US20050051258A1 - Method of bonding fluororesin films, and fluororesin film - Google Patents

Method of bonding fluororesin films, and fluororesin film Download PDF

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Publication number
US20050051258A1
US20050051258A1 US10/943,944 US94394404A US2005051258A1 US 20050051258 A1 US20050051258 A1 US 20050051258A1 US 94394404 A US94394404 A US 94394404A US 2005051258 A1 US2005051258 A1 US 2005051258A1
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US
United States
Prior art keywords
films
fluororesin
film
bonding
bonded
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Abandoned
Application number
US10/943,944
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English (en)
Inventor
Tetsuro Tsukada
Tomomi Takahashi
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
AGC Inc
Original Assignee
Asahi Glass Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Asahi Glass Co Ltd filed Critical Asahi Glass Co Ltd
Assigned to ASAHI GLASS COMPANY, LIMITED reassignment ASAHI GLASS COMPANY, LIMITED ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: TAKAHASHI, TOMOI, TSUKADA, TETSURO
Publication of US20050051258A1 publication Critical patent/US20050051258A1/en
Assigned to ASAHI GLASS COMPANY, LIMITED reassignment ASAHI GLASS COMPANY, LIMITED RECORD TO CORRECT SECOND ASSIGNOR'S NAME ON AN ASSIGNMENT DOCUMENT PREVIOUSLY RECORDED AT REEL 015812 FRAMR 0493 Assignors: TAKAHASHI, TOMOMI, TSUKADA, TETSURO
Priority to US11/945,312 priority Critical patent/US7794558B2/en
Abandoned legal-status Critical Current

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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C65/00Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor
    • B29C65/48Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor using adhesives, i.e. using supplementary joining material; solvent bonding
    • B29C65/50Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor using adhesives, i.e. using supplementary joining material; solvent bonding using adhesive tape, e.g. thermoplastic tape; using threads or the like
    • B29C65/5042Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor using adhesives, i.e. using supplementary joining material; solvent bonding using adhesive tape, e.g. thermoplastic tape; using threads or the like covering both elements to be joined
    • AHUMAN NECESSITIES
    • A01AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01GHORTICULTURE; CULTIVATION OF VEGETABLES, FLOWERS, RICE, FRUIT, VINES, HOPS OR SEAWEED; FORESTRY; WATERING
    • A01G9/00Cultivation in receptacles, forcing-frames or greenhouses; Edging for beds, lawn or the like
    • A01G9/14Greenhouses
    • A01G9/1438Covering materials therefor; Materials for protective coverings used for soil and plants, e.g. films, canopies, tunnels or cloches
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C65/00Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor
    • B29C65/02Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor by heating, with or without pressure
    • B29C65/18Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor by heating, with or without pressure using heated tools
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C65/00Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor
    • B29C65/48Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor using adhesives, i.e. using supplementary joining material; solvent bonding
    • B29C65/4805Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor using adhesives, i.e. using supplementary joining material; solvent bonding characterised by the type of adhesives
    • B29C65/481Non-reactive adhesives, e.g. physically hardening adhesives
    • B29C65/4815Hot melt adhesives, e.g. thermoplastic adhesives
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C66/00General aspects of processes or apparatus for joining preformed parts
    • B29C66/01General aspects dealing with the joint area or with the area to be joined
    • B29C66/03After-treatments in the joint area
    • B29C66/034Thermal after-treatments
    • B29C66/0342Cooling, e.g. transporting through welding and cooling zone
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C66/00General aspects of processes or apparatus for joining preformed parts
    • B29C66/01General aspects dealing with the joint area or with the area to be joined
    • B29C66/05Particular design of joint configurations
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    • B29C66/11Joint 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
    • B29C66/112Single lapped joints
    • B29C66/1122Single lap to lap joints, i.e. overlap joints
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C66/00General aspects of processes or apparatus for joining preformed parts
    • B29C66/01General aspects dealing with the joint area or with the area to be joined
    • B29C66/345Progressively making the joint, e.g. starting from the middle
    • B29C66/3452Making complete joints by combining partial joints
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C66/00General aspects of processes or apparatus for joining preformed parts
    • B29C66/01General aspects dealing with the joint area or with the area to be joined
    • B29C66/347General aspects dealing with the joint area or with the area to be joined using particular temperature distributions or gradients; using particular heat distributions or gradients
    • B29C66/3472General aspects dealing with the joint area or with the area to be joined using particular temperature distributions or gradients; using particular heat distributions or gradients in the plane of the joint, e.g. along the joint line in the plane of the joint or perpendicular to the joint line in the plane of the joint
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C66/00General aspects of processes or apparatus for joining preformed parts
    • B29C66/40General 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
    • B29C66/41Joining substantially flat articles ; Making flat seams in tubular or hollow articles
    • B29C66/43Joining a relatively small portion of the surface of said articles
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C66/00General aspects of processes or apparatus for joining preformed parts
    • B29C66/70General 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
    • B29C66/71General 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
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C66/00General aspects of processes or apparatus for joining preformed parts
    • B29C66/70General 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
    • B29C66/72General 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
    • B29C66/723General 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
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C66/00General aspects of processes or apparatus for joining preformed parts
    • B29C66/80General aspects of machine operations or constructions and parts thereof
    • B29C66/81General aspects of the pressing elements, i.e. the elements applying pressure on the parts to be joined in the area to be joined, e.g. the welding jaws or clamps
    • B29C66/818General aspects of the pressing elements, i.e. the elements applying pressure on the parts to be joined in the area to be joined, e.g. the welding jaws or clamps characterised by the cooling constructional aspects, or by the thermal or electrical insulating or conducting constructional aspects of the welding jaws or of the clamps ; comprising means for compensating for the thermal expansion of the welding jaws or of the clamps
    • B29C66/8181General aspects of the pressing elements, i.e. the elements applying pressure on the parts to be joined in the area to be joined, e.g. the welding jaws or clamps characterised by the cooling constructional aspects, or by the thermal or electrical insulating or conducting constructional aspects of the welding jaws or of the clamps ; comprising means for compensating for the thermal expansion of the welding jaws or of the clamps characterised by the cooling constructional aspects
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C66/00General aspects of processes or apparatus for joining preformed parts
    • B29C66/80General aspects of machine operations or constructions and parts thereof
    • B29C66/83General aspects of machine operations or constructions and parts thereof characterised by the movement of the joining or pressing tools
    • B29C66/832Reciprocating joining or pressing tools
    • B29C66/8322Joining or pressing tools reciprocating along one axis
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C66/00General aspects of processes or apparatus for joining preformed parts
    • B29C66/90Measuring or controlling the joining process
    • B29C66/91Measuring or controlling the joining process by measuring or controlling the temperature, the heat or the thermal flux
    • B29C66/914Measuring or controlling the joining process by measuring or controlling the temperature, the heat or the thermal flux by controlling or regulating the temperature, the heat or the thermal flux
    • B29C66/9141Measuring or controlling the joining process by measuring or controlling the temperature, the heat or the thermal flux by controlling or regulating the temperature, the heat or the thermal flux by controlling or regulating the temperature
    • B29C66/91411Measuring or controlling the joining process by measuring or controlling the temperature, the heat or the thermal flux by controlling or regulating the temperature, the heat or the thermal flux by controlling or regulating the temperature of the parts to be joined, e.g. the joining process taking the temperature of the parts to be joined into account
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C66/00General aspects of processes or apparatus for joining preformed parts
    • B29C66/90Measuring or controlling the joining process
    • B29C66/91Measuring or controlling the joining process by measuring or controlling the temperature, the heat or the thermal flux
    • B29C66/914Measuring or controlling the joining process by measuring or controlling the temperature, the heat or the thermal flux by controlling or regulating the temperature, the heat or the thermal flux
    • B29C66/9141Measuring or controlling the joining process by measuring or controlling the temperature, the heat or the thermal flux by controlling or regulating the temperature, the heat or the thermal flux by controlling or regulating the temperature
    • B29C66/91441Measuring or controlling the joining process by measuring or controlling the temperature, the heat or the thermal flux by controlling or regulating the temperature, the heat or the thermal flux by controlling or regulating the temperature the temperature being non-constant over time
    • B29C66/91443Measuring or controlling the joining process by measuring or controlling the temperature, the heat or the thermal flux by controlling or regulating the temperature, the heat or the thermal flux by controlling or regulating the temperature the temperature being non-constant over time following a temperature-time profile
    • B29C66/91445Measuring or controlling the joining process by measuring or controlling the temperature, the heat or the thermal flux by controlling or regulating the temperature, the heat or the thermal flux by controlling or regulating the temperature the temperature being non-constant over time following a temperature-time profile by steps
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C66/00General aspects of processes or apparatus for joining preformed parts
    • B29C66/90Measuring or controlling the joining process
    • B29C66/91Measuring or controlling the joining process by measuring or controlling the temperature, the heat or the thermal flux
    • B29C66/919Measuring or controlling the joining process by measuring or controlling the temperature, the heat or the thermal flux characterised by specific temperature, heat or thermal flux values or ranges
    • B29C66/9192Measuring or controlling the joining process by measuring or controlling the temperature, the heat or the thermal flux characterised by specific temperature, heat or thermal flux values or ranges in explicit relation to another variable, e.g. temperature diagrams
    • B29C66/91921Measuring or controlling the joining process by measuring or controlling the temperature, the heat or the thermal flux characterised by specific temperature, heat or thermal flux values or ranges in explicit relation to another variable, e.g. temperature diagrams in explicit relation to another temperature, e.g. to the softening temperature or softening point, to the thermal degradation temperature or to the ambient temperature
    • B29C66/91931Measuring or controlling the joining process by measuring or controlling the temperature, the heat or the thermal flux characterised by specific temperature, heat or thermal flux values or ranges in explicit relation to another variable, e.g. temperature diagrams in explicit relation to another temperature, e.g. to the softening temperature or softening point, to the thermal degradation temperature or to the ambient temperature in explicit relation to the fusion temperature or melting point of the material of one of the parts to be joined
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C66/00General aspects of processes or apparatus for joining preformed parts
    • B29C66/90Measuring or controlling the joining process
    • B29C66/91Measuring or controlling the joining process by measuring or controlling the temperature, the heat or the thermal flux
    • B29C66/919Measuring or controlling the joining process by measuring or controlling the temperature, the heat or the thermal flux characterised by specific temperature, heat or thermal flux values or ranges
    • B29C66/9192Measuring or controlling the joining process by measuring or controlling the temperature, the heat or the thermal flux characterised by specific temperature, heat or thermal flux values or ranges in explicit relation to another variable, e.g. temperature diagrams
    • B29C66/91921Measuring or controlling the joining process by measuring or controlling the temperature, the heat or the thermal flux characterised by specific temperature, heat or thermal flux values or ranges in explicit relation to another variable, e.g. temperature diagrams in explicit relation to another temperature, e.g. to the softening temperature or softening point, to the thermal degradation temperature or to the ambient temperature
    • B29C66/91931Measuring or controlling the joining process by measuring or controlling the temperature, the heat or the thermal flux characterised by specific temperature, heat or thermal flux values or ranges in explicit relation to another variable, e.g. temperature diagrams in explicit relation to another temperature, e.g. to the softening temperature or softening point, to the thermal degradation temperature or to the ambient temperature in explicit relation to the fusion temperature or melting point of the material of one of the parts to be joined
    • B29C66/91933Measuring or controlling the joining process by measuring or controlling the temperature, the heat or the thermal flux characterised by specific temperature, heat or thermal flux values or ranges in explicit relation to another variable, e.g. temperature diagrams in explicit relation to another temperature, e.g. to the softening temperature or softening point, to the thermal degradation temperature or to the ambient temperature in explicit relation to the fusion temperature or melting point of the material of one of the parts to be joined higher than said fusion temperature
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C66/00General aspects of processes or apparatus for joining preformed parts
    • B29C66/90Measuring or controlling the joining process
    • B29C66/91Measuring or controlling the joining process by measuring or controlling the temperature, the heat or the thermal flux
    • B29C66/919Measuring or controlling the joining process by measuring or controlling the temperature, the heat or the thermal flux characterised by specific temperature, heat or thermal flux values or ranges
    • B29C66/9192Measuring or controlling the joining process by measuring or controlling the temperature, the heat or the thermal flux characterised by specific temperature, heat or thermal flux values or ranges in explicit relation to another variable, e.g. temperature diagrams
    • B29C66/91921Measuring or controlling the joining process by measuring or controlling the temperature, the heat or the thermal flux characterised by specific temperature, heat or thermal flux values or ranges in explicit relation to another variable, e.g. temperature diagrams in explicit relation to another temperature, e.g. to the softening temperature or softening point, to the thermal degradation temperature or to the ambient temperature
    • B29C66/91931Measuring or controlling the joining process by measuring or controlling the temperature, the heat or the thermal flux characterised by specific temperature, heat or thermal flux values or ranges in explicit relation to another variable, e.g. temperature diagrams in explicit relation to another temperature, e.g. to the softening temperature or softening point, to the thermal degradation temperature or to the ambient temperature in explicit relation to the fusion temperature or melting point of the material of one of the parts to be joined
    • B29C66/91935Measuring or controlling the joining process by measuring or controlling the temperature, the heat or the thermal flux characterised by specific temperature, heat or thermal flux values or ranges in explicit relation to another variable, e.g. temperature diagrams in explicit relation to another temperature, e.g. to the softening temperature or softening point, to the thermal degradation temperature or to the ambient temperature in explicit relation to the fusion temperature or melting point of the material of one of the parts to be joined lower than said fusion temperature
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C66/00General aspects of processes or apparatus for joining preformed parts
    • B29C66/01General aspects dealing with the joint area or with the area to be joined
    • B29C66/05Particular design of joint configurations
    • B29C66/10Particular design of joint configurations particular design of the joint cross-sections
    • B29C66/11Joint 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
    • B29C66/114Single butt joints
    • B29C66/1142Single butt to butt joints
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
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    • B29C66/40General 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
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    • B29C66/43Joining a relatively small portion of the surface of said articles
    • B29C66/435Making large sheets by joining smaller ones or strips together
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C66/00General aspects of processes or apparatus for joining preformed parts
    • B29C66/90Measuring or controlling the joining process
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29KINDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2027/00Use of polyvinylhalogenides or derivatives thereof as moulding material
    • B29K2027/12Use of polyvinylhalogenides or derivatives thereof as moulding material containing fluorine
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29KINDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2027/00Use of polyvinylhalogenides or derivatives thereof as moulding material
    • B29K2027/12Use of polyvinylhalogenides or derivatives thereof as moulding material containing fluorine
    • B29K2027/18PTFE, i.e. polytetrafluorethene, e.g. ePTFE, i.e. expanded polytetrafluorethene
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29LINDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
    • B29L2009/00Layered products
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02ATECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A40/00Adaptation technologies in agriculture, forestry, livestock or agroalimentary production
    • Y02A40/10Adaptation technologies in agriculture, forestry, livestock or agroalimentary production in agriculture
    • Y02A40/25Greenhouse technology, e.g. cooling systems therefor

Definitions

  • the present invention relates to a method of bonding fluororesin films, a wide fluororesin film obtained by the method, and a covering material for agricultural use and a film structure, made thereof.
  • a wide film is usually used for a covering material for agricultural use.
  • a film to be industrially produced such as a polyvinyl chloride film for agricultural use (hereinafter referred to as an agricultural PVC film) has a width of from 1 to 4 m, and films are bonded to one another to obtain a wider film which is used for a covering material for agricultural use.
  • As a bonding method it is common to employ a bonding method in which edges of two sheets of films are overlapped, and the overlapping portion is welded by press bonding under heating.
  • Another object of the present invention is to provide a wide fluororesin film having a width of from 1 to 150 m, having at least two sheets of fluororesin films bonded by repeating the above bonding method at least once, and a covering material for agricultural use, made of such a wide fluororesin film.
  • the present invention provides a method of bonding fluororesin films, which is a method of bonding films (A) made of a fluororesin, characterized in that two sheets of films (A) are disposed so that their edges overlap each other, a central part (b 1 ) of the overlapping portion (B) is press-bonded under heating at a temperature within a range of from lower by 5° C. to higher by 20° C. than the melting point of the fluororesin, and then the entire area of the portion (B) is press-bonded at a temperature within a range of from lower by 30° C. to lower by more than 5° C., than the melting point, to weld the two sheets of films (A).
  • the present invention provides a method of bonding fluororesin films, which is a method of bonding films (A) made of a fluororesin, characterized in that two sheets of films (A) are disposed so that their edges overlap each other to form an overlapping portion (B), then a film (C) made of a fluororesin is disposed so that it overlaps on the overlapping portion (B), then a central part (b 1 ) of the overlapping portion (B) is press-bonded from above the film (C) under heating at a temperature within a range of from lower by 5° C. to higher by 20° C.
  • the overlapping portion (B) and the film (C) are press-bonded at a temperature within a range of from lower by 30° C. to lower by more than 5° C., than the melting point, to weld the two sheets of films (A) and the film (C).
  • the present invention provides a wide fluororesin film having a width of from 1 to 150 m, having at least two sheets of films (A) bonded by repeating the above bonding method at least once, a covering material for agricultural use, made of such a wide fluororesin film, and a material for a film structure, made of such a wide fluororesin film.
  • FIG. 1 is a view illustrating an example of the cross-sectional shape of fluororesin films bonded by the bonding method of the present invention.
  • FIG. 2 is a view illustrating an example of the cross-sectional shape of fluororesin films bonded by the bonding method of the present invention.
  • FIG. 3 is a view illustrating an example of the cross-sectional shape of fluororesin films having a hydrophilic surface-treatment layer on one side, bonded by the bonding method of the present invention.
  • FIG. 4 is a view illustrating an example of the process for bonding fluororesin films.
  • FIG. 5 is a view illustrating an example of the process for bonding fluororesin films having a hydrophilic surface-treatment layer on one side.
  • FIG. 6 is a view illustrating the cross section of a heat press bonding section of a heat press bonding machine to be used for bonding fluororesin films by press bonding under heating.
  • FIG. 7 is a top view of the heat press bonding section of the heat press bonding machine to be used for bonding fluororesin films by press bonding under heating.
  • FIGS. 1 to 3 illustrate examples of the cross-sectional shape of the bonded portion of films (A) made of a fluororesin, as bonded by the bonding method of the present invention.
  • FIG. 1 illustrates the cross-sectional shape of the bonded portion of films (A) 1
  • FIG. 2 illustrates the cross-sectional shape of the bonded portion wherein a film (C) made of a fluororesin was overlaid on and welded to films (A) 1
  • FIG. 3 illustrates the cross-sectional shape of the bonded portion wherein a film (C) 6 made of a fluororesin is overlaid on and welded to films (A) 1 having a hydrophilic surface-treatment layer (D) 9 on one side.
  • D hydrophilic surface-treatment layer
  • the central part (b 1 ) 3 of the overlapping portion (B) 2 of two sheets of films (A) 1 is welded by press-bonding under heating at a temperature within a range of from lower by C to higher by 20° C. than the melting point of the fluororesin, and other portion is welded by press bonding under heating at a temperature within a range of from lower by 30° C. to lower by more than 5° C., than the melting point.
  • the portion welded at a temperature within a range of from lower by 5° C. to higher by 20° C. than the melting point will be referred to as a high temperature welded portion 4
  • the portion welded at a temperature within a range of from lower by 30° C. to lower by more than 5° C. than the melting point will be referred to also as a low temperature welded portion 5 .
  • a welded portion having two layers of a film (A)/a film (C) overlapped each other and a welded portion having three layers of a film (A)/a film (A)/a film (C) overlapped one on another are formed. Also in this case, a high temperature welded portion 4 and a low temperature welded portion 5 are formed. Further, in this example, both edges (c 2 ) 8 of the film (C) 6 are not welded.
  • FIG. 3 is a cross-sectional view similar to FIG. 2 except that the films to be bonded are films (A) 1 having a hydrophilic surface-treatment layer (D) 9 on one side.
  • a welded portion having two layers of a film (A)/a film (C) overlapped each other and a welded portion having three layers of a film (A)/a film (A)/a film (C) overlaid one on another, are formed.
  • heat press bonding is carried out via a hydrophilic surface-treatment layer (D)
  • welding will be inadequate, and accordingly, no hydrophilic surface-treatment layer (D) 9 is formed along the edge of one of the films (A) 1 forming the overlapping portion (B) 2 .
  • such a film may be produced, for example, by a method of preliminarily making such an edge when the hydrophilic surface treatment layer (D) is formed on the film (A).
  • FIGS. 4 and 5 illustrate examples for the process of bonding films (A) of the present invention.
  • FIG. 4 illustrates a process of bonding films having the cross-sectional shape of the bonded portion as illustrated in FIG. 1 .
  • step (I) two sheets of films (A) 1 are put together to overlap each other. Then, in a state where a transport belt 12 made of a release sheet is interposed between a heater and a film (A), step (II) will be carried out.
  • Step (II) by means of a central upper heater (H 1 ) 10 and a bottom heater (H 2 ) 11 , the central part (b 1 ) 3 of the overlapping portion (B) 2 is press-bonded at a temperature within a range of from lower by at least 5° C.
  • step (III) by means of the upper heater (H 3 ) 14 and the bottom heater (H 4 ) 15 , the entire area of the overlapping portion (B) 2 is press-bonded under heating at a temperature within a range of from lower by C to lower by more than 5° C. than the melting point of the fluororesin to form a low temperature welded portion 5 .
  • step (IV) the welded films (A) are cooled by cooling plates 13 .
  • FIG. 5 illustrates a process for bonding films having the cross-sectional shape of the bonded portion as illustrated in FIG. 3 .
  • step (I) two sheets of films (A) 1 having a hydrophilic surface-treatment layer (D) 9 on one side are put together to overlap each other. At that time, the upper film (A) 1 is overlaid along the edge having no hydrophilic surface treatment layer (D) 9 . Then, in step (II), a film (C) 6 having a width wider than the overlapping portion (B) 2 is overlaid on the overlapping portion (B) 2 .
  • step (III) by means of a central upper heater (H 1 ) 10 and a bottom heater (H 2 ) 11 , the central part (b 1 ) 3 of the overlapping portion (B) 2 is press-bonded under heating at a temperature within a range of from lower by 5° C. to higher by less than 20° C. than the melting point of the fluororesin to form a high temperature welded portion 4 .
  • step (IV) by means of an upper heater (H 3 ) 14 and a bottom heater (H 4 ) 15 , the overlapping portion (B) and the film (C) are press-bonded under heating at a temperature within a range of from lower by 30° C. to lower by more than 5° C.
  • step (V) the welded films (A) and film (C) are cooled by cooling plates 13 .
  • FIG. 6 illustrates a cross-sectional view of a heat press bonding portion of a heat press bonding machine to be used for welding by heat press bonding of films (A) 1 made of a fluororesin
  • FIG. 7 illustrates a top surface view of the heat press bonding portion.
  • the heat press bonding portion comprises an upper central heater (H 1 ) 10 and a lower heater (H 2 ) 11 for heat press bonding of the central part (b 1 ) of the films (A) at a temperature within a range of from lower by 5° C. to higher by less than 20° C.
  • the films are transported by a transporting belt 12 .
  • the pressure for heat press bonding the pressure due to the heater's own weight may be sufficient, but a load may additionally be exerted to increase the pressure.
  • the pressure is preferably from 0.01 to 10 MPa, more preferably from 0.1 to 1 MPa.
  • the order of the upper central heater (H 1 ) 10 and the lower heater (H 2 ) 11 , and the upper heater (H 3 ) 14 and the lower heater (H 4 ) 15 may be reversed.
  • the width of the lower heater (H 2 ) or (H 4 ) is preferably the same or wider than the width of the upper heater (H 3 ).
  • the step of cooling the welded films (A) is not necessarily required, but it is usually preferred to insert the cooling step. It is preferred to insert the cooling step, whereby the releasability between the film (A) and the release sheet (the transport belt) will be further improved.
  • the cooling other than employing cooling plates, etc., it is also preferred to use air for cooling.
  • two sheets of films (A) are disposed so that their edges overlap each other, a central part (b 1 ) of the overlapping portion (B) is press-bonded under heating at a temperature within a range of from lower by 5° C. to higher by 20° C. than the melting point of the fluororesin, and then, the entire area of the portion (B) is press-bonded at a temperature within a range of from lower by 30° C. to lower by more than 5° C., than the melting point, to weld the two sheets of films (A).
  • two sheets of films (A) are disposed so that their edges overlap each other to form an overlapping portion (B), then a film (C) made of a fluororesin is disposed so that it overlaps on the overlapping portion (B), then a central part (b 1 ) of the overlapping portion (B) is press-bonded from above the film (C) under heating at a temperature within a range of from lower by 5° C. to higher by 20° C. than the melting point of the fluororesin, and then the overlapping portion (B) and the film (C) are press-bonded at a temperature within a range of from lower by 30° C. to lower by more than 5° C., than the melting point, to weld the two sheets of films (A) and the film (C).
  • the heating temperature at the central portion (b 1 ) is preferably within a range of from lower by 0° C. to higher by 10° C., more preferably from lower by 0° C. to higher by 5° C., than the melting point of the fluororesin.
  • the heating temperature at the overlapping portion (B), or the overlapping portion (B) and the film (C) is preferably within a range of from lower by 20° C. to lower by more than 5° C., more preferably from lower by 15° C. to lower by more than 5° C., than the melting point of the fluororesin.
  • the width of the overlapping portion (B) of films (A) is preferably from 5 to 100 mm, more preferably from 10 to 50 mm, most preferably from 11 to 29 mm.
  • the width of the central portion (b 1 ) is preferably from 1 to 50 mm, more preferably from 5 to 20 mm.
  • the width of the overlapping portion (c 1 ) of the film (C) made of a fluororesin is preferably from 15 to 110 mm, more preferably from 20 to 60 mm, most preferably from 21 to 39 mm.
  • both edges (c 2 ) of the film (C) may be welded or may not be welded to the films (A).
  • the width not welded is preferably from 0.5 to 10 mm, more preferably from 0.5 to 5 mm, most preferably from 0.5 to 2.5 mm, from the end. It is preferred that the edges (c 2 ) are not welded, whereby the tear strength at the welded portion and its peripheral portion will be improved.
  • the width of a film (A) is preferably from 50 to 210 cm, more preferably from 110 to 160 cm. This range is preferred, since it is usually the prescribed width of a covering material for agricultural use.
  • the thickness of a film (A) is preferably from 10 to 300 ⁇ m, more preferably from 50 to 100 ⁇ m. When the thickness is within this range, the strength will be high, and the heat conduction will also be excellent.
  • the width of the film (C) is preferably from 18 to 113 cm, more preferably from 23 to 63 cm, most preferably from 24 to 43 cm.
  • the width of the film (C) is preferably wider than the overlapping portion (B), and it is preferably wider by from 1 to 10 mm, more preferably wider by from 2 to 5 mm, than the overlapping portion (B).
  • the thickness of the film (C) is preferably from 10 to 300 ⁇ m, more preferably from 50 to 100 ⁇ m. When the thickness is within this range, the strength will be high, and the heat conduction will be excellent.
  • the bonding method of the present invention it is possible to obtain a wide fluororesin film having at least two sheets of films (A) made of a fluororesin, bonded by repeating the above-mentioned bonding method at least once.
  • a wide fluororesin film having a width of from 1 to 150 m is preferred, and a wide fluororesin film having a width of from 8 to 60 m is more preferred.
  • a covering material for agricultural use can be obtained which is made of the wide fluororesin film having a width of from 1 to 150 m. More preferred is a covering material for agricultural use made of a wide fluororesin film having a width of from 8 to 60 m.
  • the fluororesin for the films (A) of the present invention may, for example, be ETFE, a tetrafluoroethylene/perfluoro(alkyl vinyl ether) copolymer (hereinafter referred to as PFA), a tetrafluoroethylene/hexafluoropropylene copolymer (hereinafter referred to as FEP), a polychlorotrifluoroethylene (PCTFE), a polyvinylidene fluoride (PVDF) or a polyvinyl fluoride (PVF).
  • PFA tetrafluoroethylene/perfluoro(alkyl vinyl ether) copolymer
  • FEP tetrafluoroethylene/hexafluoropropylene copolymer
  • PCTFE polychlorotrifluoroethylene
  • PVDF polyvinylidene fluoride
  • PVDF polyvinylidene fluoride
  • PVF polyvinyl fluoride
  • ETFE is preferably a copolymer of tetrafluoroethylene (hereinafter referred to as TFE) with ethylene (hereinafter referred to as E), or a copolymer of TFE, E and other monomers.
  • Such other monomers may, for example, be a fluoroolefin such as chlorotrifluoroethylene, hexafluoropropylene, a perfluoro(alkyl vinyl ether) or vinylidene fluoride, a polyfluoroalkylethylene such as CH 2 ⁇ CHR f (wherein R f is a C 1-8 polyfluoroalkyl group, the same applies hereinafter) or CH 2 ⁇ CFR f , and a polyfluoroalkyltrifluorovinyl ether such as CF 2 ⁇ CFOCH 2 R f .
  • fluoroolefin such as chlorotrifluoroethylene, hexafluoropropylene, a perfluoro(alkyl vinyl ether) or vinylidene fluoride
  • a polyfluoroalkylethylene such as CH 2 ⁇ CHR f (wherein R f is a C 1-8 polyfluoroalkyl group, the same
  • R f is more preferably a C 3-6 perfluoroalkyl group, most preferably C 4 F 9 .
  • the molar ratio of polymerized units based on TFE/polymerized units based on E is preferably from 70/30 to 30/70, more preferably from 65/35 to 40/60, most preferably from 60/40 to 4
  • the content of polymerized units based on such other monomers is preferably from 0.01 to 30 mol %, more preferably from 0.05 to 15 mol %, most preferably from 0.1 to 10 mol %, based on the total molar amount of polymerized units based on TFE and ethylene.
  • the film (C) is preferably a film made of a fluororesin having a melting point which is the same or close to the fluororesin for the films (A). It is more preferably a film made of the same fluororesin as the fluororesin for the films (A). If they are made of the same fluororesin, the film (C) and the films (A) will be excellent in the welding property.
  • a wet method or a dry method may be employed as a method of forming the hydrophilic surface-treatment layer for the production of a film (A) having a hydrophilic surface-treatment layer on one side.
  • the wet method may, for example, be a method of coating a solution of a hydrophilic substance by a roller, a method of spray coating such a solution, a method of coating such a solution by a brush, or a method of coating such a solution by a coating machine.
  • Preferred is a method of coating a solution of a hydrophilic substance by a coating machine, or a method of spray coating such as solution.
  • the dry method may, for example, be a sputtering method, a vacuum vapor deposition method, a CVD method or an ion plating method, of a hydrophilic substance.
  • a sputtering method a vacuum vapor deposition method, a CVD method or an ion plating method, of a hydrophilic substance.
  • Preferred is a method of sputtering a hydrophilic substance, whereby the productivity is high, and retention of the hydrophilic property will be excellent.
  • the hydrophilic substance may, for example, be a colloidal sol of an inorganic substance such as SiO 2 or Al 2 O 3 , a polyvinyl alcohol, a hydrophilic resin of e.g. acrylic acid, or an oxide of a metal such as Si, Sn, Ti, Nb, Al or Zn.
  • a sputtering method of an oxide of a metal such as Si, Sn or Ti is particularly preferred.
  • the covering material for agricultural use of the present invention will be stretched for an agricultural house so that the hydrophilic surface treatment layer (D) after heat press bonding will be located inside.
  • the inside surface of the agricultural house is subjected to hydrophilic treatment by a method such as spray coating of a hydrophilic treatment agent.
  • a method such as spray coating of a hydrophilic treatment agent.
  • the inside surface is excellent in a droplet flowing property, and even if moisture in the house is condensed on the inside surface of the house, the water droplets tend to readily flow, whereby it will be less likely that water droplets fall on crop plants to hinder the growth of the crop plants.
  • the covering material for agricultural use of the present invention is excellent in the welding strength and the tear strength of the film, whereby it is possible to prevent penetration of water or soil without peeling of the bonded portions over a long period of time.
  • a fluororesin film having a width of from 1 to 150 m, bonded by the bonding method of the present invention is applicable not only to a covering material for agricultural use for e.g. an agricultural house or a horticultural house, but also to a material for a film structure such as a tent material, a film for a solar collector or a film for a roof of a large building, a material for bags, a material for waterproof sheets, or a material for water stopping sheets.
  • the cross-sectional shape of the bonded portion was the same as shown in FIG. 1 .
  • the width of the overlapping portion (B) 2 was 20 mm, and the width of the central part (b 1 ) 3 was 10 mm.
  • the portion where the two sheets of the films were heat press-bonded, was in a sufficiently welded state.
  • the Elmendorf tear strength of the bonded portion of the ETFE films was 5.3 N, thus showing excellent tear strength.
  • the Elmendorf tear strength was measured in accordance with JIS K6732 (1996) by using a sample having a size of 63 mm ⁇ 76 mm and by imparting a cut line of 20 mm in length at a non-welded portion along the edge of the bonded portion.
  • Example 2 Two sheets of the same ETFE film as used in Example 1 were prepared and disposed so that their edges overlapped each other. Then, an ETFE film having a thickness of 100 ⁇ m and a width of 33 mm was overlaid thereon.
  • the overlapping portion was bonded by means of the same heat press bonding machine as used in Example 1. The bonding was carried out in accordance with the procedure shown in FIG. 5 . Firstly, the central part (b 1 ) 3 of the overlapping portion was welded by press-bonding under heating at 260° C. Then, a width of 15 mm on both sides of the center was welded by press bonding under heating at 250° C. The cross-sectional shape of the bonded portion was the same as shown in FIG. 2 .
  • the width of the overlapping portion (B) 2 was 20 mm
  • the width of the central part (b 1 ) 3 was 10 mm
  • the width of the overlapping portion (c 1 ) 7 was 30 mm
  • the width of the non-welded edge (c 2 ) 8 was 1.5 mm.
  • the portion where two or three sheets of the overlapped films were heat press-bonded, was in a sufficiently welded state. Further, the Elmendorf tear strength of the bonded portion of the ETFE films was 7.7 N, as measured in the same manner as in Example 1, thus showing excellent tear strength.
  • Example 2 Two sheets of the same ETFE film as used in Example 1 were prepared and disposed so that their edges overlapped each other. The entire area of the overlapping portion was bonded by welding at 280° C. by means of a heat press bonding machine. The width of the overlapping portion was 20 mm. The portion where two sheets of the films were heat press-bonded, was in a sufficiently welded state. The Elmendorf tear strength at the bonded portion of the ETFE films was 4.6 N, as measured in the same manner as in Example 1, and thus, the tear strength was lower than in Example 1.
  • a method of bonding films made of a fluororesin whereby the welding strength at the welded portion is high, the tear strength is excellent, and the bonded portion will not easily be peeled. Further, by repeating the bonding method of the present invention, it is possible to obtain a wide fluororesin film. Further, the obtained wide fluororesin film is suitable for a covering material for agricultural use.
  • a fluororesin film formed by bonding by the bonding method of the present invention is used for a covering material for agricultural use, such as a stretching film for an agricultural house, it is excellent in the welding strength and the tear strength at the bonded portion of the films, whereby the welded portion will not be peeled, and penetration of water or soil can be prevented, over a long period of time.

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US6512064B2 (en) * 2000-11-10 2003-01-28 Asahi Glass Company, Limited Fluororesin film of high mechanical strength
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ES2314183T3 (es) 2009-03-16
EP1486316A4 (de) 2006-05-17
JPWO2003078139A1 (ja) 2005-07-14
US20080073021A1 (en) 2008-03-27
JP3952020B2 (ja) 2007-08-01
CN1305659C (zh) 2007-03-21
ATE412507T1 (de) 2008-11-15
ZA200407491B (en) 2006-07-26
AU2003213431A1 (en) 2003-09-29
CN1642715A (zh) 2005-07-20
AU2003213431B2 (en) 2008-06-12
DE60324396D1 (de) 2008-12-11
EP1486316A1 (de) 2004-12-15
US7794558B2 (en) 2010-09-14
EP1486316B1 (de) 2008-10-29
WO2003078139A1 (fr) 2003-09-25

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