JPH044149B2 - - Google Patents

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Publication number
JPH044149B2
JPH044149B2 JP62503724A JP50372487A JPH044149B2 JP H044149 B2 JPH044149 B2 JP H044149B2 JP 62503724 A JP62503724 A JP 62503724A JP 50372487 A JP50372487 A JP 50372487A JP H044149 B2 JPH044149 B2 JP H044149B2
Authority
JP
Japan
Prior art keywords
layer
resin
laminated film
resin layer
cylindrical
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
JP62503724A
Other languages
English (en)
Other versions
JPS64500180A (ja
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Family has litigation
First worldwide family litigation filed litigation Critical https://patents.darts-ip.com/?family=15289800&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=JPH044149(B2) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Application filed filed Critical
Publication of JPS64500180A publication Critical patent/JPS64500180A/ja
Publication of JPH044149B2 publication Critical patent/JPH044149B2/ja
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • 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
    • B32B1/00—Layered products having a non-planar shape
    • B32B1/08—Tubular products
    • 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
    • B29C35/00—Heating, cooling or curing, e.g. crosslinking or vulcanising; Apparatus therefor
    • B29C35/02—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould
    • B29C35/08—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould by wave energy or particle radiation
    • 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
    • B29C48/09—Articles with cross-sections having partially or fully enclosed cavities, e.g. pipes or channels
    • B29C48/10—Articles with cross-sections having partially or fully enclosed cavities, e.g. pipes or channels flexible, e.g. blown foils
    • 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
    • B29C48/30—Extrusion nozzles or dies
    • 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
    • B29C48/30—Extrusion nozzles or dies
    • B29C48/32—Extrusion nozzles or dies with annular openings, e.g. for forming tubular articles
    • B29C48/335—Multiple annular extrusion nozzles in coaxial arrangement, e.g. for making multi-layered tubular articles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C55/00—Shaping by stretching, e.g. drawing through a die; Apparatus therefor
    • B29C55/02—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets
    • B29C55/023—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets using multilayered plates or sheets
    • 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
    • B29C55/00—Shaping by stretching, e.g. drawing through a die; Apparatus therefor
    • B29C55/28—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of blown tubular films, e.g. by inflation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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    • B29C61/00—Shaping by liberation of internal stresses; Making preforms having internal stresses; Apparatus therefor
    • B29C61/06—Making preforms having internal stresses, e.g. plastic memory
    • B29C61/0608—Making preforms having internal stresses, e.g. plastic memory characterised by the configuration or structure of the preforms
    • B29C61/0616—Making preforms having internal stresses, e.g. plastic memory characterised by the configuration or structure of the preforms layered or partially layered preforms, e.g. preforms with layers of adhesive or sealing compositions
    • 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
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • 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
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/304—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising vinyl halide (co)polymers, e.g. PVC, PVDC, PVF, PVDF
    • 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
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/306—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising vinyl acetate or vinyl alcohol (co)polymers
    • 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
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • 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
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
    • C08J3/245—Differential crosslinking of one polymer with one crosslinking type, e.g. surface crosslinking
    • 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
    • B29C35/00—Heating, cooling or curing, e.g. crosslinking or vulcanising; Apparatus therefor
    • B29C35/02—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould
    • B29C35/08—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould by wave energy or particle radiation
    • B29C35/0866—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould by wave energy or particle radiation using particle radiation
    • B29C2035/0877—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould by wave energy or particle radiation using particle radiation using electron radiation, e.g. beta-rays
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2027/00—Use of polyvinylhalogenides or derivatives thereof as moulding material
    • B29K2027/08—PVDC, i.e. polyvinylidene chloride
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2031/00—Use of polyvinylesters or derivatives thereof as moulding material
    • B29K2031/04—Polymers of vinyl acetate, e.g. PVAc, i.e. polyvinyl acetate
    • 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/724—Permeability to gases, adsorption
    • B32B2307/7242—Non-permeable
    • B32B2307/7244—Oxygen barrier
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    • B32B2307/70—Other properties
    • B32B2307/732—Dimensional properties
    • B32B2307/734—Dimensional stability
    • B32B2307/736—Shrinkable
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B32B2327/00—Polyvinylhalogenides
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
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    • B32B2327/06—PVC, i.e. polyvinylchloride
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    • B32B2329/00—Polyvinylalcohols, polyvinylethers, polyvinylaldehydes, polyvinylketones or polyvinylketals
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B32B2439/00—Containers; Receptacles
    • B32B2439/70—Food packaging
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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    • Y10S428/913—Material designed to be responsive to temperature, light, moisture
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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    • Y10T428/31913—Monoolefin polymer
    • Y10T428/31917—Next to polyene polymer
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31855—Of addition polymer from unsaturated monomers
    • Y10T428/31909—Next to second addition polymer from unsaturated monomers
    • Y10T428/31913—Monoolefin polymer
    • Y10T428/3192—Next to vinyl or vinylidene chloride polymer
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31855—Of addition polymer from unsaturated monomers
    • Y10T428/31909—Next to second addition polymer from unsaturated monomers
    • Y10T428/31928—Ester, halide or nitrile of addition polymer
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31855—Of addition polymer from unsaturated monomers
    • Y10T428/31935—Ester, halide or nitrile of addition polymer
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31855—Of addition polymer from unsaturated monomers
    • Y10T428/31938—Polymer of monoethylenically unsaturated hydrocarbon

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Description

請求の範囲 １ 塩化ビニリデン系樹脂層［］をガスバリア
ー性芯層とし、 上記［］層の一方の面には架橋ポリオレフイ
ン系樹脂層［］が、その外面部（［］層より
離れた側）のゲル分率［ｘ］が25〜70重量％、内
面部（［］層側）のゲル分率［ｙ］が40重量％
以下、［ｙ／ｘ］で示されるゲル分率勾配が0.6以
下の状態で配されており、且つ上記［］層と
［］層との接合部は電子線変性された状態の接
合部であり、且つ上記［］層の他方の面には、
接着性・収縮性樹脂層［］を介して実質的に未
架橋のシール性樹脂層［］が配されていること
を特徴とする熱収縮性筒状積層フイルム。
２ 架橋ポリオレフイン系樹脂層［］は平均ゲ
ル分率が20〜60重量％の範囲にあり、層厚み比率
はフイルム全体の25〜65％の範囲である請求の範
囲第１項に記載の積層フイルム。
３ 架橋ポリオレフイン系樹脂層［］は、電子
線による架橋効率が異なる２種の樹脂層でできて
いて架橋効率の悪い方の樹脂層を最表層とする二
層構造である請求の範囲第１項又は第２項のいず
れかに記載の積層フイルム。
４ 接着性・収縮性樹脂層［］は、酢酸ビニル
含量が13〜20重量％の範囲のエチレン−酢酸ビニ
ル共重合体樹脂である請求の範囲第１項から第３
項のいずれか１項に記載の積層フイルム。
５ シール性樹脂層［］は、密度が0.88〜0.93
で、結晶融点が110〜130℃のエチレン−α−オレ
フイン共重合体樹脂［Ａ樹脂］、又は上記Ａ樹脂
を60重量％以上とエチレン−α−オレフイン共重
合体エラストマー［Ｂ樹脂］を40重量％以下とで
なる混合樹脂、又は上記Ａ樹脂を40重量％以上、
上記Ｂ樹脂を５〜40重量％、且つエチレン−酢酸
ビニル共重合体樹脂［Ｃ樹脂］を55重量％以下を
含む［但し合計100％］ＡとＢとＣとの混合樹脂
のいずれかの樹脂層である請求の範囲第１項から
第４項のいずれか１項に記載の積層フイルム。
６ 架橋ポリオレフイン系樹脂層［］は、密度
が0.88〜0.93で、結晶融点が110〜130℃のエチレ
ン−α−オレフイン共重合体樹脂［Ａ樹脂］とエ
チレン−酢酸ビニル共重合体樹脂［Ｄ樹脂］との
いずれかでなり、その層構成は「Ａ樹脂］か［Ｄ
樹脂］かの単独の一層、又は［Ｄ樹脂］を組合わ
せた二層、又は最表層［Ａ樹脂］で中表層が［Ｄ
樹脂］の二層の組合わせである請求の範囲第１項
から第５項のいずれか１項に記載の積層フイル
ム。
７ 塩化ビニリデン系樹脂層［］は、コモノマ
ーの塩化ビニル成分が10〜25重量％の塩化ビニリ
デン−塩化ビニル共重合体樹脂である請求の範囲
第１項から第６項のいずれか１項に記載の積層フ
イルム。
８ 塩化ビニリデン系樹脂層［］は、コモノマ
ーのアクリル酸メチル成分が３〜15重量％の塩化
ビニリデン−アクリル酸メチル共重合体樹脂であ
る請求の範囲第１項から第６項のいずれか１項に
記載の積層フイルム。
９ 架橋ポリオレフイン系樹脂層［］とシール
性樹脂層［］との双方に、シール性樹脂層の樹
脂から選ばれた同一樹脂が配されている請求の範
囲第１項から第８項のいずれか１項に記載の積層
フイルム。
１０ 架橋ポリオレフイン系樹脂層［］の中表
層と接着性・収縮性樹脂層［］との双方に、エ
チレン−酢酸ビニル共重合体樹脂が配されている
請求の範囲第１項から第９項のいずれか１項に記
載の積層フイルム。
１１ 積層フイルムは全体で40〜80μであり、各
層の厚み構成は芯層［］の厚みが４〜15μ、シ
ール性樹脂層［］は4μ以上で全体厚みの40％
以下の比率の厚み、架橋ポリオレフイン系樹脂層
［］は全体厚みの25〜65％の比率の厚みで、そ
の余は接着性・収縮性樹脂層［］の厚みである
請求の範囲第１項から第１０項のいずれか１項に
記載の積層フイルム。
１２ 積層フイルムが、共押出積層であり且つシ
ームレスの筒状フイルムである請求の範囲第１項
から第１１項のいずれか１項に記載の積層フイル
ム。
１３ 積層フイルムの用途は内容物が脂肪性不規
則形状の食品である熱収縮性包装のものである請
求の範囲第１項から第１２項のいずれか１項に記
載の積層フイルム。
１４ ガスバリアー性芯層［］の一方の面にポ
リオレフイン系樹脂層［］を、［］層の他方
の面に接着性・収縮性樹脂層［］とシール性樹
脂層［］とを配した積層体を作成した後、その
積層物の［］層の表面側から電子線を照射し
［］層の外面部を［］層の［］層側内面部
より強い線量にて架橋変性させ、且つ［］層と
［］層の接合部も照射変性させ、且つ少なくと
も［］層は、照射変性されて無いところの状態
に照射処理をした積層体を形成し、後該積層体を
延伸してフイルムとする積層フイルムの製造方
法。
技術分野 本発明は、生肉、加工肉等の脂肪性不規則現状
の食品類を内容物とし、これを熱収縮包装して包
装体にする用途に利用する筒状積層フイルムの改
良技術に関する。
背景技術 塩化ビニリデン系樹脂（以下PVDCと略す）層
をガスバリアー層として、層構成が３〜５層、合
計肉厚みが40〜80ミクロンである熱収縮性筒状積
層フイルムは公知である。現在、市販されている
ものとしては、例えば、特公昭58−43024号公報
［米国特許第3741253号明細書］に記載の技術に基
づく（筒表面側）エチレン酢酸ビニル共重合樹脂
（以下EVAと略す）／PVDC／架橋EVA（筒内面
側）の３層積層筒状フイルム、特公昭60−40988
号公報［米国特許第4390587号明細書］に記載の
技術に基づく、（筒表面側）特定ポリオレフイン
混合樹脂／PVDC／特定ポリオレフイン混合樹脂
（筒内面側）の３〜５層の積層筒状フイルム、及
び特公昭55−2192号公報［米国特許第4161562号
明細書］の記載技術に基づく、（筒表面側）
EVA／PVDC／アイオノマー樹脂（筒内面側）
の４〜５層の積層筒状フイルムが代表的なもので
ある。これ等は、脂肪性不規則形状の食品類を内
容物にし、熱収縮させて内容物をタイトに包装す
る使い方の包装材として、各々の独自の利点、例
えば、透明感による優れた外観品位、内容物の鮮
度を損なわない低温熱収縮性、及び優れた取扱い
作業性等を各々のセールスポイントにして市場を
占めて来た。
しかしながらこれ等の包装分野でもロータリー
方式の高速包装法を採用する等包装の能率化が進
められるにつれ、上記包装材では設計品質上対処
しきれない新しい品質問題が生じて来ている。
則ち、本発明者等の究明によると、この高速包
装の適用性の可否を決める３つのポイントは、第
１に内容物を挿填した包装袋を減圧下において密
封シールする際、そのシール開始から完了するま
での時間を如何に短かくでき、且つそれでいて、
耐油性をもつた確実なシール部となし得るかとい
う点、及び第２に、高速化につれどうしても生じ
てくる包装体扱いの乱雑さに耐えるフイルムの耐
虐待性の確保という点、第３番に、内外層の耐油
性、ことに高温処理時の耐油性を高めるという点
にあると考えている。しかもこれ等の新しい要求
品質は、従来備わつている品質水準を損ねないで
満さねばならないところに難かしさがあるし、要
求品質の水準も高いのである。
具体例として、包装体の取扱いに際し、ピンホ
ール不良や破袋不良が生じないことの指標に当る
耐虐待性を例にとると、EVA／PVDC／架橋
EVA構成の市販のフイルムでは、当初の使われ
方では鋭い骨付き肉の直接包装に耐えるタフネス
さを、有すると評価されていたもの［特公昭58−
43024号公報の効果参照］が、新しい市場要求に
あつては、内容物は手で触れてみて鋭い突起部が
ない状態に骨抜きしたものに変更しても尚その取
扱上に生じるピンホール不良や、シール部パンク
不良の発生率から、タフネス性が不足していると
評価される程、市場の要求水準が高まつている。
しかしながら、これ等のフイルムの改質・改良
は、容易なことではないのである。その理由は、
芯層に当るPVDC層は、電子線の照射を受けると
変色・劣化するので、積層体にした状態での照射
架橋が難かしく、従つて、層間接合力に優れる共
押出積層の技術が利用できない。ましてこれを筒
状体の共押出積層にして、その外表面側が架橋さ
れた状態の積層フイルムとして完成させることは
極めて困難と云える。他方、使用樹脂種及びその
層構成を検討して無架橋のもので対処しようとす
る考え方もあるが、延伸製膜性と膜質自体の双方
を改善する架橋層の採用効果には及ぶべきもな
い。従つて、充分な架橋度（ゲル分率）のポリオ
レフイン系樹脂層を改質層として持つ積層フイル
ムは、例えばUSP3741253第１図に記載されてい
る様な方法、即ち、筒状EVA層を押出しこれを
照射架橋する、その上にPVDC層を、更にEVA
層を筒状に押出して、ダイ外接合し、このダイ外
積層体をインフレーシヨン延伸して筒状積層フイ
ルムにする製法を採用せざるを得ない。この方法
は、高度な技術力を要する不経済な製法で、しか
も得られるフイルムの架橋層は、筒状フイルムの
最内層になつてしまう問題点がある。
とは云え、特開昭62−23752号公報［優先権主
張米国特許出願第735082号（1985）］に示される
様に、共押出−延伸後の既成積層フイルムに全層
に渡つて電子線をかける方法は、架橋−延伸の効
果面を放棄し、架橋によるポリオレフイン系樹脂
層自体の改質効果とポリオレフイン系樹脂層と
PVDC層との接合性向上効果の双方のみを取出し
て活用しようとした発想は評価されるものの、電
子線照射によるPVDC層の劣化（バリアー性の低
下）はさけ難い上に、放棄してしまう架橋延伸効
果はあまりにも大きすぎるという問題点がある。
又特開昭51−143086号公報［米国特許第4044187
号明細書］、及び米国特許第3821182号明細書で代
表される全層照射の方法で得られた積層フイルム
は、そのPVDC層の劣化が著るしいことが確かめ
られている［第４、５表参照］。
発明の開示 こうした観点に立つて本発明の目的は、PVDC
層を芯層にした共押出による筒状積層フイルム
の、芯層の変色・劣化を最少限にして、筒外層側
が架橋改質されている積層フイルムを完成させ、
且つ、その層構成のあり方を最適なものにするこ
とによつて、前記の新しい品質要求を満し得る
［第11表に記載の評価項目の大部分が高水準に兼
備されている］筒状積層フイルムを提供すること
にある。
塩化ビニリデン系樹脂層［］をガスバリアー
性芯層とし、 上記［］層の一方の面には架橋ポリオレフイ
ン系樹脂層［］が、その外面部（［］層より
離れた側）のゲル分率［ｘ］が25〜70重量％、内
面部（［］層側）のゲル分率［ｙ］が40重量％
以下、［ｙ／ｘ］で示されるゲル分率勾配が0.6以
下の状態で配されており、且つ上記［］層と
［］層との接合部は電子線変性された状態の接
合部であり、且つ上記［］層の他方の面には、
接着性・収縮性樹脂層［］を介して実質的に未
架橋のシール性樹脂層［］が配されていること
を特徴とする熱収縮性筒状積層フイルムを提供す
ることにある。
【図面の簡単な説明】
第１，２，３Ａ，３Ｂ、及び４図は共に、電子
線照射量に係る実験結果図、第５図は本発明のフ
イルムの製造工程例を示す概念図、第６，８，９
図は各々電子線照射の効果に係る実験結果図、第
７図は本発明のフイルムのシール性樹脂層の成分
を示す解析図である。
発明を実施するための最良の形態 以下本発明の内容を図・表等に基づいて詳述す
る。殊に本発明は新規な積層フイルムである関係
で、その新規さの生じる根源の理解を早める意味
で、本発明の積層フイルムの製法面から先ず説明
する。
本発明の積層フイルムの製法は端的には○…廼Σ
JP62503724A 1986-06-19 1987-06-18 Expired - Lifetime JPH044149B2 (ja)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP14134586 1986-06-19
PCT/JP1987/000401 WO1987007880A1 (en) 1986-06-19 1987-06-18 Heat shrinkable cylindrical laminated film

Publications (2)

Publication Number Publication Date
JPS64500180A JPS64500180A (ja) 1989-01-26
JPH044149B2 true JPH044149B2 (ja) 1992-01-27

Family

ID=15289800

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Country Link
US (2) US4863768A (ja)
EP (1) EP0273059B1 (ja)
JP (1) JPH044149B2 (ja)
CA (1) CA1333269C (ja)
DE (1) DE3772946D1 (ja)
WO (1) WO1987007880A1 (ja)
ZA (1) ZA874452B (ja)

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JPS64500180A (ja) 1989-01-26
DE3772946D1 (de) 1991-10-17
AU7547887A (en) 1988-01-12
US4985188A (en) 1991-01-15
EP0273059A1 (en) 1988-07-06
ZA874452B (en) 1988-02-24
WO1987007880A1 (en) 1987-12-30
AU595051B2 (en) 1990-03-22
CA1333269C (en) 1994-11-29
US4863768A (en) 1989-09-05
EP0273059B1 (en) 1991-09-11

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