WO1997003803A1 - Procedes de fabrication de stratifies multicouche, stratifies multicouche polyolefiniques et leur application - Google Patents

Procedes de fabrication de stratifies multicouche, stratifies multicouche polyolefiniques et leur application Download PDF

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Publication number
WO1997003803A1
WO1997003803A1 PCT/JP1996/002055 JP9602055W WO9703803A1 WO 1997003803 A1 WO1997003803 A1 WO 1997003803A1 JP 9602055 W JP9602055 W JP 9602055W WO 9703803 A1 WO9703803 A1 WO 9703803A1
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WIPO (PCT)
Prior art keywords
laminar flow
layers
divided
layer
laminated
Prior art date
Application number
PCT/JP1996/002055
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English (en)
Japanese (ja)
Inventor
Masanori Motooka
Toshio Kimura
Takashi Nakagawa
Original Assignee
Mitsui Petrochemical Industries, Ltd.
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Filing date
Publication date
Application filed by Mitsui Petrochemical Industries, Ltd. filed Critical Mitsui Petrochemical Industries, Ltd.
Publication of WO1997003803A1 publication Critical patent/WO1997003803A1/fr

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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
    • B29C69/00—Combinations of shaping techniques not provided for in a single one of main groups B29C39/00 - B29C67/00, e.g. associations of moulding and joining techniques; Apparatus therefore
    • B29C69/001—Combinations of shaping techniques not provided for in a single one of main groups B29C39/00 - B29C67/00, e.g. associations of moulding and joining techniques; Apparatus therefore a shaping technique combined with cutting, e.g. in parts or slices combined with rearranging and joining the cut parts
    • 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
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
    • B29C48/07—Flat, e.g. panels
    • B29C48/08—Flat, e.g. panels flexible, e.g. films
    • 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
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/16—Articles comprising two or more components, e.g. co-extruded layers
    • B29C48/18—Articles comprising two or more components, e.g. co-extruded layers the components being layers
    • B29C48/21—Articles comprising two or more components, e.g. co-extruded layers the components being layers the layers being joined at their surfaces
    • 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
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25—Component parts, details or accessories; Auxiliary operations
    • B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
    • B29C48/50—Details of extruders
    • B29C48/695—Flow dividers, e.g. breaker plates
    • B29C48/70—Flow dividers, e.g. breaker plates comprising means for dividing, distributing and recombining melt flows
    • B29C48/71—Flow dividers, e.g. breaker plates comprising means for dividing, distributing and recombining melt flows for layer multiplication
    • 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
    • B29C53/00—Shaping by bending, folding, twisting, straightening or flattening; Apparatus therefor
    • B29C53/36—Bending and joining, e.g. for making hollow articles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B38/00—Ancillary operations in connection with laminating processes
    • B32B38/18—Handling of layers or the laminate
    • B32B38/1808—Handling of layers or the laminate characterised by the laying up of the layers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F32/00—Homopolymers and copolymers of cyclic compounds having no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic ring system
    • C08F32/08—Homopolymers and copolymers of cyclic compounds having no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic ring system having two condensed rings
    • 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
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • 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
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/001—Combinations of extrusion moulding with other shaping operations
    • 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
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/001—Combinations of extrusion moulding with other shaping operations
    • B29C48/0013—Extrusion moulding in several steps, i.e. components merging outside the die
    • B29C48/0014—Extrusion moulding in several steps, i.e. components merging outside the die producing flat articles having components brought in contact outside the extrusion die
    • 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
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/001—Combinations of extrusion moulding with other shaping operations
    • B29C48/0013—Extrusion moulding in several steps, i.e. components merging outside the die
    • B29C48/0015—Extrusion moulding in several steps, i.e. components merging outside the die producing hollow articles having components brought in contact outside the extrusion die
    • 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
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/001—Combinations of extrusion moulding with other shaping operations
    • B29C48/0018—Combinations of extrusion moulding with other shaping operations combined with shaping by orienting, stretching or shrinking, e.g. film blowing
    • 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
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/001—Combinations of extrusion moulding with other shaping operations
    • B29C48/0019—Combinations of extrusion moulding with other shaping operations combined with shaping by flattening, folding or bending
    • 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
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/001—Combinations of extrusion moulding with other shaping operations
    • B29C48/0022—Combinations of extrusion moulding with other shaping operations combined with cutting
    • 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
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
    • B29C48/07—Flat, e.g. panels
    • 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
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
    • B29C48/09—Articles with cross-sections having partially or fully enclosed cavities, e.g. pipes or channels
    • 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
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
    • B29C48/12—Articles with an irregular circumference when viewed in cross-section, e.g. window profiles
    • 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
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
    • B29C48/13—Articles with a cross-section varying in the longitudinal direction, e.g. corrugated pipes
    • 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
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/16—Articles comprising two or more components, e.g. co-extruded layers
    • B29C48/18—Articles comprising two or more components, e.g. co-extruded layers the components being layers
    • B29C48/185—Articles comprising two or more components, e.g. co-extruded layers the components being layers comprising six or more components, i.e. each component being counted once for each time it is present, e.g. in a layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
    • B29L2009/00—Layered products

Definitions

  • the present invention relates to a method for producing a multilayer laminate in which different types of layers are stacked in multiple layers, in particular, a multilayer laminate in which different types of thin film layers made of an organic high molecular weight polymer are multilayered and integrated.
  • the present invention relates to a multilayer laminate in which a polyolefin-based sheet or film is laminated, a method for producing the same, and a packaging material using the same, and more particularly, to a polyolefin-based multilayer suitable as a molding material for packaging.
  • the present invention relates to a laminate, a method for producing the same, and a packaging material using the same.
  • Such a multilayer laminate has, for example, a thickness of 0.0
  • a laminate formed from various kinds of different materials is desired.
  • a resin thin film containing a foaming agent and a resin thin film containing no foaming agent are alternately laminated.
  • Foamed laminate or resin layer with excellent gas palliability and resin with excellent flexibility and toughness are alternately laminated There is a demand for such composite laminates.
  • Multi-extrusion molding or co-injection molding is known as a method for producing a laminate in which organic high molecular weight polymers are laminated in multiple layers. These molding methods form a multi-composite by co-extrusion or co-injection molding of different layers, and a laminate having the properties of each layer can be obtained.
  • the conventional molding method has a limitation on the thickness of each layer to be laminated, so that a thin film-like laminate cannot be obtained.
  • Japanese Patent Application Laid-Open No. Hei 4-278832 discloses that a laminar flow in which different types of layers are laminated is divided and laminated.
  • a method has been proposed in which the flow is made thinner to further divide, laminate, and reduce the thickness, and this division, bonding, lamination, and thinning are repeated many times to form a laminate of thin film layers.
  • this laminate of thin film layers since each layer is uniformly distributed in a thin layer, a composite having characteristics different from those of a laminate by coextrusion can be obtained.
  • the first laminar flow before splitting is formed by co-extrusion under relatively high temperature and high pressure, so that the adhesion of each layer is high. Therefore, there is a problem that the adhesion between different layers to be stacked is lowered.
  • Japanese Patent Publication No. 54-23025 (corresponding to U SP No. 3, 759, 6)
  • Japanese Patent Application Laid-open No. Hei 4 (1995) 78332 (corresponding USPN No. 5,094, 793), Japanese Patent Laid-Open No. 94, 788) describes an apparatus for forming an ultra-multilayer film having several hundreds to several thousand layers.
  • a resin film is branched and laminated to form a multilayer film.
  • these devices have a special and complicated structure, and it is difficult to obtain a uniformly branched resin flow. It is difficult to obtain a uniform multilayer film.
  • packaging materials such as daily necessities, miscellaneous goods, food, and tablet medicine are required to have many functions such as transparency, moisture proof, heat sealability, vacuum or pressure forming, and hand twisting. For this reason, these functions cannot be sufficiently satisfied with only one type of resin, and a multilayer laminate in which a sheet or film made of a certain resin is laminated with a sheet or film made of a resin having another characteristic is used. It is heavily used.
  • Cyclic olefin resin tends to be preferred as a material.
  • Cyclic olefin resin has good transparency, moisture-proof properties, vacuum or compressed air formability, dead-hold properties, etc., and is suitable as a packaging material for blister packs and press-through packs (hereinafter sometimes referred to as PTP).
  • PTP blister packs and press-through packs
  • it since it is an amorphous resin, it softens rapidly near the glass transition temperature, and its elastic modulus, moisture resistance and strength are reduced. As a result, the range of molding conditions for heat sealing, inflation molding, vacuum or compressed air molding is narrow, and there is a problem that flexibility is poor depending on the application.
  • An object of the present invention is to propose a method for manufacturing a multilayer laminate in which a multilayer laminate in which each layer is uniformly distributed can be easily produced in order to solve the above problems.
  • An object of the present invention is to solve the above problems, An object of the present invention is to propose a method for producing a multilayer laminate having high adhesion and capable of producing a multilayer laminate in which each layer is uniformly distributed.
  • Another object of the present invention is to solve the above-mentioned problems by providing appropriate flexibility and surface hardness, interlayer adhesion, moldability, moisture-proofing, transparency, hand-cutting, heat-sealing, and
  • An object of the present invention is to provide a polyolefin-based multi-layer laminate excellent in holdability, easy in vacuum forming and pressure forming, and excellent in design, a method for producing the same, and a packaging material using the same. Disclosure of the invention
  • the method includes a step of twisting the divided laminar flow around a longitudinal direction as a rotation axis, and a step of laminating and integrating the twisted divided laminar flow to form a laminated laminar flow.
  • Ri R 18 and Ra and R b are each independently a hydrogen atom Represents an atom or a group selected from the group consisting of a halogen atom and a hydrocarbon group, and R 15 to R 18 may be bonded to each other to form a monocyclic or polycyclic ring; May have a double bond, and R 15 and R 16 or R 17 and R 18 may form an alkylidene group.
  • q is 0, Are combined to form 5 members.
  • m is 0 or a positive integer
  • h is 0 or a positive integer
  • j and k are 0, 1 or 2
  • R 7 to R 15 and R 17 to R 18 Each independently represents an atom or a group selected from the group consisting of a hydrogen atom, a halogen atom, and a hydrocarbon group
  • R 19 to R 27 each independently represent a hydrogen atom, a halogen atom, or a hydrocarbon group.
  • the method for producing a polyolefin-based multilayer laminate of the present invention comprises the steps of: forming a laminar flow in which at least two of the first layer and the second layer are laminated;
  • the packaging material of the present invention comprises the polyolefin-based multilayer laminate.
  • the layer forming the multilayer laminate include a layer made of a thermoplastic high molecular weight polymer.
  • a material for forming each layer for example, a thermoplastic resin, an elastomer, One is widely used.
  • Specific materials for forming each layer include, for example, polycarbonate (PC), linear low-density polyethylene (LLDPE), high-density polyethylene (HD.PE), polypropylene (PP), and ethylene'cycloolefin.
  • Polyesters such as copolymers (COC), ethylene-vinyl alcohol copolymer (EVOH), ionomers, polyethylene terephthalate, polyamides, and other known degradable polymers, conductive polymers, piezoelectric polymers, etc. can give.
  • first and second methods for producing a multilayer laminate of the present invention at least two types of different materials having different characteristics are selected from such materials, and these are alternately laminated.
  • combinations of different types of layers include a combination of EVOH and PP, a combination of LLDPE and PP, and a combination of COC and PP.
  • These layers may contain dyes, pigments or foaming agents, fillers, stabilizers and the like.
  • a combination of a layer containing a dye (or facial) and a layer not containing a dye (or pigment), or a combination of two layers each containing a dye (or pigment) of a different color is exemplified. You. Further, a combination of a layer containing a blowing agent and a layer not containing a blowing agent is exemplified.
  • a laminar flow in which at least two different types of layers are laminated is formed. Since such a laminar flow is usually formed at relatively high temperature and high pressure by co-extrusion molding, the adhesion of each layer is high.
  • this laminar flow is divided at a longitudinal division plane that intersects the interface with the stratification layer, and a plurality of divided laminar flows are formed.
  • the number of divided laminar flows is preferably about 2 to 6.
  • the laminar flow can be divided at a time to form a desired number of divided laminar flows, or can be performed in multiple stages. In the latter case, the desired number of divided laminar flows can be formed, for example, by sequentially performing two divisions.
  • the divided laminar flow is twisted with the longitudinal direction as a rotation axis. Twist angle is usually 1 The angle is preferably set to 0 to 90 °.
  • the torsional direction may be any direction around the axis of rotation.
  • the divided laminar flows may be twisted in the same direction, or the adjacent laminar flows may be twisted in opposite directions. It is preferable that the twisted divided laminar flows are arranged with a space therebetween, and are maintained parallel to each other.
  • the twisted divided laminar flows are overlapped and laminated to form a laminar laminar flow.
  • the laminar flow has almost the same shape as the first laminar flow, and each layer is thinned and the number of laminated layers increases A laminar flow is obtained.
  • Such a laminar flow can be further thinned and multilayered by repeating the same steps of dividing, twisting, laminating and thinning as in the previous case. By repeating this operation, each layer is thinned, and the thin film layer is multi-layered to produce a multilayer laminate in which the thin film layers are uniformly distributed.
  • the above-mentioned laminar flow may be two layers or three or more layers, and the front-side layer and the back-side layer may be the same layer or different layers.
  • the initial thickness of each layer is determined so that the final laminated layer has the desired ratio.
  • the number of layers in the first laminar flow is 2 to 10, preferably 2 to 4.
  • the overall thickness of the first laminar flow is usually about 100 ⁇ ! To about 5 O mm, and the thickness of each layer is usually preferably about 50 ⁇ to about 20 mm.
  • the number of repetitions of each step is 1 to 10 times, preferably 1 to 4 times.
  • the thickness of each thin film layer of the finally formed multilayer laminate is 0.01 to about 500 ⁇ , preferably 0.05 to 300 ⁇ , and the number of thin film layers is 1 0 to 20000, preferably 20 to 500, and the total thickness of the multilayer laminate is 100 ⁇ ! 55 O mm.
  • each step is performed by passing a laminar flow formed by co-extrusion molding through a molding die in a heat-softened state. It is preferred to do so. In this case, if one cycle of each step can be performed by one mold, each step can be repeated by connecting many molds having the same shape in series.
  • the multilayer laminate obtained as described above can be obtained as a molded article of any shape such as a film, a sheet, and a block.
  • a multilayer film having a thickness of about ⁇ ⁇ 3 mm, a multilayer sheet having a thickness of about 3 to 1 Omm, a block-like laminate having a thickness of about 10 to 5 Omm, and the like can be given.
  • the material of each layer unique characteristics can be obtained by combining the respective characteristics. For example, by combining a layer excellent in gasparity and a layer excellent in rigidity, a molded article having a composite property of both can be obtained.
  • the type, material, combination, number of layers, shape, and the like of each layer can be selected according to the characteristics of the target molded product, and the layer can be used for the target application.
  • a laminar flow in which at least two different types of layers are laminated is formed. Since such a laminar flow is usually formed at relatively high temperature and high pressure by co-extrusion molding, the adhesion of each layer is high.
  • this laminar flow is bent to form a corrugated laminar flow so as to have a corrugated cross-sectional shape.
  • the corrugated laminar flow is folded, and the pieces are laminated and integrated to form a laminar laminar flow.
  • the same layers are joined by lamination, so that even when the temperature and pressure drop, they are integrated and the adhesion is increased. Therefore, the adhesiveness of each layer is increased as a whole.
  • the laminar flow has almost the same shape as the first laminar flow, and each layer is thinned and the number of laminated layers increases A laminar flow is obtained.
  • Such a laminar flow can be further thinned and multilayered by repeating the same steps of corrugating, folding, and laminating as in the previous case. By repeating this operation, each layer is thinned, and the thin film layers are stacked in multiple layers and distributed uniformly. A sperm body is produced.
  • the above-mentioned laminar flow may be two layers or three or more layers, and the front-side layer and the back-side layer may be the same layer or different layers.
  • the initial thickness of each layer is determined so that the final laminated layer has the desired ratio.
  • the shape of the waveform can be any shape such as a triangular wave and a sine curve wave, but is preferably a triangular wave so that it can be easily folded. '
  • the configuration of the waveform may be such that the layer on the front side and the layer on the back side after lamination may be folded so as to be the same kind of layer, or may be folded so as to be different kinds of layers.
  • the number of layers in the first laminar flow is 2 to 10, preferably 2 to 4.
  • the number of waveforms formed by bending can be 2 to 20, preferably 4 to 10, as the number of peaks.
  • the number of repetitions of each step is 1 to 10 times, preferably 2 to 6 times.
  • the thickness of each thin film layer of the finally formed multilayer laminate is 0.01 to 500 / Xm, preferably 0.05 to 300 / xm, and the number of stacked thin film layers is 1. It can be 0 to 20000, preferably 20 to 500.
  • the operations of the respective steps are performed by passing a laminar flow formed by coextrusion molding through a mold in a heat-softened state. In this case, if one cycle of each step can be performed by one mold, each step can be repeated by connecting many molds having the same shape in series.
  • the multilayer laminate obtained as described above can be obtained as a molded article of any shape such as a film, a sheet, and a block.
  • unique characteristics can be obtained by combining the respective characteristics.
  • An example For example, by combining a layer excellent in gasparity and a layer excellent in rigidity, a molded article having a composite property of both can be obtained. In this way, the type, material, combination, number of layers, shape, and the like of each layer can be selected according to the characteristics of the target molded product, and the layer can be used for the target application.
  • the cyclic olefin-based resin used in the polyolefin-based multilayer laminate of the present invention includes:
  • the first layer may be formed from the above-mentioned (a-1) to (a-3) resins, or may be formed of any of these resins and polyolefin (b) described later. It may be formed from a resin composition.
  • the (A) cyclic olefin-based resin used in the polyolefin-based multilayer laminate of the present invention generally has a softening temperature (TMA) of 140 ° C. or higher, as measured by a thermal mechanical analyzer, and is preferably The temperature is 0 to 180 ° C, more preferably 50 to 180 ° C.
  • the softening temperature (TMA) was determined by placing a quartz needle with a diameter of 1. Omm on the sheet, applying a load of 49 g, and raising the temperature at a rate of 5 ° C. This is the temperature at which 3 5 mm has entered.
  • Cyclic olefin resin was measured in decalin at 135 ° C.
  • Intrinsic viscosity (")" is usually 0.01 to 10 dl Zg, preferably 0.05 to 2.0 dl / g, more preferably 0.4 to 1.2 d 1 / g. is there.
  • this (A) cyclic olefin resin has a glass transition point (T g) of usually 130 ° C. or more, preferably 110 ° C. to 170 ° C., and is measured by an X-ray diffraction method.
  • T g glass transition point
  • the obtained crystallinity is usually 0 to 20%, preferably 0 to 2%.
  • cyclic olefin a compound represented by the above formula [1] or [2] is used.
  • n is 0 or 1
  • m is 0 or a positive integer.
  • R 1 to R 18 and R a and R b each independently represent an atom or a group selected from the group consisting of a hydrogen atom, a halogen atom and a hydrocarbon group.
  • the halogen atom is a fluorine atom, a chlorine atom, a bromine atom or an iodine atom.
  • hydrocarbon group examples include an alkyl group having 1 to 20 carbon atoms, a halogenated alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 15 carbon atoms, and an aromatic group having 6 to 20 carbon atoms.
  • examples include a hydrocarbon group. More specifically,
  • alkyl group examples include a methyl group, an ethyl group, a propyl group, an isopropyl group, an amyl group, a hexyl group, an octyl group, a decyl group, a dodecyl group and an octadecyl group.
  • halogenated alkyl group examples include groups in which at least a part of the hydrogen atoms forming the above-described alkyl group has been substituted with a fluorine atom, a chlorine atom, a bromine atom or an iodine atom.
  • examples of the cycloalkyl group include a hexyl group and the like, and examples of the aromatic hydrocarbon group include a phenyl group and a naphthyl group.
  • R 15 and R 17 combine with R 16 and R 18 and the force R 15 and R 18 and the force or R 16 and R 17 respectively to form a monocyclic or polycyclic ring
  • the monocyclic or polycyclic ring thus formed may have a double bond.
  • Specific examples of the monocyclic or polycyclic ring formed here include the following.
  • the carbon atoms numbered 1 or 2 represent the carbon atoms to which R 15 (R 16 ) or R 17 (R 18 ) are bonded in the formula [1].
  • R 15 and R 16 or R 17 and R 18 may form an alkylidene group.
  • Such an alkylidene group is usually an alkylidene group having 2 to 20 carbon atoms, and specific examples of such an alkylidene group include an ethylidene group, a propylidene group and an isopropylidene group.
  • Preferred examples of the cyclic olefins in the above formula [1] include the cyclic olefins represented by the following formula [111].
  • a compound represented by the above formula [2] can also be used.
  • m is 0 or a positive integer
  • h is 0 or a positive integer
  • j and k are 0, 1 or 2.
  • R 7 to R 15 and R 17 to R 18 represent the same as in the formula [1].
  • R 19 to R 27 each independently represent an atom or a group selected from the group consisting of a hydrogen atom, a halogen atom, a hydrocarbon group and an alkoxy group ( where the halogen atom is a halogen atom in the above formula [1] Is the same as
  • the hydrocarbon group of R 19 to R 27 in the formula [2] includes an alkyl group having 1 to 20 carbon atoms, a halogenated alkyl group having 1 to 20 carbon atoms, and a hydrocarbon group having 3 to 15 carbon atoms. Examples thereof include a cycloalkyl group and an aromatic hydrocarbon group having 6 to 20 carbon atoms. More specifically,
  • alkyl group examples include a methyl group, an ethyl group, a propyl group, an isopropyl group, an amyl group, a hexyl group, an octyl group, a decyl group, a dodecyl group and an octadecyl group.
  • halogenated alkyl group examples include groups in which at least a part of the hydrogen atoms forming the above-mentioned alkyl group has been substituted with a fluorine atom, a chlorine atom, a bromine atom or an iodine atom.
  • Examples of the cycloalkyl group include a cyclohexyl group, and examples of the aromatic hydrocarbon group include an aryl group and an aralkyl group. Specific examples include a phenyl group, a tolyl group, and a naphthyl group. Group, benzyl group and phenylethyl group.
  • alkoxy group examples include a methoxy group, an ethoxy group, and a propoxy group.
  • the carbon atom to which R 17 and R 18 are bonded and the carbon atom to which R 21 is bonded or the carbon atom to which R 19 is bonded are directly or an alkylene group having 1 to 3 carbon atoms. And may be bonded via That is, when the two carbon atoms are linked via an alkylene group, the groups represented by R 17 and R 21 or the groups represented by R 18 and R 19 are mutually linked. As a result, an alkylene group of a methylene group (one CH 2 —), an ethylene group (one CH 2 CH 2 one) or a trimethylene group (one CH 2 CH 2 CH 2 —) is formed.
  • R 23 and R 20 or R 23 and R 27 may be bonded to each other to form a monocyclic or polycyclic aromatic ring.
  • h represents the same as h in Formula [2].
  • Pentacyclo [6. 6. 1. I 3 '6 . 0 2 ⁇ 7. 0 9 ⁇ 14] -4- to Kisadesen derivatives, heptacyclo-5-eicosene derivatives,
  • Pentacyclo [6. 5. 1. I 3 ⁇ 6 . 0 2 '7. 0 9' 13] -4- pentadecene derivatives, penta cyclopentadiene deca Zhen derivatives,
  • Pentacyclo [7. 4. 0. I 2 '5 . I 9' 12. 0 8 ⁇ 13] -3- pentadecene derivatives, heptacyclo [8. 7. 0. I 3 '6 . I 10 ⁇ 17. I 12' 15.0 2 '7.0 11,16] -4-eicosene derivatives, Nonashikuro [10. 9. 1. 1 4,7. I 13 '20. 115,18 ⁇ 0 3' 8 ⁇ O 2, 10. Q12,21. 0 14,19]
  • Pentacyclo [8. 4. 0. I 2 '5 . 1 9,12. 0 8,13] -3- to Kisadesen derivatives, heptacyclo [8. 8. 0. I 4' 7 . I 11 '18. I 13 - 16.0 3 '8.0 12' 17] -5- Hen'eiko Sen derivatives,
  • Pentashiku port such as single 4 to Kisadesen [6.6.1.1 3 '6 .0' 7 . 0. , 14 ] -4 ⁇
  • Pentashiku ports such as single 4-pair Ntadesen [6.5. L 3,6. 0 2,7 . 0 9,13 door 4 one
  • Pentadecene derivative pentacyclo
  • Pentashiku port such as single 3-Bae Ntadesen [7.4.0 l ⁇ '5 l 9 .' 12 o 8.. 'L3] -3- pentadecene derivatives; the full' Tasik b
  • Nonasic mouth [10.9.1.1 4 '13,20 1 15,18 0 3,8 Q 2,10 1 21. ol4,19] -5-pentacocene derivative; pentacyclo
  • Nonashiku mouth such as 5,8 14,21 ⁇ 16,19 Q 2, ll Q 4,9 [10.10.
  • the cyclic olefins represented by the above formula [1] or [2] can be produced by a Diels-Alder reaction between cyclopentagens and olefins having a corresponding structure.
  • cyclic olefins can be used alone or in combination of two or more.
  • the cyclic olefin resin (a-1) to (a-13) used in the polyolefin-based multilayer laminate of the present invention is obtained by using the cyclic olefin represented by the above formula [1] or [2].
  • JP-A-60-168708 corresponding EPN No. 1 564 64 A
  • JP-A-61-120816 JP-A-6-11-15912 (corresponding EP No. 1 564 64 A)
  • Japanese Patent Publication No. 61-11151916 Japanese Patent Application Laid-Open No. 61-271130 (corresponding EPN o.2037 99A), Japanese Patent Application Laid-Open No. 61-27222 No. 16 (corresponding EPN No. 203979A), Japanese Patent Application Laid-Open No.
  • the (a-1) ethylene 'cyclic-olefin random copolymer used as the cyclic olefin resin (A-1) generally contains 52 to 90 mol% of a structural unit derived from ethylene. , the good Mashiku in an amount of 55-80 mol%, structural units derived from cyclic Orefin 1 0-48 mol 0/0, preferably in an amount of 20 to 45 mol%.
  • the ethylene composition and cyclic olefin composition were 13 C-NM. Therefore, it is measured.
  • the structural units derived from ethylene and the structural units derived from the cyclic olefin as described above are randomly arranged and bonded, and It has a linear structure.
  • the fact that the copolymer is substantially linear and does not have a substantially gel-like bridge structure is confirmed by the fact that the copolymer is soluble in an organic solvent and does not contain insolubles. be able to. For example, when the intrinsic viscosity [ ⁇ ] is measured as described later, it can be confirmed by the fact that this copolymer is completely dissolved in decalin at 135 ° C.
  • the structural unit derived from the cyclic alphafin represented by the formula [1] or [2] It is considered that at least the — part has a structure represented by the following structural formula [1-1a] or [2-a], respectively. Further, it is considered that at least a part of the cyclic olefin represented by the formula [1-1] has a structure represented by the following structural formula [111].
  • the (a-1) ethylene 'cyclic olefin random copolymer used in the polyolefin-based multilayer laminate of the present invention can be optionally copolymerized with another copolymer within a range that does not impair the object of the present invention. It may contain a structural unit derived from a monomer.
  • Examples of such other monomers include olefins other than the above-described ethylene or cyclic olefins, norbornenes, and non-conjugated gens.
  • olefins other than the above-described ethylene or cyclic olefins, norbornenes, and non-conjugated gens.
  • 2-norbornene 5-methyl-2-norbornene, 5-ethyl-2-norbornene, 5-isopropyl-12-norbornene, 5-n-butyl-12-norbornene, 5-isobutyl-2-norbornene, .5-, 6-dimethyl- 2-norbornolene, 5-chloro-2-norbornene, 5-f Norbornenes such as Luoreau 2-norbornene,
  • 1,4-hexadiene 4-methyl-1,4-hexadiene, 5-methyl-1,4-hexadiene, 1,7-octadiene, dicyclopentadiene, 5-ethylidene-2-norbornene, 5-vinyl-2-norbornene And the like.
  • the constitutional unit derived from the other monomer as described above is usually 20 mol% or less, preferably 10 mol% or less. It may be contained in an amount.
  • the (a-1) ethylene / cycloolefin random copolymer used in the polyolefin-based multilayer laminate of the present invention comprises ethylene and the formula [1] or
  • the (a-2) ring-opened (co) polymer of cyclic olefin used in the present invention comprises a structural unit derived from the cyclic olefin shown by the above formula [1] or [2]. At least a part of the following formula [11-b] Or, it is considered to have the structure represented by [2-b]. Also the formula.
  • the cyclic olefin-based ring-opened (co) polymer (a-2) contains the above-mentioned cyclic olefin as an essential component, but other copolymers can be optionally used as long as the object of the present invention is not impaired. Or unsaturated unsaturated monomer components. Examples of the unsaturated monomer which may be optionally copolymerized include, for example, cyclic olefins represented by the following formula [3].
  • R 28 and R 29 are a hydrogen atom, a hydrocarbon group or a halogen atom, and may be the same or different.
  • t is an integer of 2 or more, and when R 28 and R 29 are repeated a plurality of times, they may be the same or different.
  • cyclobutene As one component of the monomer represented by the formula [3], for example, cyclobutene, cyclopentene, cyclohexene, cycloheptene, cyclootaten, cyclononene, cyclodecene, methylcyclopentene, methylcyclohexene, methylcycloheptene, methylcyclooctene, methylcyclononene , Methylcyclodecene, ethylcyclopentene, ethylcyclobutene, ethylcyclopentene, dimethylcyclopentene, dimethylcyclohexene, dimethylcycloheptene, dimethylcyclooctene, trimethylcyclodecene, 2- (2-methylbutyl) 1-1 -Cyclohexene And the like.
  • Unsaturated monomers which may optionally be copolymerized in addition to the formula [3] include, specifically, 2,3,3a, 7a-tetrahydro-14,7-methano 1H-indene, Cyclic olefins such as 3,5,6,7a-tetrahydro-4,7-methano-1H-indene can be mentioned.
  • Such unsaturated monomers which may be optionally copolymerized, can be used alone or in combination, and are usually required to constitute the cyclic olefin-opened (co) polymer (a-2). It is used in an amount of less than 50 mol% based on 100 mol% of the component.
  • Such a ring-opened (co) polymer can be produced by the production method disclosed in the above publication. Specifically, it can be produced by polymerizing or copolymerizing the cyclic olefin represented by the formula [1] or [2] in the presence of a ring-opening polymerization catalyst.
  • ring-opening polymerization catalyst examples include a catalyst comprising a halide of a metal selected from ruthenium, rhodium, palladium, osmium, iridium or platinum, a nitrate or acetylacetone compound, and a reducing agent;
  • a catalyst comprising a metal halide or an acetyl aceton compound selected from metal, palladium, zirconium and molybdenum, and an organic aluminum compound can be used.
  • the hydride of the (a-2) ring-opening (co) polymer used in the polyolefin-based multilayer laminate of the present invention is obtained by converting the (a-2) ring-opening (co) polymer obtained as described above into a conventional one. It is obtained by hydrogenation in the presence of a known hydrogenation catalyst.
  • the (a-3) graphitically modified product used in the polyolefin-based multilayer laminate of the present invention includes the (a-1) ethylene 'cyclic-olefin random copolymer or (a-2) cyclic-olefin as described above. It is obtained by graft-modifying a ring-opening (co) polymer or a part of its hydride with a modifying agent.
  • the modifier include unsaturated carboxylic acids such as acrylic acid, maleic acid, and maleic anhydride, and derivatives thereof such as acid anhydrides and alkyl esters of unsaturated carboxylic acids.
  • the content of the structural unit derived from the modifier is usually 10 mol% or less.
  • Such a modified (a-3) graft is prepared by subjecting the (a-1) ethylene-cycloolefin random copolymer or (a-2) cyclic olefin to ring-opening (copolymerization) so as to obtain a desired modification rate.
  • a polymer or a hydrogenated product thereof may be blended with a modifying agent to produce a graft polymer, or a modified product having a high modification rate may be prepared in advance, and then the modified product and an unmodified cyclic olefin resin may be combined. Can also be produced by mixing.
  • the (A) cyclic olefin-based resin used in the polyolefin-based multilayer laminate of the present invention is a resin selected from the group consisting of (a-1), (a-2) and (a-3) as described above. (A-1),
  • the resin of (a-2) or (a-3) may be a single resin or a combination of two or more of these resins.
  • (A-1), (a- It may be a resin composition in which another resin is blended with the resin of 2) or (a-3).
  • (a-1) a random copolymer of ethylene and cyclic olefin is preferably used as (A) the cyclic olefin resin.
  • resins that can be blended with the resin (a-1), (a-2) or (a-3) include (b) polyolefin.
  • the (b) polyolefin a (co) polymer of ⁇ -olefin having 2 to 20 carbon atoms is usually used.
  • examples of the carbon olefin having 2 to 20 carbon atoms include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 3-methyl-1-butene, and 3-methyl-1-pentene. , 3-Ethyl-1-pentene, 4-Methyl-11-pentene, 4-Methyl-11-hexene, 4,4-Dimethyl-11-hexene, 4,4-Dimethyl-11-pentene, 4-Ethynol-1-hexene , 3-ethyl- 1-hexene, 1-octene, 1-decene, 1-dedecene, 1-tetradecene, 1-hexadecene, 1-octa-decene and 1-eicosene.
  • the polyolefin may be a homopolymer of ⁇ -olefin as described above, or may be a copolymer of two or more ⁇ -olefins.
  • the (b) polyolefin other monomers such as norbornene and non-conjugated diene are copolymerized with the above-mentioned ⁇ -olefin within a range that does not impair the characteristics of the polyolefin. Is also good.
  • examples of such other monomers include cyclobutene, cyclopentene, cyclohexene, 3,4-dimethylcyclopentene, 3-methylcyclohexene, 2- (2-methylbutyl) 1-1-cyclohexene, cyclooctene, 3 a, 5,6,7 a—Tetrahydro 4,7—Methanolau 1 H—Cycloindene such as indene,
  • 2-norbornene 5-methyl-2-norbornene, 5-ethyl-2-norbornene, 5-isopropyl-1-2-norbornene, 5-n-butyl-2-norbornene, 5-isobutyl-2-norbornene, 5,6-dimethyl-2- Norbornene, 5-chloro-2-norbornene, 5-f
  • Non-conjugated dienes such as bornene can be exemplified.
  • These other monomers can be used alone or in combination of two or more.
  • polyethylene and poly or propylene are preferred.
  • polyethylene may be a homopolymer of ethylene or a copolymer of ethylene and another ⁇ -olefin.
  • the polyethylene used as the polyolefin is a homopolymer of ethylene or a copolymer of ethylene having an ethylene content of 60 mol% or more, preferably 70 mol% or more, and another ⁇ -branched olefin, density 0. 8 30 gZcm 3 or more, preferably 0. 8 7 ⁇ 0. 94 gZcm 3, 1 9 0 ° Merutofu opening one rate from 0.01 to 1 of C 00 g / 1 0 min, preferably 0. 0 to 50 gZlO and a Vicat softening point of 50 to 140 ° C, preferably 80 to 130 ° C.
  • olefins copolymerized with ethylene include propylene, 1-butene, 1-pentene, 1-hexene, 3-methyl-1-butene, 3-methyl-1-pentene, 3-ethyl-1-pentene, 4-methyl-1 1-pentene, 4-methyl-1-hexene, 4,4-dimethyl-11-hexene, 4,4-dimethyl-11-pentene, 4-ethyl-1-hexene, 3-ethyl-11-hexene, 1-octene Examples thereof include those having 3 to 14 carbon atoms, preferably 3 to 10 carbon atoms, such as, 1-decene, 1-dedecene, and 1-tetradecene.
  • the polypropylene may be a homopolymer of propylene or a copolymer of propylene and another a-olefin.
  • the polypropylene used as the polyolefin is a propylene homopolymer or a propylene content of 70 mol% or more, preferably 80 mol 0/0 .
  • Mouth rate is 0.01 to: L 00 g / 10 min, preferably 0.05 to 50 g / 10 min, Vicat softening point is 100 to 170 ° C, preferably 110 Those in the range of ⁇ 160 ° C are desirable.
  • alpha-olefins copolymerized with propylene include ethylene, 1-butene, 1-pentene, 1-hexene, 3-methyl-1-butene, 3-methyl-1-pentene, 3-ethyl-1-pentene, 4 1-methyl-1-pentene, 4-methyl-1-hexene, 4,4-dimethyl-1-hexene, 4,4-dimethyl-11-pentene, 4-ethyl-1-hexene, 3-ethyl-1-hexene, 1 Examples thereof include those having 2 to 14 carbon atoms (excluding propylene), preferably 2 to 10 (excluding propylene), such as octene, 1-decene, 1-dodecene, and 1-tetradecene.
  • the polyolefin may be a graft modified product.
  • the modifying agent used herein include unsaturated carboxylic acids such as acrylic acid, maleic acid, and maleic anhydride; and anhydrides of these acid anhydrides or unsaturated carboxylic acids. Derivatives such as a kill ester can be exemplified.
  • the content of the structural unit derived from the modifying agent in the polyolefin (b) is usually 10 mol% or less.
  • Such a graft-modified product can be produced by blending a polyolefin with a modifier so as to obtain a desired modification rate, and then performing graft polymerization. Then, it can be produced by mixing the modified product with an unmodified polyolefin.
  • the proportion of the cyclic olefin resin (a-1) to (a-3) in the cyclic olefin resin composition (A) is usually 50% by weight or more, preferably 60% by weight or more, and polyolefin (b) Is usually 50% by weight or less, preferably 40% by weight or less.
  • the (A) cyclic olefin-based resin or cyclic olefin-based resin composition used in the polyolefin-based multilayer laminate of the present invention includes the above-mentioned (a-1) to (a) as long as the object of the present invention is not impaired.
  • a component other than (3) and (b) a rubber component for improving impact strength is compounded, and other resin components, heat stabilizers, weather stabilizers, light stabilizers, and antistatic agents are included.
  • the amount of these other components is based on the total amount of the cyclic olefin resin (A) and other components, or the proportion of the total amount of the cyclic olefin resin (A), polyolefin (b) and other components. Usually, it is desirable to use less than 50% by weight.
  • a stabilizer to be blended as an optional component specifically, tetrakis [methylene-1- (3,5-di-tert-butyl-4-hydroxyhydrazine)] Yl) propionate] methane, ⁇ -(3,5-di-tert-butyl-41-hydroxyphenyl) propionic acid alkyl ester, 2, 2'-oxamidobis [ethyl-3- (3,5-di-tert-butyl-1 4) Phenolic antioxidants such as [hydroxyphenyl) probionate]; fatty acid metal salts such as fatty acid calcium such as zinc stearate, calcium stearate and calcium 12-hydroxystearate; fatty acid esters of polyhydric alcohols And the like.
  • a combination of a phenolic antioxidant and a fatty acid ester of a polyhydric alcohol and the fatty acid ester of such a polyhydric alcohol is preferably an alcoholic hydroxyl group of a trihydric or higher polyhydric alcohol.
  • examples thereof include polyhydric alcohol fatty acid esters in which a part of the ester is esterified.
  • fatty acid esters of polyhydric alcohols include glycerin monostearate, glycerin monolaurate, glycerin monorestate, glycerin monopalmitate, glycerin distearate, glycerin dilaurate and the like.
  • the amount of the phenolic antioxidant is 1 to 100 parts by weight of the total of the essential components. It is desirable to use it in a proportion of less than 0 parts by weight, preferably less than 5 parts by weight, more preferably less than 2 parts by weight.
  • the fatty acid ester of the polyhydric alcohol is preferably used in a proportion of less than 10 parts by weight, preferably less than 5 parts by weight, based on 100 parts by weight of the essential components.
  • a known mixing method can be employed.
  • a Henschel mixer Methods such as mixing with a blender, ribond blender, tumbler and blender, etc., and after mixing, melt-kneading with a screw extruder, twin-screw extruder, twin-drum, etc., and then granulating or pulverizing.
  • a Henschel mixer Methods such as mixing with a blender, ribond blender, tumbler and blender, etc., and after mixing, melt-kneading with a screw extruder, twin-screw extruder, twin-drum, etc., and then granulating or pulverizing.
  • the ⁇ -olefin copolymer forming the second layer of the polyolefin-based multilayer laminate of the present invention is a copolymer of ⁇ -olefin having 2 to 20 carbon atoms. It is desirable that the MFR measured under a load of 16 kg is in the range of 0.01 to 100 g / 10 minutes, preferably 0.05 to 510 minutes.
  • Such (B) ⁇ -olefin copolymer has a crystallinity of less than 40% as measured by X-ray diffraction. Above all, the content is less than 30%, and it is preferable that the material is amorphous.
  • ⁇ -olefins having 2 to 20 carbon atoms include, for example, ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 4-methylinole 1-pentene, 1-octene, 1-decene and mixtures thereof. Can be Of these, ⁇ -olefins having 2 to 10 carbon atoms are particularly preferred.
  • the ⁇ -olefin copolymer is preferably a copolymer of ethylene and ⁇ -olefin, and the ⁇ -olefin is a-olefin having 3 to 20 carbon atoms, and preferably 3 to 20 carbon atoms. 6 alpha-olefins And particularly preferably propylene.
  • the ⁇ -olefin copolymer may contain a component unit other than the component unit derived from ⁇ -olefin, such as a component unit derived from a gen compound, as long as its properties are not impaired.
  • Component units that are permitted to be contained in the monoolefin copolymer include, for example, 1,4-hexadiene, 1,6-octadiene,
  • Chain unconjugated genes such as 2-methyl-1,5-hexadiene, 6-methyl-1,5-heptagen, 7-methyl-1,6-octadiene; cyclohexadiene, dicyclopentadiene, methyltetrahydroidene
  • Cyclic non-conjugated genes such as, 5-vinyl norbornene, 5-ethylidene-2-norbornene, 5-methylene-12-norbornene, 5-isopropylidene-2-norbonorenene, 6-chloromethyl-5-isopropenyl-2-norbornene;
  • Component units derived from gen compounds such as 3-isopropylidene-5-norbornene and 2-propenyl-2,2-norbornadiene can be listed.
  • Such gen components can be used alone or in combination.
  • the content of the gen component is usually 10 mol% or less, preferably 0 to 5 mol%.
  • derived Ru component unit from ethylene has 0-9 5 mol 0/0, preferably 3 0-9 2 mol%, more preferred properly 4 0-9 0 mol 0 / 0, alpha-Orefuin are the component unit derived from 1 to 1 0 0 mole 0/0 of 3 to 2 0 carbon atoms, preferably 4-7 0 mole 0/0, more favorable Mashiku 8-6 0 mol%, 0 a component unit derived from diene components 1 0 mole 0/0, preferably from 0 to 5 mol 0/0, more preferably from 0 to 3 mol% Can be mentioned.
  • Such a (B) phosphoric acid-based copolymer can be produced by a conventionally known method using a titanium-based, vanadium-based, zirconium-based catalyst, or the like, and a meta-opensene-based catalyst or the like. .
  • the (B) ⁇ -olefin copolymer may be a graft-modified product.
  • the modifier used herein include unsaturated carboxylic acids such as acrylic acid, maleic acid, and maleic anhydride, and derivatives thereof such as acid anhydrides and alkyl esters of unsaturated carboxylic acids.
  • the content of the structural unit derived from the modifying agent in the (II) ⁇ -olefin copolymer is usually 10 mol%. It is as follows.
  • the polyolefin multilayer laminate of the present invention comprises: ( ⁇ ) a first layer mainly composed of a cyclic olefin resin; and ( ⁇ ) a second layer mainly composed of an ⁇ -olefin copolymer. Is a multilayer laminate.
  • the first and second layers are respectively laminated at 5 to 10,000 layers, preferably at 20 to 1,000 layers.
  • the ratio of the total thickness of the first layer to the total thickness of the second layer is preferably 1:99 to 99: 1, preferably 5:95 to 60:40. It is.
  • each layer has a thickness of 0.01 to 5004! 11, preferably 0.05 to 300 ⁇ .
  • the total thickness of the polyolefin-based multilayer laminate depends on the application, but is generally ⁇ ! To 50 mm, preferably about 10 ⁇ m to 2 mm. When used as a blister pack and as a packaging material for PTP, it should be 100 to 600 ⁇ , preferably 200 to 400 ⁇ .
  • the first and second layers in the polyolefin-based multilayer laminate of the present invention The joining method is not limited, but can be joined directly or via an adhesive as needed. Generally, it is preferable that the first and second layers are laminated by laminating by heat bonding.In this case, by repeating rolling and laminating, the layers are integrally joined by a crimping process with a small thickness. Are preferred.
  • the properties of the respective resins constituting the first and second layers appear in the polyolefin-based multilayer laminate thus laminated. And, even if the thickness ratio becomes opaque when each resin is blended, it is kept transparent. Further, the polyolefin-based multilayer laminate of the present invention has excellent interlayer adhesion because both the first and second layers are of olefin type, and can obtain a good adhesion without intervening an adhesive. In particular, those obtained by pressure bonding in a state where the thickness of the multilayer is reduced can provide excellent interlayer adhesion. As described above, when a resin modified with an unsaturated carboxylic acid is used as the resin of each layer, the interlayer adhesion of each layer is further increased.
  • Examples of the method for producing the above-mentioned polyolefin-based multilayer laminate include, for example, a multilayer T die & co-extrusion molding method such as a multilayer inflation method, an extrusion lamination method, a wet 0 r dry lamination method, a multilayer blow method, A general multi-layer laminate molding method such as a color molding method, a sandwich molding method, and a stamping molding method can be employed.
  • A a first layer mainly composed of a cyclic olefin resin;
  • the second layer mainly composed of the ⁇ -olefin copolymer can be ferromagnetically formed.
  • a preferred manufacturing method is to first form a laminar flow comprising at least two layers of a first layer and a second layer in a forming step, and then divide the laminar flow in a longitudinal direction intersecting an interface in a dividing step.
  • the laminated laminar flow is formed by laminating and integrating the divided laminar flows in a plane parallel to the interface in a heated state.
  • the forming step, the dividing step and the laminating step are preferably repeated one or more times, preferably 2 to 10 times. In that case, it is preferable to reduce the thickness of the laminar flow obtained in the laminating step.
  • the polyolefin-based multilayer laminate of the present invention produced as described above has appropriate flexibility and surface hardness, and is excellent in interlayer adhesion, moisture proofing, transparency, hand-cutting, heat-sealing and dead-holding properties, and has a vacuum. Or, because it is easily pressurized and excellent in design, it exhibits sufficient performance as a packaging material for medicines, foods, tobacco, etc. For this reason, the polyolefin-based multilayer laminate of the present invention can be suitably used as a container such as a sheet or film for packaging, a bottle, and a container.
  • any items such as medicines, foods, articles, and miscellaneous goods can be used.
  • drugs such as tablets and capsules
  • foods such as rice crackers, snacks and cookies, and hygroscopic packages
  • moisture proofness and transparency are guaranteed.
  • Packaging forms include bags, packs, PTP (press through pack), blister packs, hand twists, wrappings, shrink, pills, etc., films, tetra packs, and milk packs, etc.
  • Examples include containers to be assembled, medical containers such as medicine bottles, piarbins, infusion bottles, and syringes, physicochemical equipment such as petri dishes, test tubes, and analysis cells, and cosmetic bottles.
  • the polyolefin-based multilayer laminate of the present invention is particularly suitable as a blister pack or a PTP packaging material.
  • FIG. 1 is a perspective view showing a method for producing a first multilayer laminate of the present invention according to an embodiment, and shows each step.
  • FIG. 2 is a perspective view showing a state in which the torsion of the laminar flow is returned to the original angle.
  • FIG. 3 is a schematic plan view showing a preferred embodiment of each step shown in FIG.
  • FIG. 4 is a schematic side view showing a preferred embodiment of each step shown in FIG.
  • FIG. 5 is a partially cutaway perspective view showing the method for manufacturing the second multilayer laminate of the present invention according to the embodiment.
  • FIG. 6 are cross-sectional views of A-A, B-B, C-C, D-D, and E-E of FIG. 5, respectively.
  • FIG. 7 is a partially cut-away perspective view showing a repetition cycle in the second method for manufacturing a multilayer laminate of the present invention.
  • FIG. 8 is a partially cutaway perspective view showing a step of forming a multilayer flow according to the embodiment.
  • FIG. 9 are cross-sectional views of A-A, B-B, C-C, DD, and E-E of FIG. 8, respectively, and (f) Is a cross-sectional view corresponding to DD in the next cycle.
  • FIG. 10 is a partially cutaway perspective view showing a step of forming a multilayer tubular body.
  • FIG. 11A is a sectional view taken along line FF of FIG. 10
  • FIG. 11B is a sectional view taken along line GG
  • FIG. 11C is a sectional view taken along line HH.
  • FIG. 12 is a partially cutaway perspective view showing a step of further dividing and joining the multilayer tubular body to form a multilayer.
  • FIG. 13 shows another multi-layer cylindrical body forming step.
  • (A), (b), and (c) are cross-sectional views corresponding to FF, GG, and HH in FIG. 10, respectively.
  • FIG. 14A is a perspective view of the multilayer tubular body according to the embodiment, and FIG. 14B is a cross-sectional view of a W portion thereof.
  • FIG. 15 is a partially cutaway perspective view showing the method for manufacturing the multilayer tubular body according to the embodiment.
  • 16A is a cross-sectional view taken along the line AA of FIG. 15, and
  • FIG. 16B is a cross-sectional view taken along the line BB.
  • FIG. 17 is a partially cutaway perspective view showing another method for manufacturing a multilayer tubular body.
  • FIG. 18 (a) is a cross-sectional view corresponding to A-A in FIG. 15 showing a method for manufacturing another multilayer cylindrical body, (b) is a cross-sectional view corresponding to C-C, and (c) is BB It is sectional drawing.
  • FIG. 19 is a cross-sectional view illustrating the packaging material according to the embodiment of the present invention. BEST MODE FOR CARRYING OUT THE INVENTION
  • FIG. 1 is a perspective view showing a method for producing a first multilayer laminate of the present invention according to one embodiment.
  • a laminar flow 1 is a flat laminar flow in which different types of resin layers 2 and 3 are laminated in a molten state, and moves in the direction of arrow X.
  • the laminar flow 1 is obtained by co-extrusion molding or co-injection molding.
  • the laminar flow 1 is divided into four divided laminar flows 1a, lb, lc and Id by dividing surfaces 8a, 8b and 8c orthogonal to the lamination interface 4 of the resin layers 2 and 3.
  • the split laminar flows l a, lb, lc and 1 d are twisted 90 ° in the same direction.
  • the twisted divided laminar flows 1a, 1b, 1c, Id are preferably kept parallel to one another.
  • the twisted divided laminar flows 1a, lb, lc, and Id are laminated and integrated to form a laminated laminar flow 7 composed of eight layers of 2 / 3Z2Z3Z2Z3Z23.
  • the divided laminar flows 1a, lb, lc, and 1d may be laminated and integrated at once, or may be laminated and integrated in multiple stages, for example, two stages.
  • the laminar flow 7 thus formed is sent to the next division step in order to control each step.
  • the laminar flow 7 is thinned and its width is expanded.
  • This thinning and widening can be performed, for example, by moving the laminated laminar flow 7 in a tapered flow path having a smaller thickness and a wider width in the traveling direction. It can also be performed by rolling the laminar flow 7 with a roll.
  • the laminated laminar flow 7 is sent to the dividing step, as shown in FIG. 2, it is preferable that the laminar flow 7 is turned to the original angle. By doing so, the continuous laminar flow 7 obtained continuously can be moved to the next division step on the pallet.
  • the resin layers 2 and 3 are further thinned and multilayered, and a multilayer laminate in which thin film layers are laminated is obtained.
  • a multilayer laminate in which thin film layers are laminated is obtained.
  • 32 layers are obtained by repeating each step once, 128 layers are obtained by repeating twice, 204 layers are obtained by repeating 4 times, and 2 X 4 is obtained by repeating n times.
  • ⁇ + 1 multilayer sperm body is obtained.
  • the number of repetitions can be arbitrarily selected.
  • the thickness of each layer can also be set to an arbitrary value by selecting the thickness of the resin layers 2 and 3 of the first laminar flow 1 or the number of repetitions. For example, it is possible to obtain a multilayer laminate that is an ultra-thin layer in which each layer has a thickness of about 0.09 to 0.45 nm.
  • the multilayer laminate unique characteristics in which the respective characteristics are combined can be obtained by arbitrarily combining the materials of the resin layers 2 and 3. For example, by combining a resin having excellent gas barrier properties and a resin having excellent rigidity, composite properties of both can be obtained.
  • Such a multilayer laminate can be used for containers, packaging materials, and other applications as it is, or as required, by further processing such as stretching and rolling to further reduce the thickness of each layer.
  • FIG. 1 shows an example in which the laminar flow has two resin layers, three or more resin layers may be used. Also, the number of divided laminar flows can be arbitrarily selected, for example, two.
  • a multilayer laminate of 2 ⁇ 2n + 1 layers can be obtained.
  • the direction and angle of the torsion can be arbitrarily selected. For example, minutes The laminar flow la, 1c may be twisted by + 90 °, and the laminar flow 1b, Id may be twisted by 90 °. In this case, a laminated laminar flow composed of five layers of 2 / (3 3) / (2 2) / (3 3) / 2 is formed.
  • the torsion angle is usually 10 to 90 °. If the torsion angle is small, the interval between each of the divided laminar flows is too narrow, and it becomes difficult to secure a flow path for each of the divided laminar flows in the die. On the other hand, if the torsion angle is large, the flow path interval between the divided laminar flows can be sufficiently ensured, but a long flow path is required when returning the torsion to the original angle.
  • FIGS. 3 and 4 are schematic diagrams showing a particularly preferred embodiment of the first method for producing a multilayer laminate of the present invention
  • FIG. 3 shows a flow diagram of a heated multilayer resin flow moving through a flow path in a molding die.
  • FIG. 4 is a schematic side view of FIG.
  • points 1 to 2 represent the process of forming a laminar flow 1 in which different layers are stacked
  • points 2 to 4 represent the processes of forming the divided laminar flows 1 a, lb, lc, and Id.
  • Steps 4 to 5 twist the laminar flow 1 a, lb, lc, Id.
  • Points 5 to 7 laminate the laminar flow 1 a, lb, 1 c, 1 d. Is shown.
  • Laminar flow 1 expands in the width direction from point 1 to point ⁇ . At point 2, the thickness is thinner and wider than point 1.
  • the laminar flow 1 is divided into two at point ⁇ ⁇ ⁇ while expanding in the width direction between points 2 and 4, and then again at point 3, and finally the divided laminar flow 1 a, lb, lc, I Divided into four by d. Since the laminar flow 1 is evenly distributed by such sequential division, the resin flow is prevented from being biased, and the molding can be performed stably.
  • the laminar flows la, lb, lc, 1 d are twisted by 90 °, but since the distance between points 4 and ⁇ of each laminar flow 1 a, lb, lc, 1 d is the same, each laminar flow is Molding without variation among la, lb, lc and 1d can be performed.
  • the divided laminar flows la, lb, lc, and 1d are laminated and integrated. At point 6, two divided laminar flows are once laminated and integrated, and finally at point 7, they are finally laminated and integrated.
  • a laminated laminar flow 7 in which the interlayer adhesion is further strengthened and the homogeneity is enhanced as compared with the case where the lamination and integration are performed one by one.
  • Such a laminar flow 7 can sufficiently exhibit mechanical strength and desired performances.
  • the resin flow path between points (1) and (2) has a taper having a smaller thickness and a wider taper in the traveling direction, and a laminar flow 7 that is thinner and wider than point (2) is obtained at point (4).
  • FIG. 5 is a partially cutaway perspective view showing a method for manufacturing the second multilayer laminate of the present invention according to one embodiment, and FIGS. 6 (a), (b), (c), (d), (e).
  • Fig. 5 is a cross-sectional view of A-A, B-B, CC, DD, E-E in Fig. 5
  • Fig. 7 is a partially cutaway perspective view showing the repetition cycle
  • Fig. 6 (e) is an enlarged view. Is shown.
  • the cut surface in FIGS. 5 and 7 is shown as an end surface.
  • laminar flow 1 is a flat laminar flow as shown in part A of FIG. 5, and as shown in FIG. 6 (a), where different types of resin layers 2 and 3 are laminated in a molten state. Move in X direction.
  • the laminar flow 1 is obtained by co-extrusion at a relatively high temperature and high pressure, and the adhesion at the interface 4 between the resin layers 2 and 3 is high.
  • the corrugated laminar flow 5 is formed by bending the cross section so as to have a corrugated shape as shown in (b) and (c).
  • the corrugated laminar flow 5 has 4.5 peaks, and the resin layers outside the strips 6 at both ends are resin layers 2 and 3 of different types.
  • in another embodiment of the second method for producing a multilayer laminate according to the present invention in the step of bending and forming a laminar flow into a waveform, for example, at the bent portion (corner) of the laminar flow at the stage B, C or D in FIG.
  • the cutting of the laminar flow is also performed in the part of ()). In this case, multiple laminar flows And the layers are integrated.
  • the laminated laminar flow 7 is the same as the first laminar flow 1 by moving the resin layers 2 and 3 into thin layers and expanding the width as it moves to the part E in Fig. 5 and (e) in Fig. 6. With the shape, a laminated laminar flow 7 in which the resin layers 2 and 3 are thinned and multilayered is formed. In the process of thinning, the resin layers 2 and 3 of the same type which are overlapped are integrated, and the interfaces 4a and 4b disappear to form a 10-layer multilayer body. The resin layers 2 and 3 have a structure in which the user is uniformly distributed while maintaining high adhesion at the interface 4.
  • laminar laminar flow 7 is formed in a fan shape, and flows from part D to part E corresponding to the main part of the fan.
  • the lamination has a shape in which the width of the laminar flow 7 formed in a flat plate shape increases.
  • the laminar flow 1 and the laminar flow 7 have a phase difference of 90 °, but the laminar flow 7 can be twisted by 90 ° to change the phase in the same direction as the laminar flow 1.
  • the laminar flow 1 is heated to the molding die 10 having a resin flow path corresponding to the shape of the laminar flow from the part A to the part E in FIG.
  • the co-extrusion can be performed continuously by passing in a softened state, thereby producing a multilayer laminate.
  • Figure 7 shows each step of the repetition cycle, and the mold 1 used in Figure 5
  • the molding die 11 having the same shape as 0 is connected in series after the molding die 10 while being rotated 90 °, and the laminar flow 7 is supplied to the molding die 11 to perform the same process. Is shown. That is, at the stage of the part in FIG. 7, the flat laminar laminar flow 7 is formed into a corrugated laminar flow 5a as shown in the part, and the layer is gradually thinned and widened as shown in the part C 'and folded. As shown in FIGS. 3 and 4, each piece 6a is laminated and integrated to form a laminated laminar flow 7a.
  • the laminated laminar flow 7a is further thinned and widened as shown in the section to form a laminated laminar flow 7a having the same shape as the original laminated laminar flow 7 and having a reduced thickness and a multilayer structure. Even at this stage, the same type of resin layer that has overlapped is integrated, so that a multilayer laminate of 82 layers is obtained.
  • the resin layer is further thinned and multilayered, and a multilayer laminate in which thin film layers are laminated is obtained.
  • the number of layers can be arbitrarily changed by selecting the number of layers to be stacked in the first laminar flow 1, the number of peaks of the waveform of the corrugated laminar flow 5, 5a, and the number of repetitions.
  • the thickness of each layer can also be set to an arbitrary value depending on the thickness of the resin layer of the first laminar flow 1, the number of peaks in the waveform, and the number of repetitions.
  • the outermost resin layer has a thickness of one to two of other resin layers.
  • the layers on the front side and the back side can be different layers, but the number of peaks is an integer. Thereby, both can be made of the same kind of resin.
  • the interface 4 between the resin layers 2 and 3 has high adhesion by co-extrusion molding, and the interfaces 4a and 4b to be joined thereafter are also joining of the same kind of resin layers. Therefore, it shows high adhesion when integrated. Therefore, the interlayer adhesion of the resin layers constituting the multilayer laminate is increased, and the respective layers are uniformly distributed, and the characteristics are homogenized.
  • FIG. 8 is a partially cutaway perspective view showing a process of forming a multilayer laminar flow in the embodiment
  • FIGS. 9 (a), (b), (c), (d), and (e) are A— A, B-B, C-C, D-D, E-E sectional views
  • (f) is a D-D equivalent sectional view in the next cycle
  • the cut surface in FIG. 8 is shown as an end face. I have.
  • laminar flow 1 is part A of FIG. 8, and as shown in FIG. 9 (a), laminar flow is a flat laminar flow, and different types of resin layers 2 and 3 are laminated in a molten state. Move in X direction.
  • the laminar flow 1 is obtained by coextrusion molding under a relatively high temperature and a high pressure, and the adhesion between the resin layers 2 and 3 at the lamination interface 4 is high.
  • the laminar flow 1 is equally divided by the longitudinal division surface 8 intersecting with the lamination interface 4 to form divided laminar flows 1a and 1b.
  • the divided laminar flows 1a and 1b move symmetrically parallel to each other in the direction intersecting with the laminating interface 4 and in the direction parallel to the laminating interface 4.
  • the laminar flows 1a and 1b move as shown in part B of Fig. 8 and (b) of Fig. 9
  • the layers are rearranged so that the lamination interfaces 4 are opposed to each other in parallel with an interval therebetween.
  • the divided laminar flows 1a and 1b are rearranged in the center of the original laminar flow 1 by symmetrically translating. And since each moving distance, moving angle, etc. become equal, the flow conditions at the rearrangement position become equal.
  • each divided laminar flow 1a, 1b is widened in the direction of extension of the lamination interface 4 and thinned to form a laminar flow 21a and 2lb as shown in part C of FIG. 8 and FIG. 9 (c).
  • the flow rate of each laminar flow is kept constant by forming so that the cross-sectional area of the divided laminar flows 1a and 1b does not change.
  • the laminar flows 21a and 21b formed here have the same width as the laminar flow 1 before the division and have a thickness of 12.
  • the divided laminar flows la and 1b whose flow conditions have become uniform due to the symmetrical movement are widened and thinned under the same conditions, so that the respective laminar flows 21a and 21b formed are the same.
  • Laminar flow with uniform flow conditions can be obtained.
  • the laminar flows 21a and 21b formed in the opposed state as described above are symmetrically moved so as to approach each other and laminated and integrated, and the same cross-sectional shape and the same flow conditions are obtained. Since the laminar laminar flows 21a and 21b are joined and integrated, the laminar laminar flow 7 having a uniform layer shape and layer thickness is obtained as shown in part D of Fig. 8 and Fig. 9 (d). It is formed. In this case, since the two thin laminar flows 21a and 21b are stacked and integrated, the pressing force is directly and uniformly applied as compared with the case where a large number of thin laminar flows 21a and 21b are stacked and integrated at the same time. Even when the pressure decreases, a laminar flow 7 with excellent adhesion at the newly formed laminating interface 4a can be obtained.
  • the lamination of the divided laminar flows 1a and 1b may be performed after the lamination and integration, or at the same time, but in this case, a uniform laminar flow 7 is obtained by uneven distribution of the laminar flow. Therefore, it is preferable to perform lamination and integration as described above after laminating the laminar flows.Thus, laminar flows 21a and 21b, which have been laminated to have the same shape, are simply laminated and joined. A homogeneous laminar flow 7 can be formed. The lamination may be widened and thinned after lamination, but in this case, the uneven distribution of the laminar flow is liable to be amplified. It is preferable to integrate them. As a result, in a state where uneven distribution of the laminar flow is prevented, the lamination can be integrated by pressing directly and with a uniform pressing force, so that the uniformity of the obtained laminar flow 7 is further improved.
  • the laminated laminar flow 7 obtained as described above is equally divided by the new dividing surface 8a, the divided laminar flows 22a and 22b are formed as shown in part E of Fig. 8 and Fig. 9 (e). Therefore, by repeating the same steps of rearrangement, widening and thinning, and lamination and integration as described above, the laminated laminar flow 23 further thinned and multilayered as shown in FIG. 9 (f) is obtained. can get. By repeating each of the above steps in this manner, each layer is thinned and laminated, whereby a multilayer laminar flow is formed in which the thin film layers are multilayered and uniformly distributed.
  • the above steps correspond to the shape of laminar flow from A to D in Fig. 8 (1) 1-layer laminar flow 1a, 1b- 1-layer laminar flow 21a, 21b-laminated laminar flow 7
  • a mold 24 having a resin flow path By passing the laminar flow 1 in a heat-softened state through a mold 24 having a resin flow path, co-extrusion molding can be performed continuously.
  • a laminated laminar flow is continuously produced.
  • the laminar flow 1 is divided into two and divided into two divided laminar flows 1a and 1b, but may be further divided into a number of divided laminar flows.
  • a large number of divided laminar flows may be laminated simultaneously, but as described above, it is preferable to laminate two layers sequentially.
  • the lamination method is not limited to parallel movement, and the lamination may be performed after each divided laminar flow is twisted. Further, as described above, either the widening and thinning and the lamination integration may be performed first or simultaneously.
  • FIG. 10 is a partially cutaway perspective view showing a step of forming a multilayer tubular body in the embodiment, and the cut surface is shown as an end surface.
  • 11A is a sectional view taken along line FF of FIG. 10
  • FIG. 11B is a sectional view taken along line GG
  • FIG. 11C is a sectional view taken along line HH.
  • This manufacturing method includes the step of forming the plate-like member formed in the step of FIG. By dividing the multilayered laminar flow into four parts and adjusting the torsional direction of the obtained divided laminar flow, the two laminar flows are joined on the outer and inner sides to form two cylindrical bodies. An example of stacking is shown.
  • the laminated laminar flow 23 manufactured in the step of FIG. 8 is represented by a single cross section by omitting the multilayer structure.
  • This laminated laminar flow 23 moves in the direction of arrow Y, and as shown in the F section of FIG. 10 and the dividing surface 8 b orthogonal to the lamination interface, as shown in FIG. It is divided into 1a, 31b, 31c, and 31d.
  • the outer divided laminar flows 31a and 31d are spread thinly while twisting to form a widened thin layer, and the dividing surface 8
  • the b is joined in the circumferential direction as the joining portion 32a to form a cylindrical first joining laminar flow 33a having a relatively large diameter.
  • the inner divided laminar flows 31b and 31c are thinned and widened by twisting while twisting, and are joined in the circumferential direction at the joint 32b.
  • a relatively small-diameter cylindrical second joining laminar flow 33b is formed on the ⁇ side of the first joining laminar flow 33a.
  • first and second junction laminar flows 33a and 33b are formed doubly with the outer and inner sides separated from each other. As shown in FIG. 10 and the H section in FIG. 10 and FIG. 11 (c), they are laminated and integrated. If necessary, the entire structure is further expanded to reduce the diameter and the thickness of the layer, thereby forming the multilayer cylindrical body 34.
  • molding can be performed by passing the laminated laminar flow through the mold 24b having a molding space corresponding to the laminar flow.
  • the step of forming the multilayer tubular body 34 may be performed once, but the multilayer tubular body formed here may be further divided and joined to form a multilayer.
  • Fig. 12 shows the process of further dividing and joining the above multilayer cylindrical body to form a multilayer. It is a partially cut-away perspective view, and the cut surface is shown as an end face.
  • the multilayer cylindrical body is divided into four parts, and two divided laminar flows are joined on the outside and ⁇ side to form two parts.
  • An example is shown in which a cylindrical body is formed and laminated.
  • the multilayer cylindrical body 34 is moved in the direction of arrow Z using the mold 24d, and the four divided laminar flows 38a, 38 are formed by the dividing surface 8c orthogonal to the lamination interface 35. b, 38c, 38d.
  • the divided laminar flows 38a, 38b ... formed by the division the divided laminar flows 38a and 38c that are not adjacent to each other are thinly spread and thinned, and the divided surface 8c is joined to the junction 32c.
  • the other divided laminar flows 38b and 38d are joined in the circumferential direction at the joint 32d as they are or slightly expanded and spread, and a relatively small-diameter cylindrical shape is formed inside the joint laminar flow 33c. A second bonding laminar flow 33d is formed.
  • first and second junction laminar flows 33c and 33d are formed double with the outer and inner sides separated, but then both expand the inner junction laminar flow 33d.
  • the layers are thinned and joined, and the layers are integrated. Then, the whole is further pressed to reduce the thickness, and is formed so as to have the same diameter as the first multilayer tubular body 34, thereby forming the multilayer tubular body 34a.
  • FIG. 13 shows still another multilayer cylindrical body forming step
  • (a), (b), and (c) are cross-sectional views corresponding to FF, GG, and HH in FIG. 10, respectively.
  • the laminated laminar flow 23 is divided into 16 by the dividing surface 8d to form 16 divided laminar flows 31a, 31b ....
  • the thickness of each of the divided laminar flows 31a, 31b ... and the joining laminar flows 33a, 33b ... becomes thicker toward the inside, but they are all the same in Fig. 13. I have.
  • the first, fifth, ninth, and thirteenth divided laminar flows 31a, 31e, 31i, and 31n are positioned outside.
  • 2, 6, 10th and 14th divided laminar flows 31b, 31f, 31j, and 3lp are located inside and thinned and joined at the junction 32f to form the second joint laminar flow 33 b, and the third junction laminar flow 1 3 c with the third, seventh, 11th and 15th laminar flows 3 1 c, 31 g, 31 k, and 31 q positioned inside
  • the 4th, 8th, 12th, and 16th laminar flows 31d, 31h, 31m, and 3lr are positioned further inside to form a fourth junction laminar flow 33d.
  • these joining laminar flows are thinned, laminated and integrated to form a multilayer tubular body 34.
  • the multilayer cylindrical body 34 obtained in this way has the junctions 32e, 32f, 32g, and 32h dispersed, so that a multilayer cylindrical body that can withstand use as it is can be obtained.
  • further division and joining can be repeated to form a multilayer.
  • the joining laminar flow formed at one time is increased to disperse the junctions 32 e, 32 f.
  • the portion where the composite characteristic is lacked by the joint can be limited to a narrow range.
  • the diameter and thickness of the cylindrical joining laminar flow can be arbitrarily selected according to the intended multilayer tubular body. For example, diameter 10 ⁇ 1 0001 ⁇ 11, thickness :! 1100 mm.
  • the number of divisions of one laminar flow is shown as 2 to 16, an arbitrary number in the above range can be set according to the size of the cylindrical body to be manufactured. The number of repetitions of the process can be arbitrarily selected in the range (1) according to the target tubular body.
  • the multilayer tubular body obtained as described above exhibits characteristics due to the composite of the respective layers, and furthermore, is limited to a region in which the lack of the characteristic due to the joint is small, thereby obtaining a multilayer tubular body having the characteristics due to the composite as a whole.
  • a cylindrical body having excellent properties of rigidity and gas barrier properties can be obtained.
  • a multilayer cylindrical body having arbitrary composite characteristics can be obtained by combining arbitrary characteristics as the resin layers 2 and 3.
  • it is possible to obtain an arbitrary characteristic by arbitrarily selecting and combining the types and numbers of the resin layers. For example, by combining three or more layers of different resins, it is possible to obtain unique characteristics in which these are combined.
  • a plate-shaped laminar flow is used in the first stage, which is divided and joined, so that division, widening, thinning and lamination at each stage are easy, and By forming the tubular body, it is possible to efficiently manufacture a multilayer tubular body.
  • a plurality of molds are connected in series, and each step can be continuously repeated in the molds, whereby molding can be performed under the same heating conditions without contact with the atmosphere. Yes, but it is also possible to direct some steps out of the mold and perform them in air.
  • a laminar flow in which at least two types of layers are laminated is divided by a longitudinal division surface that intersects a lamination interface to form a plurality of divided laminar flows.
  • Forming a multilayer laminar flow by widening and laminating the obtained plurality of divided laminar flows and laminating them integrally;
  • the multi-layer laminar flow is divided at a longitudinal dividing plane intersecting with the interface of the stratified layer to form a multi-layer laminar flow, and a part of the obtained multi-layer laminar flow is formed to form a joint in the longitudinal direction.
  • Joining to form a cylindrical joining laminar flow forming another part of the multilayer divided laminar flow at a position different from the joining position in the longitudinal direction
  • To form another cylindrical bonding laminar flow inside or outside the cylindrical bonding laminar flow, and a plurality of cylindrical bonding laminar flows formed in multiple inward and outward directions are laminated and integrated.
  • FIG. 14A is a perspective view of the multilayer tubular body according to the embodiment, and FIG. 14B is a cross-sectional view of a W portion thereof.
  • the multilayer tubular body 41 is formed in a cylindrical shape by alternately stacking and integrating multiple thin film layers 42 and 43 composed of two different resin layers.
  • the thin film layers 42, 43 are alternately stacked and joined by longitudinal joints 44 to form a cylindrical shape.
  • FIGS. 14A and 14B the positions of the joints 44 are shown differently.
  • the thin film layers 42 and 43 made of different kinds of resins are uniformly formed.
  • FIG. 15 is a partially cutaway perspective view showing the method for manufacturing the multilayer tubular body according to the embodiment, and the cut surface is illustrated as an end surface (the same applies to FIGS. 17 and 18 described later).
  • FIG. 16 (a) is a cross-sectional view taken along the line AA of FIG. 15, (b) is a cross-sectional view taken along the line BB, and (c) is a cross-sectional view at different stages.
  • This manufacturing method is an example in which a cylindrical laminar flow in which different types of resin layers are laminated is divided into four parts, and the two divided laminar flows are joined on the outside and inside to form two cylindrical bodies and laminate them. Is shown.
  • reference numeral 51 denotes a cylindrical laminar flow
  • FIG. 16 (a) different types of resin layers 52, 53 are laminated in a molten state, and are co-extruded. It is obtained by molding and moves in the direction of arrow X.
  • the cylindrical laminar flow 51 is divided into four divided laminar flows 51a, 51b, 51c and 51d by a dividing surface 55a orthogonal to the resin layer interface 54.
  • the dividing plane 55a is indicated by an arrow.
  • the non-adjacent divided laminar flows 51a and 51c are widened and thinned, and the dividing surface 55a is joined to the junction 5 6 a is joined in the circumferential direction to form a cylindrical first joining laminar flow 57 a having a relatively large diameter.
  • the other divided laminar flows 51b and 51d are left as they are, or are slightly widened and thinned, and are joined in the circumferential direction at the joint 56b.
  • a small cylindrical second bonding laminar flow 57b is formed.
  • first and second bonded laminar flows 57a and 57b are formed double with the outer and inner sides separated, and then both expand the inner bonded laminar flow 57b. Thinned and joined, and laminated and integrated. Then, the whole is further expanded and thinned, and is formed so as to have the same diameter as the first cylindrical laminar flow 51, and a laminated laminar flow 61 is formed.
  • the cross-sectional structure of the laminated laminar flow 61 is shown in Fig. 16 (b), and different types of resin layers 62, 63, which are thinner than in Fig. 16 (a), are alternately laminated in multiple layers.
  • junctions 56a, 56b of the first and second junction laminar flows 57a, 57b are formed at different positions so as not to overlap.
  • the junctions 56a and 56b of the inner and outer junction laminar flows are necessarily formed at different positions by widening and thinning non-adjacent divided laminar flows in a natural state and joining and laminating them. You.
  • Figure 15 shows that the laminated laminar flow 61 is further divided into four at the dividing surface 55b to form four divided laminar flows 61a, 61b, 61c and 61d. Similar to the above, non-adjacent divided laminar flows 6 la and 6 1 c and 6 1 b and 6 1 d are joined to form a double cylindrical joining laminar flow on the outside and inside, and this joining The laminar flow is expanded and thinned and laminated and integrated to form a laminar flow 71 having a cross-sectional shape as shown in FIG. 16 (c).
  • the laminated laminar flow 71 different types of resin layers 72 and 73 thinner than the resin layers 62 and 63 of the laminated laminar flow 61 are alternately laminated and integrated in multiple layers.
  • the split surface 55b is assumed to be the surface that coincides with the joints 56a, 56b, so only the new joints 56c, 56d are included in the laminar flow 71. Is formed.
  • dividing surfaces 55b and 55c are indicated by arrows, and the laminar flow 71 is also divided into surfaces that coincide with the joints 56c and 56d.
  • a surface 55c is formed.
  • the resin layer of the divided surfaces 55b, 55c is disturbed by setting the joints 56a, 56b or 56c, 56 The resin layer can be thinly removed along the dividing surfaces 55b and 55c.
  • the laminated laminar flow 71 is divided at the dividing surface 55c, and the divided laminar flow is joined and laminated and integrated as described above, so that a thinner resin layer is further laminated. A layered laminar flow is obtained. By repeating this, the resin layer becomes the thin film layers 42 and 43, and the multilayered cylindrical body 41 shown in FIG. 14 is formed by being multilayered and laminated and integrated. In each of the above steps, division and joining are performed in a state where the laminar flow or the laminar laminar flow keeps the ripened and softened state.
  • the multilayer tubular body formed as described above has basically the same structure as the laminated laminar flow 71 in FIG. 16 (c), but the resin layers 72 and 73 are further thinned. It has a structure in which the thin film layers 42 and 43 are formed, and the number of layers is multi-layered. By joining the joints 56a, 56b ... with the divided surfaces 55b ..., the joint surface formed in the final step remains as the joint 44.
  • a molding tool 75 can be used as an apparatus for producing the above-mentioned multilayer tubular body, and the resin can be passed through this.
  • the molding die 75 is an extrusion die having a resin flow path corresponding to the laminar flow of the resin from the A-A section to the BB section in FIG.
  • the mold 75 has a portion that forms a cylindrical laminar flow in which different layers corresponding to the cylindrical laminar flow 51 in FIG. 15 are laminated, and a divided laminar flow 51 a, 51 1) —
  • the laminar flow corresponding to is divided by the dividing surface 5 5a intersecting with the resin layer interface 5 4 to form the divided laminar flows 5 1a, 5 1b... and the joining laminar flows 5 7a, 5 7
  • a part of the divided laminar flow corresponding to the alligator is joined in the longitudinal direction so as to form a joining part 5 6a to form a cylindrical body, and another part of the divided laminar flow is joined to the joining part 5 6a is joined to a position different from that of the cylindrical body so as to form a joint 56b in the longitudinal direction, and another cylindrical body is formed on or outside of the cylindrical body;
  • This is a molding die in which a plurality of tubular bodies formed in multiple layers in the corresponding inward and outward directions are laminated and integrated to form
  • a cylindrical laminar flow 5 1 in which different layers extruded from the outlet are laminated is divided into multiple stages, and is repeatedly joined, joined, laminated, and thinned, and the thin film layer 42,
  • FIG. 17 is a partially cutaway perspective view showing another manufacturing method.
  • a cylindrical laminar flow 51 in which different types of resin layers 52 and 53 are laminated is divided into divided surfaces.
  • FIG. 18 shows still another manufacturing method, and (a), (b), and (c) are cross-sectional views corresponding to A--A, C--C, and B--B in FIG. 15, respectively.
  • this manufacturing method as shown in (a), a cylindrical laminar flow 51 composed of different types of resin layers 52 and 53 is divided into 16 by a dividing surface 55a, and 16 divided laminar flows are formed. 5 1a, 5 1b
  • the thicknesses of a, 57b ... are thicker as they are inside, but they are all the same in Fig. 18.
  • the first, fifth, ninth, and thirteenth divided laminar flows 51 a, 51 e, 51 i, and 51 ⁇ are located outside and thinned. , Joined at junction 56a to form a first junction laminar flow 57a, 2, 6, 10, 0, 1
  • the fourth divided laminar flow 5 1 b, 51 f, 51 j, 5 lp is located inside and thinned and bonded to form a second bonded laminar flow 57 b, 3, 7 , 1 1,
  • the multilayer laminar flow 61 thus obtained is further divided, thinned, joined, and integrated into a single layer to obtain a multilayer tubular body in which thin film layers are integrated.
  • the diameter and the thickness of the cylindrical laminar flow 51 can be arbitrarily selected according to the intended multilayer cylindrical body 41. 10 to: L 00 Omm, thickness 1 to 100 mm. Although the number of divisions of one laminar flow is shown as 2 to 16, an arbitrary number within the above range can be set according to the size of the cylindrical body to be manufactured. The number of times the process is repeated can be arbitrarily selected within the above range according to the intended tubular body.
  • each step is repeated 1 to 4 times to obtain a laminated body of 8 to 64 layers, and by repeating n times, a 2 ⁇ 2n + 1 laminated body is obtained.
  • a laminate of 16 to 128 layers is obtained by repeating 1 to 4 times, and 4 X 2 n + 1 A laminate of the layers is obtained.
  • the multilayer tubular body obtained as described above exhibits characteristics due to the composite of the respective layers, and furthermore, is limited to a region in which the lack of the characteristic due to the joint is small, thereby obtaining a multilayer tubular body having the characteristics due to the composite as a whole.
  • a cylindrical body having both properties of rigidity and gas barrier properties is obtained. If the layers are not continuous at the joint 44, the above characteristics are lacking at the joint 44, but since the joints 44 are dispersed so as not to cover the entire length in the thickness direction, the entire cylinder The composite exhibits the above-described composite properties.
  • a multilayer tubular body having arbitrary composite characteristics can be obtained by combining arbitrary characteristics as the thin film layers 42 and 43.
  • arbitrary characteristics can be obtained by arbitrarily selecting and combining the types and numbers of the thin film layers. For example, by combining three or more layers of different kinds of resins, it is possible to obtain unique characteristics in which these are combined.
  • a cylindrical laminar flow is used in the first stage, and this is divided and joined, there is an advantage that the same mold can be used in each stage.
  • the shape may not be a shape, and may be, for example, a flat shape. If this is divided and joined, a multiple cylindrical body can be formed. It is also possible to extrude the first laminar flow in a divided state.
  • a plurality of molding dies are connected in series, and each process is repeated in the molding dies.
  • molding can be performed without performing molding, it is also possible to conduct some steps outside the molding die and perform it in air.
  • the multilayer cylindrical body described with reference to FIGS. 14 to 18 has a structure in which at least two types of thin film layers are laminated and integrated to form a cylindrical body, and each of the thin film layers has a joint in the longitudinal direction, and The joints are arranged so as not to coincide with the joints of the different layers over the entire length of the cylindrical body in the thickness direction. For this reason, the part lacking the characteristics due to the joining portion can be limited to a small region, whereby the characteristics of the composite of each layer can be exhibited over the entire region of the cylindrical body.
  • the thin film layers are laminated in multiple layers, they have strength characteristics different from those of co-extruded products, and cracks and the like stop on the way, and extend to all layers.
  • the method for manufacturing a multilayer cylindrical body described with reference to FIGS. 14 to 18 includes a step of forming a laminar flow in which at least two types of layers are laminated, and a step of dividing the laminar flow in a longitudinal direction crossing a lamination interface. Forming a tubular body by joining a part of the divided laminar flow so as to form a joint in the longitudinal direction, and forming another part of the divided laminar flow.
  • the apparatus for manufacturing a multilayer cylindrical body described with reference to FIGS. 14 to 18 includes a laminar flow in which different types of layers are stacked and a laminar flow that divides the laminar flow in a longitudinal direction intersecting a lamination interface.
  • a cylindrical body by joining a part of the divided laminar flow and a part of the divided laminar flow so as to form a joint in the longitudinal direction, and joining the other part of the divided laminar flow as described above.
  • the cylindrical body is laminated and integrated Since a mold having a portion for forming a multilayer laminate is used, the multilayer cylindrical body can be easily manufactured simply by connecting molds of the same shape and simply passing a high molecular weight polymer or the like.
  • a laminar flow 1 is a flat laminar flow in which a first resin layer 2 mainly composed of the cyclic olefin resin and a second resin layer 3 mainly composed of a olefin copolymer are melted. They are stacked in a state and move in the direction of arrow X.
  • the laminar flow 1 is continuously formed into a film, a sheet, or a block, in a heated state, preferably in a molten state in the longitudinal direction, by coextrusion molding or coinjection molding.
  • the thickness of the laminar flow 1 is usually about 100 ⁇ to about 5 Omm, and the thickness of each layer is usually about 50 ⁇ to about 2 Omm.
  • the laminar flow 1 is divided into four divided laminar flows 1a, lb, lc, and Id by dividing surfaces 8a, 8b, and 8c orthogonal to the lamination interface 4 between the first layer 2 and the second layer 3. Divided.
  • the divided laminar flows l a, l b, l c and 1 d are respectively twisted by 90 ° in the same direction.
  • the twisted divided laminar flows 1a, 1b, 1c, Id are preferably kept parallel to one another.
  • the twisted divided laminar flows 1a, 1b, lc, and Id are laminated and integrated to form a laminated laminar flow 7 composed of 8 layers of 2 3 2Z3Z2Z33.
  • each of the divided laminar flows la, lb, lc, and 1d may be laminated and integrated at once, or may be laminated and integrated in multiple stages, for example, two stages.
  • the laminar flow 7 formed in this way is sent to the next division step in order to repeat each step. At this time, it is preferable that the laminar flow 7 is made thinner to increase the width. This thinning and widening can be performed, for example, by moving the laminated laminar flow 7 along a tapered flow path ⁇ ⁇ ⁇ having a smaller thickness and a wider width in the traveling direction. Laminar flow 7 It can be performed by rolling with a roll. When the laminated laminar flow 7 is sent to the dividing step, as shown in FIG. 2, the laminated laminar flow 7 preferably returns the twist to the original angle. In this way, the continuously obtained laminar flow 7 can be moved to the next division step on the portal.
  • the first layer 2 and the second layer 3 are further thinned and multilayered, and a multilayer laminate in which thin film layers are laminated is obtained.
  • a multilayer laminate consisting of 32 layers by repeating each step once, 128 layers by repeating twice, 2 048 layers by repeating 4 times, and 2 X 4 n + 1 layers by repeating n times Is obtained.
  • the number of repetitions can be arbitrarily selected.
  • the thickness of each layer can also be set to an arbitrary value by selecting the thickness of the first layer 2 and the second layer 3 of the first laminar flow 1 or the number of repetitions. For example, it is possible to obtain a multilayer laminate in which each layer is an ultra-thin film layer having a thickness of about 0.09 to 0.45 nm.
  • Such a multilayer laminate can be subjected to secondary processing such as stretching or rolling as it is, or if necessary, to further reduce the thickness of each layer.
  • the thickness is about 1 ⁇ !
  • a multi-layered film, sheet, or block laminate of about 5 to 5 Omm can be obtained.
  • a thickness of about 10 ⁇ ! A multi-layer sheet (film) of about 1 to about Omm and a block-like laminate of about 10 to 5 Omm in thickness can be obtained, which can be used for containers, packaging materials and other uses.
  • FIG. 1 shows an example in which the laminar flow has two layers, the first layer and the second layer, three or more layers may be used.
  • the number of divided laminar flows can be arbitrarily selected, for example, two. In this case, by repeating each step n times, a multilayer laminate of '2 X 2 n + 1 layers can be obtained.
  • the direction and angle of the torsion can be arbitrarily selected. For example, the divided laminar flow 1 a, 1 c is twisted by + 90 °, and the divided laminar flow 1 b,
  • 1 d may be twisted by one 90 °.
  • a laminar flow composed of five layers of Z2 is formed.
  • the torsion angle is usually 10 to 90 °. If the torsion angle is small, the interval between each of the divided laminar flows is too small, and it becomes difficult to secure a flow path for each of the divided laminar flows in the die. —If the torsional angle is large, the flow path spacing of each divided laminar flow can be sufficiently secured, but a long flow path is required when returning the twist to the original angle.
  • FIGS. 3 and 4 are schematic diagrams showing a particularly preferred embodiment of the method for producing a polyolefin-based multilayer laminate of the present invention
  • FIG. 3 is a schematic diagram of a heated multi-layer resin flow moving through a flow path in a molding die.
  • FIG. 4 is a schematic side view of FIG. In FIGS.
  • points 1 to 2 represent a step of forming a laminar flow 1 in which the first layer and the second layer are stacked, and points 2 to 4 represent a divided laminar flow 1 a, lb, lc, 1 d From point 4 to 5: torsion of the laminar flow la, lb, lc, Id, from point 7 to 7: lamination and integration of the twisted laminar flow la, lb, lc, 1 d The step of forming the laminar flow 7 is shown.
  • Laminar flow 1 expands in the width direction from point 1 to point ⁇ . At point 2, the thickness is thinner and wider than point 1.
  • the laminar flow 1 is divided into two at point ⁇ ⁇ ⁇ while expanding in the width direction between points 2 and 4, and then again at point 3, and finally the divided laminar flow 1 a, lb, lc, I Divided into four by d. Since the laminar flow 1 is evenly distributed by such sequential division, the resin flow is prevented from being biased, and the molding can be performed stably.
  • the laminar flows la, lb, lc and id are twisted by 90 °, but the distance between points 4 and ⁇ of each laminar flow 1 a, lb, 1 c and 1 d is the same. Molding without variation between la, lb, lc and 1d can be performed.
  • the laminar flow la, lb, lc, 1 d is laminated and integrated, but point 6 After two laminar flows are once laminated and integrated, the final lamination and integration are further performed at point 7.
  • a laminated laminar flow 7 in which the interlayer adhesion is further strengthened and the homogeneity is enhanced as compared with the case where the lamination and integration are performed one by one.
  • Such a laminar flow 7 can sufficiently exhibit mechanical strength and desired performances.
  • the resin flow path between points (1) and (2) has a smaller thickness and a wide taper in the traveling direction, and at point (2), a laminar laminar flow 7 that is thinner and wider than point (2) is obtained.
  • FIG. 19 is a cross-sectional view showing a PTP package using the polyolefin-based multilayer laminate obtained as described above.
  • a package 81 is a PTP package using a blister pack
  • 82 is a molded product made of the above multilayer laminate
  • 83 is a sealing material
  • 84 is a packaged object
  • 85 is a blister.
  • Reference numeral 86 denotes a flange portion
  • reference numeral 87 denotes an aluminum foil
  • reference numeral 88 denotes a heat-sealing resin layer.
  • the above-mentioned polyolefin-based multilayer laminate is softened by heating with infrared rays or the like, and is formed into a molded body 82 by vacuum molding or pressure forming so as to have a blister 85 and a flange portion 86, and is used as a packaging material. Then, the packaged object 84 is accommodated in a blister 85, and an aluminum foil 87 is laminated and heat-sealed with the heat-sealable resin layer 88 interposed therebetween to form a package 81.
  • Polyolefin-based multilayer laminates have excellent vacuum moldability and air pressure moldability, so blisters 85 can be easily formed and also have excellent heat sealability, and can be used as packaging materials for blister packs and PTPs. It is. With moderate flexibility and surface hardness, the packaged product 84 can be stably held, and there is no danger of damaging other items during handling in the packaged state or processing after opening, making handling and processing easy and safe. Done in Next, examples of the present invention will be described, but the present invention is not limited thereto.
  • first layer cyclic olefin resin layer
  • second layer ⁇ -olefin copolymer layer
  • the obtained multilayer laminate comprising 513 layers was formed into a sheet shape from a coat hanger type T-die.
  • the thickness of the obtained transparent sheet was about 270 ⁇ .
  • the initial elastic modulus, elongation at break, and moisture permeability of this sheet were measured. Table 1 shows the results.
  • Example 3 3 3. 3 7 4 0 2 54. 0 0. 2 6 0
  • Example 4 2 0. 0 3 6 0 4 9 0. 0 0. 4 84
  • Example 5 1 1. 0 1 9 0 6 3 0.0
  • the laminar flow in which at least two types of layers are laminated is divided in the longitudinal direction intersecting the lamination interface, and the obtained divided laminar flow is twisted.
  • the laminar flow Therefore, it is possible to easily manufacture a multilayer laminate in which different types of thin film layers are laminated.
  • a laminar flow in which at least two types of layers are laminated is bent so that the cross-sectional shape is corrugated. Since each piece is folded and laminated to form a laminated laminar flow, the same type of layers can be joined and integrated when laminating and integrating, so that the adhesion between the layers constituting the laminated body can be improved. And a multilayer laminate in which each layer is uniformly distributed can be manufactured.
  • the polyolefin-based multilayer laminate of the present invention is composed of a multilayer laminate of a first layer mainly composed of a specific cyclic olefin resin and a second layer mainly composed of an ⁇ -olefin copolymer, Excellent flexibility and surface hardness, excellent interlayer adhesion, moldability, moisture resistance, mechanical strength, chemical resistance, transparency, hand-cutting, heat sealing and dead-holding, and vacuum or air pressure molding It is easy to use and has good design. For this reason, it is suitable for use as a packaging material, especially as a prestar pack or a packaging material for ⁇ ⁇ ⁇ .
  • a polyolefin-based multilayer laminate of the present invention at least two layers of a first layer mainly composed of a specific cyclic olefin-based resin and a second layer mainly composed of a polyolefin-based copolymer are laminated.
  • the divided laminar flow is divided in the longitudinal direction that intersects the lamination interface, and the divided laminar flows are laminated and integrated to form a multilayer laminate.Therefore, it is possible to easily increase the lamination density and increase the adhesion.
  • the polyolefin-based multilayer laminate as described above can be efficiently produced.
  • the packaging material of the present invention is composed of the above-mentioned polyolefin-based multilayer laminate, it has a moderate flexibility and surface hardness so that the packaged product can be held safely, and handling in the packaged state and treatment after opening are easy and easy. It is safe, and because of its moldability and heat sealability, it is easy to manufacture and pack the package. Industrial applicability
  • a laminar flow in which different layers are laminated can be formed into a thin film and a multilayer by a simple operation, so that a different thin film layer composed of a high molecular weight polymer can be formed. It can be suitably used when producing a multi-layered body in which a large number of layers are integrated.
  • the second method for producing a multilayer laminate of the present invention it is possible to increase the adhesion between the layers constituting the laminate and efficiently produce a multilayer laminate in which the respective layers are uniformly dispersed. It can be suitably used when producing a multilayer laminate in which a large number of different types of thin film layers are laminated and integrated.
  • the polyolefin-based multilayer laminate of the present invention has appropriate flexibility and surface hardness, and has interlayer adhesion, moldability, moisture resistance, mechanical strength, chemical resistance, transparency, hand-cutting, and heat resistance. It is excellent in the formability and dead-hold property, is easy to form by vacuum or pressure, and has excellent design. Therefore, it can be suitably used as a packaging material, especially a blister pack or a packaging material for PTP.
  • the method for producing a polyolefin-based multilayer laminate of the present invention can easily increase the lamination density and increase the adhesion, so that it can be suitably used for producing the above-described polyolefin-based multilayer laminate.
  • the packaging material of the present invention has a moderate flexibility and surface hardness, so that the packaged material can be held safely, and can be easily and safely handled in a packaged state and treated after opening. Due to its properties, the production and packaging work of the package are easy, so that it can be suitably used as a packaging material for packaging drugs, foods, daily necessities, miscellaneous goods, etc. in blister pack or PTP form.

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Abstract

L'invention a trait à des procédés facilitant la fabrication de stratifiés multicouche comportant de nombreux films minces réunis les uns aux autres et constitués respectivement de différents types de polymères de poids moléculaire élevé. Dans le cadre de l'un de ces procédés, on fabrique un stratifié multicouche en répétant un processus qui consiste à couper un écoulement laminaire comprenant deux couches, au moins, laminées ensemble dans le sens de la longueur perpendiculairement au plan de laminage, à tordre ensuite chacune des coupes obtenues à partir de l'écoulement laminaire selon un axe longitudinal de rotation puis à laminer les coupes les unes avec les autres. Selon un autre procédé, on fabrique un stratifié multicouche en répétant un processus qui consiste à courber un écoulement laminaire comprenant deux couches, au moins, laminées ensemble de manière à lui donner une section semblable à une vague, à plier l'écoulement laminaire obtenu et à laminer cet écoulement ainsi plié. Les stratifiés produits de la sorte témoignent de propriétés uniques en leur genre du fait de la combinaison de diverses caractéristiques propres aux couches les constituant, ce qui permet de les utiliser dans différents champs d'application.
PCT/JP1996/002055 1995-07-24 1996-07-23 Procedes de fabrication de stratifies multicouche, stratifies multicouche polyolefiniques et leur application WO1997003803A1 (fr)

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JP18734995 1995-07-24
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JP32480495 1995-12-13
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WO2010096608A3 (fr) * 2009-02-21 2011-02-17 Dow Global Technologies Inc. Structures multicouches présentant des profils annulaires et procédés et appareils de fabrication correspondants
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JP2012518557A (ja) * 2009-02-21 2012-08-16 ダウ グローバル テクノロジーズ エルエルシー 環状外形を有する多層構造体並びにその製造方法及び装置
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RU2500540C2 (ru) * 2009-02-21 2013-12-10 ДАУ ГЛОБАЛ ТЕКНОЛОДЖИЗ ЭлЭлСи Многослойные структуры, имеющие кольцеобразные профили, и способы и устройство для их получения
TWI418458B (zh) * 2009-02-21 2013-12-11 Dow Global Technologies Llc 具有環狀構型之多層結構及其製造方法與裝置
CN102470599A (zh) * 2009-06-30 2012-05-23 3M创新有限公司 用于由多层挤出物制备多条带挤出物的挤出模头元件、挤出模头和方法
WO2011008396A1 (fr) * 2009-06-30 2011-01-20 3M Innovative Properties Company Elément de filière d’extrusion, filière d’extrusion et procédé de réalisation d’extrudat à bandes multiples à partir d’un extrudat multicouche
JP2015508347A (ja) * 2011-12-29 2015-03-19 ダウ グローバル テクノロジーズ エルエルシー 改良された水蒸気遮断層を有する共押出多層環状オレフィンポリマーフィルムまたはシート
CN105189080A (zh) * 2013-03-15 2015-12-23 阿尔巴尼国际公司 包括挤出网状物的衬垫及其制造方法
CN105189080B (zh) * 2013-03-15 2017-07-28 阿尔巴尼国际公司 包括挤出网状物的衬垫及其制造方法
JP2015171772A (ja) * 2014-03-11 2015-10-01 住友ベークライト株式会社 多層フィルム、成形フィルム、包材および包装体
WO2020262675A1 (fr) * 2019-06-27 2020-12-30 住友ベークライト株式会社 Film multicouche et emballage
JP2021169216A (ja) * 2019-06-27 2021-10-28 住友ベークライト株式会社 多層フィルム及び包装体
JPWO2020262675A1 (ja) * 2019-06-27 2021-10-28 住友ベークライト株式会社 多層フィルム及び包装体
EP3991966A4 (fr) * 2019-06-27 2023-07-19 Sumitomo Bakelite Co.Ltd. Film multicouche et emballage

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