来の性能を低下させることなく、バリア性フィルムと不織布とが強固に接着した積層体を提供することである。   Accordingly, an object of the present invention is a laminate in which a gas barrier film and a polyester nonwoven fabric are bonded without using an adhesive, and foreign matter, residual solvent, and the like are not leached even when the laminate is used. And it is providing the laminated body to which the barrier film and the nonwoven fabric were adhere | attached firmly, without reducing the original performance of a nonwoven fabric.

本発明による積層体は、熱可塑性樹脂フィルム、前記熱可塑性樹脂フィルムの少なくとも一方の面に設けた酸化アルミニウムまたは酸化ケイ素からなる薄膜層、および前記薄膜層上に設けたガスバリア性保護層を含んでなるバリア性フィルムと、ポリエステル不織布とが、前記バリア性フィルムのガスバリア性保護層と前記ポリエステル不織布とが対向するように、積層した積層体であって、
前記ガスバリア性保護層が、少なくとも水酸基を有する水溶性高分子とアルコキシシランとを含む溶液を塗布して得られる被膜からなり、
前記ガスバリア性保護層と前記ポリエステル不織布との界面の少なくとも一部で、前記ガスバリア性保護層中の原子と、前記ポリエステル不織布中の原子との間に結合が形成されており、前記ガスバリア性保護層および前記ポリエステル不織布とが接着剤を介さずに接着されていることを特徴とするものである。 The laminate according to the present invention includes a thermoplastic resin film, a thin film layer made of aluminum oxide or silicon oxide provided on at least one surface of the thermoplastic resin film, and a gas barrier protective layer provided on the thin film layer. A laminated body in which the barrier film and the polyester nonwoven fabric are laminated so that the gas barrier protective layer of the barrier film and the polyester nonwoven fabric face each other,
The gas barrier protective layer comprises a film obtained by applying a solution containing at least a water-soluble polymer having a hydroxyl group and alkoxysilane,
In at least part of the interface between the gas barrier protective layer and the polyester nonwoven fabric, a bond is formed between an atom in the gas barrier protective layer and an atom in the polyester nonwoven fabric, and the gas barrier protective layer The polyester nonwoven fabric is bonded without using an adhesive.

また、本発明の態様として、前記ガスバリア性保護層と前記ポリエステル不織布との界面の少なくとも一部で、前記ガスバリア性保護層中の原子と、前記ポリエステル不織布中の原子との間で、酸素原子、窒素原子または水酸基を介して結合が形成されていることが好ましい。   Further, as an aspect of the present invention, at least part of the interface between the gas barrier protective layer and the polyester nonwoven fabric, between atoms in the gas barrier protective layer and atoms in the polyester nonwoven fabric, oxygen atoms, A bond is preferably formed through a nitrogen atom or a hydroxyl group.

また、本発明の態様として、前記アルコキシシランが下記一般式：
Ｒ１ｎＳｉ（ＯＲ２）ｍ
（式中、Ｒ１およびＲ２は、それぞれ独立して炭素数１〜８の有機基を表し、ｎは０以上の整数を表し、ｍは１以上の整数を表すが、ｎ＋ｍはＳｉの原子価を表す。）
で表されるものであることが好ましい。 Further, as an aspect of the present invention, the alkoxysilane is represented by the following general formula:
R 1n Si (OR 2 ) m
(In the formula, R 1 and R 2 each independently represent an organic group having 1 to 8 carbon atoms, n represents an integer of 0 or more, m represents an integer of 1 or more, and n + m represents an Si atom. Represents the value.)
It is preferable that it is represented by these.

また、本発明の態様として、前記水酸基を有する水溶性高分子が、ポリビニルアルコール、ポリビニルピロリドン、デンプン、メチルセルロース、カルボキシメチルセルロース、アルギン酸ナトリウム、およびエチレン−ビニルアルコール共重合体からなる群から選択される１種、または２種以上の混合物であることが好ましい。   In one embodiment of the present invention, the water-soluble polymer having a hydroxyl group is selected from the group consisting of polyvinyl alcohol, polyvinyl pyrrolidone, starch, methyl cellulose, carboxymethyl cellulose, sodium alginate, and an ethylene-vinyl alcohol copolymer. It is preferably a seed or a mixture of two or more.

また、本発明の態様として、前記ポリエステル不織布が、ポリエチレンテレフタレート、ポリトリメチレンテレフタレート、ポリブチレンテレフタレート、ポリエチレンナフタレート、もしくはポリブチレンナフタレートからなる繊維、または、これら樹脂を鞘とする複合繊維からなることが好ましい。   Further, as an aspect of the present invention, the polyester nonwoven fabric is made of a fiber made of polyethylene terephthalate, polytrimethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, or polybutylene naphthalate, or a composite fiber having these resins as sheaths. It is preferable.

また、本発明の別の態様としての製造方法は、バリア性フィルムとポリエステル不織布とを積層した積層体を製造する方法であって、
熱可塑性樹脂フィルム、前記熱可塑性樹脂フィルムの少なくとも一方の面に設けた酸化アルミニウムまたは酸化ケイ素からなる薄膜層、および前記薄膜層上に設けたガスバリア性保護層を含んでなるバリア性フィルムのガスバリア性保護層面、および／または前記ポリエステル不織布の少なくとも一方の面、に電子線を照射し、
前記電子線が照射された前記ガスバリア性保護層面および／またはポリエステル不織布面を重ね合わせて接着する、ことを含んでなることを特徴とするものである。 Moreover, the production method as another aspect of the present invention is a method for producing a laminate in which a barrier film and a polyester nonwoven fabric are laminated,
Gas barrier property of a barrier film comprising a thermoplastic resin film, a thin film layer made of aluminum oxide or silicon oxide provided on at least one surface of the thermoplastic resin film, and a gas barrier protective layer provided on the thin film layer Irradiating the protective layer surface and / or at least one surface of the polyester nonwoven fabric with an electron beam,
The gas barrier protective layer surface and / or the polyester nonwoven fabric surface irradiated with the electron beam are overlapped and bonded.

また、本発明の態様として、前記バリア性フィルムとポリエステル不織布とを重ね合わせる前および／または重ね合わせた後に電子線照射を行うことが好ましい。   Moreover, as an aspect of the present invention, it is preferable to perform electron beam irradiation before and / or after the barrier film and the polyester nonwoven fabric are overlapped.

また、本発明の別の態様として、前記接着を加圧して行うことが好ましく、また、前記接着を加熱して行うことが好ましい。   Moreover, as another aspect of the present invention, the bonding is preferably performed by applying pressure, and the bonding is preferably performed by heating.

本発明によれば、熱可塑性樹脂フィルム、前記熱可塑性樹脂フィルムの少なくとも一方の面に設けた酸化アルミニウムまたは酸化ケイ素からなる薄膜層、および前記薄膜層上に設けたガスバリア性保護層を含んでなるバリア性フィルムと、ポリエステル不織布とが、前記バリア性フィルムのガスバリア性保護層と前記ポリエステル不織布とが対向するように、積層した積層体において、前記ガスバリア性保護層と前記ポリエステル不織布との界面の少なくとも一部で、前記ガスバリア性保護層中の原子と、前記ポリエステル不織布中の原子との間に結合が形成されているため、接着剤を介して接着していなくても、バリア性フィルムとポリエステル不織布とが強固に接着した積層体が得られる。その結果、積層体を使用する際にも異物や残留溶剤等が滲出することがなく、かつ、不織布の本来の性能を低下させることなく、バリア性フィルムと不織布とが強固に接着した積層体を実現することができる。   According to the present invention, it comprises a thermoplastic resin film, a thin film layer made of aluminum oxide or silicon oxide provided on at least one surface of the thermoplastic resin film, and a gas barrier protective layer provided on the thin film layer. In the laminated body in which the barrier film and the polyester nonwoven fabric are laminated so that the gas barrier protective layer of the barrier film and the polyester nonwoven fabric face each other, at least an interface between the gas barrier protective layer and the polyester nonwoven fabric In some cases, since a bond is formed between the atoms in the gas barrier protective layer and the atoms in the polyester nonwoven fabric, the barrier film and the polyester nonwoven fabric may be bonded without using an adhesive. Can be obtained. As a result, a laminate in which the barrier film and the nonwoven fabric are firmly bonded to each other without causing the foreign matter or residual solvent to exude even when the laminate is used and without reducing the original performance of the nonwoven fabric. Can be realized.

本発明の積層体の一実施形態を示した概略断面図である。It is the schematic sectional drawing which showed one Embodiment of the laminated body of this invention. 積層体の界面（接着面）を拡大した模式断面図である。It is the schematic cross section which expanded the interface (adhesion surface) of the laminated body. 本発明による積層体の製造方法の一実施形態を示した概略模式図である。It is the schematic diagram which showed one Embodiment of the manufacturing method of the laminated body by this invention. 製造工程の一部を拡大した概略模式図である。It is the schematic schematic diagram which expanded a part of manufacturing process. 本発明による積層体の製造方法の別の実施形態を示した概略模式図である。It is the schematic diagram which showed another embodiment of the manufacturing method of the laminated body by this invention. 本発明による積層体の製造方法の別の実施形態を示した概略模式図である。It is the schematic diagram which showed another embodiment of the manufacturing method of the laminated body by this invention. 本発明による積層体の製造方法の別の実施形態を示した概略模式図である。It is the schematic diagram which showed another embodiment of the manufacturing method of the laminated body by this invention.

以下、本発明による積層体を、図面を参照しながら説明する。本発明による積層体は、図１に示すように、バリア性フィルム１とポリエステル不織布２とが、接着剤を介さずに積層された構造を有するものである。バリア性フィルム１は、熱可塑性不織布１１、熱可塑性樹脂フィルム１１の少なくとも一方の面に設けた酸化アルミニウムまたは酸化ケイ素からなる薄膜層１２、および薄膜層１２上に設けたガスバリア性保護層１３からなり、本発明の積層体は、バリア性フィルム１のガスバリア性保護層１３とポリエステル不織布２とが対向するように重ね合わせて積層したものである。   Hereinafter, the laminated body by this invention is demonstrated, referring drawings. As shown in FIG. 1, the laminate according to the present invention has a structure in which a barrier film 1 and a polyester nonwoven fabric 2 are laminated without using an adhesive. The barrier film 1 includes a thermoplastic nonwoven fabric 11, a thin film layer 12 made of aluminum oxide or silicon oxide provided on at least one surface of the thermoplastic resin film 11, and a gas barrier protective layer 13 provided on the thin film layer 12. The laminate of the present invention is obtained by superposing and laminating the gas barrier protective layer 13 of the barrier film 1 and the polyester nonwoven fabric 2 so as to face each other.

本発明による積層体を構成するバリア性フィルム１は、ガスバリア性保護層１３は、少なくとも水酸基を有する水溶性高分子とアルコキシシランとを含む溶液を塗布して得られる被膜からなる。本発明においては、ガスバリア性保護層１３とポリエステル不織布２との接着面の少なくとも一部で、ガスバリア性保護層１３中の原子と、ポリエステル不織布２中の原子との間に結合が形成されることにより、バリア性フィルム１とポリエステル不織布２とが強固に接着されている。ポリビニルアルコール等のような水酸基を有する水溶性高分子とアルコキシシランとを含む溶液を塗布して得られるガスバリア性保護層は、自己粘着性やヒートシール性を有していないため、通常、バリア性フィルム１のガスバリア性保護層１３表面にポリエステル不織布２を積層しても、両者の間に水素結合や共有結合が形成されないため接着剤を使用しなければ両者を接着することはできない。本発明においては、後記するように、バリア性フィルム１のガスバリア性保護層１３および／またはポリエステル不織布２の表面に電子線を照射してラジカルを発生させて、図２に示すように、ガスバリア性保護層１３中の原子とポリエステル不織布２表面の原子との間に結合が形成する、あるいは、ガスバリア性保護層１３中の原子と、ポリエステル不織布２表面の原子との間に、酸素原子、窒素原子または水酸基を介して結合を形成することにより、接着剤を介することなくバリア性フィルム１とポリエステル不織布２とを強固に接着したものである。また、電子線照射により発生したラジカルと空気中の酸素とが結合して、バリア性フィルム１のガスバリア性保護層１３および／またはポリエステル不織布２の表面にはＯＨ基が存在することがあり、その場合、ガスバリア性保護層１３とポリエステル不織布２との間に水素結合が形成される場合もある。なお、電子線照射によるラジカルの発生は、電子スピン共鳴装置（以下、ＥＳＲともいう。）を用いて、電子線照射後のフィルムに存在するフリーラジカル種を同定することにより、その発生を確認することができる。   In the barrier film 1 constituting the laminate according to the present invention, the gas barrier protective layer 13 comprises a film obtained by applying a solution containing at least a water-soluble polymer having a hydroxyl group and alkoxysilane. In the present invention, a bond is formed between an atom in the gas barrier protective layer 13 and an atom in the polyester nonwoven fabric 2 on at least a part of the adhesive surface between the gas barrier protective layer 13 and the polyester nonwoven fabric 2. Thus, the barrier film 1 and the polyester nonwoven fabric 2 are firmly bonded. A gas barrier protective layer obtained by applying a solution containing a water-soluble polymer having a hydroxyl group such as polyvinyl alcohol and an alkoxysilane does not have self-adhesiveness or heat-sealability, and therefore usually has barrier properties. Even if the polyester nonwoven fabric 2 is laminated on the surface of the gas barrier protective layer 13 of the film 1, hydrogen bonds and covalent bonds are not formed between the two, so that the two cannot be bonded without using an adhesive. In the present invention, as will be described later, the surface of the gas barrier protective layer 13 of the barrier film 1 and / or the surface of the polyester nonwoven fabric 2 is irradiated with an electron beam to generate radicals. As shown in FIG. A bond is formed between an atom in the protective layer 13 and an atom on the surface of the polyester nonwoven fabric 2, or an oxygen atom or a nitrogen atom between an atom in the gas barrier protective layer 13 and an atom on the surface of the polyester nonwoven fabric 2 Alternatively, by forming a bond through a hydroxyl group, the barrier film 1 and the polyester nonwoven fabric 2 are firmly bonded without using an adhesive. In addition, radicals generated by electron beam irradiation and oxygen in the air are combined, and there may be OH groups on the surface of the gas barrier protective layer 13 and / or the polyester nonwoven fabric 2 of the barrier film 1, In some cases, hydrogen bonds may be formed between the gas barrier protective layer 13 and the polyester nonwoven fabric 2. The generation of radicals by electron beam irradiation is confirmed by identifying the free radical species existing in the film after electron beam irradiation using an electron spin resonance apparatus (hereinafter also referred to as ESR). be able to.

また、電子線照射によりバリア性フィルム１とポリエステル不織布２とを貼り合わせて接着した積層体は、図２に示すように、バリア性フィルムのガスバリア性保護層の原子とポリエステル不織布２表面の原子との間で結合が形成されているため、接着剤を全く使用しなくても、剥離を生じない積層体とすることができる。水素結合の存在の確認は、積層体を水またはアルコール溶液中に浸積して剥離の有無を確認することにより行うことができる。水素結合のみによってバリア性フィルムとポリエステル不織布とが接着している場合、積層体を水またはアルコール溶液中に浸積すると、両者の間に形成されていた水素結合が破壊されて水またはアルコールの水素原子または酸素原子と水素結合が再形成されるため、接着力がなくなり両者が剥離する。よって、接着が、図２に示したような結合によるものなのか、水素結合のみによるものなのかを、確認することができる。   Moreover, the laminated body which bonded and bonded the barrier film 1 and the polyester nonwoven fabric 2 by electron beam irradiation, as shown in FIG. 2, the atoms of the gas barrier protective layer of the barrier film and the atoms on the surface of the polyester nonwoven fabric 2 Since a bond is formed between them, a laminate that does not peel can be obtained without using any adhesive. The presence of hydrogen bonds can be confirmed by immersing the laminate in water or an alcohol solution and confirming the presence or absence of peeling. When the barrier film and the polyester nonwoven fabric are bonded only by hydrogen bonding, when the laminate is immersed in water or an alcohol solution, the hydrogen bond formed between the two is broken, and water or alcohol hydrogen Since the hydrogen bond with the atom or oxygen atom is re-formed, the adhesive force disappears and the two peel off. Therefore, it can be confirmed whether the adhesion is due to bonding as shown in FIG. 2 or only due to hydrogen bonding.

以下、本発明による積層体を構成するバリア性フィルムおよびポリエステル不織布について、説明する。   Hereinafter, the barrier film and the polyester nonwoven fabric constituting the laminate according to the present invention will be described.

＜バリア性フィルム＞
バリア性フィルム１は、図１に示すように、熱可塑性樹脂フィルム１１、熱可塑性樹脂フィルム１１の少なくとも一方の面に設けた酸化アルミニウムまたは酸化ケイ素からなる薄膜層１２、および薄膜層１２上に設けたガスバリア性保護層１３を含む。バリア性フィルム１０は、図示しないが、薄膜層１２およびガスバリア性保護層１３を、熱可塑性樹脂フィルム１１の一方の面のみならずその両方の面に設けたものでもよい。 <Barrier film>
As shown in FIG. 1, the barrier film 1 is provided on a thermoplastic resin film 11, a thin film layer 12 made of aluminum oxide or silicon oxide provided on at least one surface of the thermoplastic resin film 11, and a thin film layer 12. A gas barrier protective layer 13. Although the barrier film 10 is not shown, the thin film layer 12 and the gas barrier protective layer 13 may be provided not only on one surface of the thermoplastic resin film 11 but also on both surfaces.

本発明による積層体に用いられるバリア性フィルム１は、薄膜層１２とガスバリア性保護膜１３とが、例えば、加水分解・共縮合反応による化学結合、水素結合、あるいは、配位結合などを形成し、薄膜層１２とガスバリア性保護層１３との密着性が向上し、その２層の相乗効果により、より良好なガスバリア性の効果を発揮し得るものである。   In the barrier film 1 used in the laminate according to the present invention, the thin film layer 12 and the gas barrier protective film 13 form, for example, a chemical bond, a hydrogen bond, or a coordinate bond by a hydrolysis / co-condensation reaction. The adhesion between the thin film layer 12 and the gas barrier protective layer 13 is improved, and a better gas barrier effect can be exhibited by the synergistic effect of the two layers.

熱可塑性樹脂フィルムとしては、酸化アルミニウムまたは酸化ケイ素からなる薄膜層を支持し得るプラスチックのフィルムであればいずれのものでも使用することができ、例えば、ポリエチレン、ポリプロピレン、ポリブテン等のポリオレフィン系樹脂、（メタ）アクリル系樹脂、ポリ塩化ビニル系樹脂、ポリスチレン系樹脂、ポリ塩化ビニリデン系樹脂、エチレン−酢酸ビニル共重合体ケン化物、ポリビニルアルコール、ポリカーボネート系樹脂、フッ素系樹脂、ポリ酢酸ビニル系樹脂、アセタール系樹脂、ポリエチレンテレフタレート(ＰＥＴ)、ポリエチレンナフタレート(ＰＥＮ)、ポリブチレンナフタレート(ＰＢＮ)等のポリエステル系樹脂、ナイロン６、ナイロン６６等のポリアミド系樹脂、その他等の各種の樹脂のフィルムを使用することができる。これらのなかでも、ポリエチレンテレフタレート（ＰＥＴ）が好ましく、透明であるものがより好ましい。   As the thermoplastic resin film, any plastic film that can support a thin film layer made of aluminum oxide or silicon oxide can be used. For example, polyolefin resin such as polyethylene, polypropylene, polybutene, ( (Meth) acrylic resin, polyvinyl chloride resin, polystyrene resin, polyvinylidene chloride resin, saponified ethylene-vinyl acetate copolymer, polyvinyl alcohol, polycarbonate resin, fluorine resin, polyvinyl acetate resin, acetal Polyester resin such as polyethylene resin, polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polybutylene naphthalate (PBN), polyamide resin such as nylon 6 and nylon 66, etc. You It is possible. Among these, polyethylene terephthalate (PET) is preferable, and transparent one is more preferable.

熱可塑性樹脂フィルムは、一軸ないし二軸方向に延伸されているものでもよく、また、その厚さとしては、１０〜２００μｍ程度、特に、１０〜１００μｍ程度が好ましい。また、必要に応じて、その表面にアンカーコート剤等をコーティングして表面平滑化処理等を施してもよい。   The thermoplastic resin film may be uniaxially or biaxially stretched, and the thickness is preferably about 10 to 200 μm, particularly about 10 to 100 μm. If necessary, the surface may be coated with an anchor coating agent or the like to be subjected to a surface smoothing treatment or the like.

薄膜層は、一般式：ＡｌＯｘ（式中、ｘは、０.５〜１.５の数を表す。）で表される酸化アルミニウムの薄膜、または、一般式：ＳｉＯｘ（式中、ｘは、０〜２の数を表す）で表される酸化ケイ素の薄膜を、熱可塑性樹脂フィルムの表面に形成したものである。上記一般式で表される酸化アルミニウムの薄膜として、膜表面から内面に向かう深さ方向に向かってｘの値が増加している酸化アルミニウムの薄膜を使用することもできる。上記において、ｘの値としては、基本的には、ｘ＝０.５以上のものを使用することができるが、ｘ＝１.０未満になると、着色し易く、かつ、透明性、電子レンジ適性に劣ることから、ｘ＝１.０以上のものを使用することが好ましい。上限としては、アルミニウムと酸素とが完全に酸化した状態のものであるｘ＝１.５までのものを使用することができる。 The thin film layer is a thin film of aluminum oxide represented by a general formula: AlO x (wherein x represents a number of 0.5 to 1.5), or a general formula: SiO x (where, x Represents a number of 0 to 2), and is formed on the surface of a thermoplastic resin film. As the aluminum oxide thin film represented by the above general formula, an aluminum oxide thin film in which the value of x increases in the depth direction from the film surface toward the inner surface can also be used. In the above, as the value of x, basically, x = 0.5 or more can be used. However, when x = less than 1.0, it is easy to be colored, and transparency, microwave oven Since it is inferior in suitability, it is preferable to use x = 1.0 or more. As the upper limit, those up to x = 1.5 in which aluminum and oxygen are completely oxidized can be used.

また、上記一般式で表される酸化ケイ素の薄膜として、ｘの値は１．３〜１．９が好ましい。また、酸化ケイ素薄膜は、酸化珪素を主体とし、さらに、炭素、水素、珪素または酸素の１種類、または２種類以上の元素からなる化合物の少なくとも１種類を化学結合等により含有してもよい。例えば、Ｃ−Ｈ結合を有する化合物、Ｓｉ−Ｈ結合を有する化合物、または、炭素単位がグラファイト状、ダイヤモンド状、フラーレン状等になっている場合、更に、原料の有機珪素化合物やそれらの誘導体を化学結合等によって含有する場合があるものである。例えば、ＣＨ3部位を持つハイドロカーボン、ＳｉＨ３シリル、ＳｉＨ２シリレン等のハイドロシリカ、ＳｉＨ２ＯＨシラノール等の水酸基誘導体等を挙げることができる。上記の化合物が酸化珪素の蒸着膜中に含有する含有量としては、０．１〜５０質量％、好ましくは５〜２０質量％である。また、酸化ケイ素薄膜が上記化合物を含有する場合、化合物の含有量が酸化珪素の蒸着膜の表面から深さ方向に向かって減少していることが好ましい。これにより、酸化珪素の蒸着膜の表面では上記化合物等により耐衝撃性等が高められ、他方、基材フィルムとの界面では、上記化合物の含有量が少ないために基材フィルムと酸化珪素の蒸着膜との密接着性が強固なものとなる。 Moreover, as a thin film of silicon oxide represented by the above general formula, the value of x is preferably 1.3 to 1.9. The silicon oxide thin film may be mainly composed of silicon oxide, and may further contain at least one kind of compound composed of one kind of carbon, hydrogen, silicon, or oxygen, or two or more kinds of elements by a chemical bond or the like. For example, when a compound having a C—H bond, a compound having a Si—H bond, or a carbon unit is in the form of graphite, diamond, fullerene, or the like, the raw material organosilicon compound or a derivative thereof is further added. It may be contained by a chemical bond or the like. For example, hydrocarbons having a CH 3 site, hydrosilica such as SiH 3 silyl, SiH 2 silylene, and hydroxyl derivatives such as SiH 2 OH silanol can be used. As content which said compound contains in the vapor deposition film | membrane of a silicon oxide, it is 0.1-50 mass%, Preferably it is 5-20 mass%. Moreover, when a silicon oxide thin film contains the said compound, it is preferable that content of a compound is reducing toward the depth direction from the surface of the vapor deposition film | membrane of a silicon oxide. As a result, the impact resistance and the like are enhanced by the above compound on the surface of the silicon oxide vapor deposition film, and on the other hand, since the content of the above compound is small at the interface with the base film, the vapor deposition of the base film and the silicon oxide is performed. The tight adhesion with the film becomes strong.

薄膜層の膜厚としては、例えば、１０〜３０００Å程度、特に、６０〜１０００Å程度の範囲内で任意に選択して形成することが好ましい。薄膜層は、結晶質のものでも非結晶質のものでもよい。   The film thickness of the thin film layer is preferably selected and formed arbitrarily within a range of, for example, about 10 to 3000 mm, particularly about 60 to 1000 mm. The thin film layer may be crystalline or non-crystalline.

本発明においては、バリア性フィルムを構成する熱可塑性樹脂フィルムの全光線透過率を１００％としたとき、蒸着後の全光線透過率が９０％未満になるように酸化アルミニウムまたは酸化ケイ素を蒸着したものが望ましく、ベースフィルムの全光線透過率を１００％としたとき、蒸着後の全光線透過率が８５％以上で９０％未満になるように酸化アルミニウムまたは酸化ケイ素を蒸着したものは、特に好ましい。蒸着後の全光線透過率が蒸着後の全光線透過率が９０％以上の場合には、透明度は十分であるものの、ガスバリア性、特に水蒸気に対するガスバリア性が十分に高くない場合がある。また、蒸着後の全光線透過率が８５％未満の場合は、ガスバリア性には優れるものの最終的な透明度が熱可塑性樹脂フィルムの全光線透過率にまで達しない場合がある。   In the present invention, when the total light transmittance of the thermoplastic resin film constituting the barrier film is 100%, aluminum oxide or silicon oxide is deposited so that the total light transmittance after deposition is less than 90%. It is particularly preferable to deposit aluminum oxide or silicon oxide so that the total light transmittance after deposition is 85% or more and less than 90% when the total light transmittance of the base film is 100%. . When the total light transmittance after vapor deposition is 90% or more after vapor deposition, although the transparency is sufficient, the gas barrier property, particularly the gas barrier property against water vapor, may not be sufficiently high. Moreover, when the total light transmittance after vapor deposition is less than 85%, although the gas barrier property is excellent, the final transparency may not reach the total light transmittance of the thermoplastic resin film.

次に、熱可塑性樹脂フィルム上に薄膜層を形成する方法について説明する。薄膜層を形成する方法としては、例えば、真空蒸着法、スパッタリング法、イオンプレーティング法等の物理気相成長法（Ｐｈｙｓｉｃａｌ Ｖａｐｏｒ Ｄｅｐｏｓｉｔｉｏｎ法、ＰＶＤ法）、あるいは、プラズマ化学気相成長法、熱化学気相成長法、光化学気相成長法等の化学気相成長法（Ｃｈｅｍｉｃａｌ Ｖａｐｏｒ Ｄｅｐｏｓｉｔｉｏｎ法、ＣＶＤ法）等を挙げることができる。なお、包装用材料に用いられる透明積層体からなるフィルムを製造する場合には、主に、真空蒸着法を用い、一部、プラズマ化学気相成長法も用いられる。   Next, a method for forming a thin film layer on a thermoplastic resin film will be described. As a method for forming the thin film layer, for example, a physical vapor deposition method (Physical Vapor Deposition method, PVD method) such as a vacuum deposition method, a sputtering method, or an ion plating method, a plasma chemical vapor deposition method, a thermochemistry, or the like. A chemical vapor deposition method (Chemical Vapor Deposition method, CVD method) such as a vapor deposition method or a photochemical vapor deposition method can be given. In addition, when manufacturing the film which consists of a transparent laminated body used for the packaging material, a vacuum vapor deposition method is mainly used and a plasma chemical vapor deposition method is also used partially.

また、例えば、物理気相成長法と化学気相成長法の両者を併用して異種の無機酸化物の蒸着膜の２層以上からなる複合膜を形成して使用することもできる。酸化アルミニウム薄膜が、その膜表面から内面に向かう深さ方向に向かってｘの値が増加している酸化アルミニウムの薄膜を形成する場合は、本出願人による特開平１０−２２６０１１号公報に開示された方法により製造することができる。蒸着チャンバーの真空度としては、酸素導入前においては、１０−２〜１０−８ｍｂａｒ程度、特に、１０−３〜１０−７ｍｂａｒ程度が好ましく、酸素導入後においては、１０−１〜１０−６ｍｂａｒ程度、特に１０−２〜１０−５ｍｂａｒ程度が好ましい。なお、酸素導入量等は、蒸着機の大きさ等によって異なる。導入する酸素には、キャリヤーガスとしてアルゴンガス、ヘリウムガス、窒素ガス等の不活性ガスを支障のない範囲で使用してもよい。基材となる熱可塑性樹脂フィルムの搬送速度としては、１０〜８００ｍ／分程度、特に５０〜６００ｍ／分程度が好ましい。また、上記したような、化合物の含有量が酸化珪素の蒸着膜の表面から深さ方向に向かって減少している酸化ケイ素薄膜層は、出願人による特開２００８−１４３０９７号公報に記載されたような方法により、形成することができる。 In addition, for example, a composite film composed of two or more vapor-deposited films of different kinds of inorganic oxides can be formed by using both physical vapor deposition and chemical vapor deposition. In the case of forming an aluminum oxide thin film in which the value of x increases in the depth direction from the film surface to the inner surface, the aluminum oxide thin film is disclosed in Japanese Patent Application Laid-Open No. 10-226011 by the present applicant. It can be manufactured by the method. The degree of vacuum deposition chamber, before introduction of oxygen 10 -2 to 10 -8 mbar approximately, in particular, is preferably about 10 -3 to 10 -7 mbar, in the post-oxygen introduction, 10 -1 to 10 - About 6 mbar, especially about 10 −2 to 10 −5 mbar is preferable. The amount of oxygen introduced varies depending on the size of the vapor deposition machine. For the oxygen to be introduced, an inert gas such as argon gas, helium gas, nitrogen gas or the like may be used as a carrier gas within a range where there is no problem. As a conveyance speed of the thermoplastic resin film used as a base material, about 10-800 m / min, especially about 50-600 m / min are preferable. Moreover, the silicon oxide thin film layer in which the content of the compound as described above decreases from the surface of the deposited silicon oxide film in the depth direction is described in Japanese Patent Application Laid-Open No. 2008-143097 by the applicant. It can be formed by such a method.

また、本発明においては、上記のようにして形成した薄膜層の表面に酸素プラズマ処理を施してもよい。酸素プラズマ処理のために導入する酸素の量は、蒸着機の大きさ等によって異なるが、通常５０ｓｃｃｍ〜２０００ｓｃｃｍ程度であり、３００ｓｃｃｍ〜８００ｓｃｃｍ程度が特に好ましい。ここで、ｓｃｃｍは標準状態（ＳＴＰ：０℃、１ａｔｍ）での１分当りの酸素の平均導入量（ｃｃ）を意味する。導入する酸素には、キャリヤーガスとしてアルゴンガス、ヘリウムガス、窒素ガス等の不活性ガスを支障のない範囲で使用してもよい。以上、熱可塑性樹脂フィルム上に酸化アルミニウムまたは酸化ケイ素からなる薄膜を形成する方法、および、所望により酸化アルミニウムまたは酸化ケイ素からなる薄膜の表面を酸素プラズマ処理する方法を説明したが、これらは一例であって、本発明がこれらの方法により得られたものに限定されるものではない。   In the present invention, the surface of the thin film layer formed as described above may be subjected to oxygen plasma treatment. The amount of oxygen introduced for the oxygen plasma treatment varies depending on the size of the vapor deposition apparatus and the like, but is usually about 50 sccm to 2000 sccm, and particularly preferably about 300 sccm to 800 sccm. Here, sccm means the average amount of oxygen introduced (cc) per minute in the standard state (STP: 0 ° C., 1 atm). For the oxygen to be introduced, an inert gas such as argon gas, helium gas, nitrogen gas or the like may be used as a carrier gas within a range where there is no problem. As described above, the method for forming a thin film made of aluminum oxide or silicon oxide on the thermoplastic resin film and the method for subjecting the surface of the thin film made of aluminum oxide or silicon oxide to oxygen plasma treatment as required have been described. Thus, the present invention is not limited to those obtained by these methods.

次に、上記のようにして形成された薄膜層上に設けられるガスバリア性保護層について説明する。ガスバリア性保護層は、少なくとも水酸基を有する水溶性高分子とアルコキシシランとを含む溶液でコーティングすることにより形成できる。少なくとも水酸基を有する水溶性高分子としては、ポリビニルアルコール、ポリビニルピロリドン、デンプン、メチルセルロース、カルボキシメチルセルロース、アルギン酸ナトリウム、又はエチレン−ビニルアルコール共重合体などが挙げられ、特に、エチレン−ビニルアルコール共重合体やポリビニルアルコールが好ましい。これら樹脂は市販のものを使用してもよく、例えばエチレン・ビニルアルコール共重合体として、株式会社クラレ製、エバールＥＰ−Ｆ１０１（エチレン含量；３２モル％）、日本合成化学工業株式会社製、ソアノールＤ２９０８（エチレン含量；２９モル％）等を使用することができる。また、ポリビニルアルコールとして、株式会社クラレ製のＲＳポリマーであるＲＳ−１１０（ケン化度＝９９％、重合度＝１,０００）、同社製のクラレポバールＬＭ−２０ＳＯ（ケン化度＝４０％、重合度＝２,０００）、日本合成化学工業株式会社製のゴーセノールＮＭ−１４（ケン化度＝９９％、重合度＝１,４００）等を使用することができる。   Next, the gas barrier protective layer provided on the thin film layer formed as described above will be described. The gas barrier protective layer can be formed by coating with a solution containing at least a water-soluble polymer having a hydroxyl group and alkoxysilane. Examples of the water-soluble polymer having at least a hydroxyl group include polyvinyl alcohol, polyvinyl pyrrolidone, starch, methyl cellulose, carboxymethyl cellulose, sodium alginate, ethylene-vinyl alcohol copolymer, and the like. Polyvinyl alcohol is preferred. These resins may be commercially available. For example, as an ethylene / vinyl alcohol copolymer, Kuraray Co., Ltd., Eval EP-F101 (ethylene content: 32 mol%), Nippon Synthetic Chemical Industry Co., Ltd., Soarnol D2908 (ethylene content; 29 mol%) and the like can be used. Also, as polyvinyl alcohol, RS-110 (degree of saponification = 99%, degree of polymerization = 1,000) manufactured by Kuraray Co., Ltd., Kuraray Poval LM-20SO (degree of saponification = 40%) manufactured by the same company. Degree of polymerization = 2,000), Gohsenol NM-14 (degree of saponification = 99%, degree of polymerization = 1,400) manufactured by Nippon Synthetic Chemical Industry Co., Ltd. can be used.

アルコキシシランとしては、一般式：
Ｒ１ｎＳｉ（ＯＲ２）ｍ
（式中、Ｒ１およびＲ２は、それぞれ独立して炭素数１〜８の有機基を表し、ｎは０以上の整数を表し、ｍは１以上の整数を表すが、ｎ＋ｍはＳｉの原子価を表す。）で表されるものが好適に使用できる。上記式において、Ｒ１で表される有機基の具体例としては、例えば、メチル基、エチル基、ｎ−プロピル基、ｉ−プロピル基、ｎ−ブチル基、ｉ−ブチル基、ｓｅｃ−ブチル基、ｔ−ブチル基、ｎ−ヘキシル基、ｎ−オクチル基、その他等のアルキル基を挙げることができる。アルコキシシランの具体例としては、例えば、テトラメトキシシラン：Ｓｉ（ＯＣＨ３）４ 、テトラエトキシシラン：Ｓｉ（ＯＣ２Ｈ５）４ 、テトラプロポキシシラン：Ｓｉ（ＯＣ３Ｈ７）４ 、テトラブトキシシラン：Ｓｉ（ＯＣ４Ｈ９）４等を使用することができる。 As alkoxysilane, the general formula:
R 1n Si (OR 2 ) m
(In the formula, R 1 and R 2 each independently represent an organic group having 1 to 8 carbon atoms, n represents an integer of 0 or more, m represents an integer of 1 or more, and n + m represents an Si atom. Can be suitably used. In the above formula, specific examples of the organic group represented by R 1 include, for example, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, sec-butyl group. , T-butyl group, n-hexyl group, n-octyl group, and other alkyl groups. Specific examples of the alkoxysilane include, for example, tetramethoxysilane: Si (OCH 3 ) 4 , tetraethoxysilane: Si (OC 2 H 5 ) 4 , tetrapropoxysilane: Si (OC 3 H 7 ) 4 , tetrabutoxysilane. : Si (OC 4 H 9 ) 4 or the like can be used.

上記した水溶性高分子とアルコキシシランとを混合し、さらに所望によりゾル−ゲル法触媒、水、および、有機溶剤を添加した溶液を、酸化アルミニウムまたは酸化ケイ素からなる薄膜の表面に塗布し、重縮合することにより、ガスバリア性保護層を形成することができる。また、本発明においては、酸化アルミニウムまたは酸化ケイ素からなる薄膜の上に、上記の塗布膜を２層以上重層した複合ポリマー層を形成することもできる。   The above-mentioned water-soluble polymer and alkoxysilane are mixed, and if desired, a solution to which a sol-gel method catalyst, water, and an organic solvent are added is applied to the surface of a thin film made of aluminum oxide or silicon oxide. A gas barrier protective layer can be formed by condensation. In the present invention, a composite polymer layer in which two or more of the above-mentioned coating films are stacked can be formed on a thin film made of aluminum oxide or silicon oxide.

また、本発明においては、上記のガスバリア性保護層形成用塗布液に、シランカップリング剤を添加することができ、これにより得られるガスバリア性保護層は特に好ましいものである。上記のシランカップリング剤としては、既知の有機反応性基含有オルガノアルコキシシランを用いることができるが、特に、エポキシ基を有するオルガノアルコキシシランが好適であり、例えば、γ−グリシドキシプロピルトリメトキシシラン、γ−グリシドキシプロピルメチルジエトキシシラン、あるいは、β−（３,４−エポキシシクロヘキシル）エチルトリメトキシシラン等を使用することができる。上記のようなシランカップリング剤は、１種ないし２種以上を混合して用いてもよい。本発明において、上記のようなシランカップリング剤の使用量は、上記のアルコキシシラン１００質量部に対して１〜２０質量部程度の範囲内で使用することができる。   Moreover, in this invention, a silane coupling agent can be added to said coating liquid for gas barrier property protective layer formation, and the gas barrier property protective layer obtained by this is especially preferable. As the silane coupling agent, known organic reactive group-containing organoalkoxysilanes can be used. In particular, an organoalkoxysilane having an epoxy group is suitable, for example, γ-glycidoxypropyltrimethoxy. Silane, γ-glycidoxypropylmethyldiethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, or the like can be used. The above silane coupling agents may be used alone or in combination of two or more. In this invention, the usage-amount of the above silane coupling agents can be used within the range of about 1-20 mass parts with respect to 100 mass parts of said alkoxysilane.

ガスバリア性保護層形成用塗布液の塗布方法としては、通常用いられる、グラビアロールコーターなどのロールコート、スプレーコート、スピンコート、デイツピング、刷毛、バーコード、アプリケータ等の従来公知の手段が用いられる。塗布膜の厚さは塗布液の種類によって異なるが、乾燥後の厚さが約０.０１〜１００μｍの範囲であればよいが、５０μｍ以上では、膜にクラックが生じやすくなるため、０.０１〜５０μｍとすることが好ましい。   As a coating method of the coating solution for forming the gas barrier protective layer, conventionally known means such as roll coating such as gravure roll coater, spray coating, spin coating, dipping, brush, bar code, applicator and the like are used. . Although the thickness of the coating film varies depending on the type of the coating solution, the thickness after drying may be in the range of about 0.01 to 100 μm. However, if the thickness is 50 μm or more, cracks are likely to occur in the film. It is preferable to be set to ˜50 μm.

塗布液と重縮合させる際のゾル−ゲル法触媒としては、水に実質的に不溶であり、かつ有機溶媒に可溶な第三アミンが用いられる。具体的には、例えば、Ｎ,Ｎ−ジメチルベンジルアミン、トリプロピルアミン、トリブチルアミン、トリペンチルアミン等を使用することができる。特に、Ｎ,Ｎ−ジメチルべンジルアミンが好適であり、アルコキシシラン、およびシランカップリング剤の合計量１００質量部当り、０.０１〜１.０質量部、特に約０.０３質量部程度を使用することが好ましい。   As a sol-gel method catalyst for polycondensation with a coating solution, a tertiary amine that is substantially insoluble in water and soluble in an organic solvent is used. Specifically, for example, N, N-dimethylbenzylamine, tripropylamine, tributylamine, tripentylamine and the like can be used. In particular, N, N-dimethylbenzylamine is suitable, and 0.01 to 1.0 part by weight, particularly about 0.03 part by weight is used per 100 parts by weight of the total amount of alkoxysilane and silane coupling agent. It is preferable to do.

また、ゾル−ゲル法の触媒として、酸を使用することもでき、例えば、硫酸、塩酸、硝酸などの鉱酸、ならびに、酢酸、酒石酸な等の有機酸、その他を使用することができる。酸の使用量としては、アルコキシシランおよびシランカップリング剤のアルコキシシラン分（例えばシリケート部分）の総モル量に対し０.００１〜０.０５モル程度、特に約０.０１モル程度が好ましい。   Moreover, an acid can also be used as a catalyst of a sol-gel method, for example, mineral acids, such as a sulfuric acid, hydrochloric acid, nitric acid, organic acids, such as an acetic acid and tartaric acid, and others can be used. The amount of the acid used is preferably about 0.001 to 0.05 mol, particularly about 0.01 mol, relative to the total molar amount of alkoxysilane and the alkoxysilane content (for example, silicate moiety) of the silane coupling agent.

塗布液に含まれる水は、溶液アルコキシドの合計モル量１モルに対して０.１〜１００モル、好ましくは０.８〜２モルの割合で添加される。また、ガスバリア性保護層形成用塗布液に含まれるポリビニルアルコールやエチレン−ビニルアルコール共重合体は、上記のアルコキシシランやシランカップリング剤などを含む塗布液中で溶解した状態であることが好ましく、そのために有機溶媒を適宜選択して添加してもよい。例えば、有機溶媒としては、メチルアルコール、エチルアルコール、ｎ−プロピルアルコール、イソプロピルアルコール、ｎ−ブタノール等を用いることができる。   Water contained in the coating solution is added in a proportion of 0.1 to 100 mol, preferably 0.8 to 2 mol, per 1 mol of the total molar amount of the solution alkoxide. Moreover, it is preferable that the polyvinyl alcohol and the ethylene-vinyl alcohol copolymer contained in the coating liquid for forming a gas barrier protective layer are in a state dissolved in a coating liquid containing the above-described alkoxysilane, silane coupling agent, etc. Therefore, an organic solvent may be appropriately selected and added. For example, as the organic solvent, methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butanol and the like can be used.

＜ポリエステル不織布＞
本発明の積層体を構成するポリエステル不織布は、ポリエチレンテレフタレート、ポリトリメチレンテレフタレート、ポリブチレンテレフタレート、ポリエチレンナフタレート、ポリブチレンナフタレート等からなる樹脂からなる繊維を不織布とすることにより得られる。これらのなかでも、汎用性樹脂であるポリエチレンテレフタレートを好適に使用することができる。 <Polyester non-woven fabric>
The polyester non-woven fabric constituting the laminate of the present invention can be obtained by using a non-woven fabric made of a resin composed of polyethylene terephthalate, polytrimethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, or the like. Among these, polyethylene terephthalate, which is a versatile resin, can be preferably used.

また、本発明において用いられるポリエステル不織布としては、芯鞘構造を有する複合繊維からなる不織布であってもよく、例えば、芯がポリオレフィン樹脂やポリアミド樹脂等からなり、鞘が上記したポリエステル樹脂からなる複合繊維なども好適に使用することができる。   Further, the polyester nonwoven fabric used in the present invention may be a nonwoven fabric composed of a composite fiber having a core-sheath structure. For example, a composite composed of a core made of a polyolefin resin or a polyamide resin, and a sheath made of the above-described polyester resin. A fiber etc. can also be used conveniently.

ポリエステル不織布には、必要に応じて、光安定剤、紫外線吸収剤、酸化防止剤、充填剤、滑剤等、従来公知の各種添加剤を適宜添加することができる。光安定剤、紫外線吸収剤としては、従来公知のものを使用でき、例えば、フェノール系、リン系、ヒンダードアミン系の光吸収剤や、ベンゾトリアゾール系、ベンゾフェノン系、サリチル酸エステル系の紫外線吸収剤が使用できる。   Various conventionally known additives such as a light stabilizer, an ultraviolet absorber, an antioxidant, a filler, a lubricant and the like can be appropriately added to the polyester nonwoven fabric as necessary. Conventionally known light stabilizers and ultraviolet absorbers can be used. For example, phenol-based, phosphorus-based, hindered amine-based light absorbers, benzotriazole-based, benzophenone-based, and salicylic acid ester-based ultraviolet absorbers are used. it can.

上記した樹脂からなる繊維を不織布とするには、通常用いられているローラーカード、フラットカード等のカード機を用いて、定法によりウェッブを作製する。ウェッブからの不織布の製造は、目的とする不織布の用途等に応じて熱融着法、スパンボンド法、メルトブロー法、溶剤系によるフラッシュ紡糸法などの従来公知の方法を適宜選択して行えばよい。また、交絡させた繊維どうしを熱融着させて不織布としてもよい。ポリエステル不織布として、市販のものを使用してもよく、例えば、エルタスシリーズ（旭化成せんい株式会社製）やマリックスシリーズ（ユニチカ株式会社製）等を好適に使用することができる。   In order to make the fiber made of the above-mentioned resin into a non-woven fabric, a web is prepared by a conventional method using a card machine such as a roller card or a flat card that is usually used. The production of the nonwoven fabric from the web may be carried out by appropriately selecting a conventionally known method such as a heat fusion method, a spunbond method, a melt blow method, or a solvent-based flash spinning method according to the intended use of the nonwoven fabric. . Further, the entangled fibers may be heat-sealed to form a nonwoven fabric. As the polyester nonwoven fabric, commercially available ones may be used, and for example, Eltus series (Asahi Kasei Fibers Co., Ltd.), Marix series (Unitika Ltd.) and the like can be suitably used.

本発明において用いられるポリエステル不織布の厚みは、概ね２０〜８００μｍ程度である。   The thickness of the polyester nonwoven fabric used in the present invention is about 20 to 800 μm.

＜積層体の製造方法＞
次に、上記したような積層体を製造する方法を、図面を参照しながら説明する。先ず、上記したバリア性フィルム１とポリエステル不織布２とを準備し（図３（１））、両者のいずれか一方または両方の、接着しようとする部分に電子線を照射する（図３（２））。その結果、図３（３）に示すように、電子線が照射された部分のみ、バリア性フィルム１とポリエステル不織布２とが接着される。 <Method for producing laminate>
Next, a method for producing the laminate as described above will be described with reference to the drawings. First, the barrier film 1 and the polyester nonwoven fabric 2 described above are prepared (FIG. 3 (1)), and either or both of them are irradiated with an electron beam (FIG. 3 (2)). ). As a result, as shown in FIG. 3 (3), the barrier film 1 and the polyester nonwoven fabric 2 are bonded only to the portion irradiated with the electron beam.

本発明においては、フィルム１および不織布２の両方または何れか一方に電子線を照射した直後に、図４に示すようにローラー６等を用いて、重ね合わせたフィルム１およびお不織布２を押圧することが好ましい。フィルム１および不織布２の表面は、図４に示すようにミクロレベルで凹凸があるため、互いのフィルムを重ね合わせても完全に密着しておらず、両フィルムの接触界面での接触面積が小さい。本発明においては、電子線を照射した直後にローラー６等でフィルム１および不織布２を押圧することにより、両者の接着面での接触面積が増加するため、密着性が向上する。   In the present invention, immediately after irradiating an electron beam to one or both of the film 1 and the nonwoven fabric 2, the superimposed film 1 and nonwoven fabric 2 are pressed using a roller 6 or the like as shown in FIG. It is preferable. As shown in FIG. 4, the surfaces of the film 1 and the nonwoven fabric 2 are uneven at the micro level, so even if the films are overlapped with each other, they are not completely adhered to each other, and the contact area at the contact interface between both films is small. . In this invention, since the contact area in both the adhesion surfaces increases by pressing the film 1 and the nonwoven fabric 2 with the roller 6 etc. immediately after irradiating an electron beam, adhesiveness improves.

バリア性フィルム１とポリエステル不織布２とを重ね合わせた後、両者１，２を押圧する際には、加熱しながら両者１，２を押圧することが好ましい。加熱しながら押圧することにより、バリア性フィルム１およびポリエステル不織布２の柔軟性が向上し、バリア性フィルム１とポリエステル不織布２との界面（接着面）での接触面積をより増加させることができるため、密着性がより向上する。加熱する温度は、使用するフィルムおよび不織布の繊維の種類にもよるが、フィルムないし繊維が熱変形できる温度であればよく、例えば、フィルムないし繊維を構成する樹脂のガラス転移温度以上に加熱することができる。例えば、ポリエステル不織布としてポリエチレンテレフタレート（ＰＥＴ）繊維からなる不織布を用いる場合には、加熱温度は８０〜１８０℃、好ましくは１００〜１６０℃である。加熱温度を高くしすぎると、発生したラジカルが失活してしまい、強固な結合を実現できなくなる。なお、押圧の力（接圧）を高くしてもよく、接圧を高くすることにより、加熱温度を低くすることができる。   After the barrier film 1 and the polyester nonwoven fabric 2 are overlapped, when pressing both 1 and 2, it is preferable to press both 1 and 2 while heating. By pressing while heating, the flexibility of the barrier film 1 and the polyester nonwoven fabric 2 is improved, and the contact area at the interface (adhesive surface) between the barrier film 1 and the polyester nonwoven fabric 2 can be further increased. , Adhesion is further improved. The temperature to be heated depends on the type of fiber used in the film and nonwoven fabric, but may be any temperature at which the film or fiber can be thermally deformed. For example, heating to a temperature higher than the glass transition temperature of the resin constituting the film or fiber. Can do. For example, when using the nonwoven fabric which consists of a polyethylene terephthalate (PET) fiber as a polyester nonwoven fabric, heating temperature is 80-180 degreeC, Preferably it is 100-160 degreeC. If the heating temperature is too high, the generated radicals are deactivated, and a strong bond cannot be realized. The pressing force (contact pressure) may be increased, and the heating temperature can be lowered by increasing the contact pressure.

バリア性フィルム１とポリエステル不織布２とを重ね合わせて押圧するには、上記したようにヒートローラ６等を好適に使用できる。また、図４に示すように、重ね合わせたフィルムがヒートローラ６と支持ローラー７との間で圧接可能となるように、ヒートローラ６と対向する位置に支持ローラー７を載置してもよい。このようにヒートローラ６と対向する位置に支持ローラー７を載置することにより、積層体（フィルム１と不織布２の積層物）とヒートローラ６との接触を線接触に近づけて、ヒートローラ６からの熱により積層体に発生する変形を最小限に抑えることができる。   In order to overlap and press the barrier film 1 and the polyester nonwoven fabric 2, the heat roller 6 or the like can be suitably used as described above. In addition, as shown in FIG. 4, the support roller 7 may be placed at a position facing the heat roller 6 so that the superposed film can be pressed between the heat roller 6 and the support roller 7. . Thus, by placing the support roller 7 at a position facing the heat roller 6, the contact between the laminate (laminated film 1 and nonwoven fabric 2) and the heat roller 6 is brought close to line contact, and the heat roller 6. It is possible to minimize the deformation that occurs in the laminated body due to the heat from the.

図５は、本発明による別の製造方法の実施形態を示した概略図である。バリア性フィルム１とポリエステル不織布２とを重ね合わせて接着する工程において、両者１，２をそれぞれガイドローラにより電子線照射位置３まで導き、電子線４を両者１，２に照射した後にヒートローラ６により両者１，２を押圧する工程を連続的に行うものである。それぞれのフィルム１および不織布２はロール状形態として供給されてもよい。   FIG. 5 is a schematic view showing another embodiment of the manufacturing method according to the present invention. In the process of laminating and bonding the barrier film 1 and the polyester nonwoven fabric 2, both 1 and 2 are guided to the electron beam irradiation position 3 by the guide rollers, respectively, and after both the 1 and 2 are irradiated with the electron beam 4, the heat roller 6 Thus, the process of pressing both 1 and 2 is performed continuously. Each film 1 and nonwoven fabric 2 may be supplied in roll form.

電子線照射装置３からそれぞれのフィルム１および不織布２に電子線４を照射する場合、厚みがより小さい方の部材側から電子線４を照射することが好ましい。電子線は加速電圧が増加するほどその透過力も増大する性質を有しているため、フィルムまたは不織布の何れか一方側から電子線を照射した場合に、フィルムまたは不織布の厚さによっては、他方の不織布またはフィルムまで電子線が届かないことがある。その場合には、電子線の加速電圧を増加させることにより、他方の部材の深部まで電子線を到達させることができるが、電子線エネルギーが高くなるにしたがって、フィルムまたは不織布自体に不必要な照射が行われ劣化させてしまう。そのため、薄肉のフィルムと厚肉の不織布とを重ね合わせて接着する際には、電子線エネルギーをそれほど増大させることなく、薄肉のフィルム側から電子線を照射するのが好ましい。例えば、バリア性フィルムの厚みが２５μｍ以下であり、ポリエステル不織布の厚みが５０μｍ以上である場合は、バリア性フィルム１側から電子線を照射する。このような電子線照射方法を採用することにより、フィルムおよび不織布の劣化を最小限に留めることができる。   When irradiating each film 1 and the nonwoven fabric 2 with the electron beam 4 from the electron beam irradiation apparatus 3, it is preferable to irradiate the electron beam 4 from the member side with smaller thickness. Since the electron beam has the property that its transmission power increases as the acceleration voltage increases, depending on the thickness of the film or non-woven fabric, when the electron beam is irradiated from either side of the film or non-woven fabric, the other The electron beam may not reach the nonwoven fabric or film. In that case, the electron beam can reach the deep part of the other member by increasing the acceleration voltage of the electron beam, but as the electron beam energy increases, unnecessary irradiation of the film or the nonwoven fabric itself is performed. Will be deteriorated. Therefore, when a thin film and a thick nonwoven fabric are laminated and bonded, it is preferable to irradiate an electron beam from the thin film side without increasing the electron beam energy so much. For example, when the thickness of the barrier film is 25 μm or less and the thickness of the polyester nonwoven fabric is 50 μm or more, the electron beam is irradiated from the barrier film 1 side. By adopting such an electron beam irradiation method, deterioration of the film and the nonwoven fabric can be minimized.

重ね合わせるフィルム１および不織布２が両方とも厚肉である場合には、図５に示すように両部材の接着面側から電子線が照射できるように、電子線照射装置３と対向する位置に、別の電子線照射装置３’を設けてもよい。この態様によれば、フィルムおよび不織布の厚みに応じて電子線の照射エネルギーを調整することができるため、フィルムおよび不織布を劣化させることなく両者を接着することができる。   When both the film 1 and the nonwoven fabric 2 to be overlapped are thick, as shown in FIG. 5, at a position facing the electron beam irradiation device 3 so that an electron beam can be irradiated from the bonding surface side of both members, Another electron beam irradiation device 3 ′ may be provided. According to this aspect, since the irradiation energy of an electron beam can be adjusted according to the thickness of a film and a nonwoven fabric, both can be adhere | attached, without deteriorating a film and a nonwoven fabric.

図６は、本発明による別の製造方法の実施形態を示した概略図である。この実施態様においては、電子線の照射が、バリア性フィルム１とポリエステル不織布２とを重ね合わせる前に行われる。先ず、供給されてきたバリア性フィルム１およびポリエステル不織布２は、両者１，２が重ね合わされる前に、電子線照射装置３（３’）により、フィルム１および不織布２へ電子線４（４’）が照射される。図５に示した実施形態では、フィルム１および不織布２の電子線照射側と反対側の面どうしが対向するように両者１，２を重ね合わせたのに対し、図６に示す実施態様では、両者１，２の電子線照射側の面どうしが対向するように両者１，２を重ね合わせる点が相違している。このように、フィルム１へ電子線を照射した側の面に不織布２を重ね合わせることにより、フィルムや不織布の厚みによらず、電子線の照射エネルギーをより小さくすることができ、その結果、フィルムおよび不織布の電子線照射による劣化をより低減することができる。   FIG. 6 is a schematic view showing an embodiment of another manufacturing method according to the present invention. In this embodiment, the electron beam irradiation is performed before the barrier film 1 and the polyester nonwoven fabric 2 are overlapped. First, the barrier film 1 and the polyester nonwoven fabric 2 that have been supplied are transferred to the film 1 and the nonwoven fabric 2 by the electron beam irradiation device 3 (3 ′) before the both 1 and 2 are superposed on each other. ) Is irradiated. In the embodiment shown in FIG. 5, both the layers 1 and 2 are overlapped so that the surfaces opposite to the electron beam irradiation side of the film 1 and the nonwoven fabric 2 face each other, whereas in the embodiment shown in FIG. The difference is that the two surfaces 1 and 2 are overlapped so that the surfaces on the electron beam irradiation side of both surfaces 1 and 2 face each other. Thus, by superimposing the nonwoven fabric 2 on the surface of the film 1 irradiated with the electron beam, the irradiation energy of the electron beam can be reduced regardless of the thickness of the film or the nonwoven fabric. As a result, the film And deterioration by electron beam irradiation of a nonwoven fabric can be reduced more.

また、図６に示した実施態様においても、一対の電子線照射装置３，３’を設けて、図５に示した実施態様と同様に、バリア性フィルム１およびポリエステル不織布２のそれぞれへ電子線４，４’を照射してもよい。これらの組み合わせにより、よりフィルムおよび不織布の劣化を少なくして接着強度を向上させることができる。   Also in the embodiment shown in FIG. 6, a pair of electron beam irradiation devices 3 and 3 ′ are provided, and in the same manner as the embodiment shown in FIG. 4,4 ′ may be irradiated. By these combinations, the deterioration of the film and the nonwoven fabric can be further reduced and the adhesive strength can be improved.

図７は、本発明による別の製造方法の実施形態を示した概略図である。この実施形態においては、バリア性フィルム１およびポリエステル不織布２を重ね合わせてヒートローラ６により押圧した後に電子線照射を行うものである。先ず、供給されてきた一対のフィルム１および不織布２は、ガイドローラに導かれて重ね合わされる。続いて、ヒートローラ６と支持ローラー７とにより両者１，２が押圧されるとともに、ヒートローラ６により加熱が行われる。その後、電子線照射装置３によりバリア性フィルム１およびポリエステル不織布２の表面に電子線４が照射されて両者１，２の接着が連続的に行われる。また、図７に示した実施形態においても、一対の電子線照射装置３，３’を設けて、図５及び６に示した実施態様と同様に両方の部材１，２へそれぞれ電子線４，４’を照射してもよい。これらの組み合わせにより、よりフィルムおよび不織布の劣化を少なくして接着強度を向上させることができる。   FIG. 7 is a schematic view showing another embodiment of the manufacturing method according to the present invention. In this embodiment, electron beam irradiation is performed after the barrier film 1 and the polyester nonwoven fabric 2 are overlapped and pressed by the heat roller 6. First, the pair of films 1 and the nonwoven fabric 2 that have been supplied are led to a guide roller and superimposed. Subsequently, both the heat roller 6 and the support roller 7 are pressed by the heat roller 6 and the support roller 7, and heating is performed by the heat roller 6. Then, the electron beam 4 is irradiated to the surface of the barrier film 1 and the polyester nonwoven fabric 2 by the electron beam irradiation apparatus 3, and adhesion | attachment of both 1 and 2 is performed continuously. Also in the embodiment shown in FIG. 7, a pair of electron beam irradiation devices 3 and 3 ′ are provided, and the electron beams 4 and 4 are respectively applied to both members 1 and 2 in the same manner as the embodiment shown in FIGS. 4 'may be irradiated. By these combinations, the deterioration of the film and the nonwoven fabric can be further reduced and the adhesive strength can be improved.

電子線の照射エネルギーは、上記したようにフィルム厚み等に応じて適宜調整する必要がある。本発明においては、２０〜７５０ｋＶ、好ましくは２５〜４００ｋＶ、より好ましくは３０〜３００ｋＶ程度の照射エネルギー範囲で電子線を照射するが、より低い照射エネルギーとすることが好ましく、４０〜２００ｋＶとすることができる。このように低い照射エネルギーとすることにより、フィルムの劣化を抑制できるだけでなく、フィルム表面のラジカル発生がより効率的におこるため、より強固な結合を実現することができる。また、電子線の吸収線量は、５〜８００ｋＧｙ、好ましくは２５〜６００ｋＧｙの範囲で行う。   The irradiation energy of the electron beam needs to be appropriately adjusted according to the film thickness and the like as described above. In the present invention, the electron beam is irradiated in an irradiation energy range of about 20 to 750 kV, preferably 25 to 400 kV, and more preferably about 30 to 300 kV. However, the irradiation energy is preferably lower, and 40 to 200 kV. Can do. Thus, by setting it as low irradiation energy, not only deterioration of a film can be suppressed, but since radical generation | occurrence | production of a film surface occurs more efficiently, stronger bond can be implement | achieved. The absorbed dose of the electron beam is 5 to 800 kGy, preferably 25 to 600 kGy.

このような電子線照射装置としては、従来公知のものを使用でき、例えばカーテン型電子照射装置（ＬＢ１０２３、株式会社アイ・エレクトロンビーム社製）やライン照射型低エネルギー電子線照射装置（ＥＢ−ＥＮＧＩＮＥ、浜松ホトニクス株式会社製）等を好適に使用することができる。   As such an electron beam irradiation apparatus, conventionally known ones can be used. For example, a curtain type electron irradiation apparatus (LB1023, manufactured by I. Electron Beam Co., Ltd.) or a line irradiation type low energy electron beam irradiation apparatus (EB-ENGINE). , Manufactured by Hamamatsu Photonics Co., Ltd.) can be preferably used.

電子線を照射する際には、酸素濃度を１００ｐｐｍ以下とすることが好ましい。酸素存在下で電子線を照射するとオゾンが発生するため環境に悪影響を及ぼす場合があるからである。酸素濃度を１００ｐｐｍ以下とするには、真空下または窒素やアルゴン等の不活性ガス雰囲気下において、フィルムに電子線を照射すればよく、例えば、電子線照射装置内を窒素充填することにより、酸素濃度１００ｐｐｍ以下を達成することができる。   When irradiating with an electron beam, the oxygen concentration is preferably 100 ppm or less. This is because irradiation with an electron beam in the presence of oxygen generates ozone and may adversely affect the environment. In order to reduce the oxygen concentration to 100 ppm or less, the film may be irradiated with an electron beam in a vacuum or in an inert gas atmosphere such as nitrogen or argon. For example, by filling the electron beam irradiation apparatus with nitrogen, A concentration of 100 ppm or less can be achieved.

上記した接着方法によって得られた、バリア性フィルムとポリエステル不織布とを積層した積層体は、従来のラミネート樹脂を用いて接着した場合と同等またはそれ以上の接着強度を実現できる。また、ラミネート樹脂等を全く用いていないため、積層体を使用する際にも異物や残留溶剤等が滲出することがなく、かつ、不織布の本来の性能を低下させることなく、バリア性フィルムと不織布とが強固に接着した積層体を実現することができる。   The laminate obtained by laminating the barrier film and the polyester nonwoven fabric obtained by the above-described adhesion method can realize an adhesive strength equal to or higher than that obtained by using a conventional laminate resin. In addition, since no laminate resin or the like is used, the barrier film and the nonwoven fabric do not exude foreign matter or residual solvent even when the laminate is used, and the original performance of the nonwoven fabric is not deteriorated. Can be realized.

＜バリア性フィルムの準備＞
厚さ１２μｍの二軸延伸ポリエチレンテレフタレートフィルムを使用し、蒸着装置を用いて、下記の条件にて、そのフィルムの一方の面に、膜厚２０ｎｍとなるように酸化アルミニウム薄膜を形成した。
蒸着条件：
蒸着チャンバー内の真空度(酸素導入後)：２×１０−４ｍｂａｒ
巻き取りチャンバー内の真空度：５×１０−３ｍｂａｒ
電子ビーム電力：２５ｋＷ <Preparation of barrier film>
A 12 μm thick biaxially stretched polyethylene terephthalate film was used, and an aluminum oxide thin film was formed on one surface of the film so as to have a film thickness of 20 nm using a vapor deposition apparatus under the following conditions.
Deposition conditions:
Degree of vacuum in the deposition chamber (after introducing oxygen): 2 × 10 −4 mbar
Vacuum degree in the winding chamber: 5 × 10 −3 mbar
Electron beam power: 25kW

次いで、下記の組成Ｉからなるポリビニルアルコール溶液とイソプロピルアルコールとイオン交換水とを含む混合液に、下記組成ＩＩからなる加水分解液を加えて充分に攪拌し、ガスバリア性保護層形成用塗工液と調製した。
組成Ｉ：
ポリビニルアルコール ２.３３（質量％）
イソプロピルアルコール ２.７０（質量％）
水 ５１.７５（質量％） Next, a hydrolyzed liquid having the following composition II is added to a mixed liquid containing a polyvinyl alcohol solution having the following composition I, isopropyl alcohol and ion-exchanged water, and the mixture is sufficiently stirred to form a coating solution for forming a gas barrier protective layer. And prepared.
Composition I:
Polyvinyl alcohol 2.33 (mass%)
Isopropyl alcohol 2.70 (mass%)
Water 51.75 (mass%)

組成ＩＩ（加水分解液）：
エチルシリケート １６.６０（質量％）
シランカップリング剤 １.６６（質量％）
イソプロピルアルコール ３.９０（質量％）
０．５Ｎ塩酸水溶液 ０.５３（質量％）
水 ２０.５３（質量％）
合計 １００.００（質量％） Composition II (hydrolyzed solution):
Ethyl silicate 16.60 (mass%)
Silane coupling agent 1.66 (mass%)
Isopropyl alcohol 3.90 (mass%)
0.5N hydrochloric acid aqueous solution 0.53 (mass%)
Water 20.53 (mass%)
Total 100.00 (mass%)

上記の塗工液を、酸化アルミニウム薄膜上にグラビアロールコート法によりコーティングして、次いで、１８０℃で６０秒間加熱処理を行い、厚み０.２μｍ（乾操状態）のガスバリア性保護層を形成することにより、バリア性フィルムを得た。   The above coating liquid is coated on the aluminum oxide thin film by a gravure roll coating method, and then heat-treated at 180 ° C. for 60 seconds to form a gas barrier protective layer having a thickness of 0.2 μm (dry operation state). Thus, a barrier film was obtained.

＜ポリエステル不織布の準備＞
ポリエステル不織布として、厚さ１２０μｍのポリエステル不織布（エルタス Ｅ０５０２０、旭化成せんい株式会社製）を準備した。 <Preparation of polyester nonwoven fabric>
A polyester nonwoven fabric having a thickness of 120 μm (ELTAS E05020, manufactured by Asahi Kasei Fibers Co., Ltd.) was prepared as a polyester nonwoven fabric.

実施例１
＜積層体の作製＞
準備したバリア性フィルムおよびポリエステル不織布を、それぞれ１５０ｍｍ×７５ｍｍの大きさに切り出した試料を準備し、電子線照射装置（ライン照射型低エネルギー電子線照射装置ＥＥＳ−Ｌ−ＤＰ０１、浜松ホトニクス株式会社製）のサンプル台に並置した。この際、電子線が試料に照射されない部分を設けるために、両試料の一方の端部５〜１０ｍｍ程度にマスキングしておいた。 Example 1
<Production of laminate>
Samples prepared by cutting the prepared barrier film and polyester nonwoven fabric into a size of 150 mm × 75 mm were prepared, and an electron beam irradiation device (line irradiation type low energy electron beam irradiation device EES-L-DP01, manufactured by Hamamatsu Photonics Co., Ltd.). ) On the sample stage. At this time, in order to provide a portion where the sample is not irradiated with the electron beam, masking is performed on one end portion of both samples of about 5 to 10 mm.

次いで、電子照射線装置のチャンバー内の酸素濃度が１００ｐｐｍ以下となるように窒素ガスでパージした後、下記の電子線照射条件により、試料の表面に電子線を照射した。なお、バリア性フィルムについては、ガスバリア性保護層形成面に電子線を照射した。
電圧：４０ｋＶ
吸収線量：２００ｋＧｙ
装置内酸素濃度：１００ｐｐｍ以下 Next, after purging with nitrogen gas so that the oxygen concentration in the chamber of the electron irradiation apparatus becomes 100 ppm or less, the surface of the sample was irradiated with an electron beam under the following electron beam irradiation conditions. In addition, about the barrier film, the electron barrier was irradiated to the gas barrier protective layer formation surface.
Voltage: 40 kV
Absorbed dose: 200kGy
In-device oxygen concentration: 100 ppm or less

電子線を照射した後、試料を装置内から取り出し、すぐに両試料の電子線照射面側が対向するようにして重ね合わせ、熱ラミネート法により、両試料を接着して積層体を得た。   After irradiating the electron beam, the sample was taken out from the apparatus, immediately overlapped so that the electron beam irradiation surface sides of both samples faced each other, and both samples were bonded by a thermal laminating method to obtain a laminate.

比較例１
電子照射を行わなかった以外は実施例１と同様にして積層体を得た。しかしながら、得られた積層体はバリア性フィルムとポリエステル不織布とは接着していなかった。 Comparative Example 1
A laminate was obtained in the same manner as in Example 1 except that electron irradiation was not performed. However, the obtained laminate was not bonded to the barrier film and the polyester nonwoven fabric.

＜積層体の接着強度の評価＞
得られた積層体を幅１５ｍｍの短冊状になるように切り出し、引張試験機（テンシロン万能材料試験機ＲＴＣ−１３１０Ａ、ＯＲＩＥＮＴＥＣ社製）を用いて、５０ｍｍ／分の速度で、９０度剥離試験を行った。なお、上記したように比較例１の積層体は、バリア性フィルム１とポリエステル不織布とが接着しておらず、積層体の接着強度を測定することができなかった。評価結果は、下記の表１に示される通りであった。 <Evaluation of adhesive strength of laminate>
The obtained laminate was cut into a strip shape with a width of 15 mm, and a 90 ° peel test was performed at a rate of 50 mm / min using a tensile tester (Tensilon Universal Material Tester RTC-1310A, manufactured by ORIENTEC). went. In addition, as above-mentioned, as for the laminated body of the comparative example 1, the barrier film 1 and the polyester nonwoven fabric were not adhere | attached, but the adhesive strength of the laminated body was not able to be measured. The evaluation results were as shown in Table 1 below.

また、実施例１の積層体の接着が共有結合によるものかどうかと間接的に調べるために、得られた積層体を水中で保管し、その後、上記と同様にして積層体の接着強度を測定した。評価結果は、下記の表１に示される通りであった。   In addition, in order to indirectly check whether the adhesion of the laminate of Example 1 is due to a covalent bond, the obtained laminate was stored in water, and then the adhesion strength of the laminate was measured in the same manner as described above. did. The evaluation results were as shown in Table 1 below.

Figure 0005835643
Figure 0005835643

表１の評価結果からも明らかなように、実施例１の積層体は、水中保管後も、水中保管後であっても、接着性を維持している。この結果から、実施例１の積層体は、バリア性フィルムとポリエステル不織布とが水素結合や分子間力のみによって接着しているものではないことがわかる。したがって、間接的にではあるが、バリア性フィルムのガスバリア性保護層中の原子とポリエステル不織布中の原子との間で共有結合が形成されていると推認でき、接着剤によりラミネート加工した従来の積層体と同程度の接着強度を有している。   As is clear from the evaluation results in Table 1, the laminate of Example 1 maintains adhesiveness even after storage in water and after storage in water. From this result, it can be seen that in the laminate of Example 1, the barrier film and the polyester nonwoven fabric are not bonded only by hydrogen bonds or intermolecular forces. Therefore, although indirectly, it can be inferred that a covalent bond is formed between the atoms in the gas barrier protective layer of the barrier film and the atoms in the polyester nonwoven fabric. It has the same adhesive strength as the body.

１ バリア性フィルム
１１ 熱可塑性樹脂フィルム
１２ 薄膜層
１３ ガスバリア性保護層
２ ポリエステル不織布
３、３’ 電子線照射装置
４、４’ 電子線
５ フィルム基材接触界面
６ ヒートローラ
７ 支持ローラー DESCRIPTION OF SYMBOLS 1 Barrier film 11 Thermoplastic resin film 12 Thin film layer 13 Gas barrier protective layer 2 Polyester nonwoven fabric 3, 3 'Electron beam irradiation apparatus 4, 4' Electron beam 5 Film substrate contact interface 6 Heat roller 7 Support roller

Claims (9)

熱可塑性樹脂フィルム、前記熱可塑性樹脂フィルムの少なくとも一方の面に設けた酸化アルミニウムまたは酸化ケイ素からなる薄膜層、および前記薄膜層上に設けたガスバリア性保護層を含んでなるバリア性フィルムと、ポリエステル不織布とが、前記バリア性フィルムのガスバリア性保護層と前記ポリエステル不織布とが対向するように、積層した積層体であって、
前記ガスバリア性保護層が、少なくとも水酸基を有する水溶性高分子とアルコキシシランとを含む溶液を塗布して得られる被膜からなり、
前記ガスバリア性保護層と前記ポリエステル不織布との界面の少なくとも一部で、前記ガスバリア性保護層中のケイ素原子と、前記ポリエステル不織布中の炭素原子との間に共有結合が形成されており、前記ガスバリア性保護層および前記ポリエステル不織布とが接着剤を介さずに接着されていることを特徴とする、積層体。 A barrier film comprising a thermoplastic resin film, a thin film layer made of aluminum oxide or silicon oxide provided on at least one surface of the thermoplastic resin film, and a gas barrier protective layer provided on the thin film layer; and polyester The nonwoven fabric is a laminated body laminated so that the gas barrier protective layer of the barrier film and the polyester nonwoven fabric face each other,
The gas barrier protective layer comprises a film obtained by applying a solution containing at least a water-soluble polymer having a hydroxyl group and alkoxysilane,
A covalent bond is formed between the silicon atom in the gas barrier protective layer and the carbon atom in the polyester nonwoven fabric at least at a part of the interface between the gas barrier protective layer and the polyester nonwoven fabric, and the gas barrier A laminate comprising the protective protective layer and the polyester nonwoven fabric bonded together without an adhesive. 前記ガスバリア性保護層と前記ポリエステル不織布との界面の少なくとも一部で、前記ガスバリア性保護層中の原子と、前記ポリエステル不織布中の原子との間で、酸素原子、窒素原子または水酸基を介して結合が形成されている、請求項１に記載の積層体。   At least part of the interface between the gas barrier protective layer and the polyester nonwoven fabric, bonded between an atom in the gas barrier protective layer and an atom in the polyester nonwoven fabric through an oxygen atom, a nitrogen atom or a hydroxyl group The laminate according to claim 1, wherein 前記アルコキシシランが下記一般式：
Ｒ１ｎＳｉ（ＯＲ２）ｍ
（式中、Ｒ１およびＲ２は、それぞれ独立して炭素数１〜８の有機基を表し、ｎは０以上の整数を表し、ｍは１以上の整数を表すが、ｎ＋ｍはＳｉの原子価を表す。）
で表される、請求項１または２に記載の積層体。 The alkoxysilane is represented by the following general formula:
R 1n Si (OR 2 ) m
(In the formula, R 1 and R 2 each independently represent an organic group having 1 to 8 carbon atoms, n represents an integer of 0 or more, m represents an integer of 1 or more, and n + m represents an Si atom. Represents the value.)
The laminated body of Claim 1 or 2 represented by these. 前記水酸基を有する水溶性高分子が、ポリビニルアルコール、ポリビニルピロリドン、デンプン、メチルセルロース、カルボキシメチルセルロース、アルギン酸ナトリウム、およびエチレン−ビニルアルコール共重合体からなる群から選択される１種、または２種以上の混合物である、請求項１〜３のいずれか一項に記載の積層体。   The water-soluble polymer having a hydroxyl group is selected from the group consisting of polyvinyl alcohol, polyvinyl pyrrolidone, starch, methyl cellulose, carboxymethyl cellulose, sodium alginate, and an ethylene-vinyl alcohol copolymer, or a mixture of two or more. The laminate according to any one of claims 1 to 3, wherein 前記ポリエステル不織布が、ポリエチレンテレフタレート、ポリトリメチレンテレフタレート、ポリブチレンテレフタレート、ポリエチレンナフタレート、もしくはポリブチレンナフタレートからなる繊維、または、これら樹脂を鞘とする複合繊維からなる、請求項１〜４のいずれか一項に記載の積層体。   The polyester non-woven fabric is composed of a fiber made of polyethylene terephthalate, polytrimethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, or polybutylene naphthalate, or a composite fiber having these resins as sheaths. The laminate according to claim 1. 請求項１〜５のいずれか一項に記載の、バリア性フィルムとポリエステル不織布とを積層した積層体を製造する方法であって、
熱可塑性樹脂フィルム、前記熱可塑性樹脂フィルムの少なくとも一方の面に設けた酸化アルミニウムまたは酸化ケイ素からなる薄膜層、および前記薄膜層上に設けたガスバリア性保護層を含んでなるバリア性フィルムのガスバリア性保護層面、および／または前記ポリエステル不織布の少なくとも一方の面、に電子線を照射し、
前記電子線が照射された前記ガスバリア性保護層面および／またはポリエステル不織布面を重ね合わせて接着する、ことを含んでなることを特徴とする、方法。 A method for producing a laminate in which a barrier film and a polyester nonwoven fabric according to any one of claims 1 to 5 are laminated,
Gas barrier property of a barrier film comprising a thermoplastic resin film, a thin film layer made of aluminum oxide or silicon oxide provided on at least one surface of the thermoplastic resin film, and a gas barrier protective layer provided on the thin film layer Irradiating the protective layer surface and / or at least one surface of the polyester nonwoven fabric with an electron beam,
A method comprising superposing and adhering the gas barrier protective layer surface and / or the polyester nonwoven fabric surface irradiated with the electron beam. 前記バリア性フィルムとポリエステル不織布とを重ね合わせる前および／または重ね合わせた後に電子線照射を行う、請求項６に記載の方法。   The method according to claim 6, wherein the electron beam irradiation is performed before and / or after the barrier film and the polyester nonwoven fabric are overlapped. 前記接着を加圧して行う、請求項６または７に記載の方法。   The method according to claim 6 or 7, wherein the adhesion is performed under pressure. 前記接着を加熱して行う、請求項６〜８のいずれか一項に記載の方法。   The method according to claim 6, wherein the adhesion is performed by heating.
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