JPS6410183B2 - - Google Patents

Info

Publication number
JPS6410183B2
JPS6410183B2 JP58228116A JP22811683A JPS6410183B2 JP S6410183 B2 JPS6410183 B2 JP S6410183B2 JP 58228116 A JP58228116 A JP 58228116A JP 22811683 A JP22811683 A JP 22811683A JP S6410183 B2 JPS6410183 B2 JP S6410183B2
Authority
JP
Japan
Prior art keywords
layer
thickness
pvdc
less
melting point
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
Application number
JP58228116A
Other languages
English (en)
Other versions
JPS60120050A (ja
Inventor
Masaki Ooya
Yoshiharu Nishimoto
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Kureha Corp
Original Assignee
Kureha Corp
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=16871450&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=JPS6410183(B2) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Application filed by Kureha Corp filed Critical Kureha Corp
Priority to JP58228116A priority Critical patent/JPS60120050A/ja
Priority to US06/675,307 priority patent/US4732795A/en
Priority to EP84308302A priority patent/EP0149321B1/en
Priority to DE8484308302T priority patent/DE3472655D1/de
Publication of JPS60120050A publication Critical patent/JPS60120050A/ja
Priority to US07/130,528 priority patent/US4883693A/en
Publication of JPS6410183B2 publication Critical patent/JPS6410183B2/ja
Granted 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
    • 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
    • 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
    • B29C48/14—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the particular extruding conditions, e.g. in a modified atmosphere or by using vibration
    • B29C48/147—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the particular extruding conditions, e.g. in a modified atmosphere or by using vibration after the die nozzle
    • B29C48/1472—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the particular extruding conditions, e.g. in a modified atmosphere or by using vibration after the die nozzle at the die nozzle exit zone
    • 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
    • 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
    • B29C48/336—Multiple annular extrusion nozzles in coaxial arrangement, e.g. for making multi-layered tubular articles the components merging one by one down streams in the 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
    • 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
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    • 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
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    • 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
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    • B32B27/00—Layered products comprising a layer of synthetic resin
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    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
    • 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
    • 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
    • B29C2791/00—Shaping characteristics in general
    • B29C2791/004—Shaping under special conditions
    • B29C2791/007—Using fluid under pressure
    • 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
    • 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
    • B29C61/08—Making preforms having internal stresses, e.g. plastic memory by stretching tubes
    • 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
    • B29K2023/00—Use of polyalkenes or derivatives thereof as moulding material
    • 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
    • B29K2023/00—Use of polyalkenes or derivatives thereof as moulding material
    • B29K2023/04—Polymers of ethylene
    • B29K2023/08—Copolymers of ethylene
    • B29K2023/083—EVA, i.e. ethylene vinyl acetate copolymer
    • 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
    • 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
    • B29K2067/00—Use of polyesters or derivatives thereof, as moulding material
    • 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
    • B29K2077/00—Use of PA, i.e. polyamides, e.g. polyesteramides or derivatives thereof, as moulding material
    • 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
    • B32B38/0012—Mechanical treatment, e.g. roughening, deforming, stretching
    • B32B2038/0028—Stretching, elongating
    • 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
    • B32B2307/732—Dimensional properties
    • B32B2307/734—Dimensional stability
    • B32B2307/736—Shrinkable
    • 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
    • B32B2323/00—Polyalkenes
    • B32B2323/04—Polyethylene
    • B32B2323/046—LDPE, i.e. low density polyethylene
    • 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
    • Y10T428/13—Hollow or container type article [e.g., tube, vase, etc.]
    • Y10T428/1328—Shrinkable or shrunk [e.g., due to heat, solvent, volatile agent, restraint removal, etc.]
    • 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
    • Y10T428/13—Hollow or container type article [e.g., tube, vase, etc.]
    • Y10T428/1334—Nonself-supporting tubular film or bag [e.g., pouch, envelope, packet, etc.]
    • Y10T428/1341—Contains vapor or gas barrier, polymer derived from vinyl chloride or vinylidene chloride, or polymer containing a vinyl alcohol unit
    • 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
    • Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
    • Y10T428/24942—Structurally defined web or sheet [e.g., overall dimension, etc.] including components having same physical characteristic in differing degree
    • Y10T428/2495—Thickness [relative or absolute]
    • 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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    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
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    • Y10T428/24942—Structurally defined web or sheet [e.g., overall dimension, etc.] including components having same physical characteristic in differing degree
    • Y10T428/2495—Thickness [relative or absolute]
    • Y10T428/24959—Thickness [relative or absolute] of adhesive layers
    • 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
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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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    • Y10T428/31743—Next to addition polymer from unsaturated monomer[s]
    • Y10T428/31746—Polymer of monoethylenically unsaturated hydrocarbon
    • 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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    • Y10T428/31725—Of polyamide
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Description

【発明の詳細な説明】
本発明は、塩化ビニリデン系樹脂層をバリヤー
層とし、特定の厚みのポリアミドもしくは熱可塑
性ポリエステル層を少くとも一層含む適度な剛性
と良好な延伸性を有する熱収縮性筒状積層フイル
ムに関する。 形状が不揃いで、かつ不規則な食品の包装に
は、一般に熱収縮包装が用いられる。又これらの
包装には長時間の保存期間が求められる為、ガス
バリヤー性を必要とする。ガスバリヤー性のある
熱収縮性フイルムとしては周知の如く塩化ビニリ
デン系樹脂（PVDC）単独フイルムが用いられて
きた。しかしPVDC単独フイルムは低温時の機械
的強度が小なため、PVDCとポリオレフイン樹脂
の積層フイルムの開発が行なわれてきた。このよ
うなフイルムとして、例えば特開昭58−128821号
は特定のエチレン−酢酸ビニル共重合体（以後
EVAと略称する）からなる外層を有するPVDC
の複合フイルムであつて、これらの問題を解決し
たものではあつたが、フイルムの剛性がやゝ不足
するため食品包装時などの作業性は必らずしも満
足し得るものではなかつた。 本発明者等は更にこれらの点を改良すべく鋭意
検討を重ねた結果、ポリアミドもしくは熱可塑性
ポリエステルを層構成に加えることによりこの目
的を達成した。すなわち、本発明による筒状積層
フイルムはガスバリヤー層が6μ以上で全層の厚
みに対して30％以下のPVDC、両外層がオレフイ
ン系樹脂からなり、内層に全層の厚みに対して５
〜40％の厚みをもつ少くとも１層の結晶融点が
240℃以下を有するポリアミドもしくは熱可塑性
ポリエステルを有し、且つ夫々の層間に接着剤層
を有するものである。 本発明の熱収縮性筒状フイルムは、ガスバリヤ
ー層であるPVDC層が比較的厚いので製造時ダイ
流路内での滞留時間が短かく、熱分解が起り難い
という製造上の長所がある。更に外層のオレフイ
ン系樹脂とPVDC層の間に少くとも１層の特定厚
みのポリアミド層もしくは熱可塑性ポリエステル
層を含むので適当な剛性を有し、包装時に内容物
によりフイルムが伸びる等の作業性の困難性が克
服されしかも特開昭58−128821号に比し均一性の
よい延伸性を得ることができた。又、勿論、ガス
バリヤー性にも優れている。 本発明でバリヤー層として使用されるPVDCは
65〜95重量％の塩化ビニリデン及びこれと共重合
可能な不飽和単量体の少なくとも１種の５〜35重
量％からなる共重合体である。共重合可能な単量
体としては、例えば塩化ビニル、アクリロニトリ
ル、アクリル酸アルキルエステル（アルキル基炭
素数１〜18個）等が包含される。これらの内塩化
ビニリデン−塩化ビニル共重合体が一般的であ
る。このPVDC中には必要に応じて、少量の可塑
剤、安定剤を含有させてもよい。これらの添加剤
は当業者には公知であり、ジオクチル・アジペー
ト、エポキシ化大豆油等が代表的なものである。 PVDC層の厚みは6μ以上で全層の厚みに対して
30％以下であることが必要である。6μ未満では
ダイ内でポリアミドもしくは熱可塑性ポリエステ
ルと積層して押出す際ダイ流路内での滞留時間が
長くなつてPVDCが熱分解し共押出が困難にな
る。又、全層厚みの30％を越えると積層フイルム
の低温時の衝撃強度が低下する。 両外層を構成するオレフイン系樹脂としては例
えば高密度、中密度、低密度の各ポリエチレン、
アイオノマー、EVA、エチレンとアクリル酸エ
ステルの共重合体、エチレン−プロピレン共重合
体、ポリプロピレン、エチレンとα・オレフイン
の共重合体であるいわゆる低密度線状ポリエチレ
ン（LLDPE）ポリブテン等が単独もしくは混合
して用いられる。これらのオレフイン系樹脂のう
ち、すぐれた延伸性の点から好ましい態様は下記
の通りである。 (i) EVA（結晶融点80〜103℃のもの）を両外層
もしくは外層のうち１層に使用する。 (ii) 外層の１層が(i)のEVAであり、他の外層が
LLDPE（結晶融点110〜130℃のもの）である。 (iii) 外層の１層が(i)のEVAであり他の外層が上
述のLLDPE40重量％以下と(i)のEVA60重量％
以上からなる混合物である。 (iv) 両外層の各々が上述のLLDPE40重量％以下
と(i)のEVA60重量％以上からなる混合物であ
る。 このうち(i)、(ii)、(iii)が透明性耐衝撃性の点から
特に好ましい。 本願の特色はポリアミドもしくは熱可塑性ポリ
エステルを内層に少くとも１層使用することにあ
り、この適度な剛性と延伸性を有する層を備える
ことによりオレフイン系樹脂とPVDCからなる積
層フイルムの延伸性及びフイルム剛性が改良され
る。 ポリアミドとしては結晶融点が240℃以下好ま
しくは220℃を有するものが用いられ、例えばナ
イロン６−66（６、66の共重合体）、ナイロン610
（ポリヘキサメチレンセバカミド）、ナイロン612
（ポリヘキサメチレンラウレート）、ナイロン11
（11−アミノウンデカン酸縮合体）、ナイロン12
（ラウロラクタムの開環重合体）、ナイロン６（ポ
リカプラミド）等が使用される。熱可塑性ポリエ
ステルとしては同様に結晶融点が240℃以下好ま
しくは220℃もしくは融点の存在しないものであ
り、酸成分の芳香族２塩基酸の１種以上と脂肪族
２塩基酸の１種以上の残基からなり、グリコール
成分が脂肪族グリコール、脂環族グリコール又は
芳香族グリコールから選ばれたグリコール残基か
らなる共重合ポリエステルが望ましく使用され
る。これらのエステルとしては例えば商品名バイ
ロン、ペルプレン〔東洋紡(株)製品〕、ハイテル
〔グツドイヤー(株)製品〕、PET−Ｇ〔イーストマン
コダツク(株)製品〕等があげられる。 尚、本発明において結晶融点は差動走査型熱量
計（パーキンエルマー社製IB型）を用い、サン
プル８mg、昇温速度８℃／分で測定して得られた
融解曲線の最大値を示す温度である。ポリアミド
もしくは熱可塑性ポリエステルは結晶融点が240
℃を越えると共押出温度が高くなりPVDCと共押
出しが困難となる。又、ポリアミドもしくは熱可
塑性ポリエステル層が２層以上あるときは相互に
同様のものであつても又異つたものであつてもよ
い。この層は全層の厚みに対し５〜40％より好ま
しくは５〜20％の厚みをもつことが必要である。
２層以上ある時はその総計の厚みが５〜40％にな
る。層厚みが５％未満では延伸性、フイルム剛性
に寄与し得ないし、40％を越えるとPVDCとの共
押出が困難となる。PVDCとの共押出性からより
好ましくは20％以上が望ましい。 接着層を形成する材料としては酢酸ビニル含量
13〜28％のEVA、アクリル酸エステル含量13〜
28％のエチレン−アクリル酸エステル樹脂を含有
するEVA、エチレンアクリル酸エステル樹脂の
不飽和カルボン酸変性物、もしくは該酸変性物の
金属変性物等が好ましく使用される。更に好まし
くは該エチレン−アクリル酸エステル樹脂の不飽
和カルボン酸変性物もしくは該変性物の金属変性
物である。これらの接着層はPVDC層、オレフイ
ン系樹脂層、ポリアミドもしくは熱可塑性ポリエ
ステル層のそれぞれの層間に設けられる。 接着層の厚みは0.5〜3μ、全層の厚みは20〜
120μであることが好ましい。 本発明の筒状積層フイルムは積層数に応じた押
出機を用いて環状ダイスを使用して筒状に押出さ
れる。本発明で使用される環状ダイスの１例とし
て第１図に全層の会合部分を示す模式図を示す。
第１図で７は複合流であり、例えば１はオレフイ
ン系樹脂、２はPVDC、４はポリアミドもしくは
熱可塑性ポリエステル、６はオレフイン系樹脂、
８は接着性樹脂の各樹脂の流路を示す。第１図の
ようにポリアミドもしくは熱可塑性ポリエステル
の流路の両側に断熱空間３，５を設けることが好
ましく、この断熱空間を設けることによりポリア
ミド、熱可塑性ポリエステルが高温に押出されて
もPVDC層などに直接温度が伝達されることを防
ぐことができ、PVDC層など比較的熱分解し易い
樹脂と共押出することが可能となる。平板状（Ｔ
−ダイ）フイルムでは、このようなポリアミド層
もしくは熱可塑性ポリエステル層と共押出すると
両端部分でPVDCが分解し易いので適当でない。
積層順はオレフイン系樹脂が両外層にある限り任
意であるが、筒状の最外層から最内層へオレフイ
ン系樹脂、接着剤、PVDC、接着剤、ポリアミド
もしくは熱可塑性ポリエステル、接着剤、オレフ
イン系樹脂の順であることが熱分解せず連続運転
できる点で望ましい。 このようにして押出された筒状の積層物は一般
常法に従い２軸延伸インフレーシヨン法により
各々延伸され所望の熱収縮フイルムが得られる。 本発明で得られた熱収縮性積層フイルムはガス
バリヤー性及び適度な剛性をもつため、食品の包
装に特に好適に使用される。以下実施例につき説
明するが、本発明は本発明特許請求の範囲内であ
る限り本実施例により限定されるものではない。 実施例 第１表記載のPVDC、接着剤樹脂、ポリアミ
ド、熱可塑性ポリエステル、オレフイン系樹脂を
複数の押出機で別々に押出し、溶融された材料を
共押出し、実施例１〜５は第１図にあるような断
熱空間を有する環状ダイス（但し比較例１〜３は
第１図のような断熱空間のない通常の環状ダイ
ス）に流入しここで積層物とする。該ダイスから
流出した積層物の筒状体は15〜25℃の冷却槽で冷
却された扁平幅120mm、厚さ540μの筒状とする。
冷却槽中の筒状体の中には、内面同志密着防止の
ため、大豆油を封入してある。次に第３表に示さ
れた延伸温度となる様に、調節された熱水槽中
を、前記筒状体を20ｍ／分の速度で送りながら、
約12秒加熱し、20ｍ／分の回転速度の第１ニツプ
ローラーを通過させる。筒状体は常温で冷却され
ながら、60ｍ／分で回転する第２のニツプローラ
ーを通過する迄に、長手方向に３倍延伸されなが
ら、筒状体内に送られる空気により、筒状体の直
径に対し、３倍に膨張され、横方向に延伸され
た。得られた２軸延伸フイルムの折り径は約350
mm、厚さ約60μであつた。 第１表に実施例、比較例で使用した重合体の物
性、第２表にフイルムの物性試験方法、第３表に
積層フイルムの層構成及びフイルムの物性試験結
果を示す。
【表】
【表】
【表】 フイルム剛性 ○；包装時に内容物によりフイルムが
伸びるなどの作業性不良が生じ難い。
△；作業性不良となる場合もある
×；作業性不良となり易い
共押出性 ○；共押出が連続10時間以上可能であつた
。
△；共押出の連続時間が10時間未満で
あつた。
×；共押出が連続１時間以内しかでき
なかつた。
第３表の実施例１〜５から明らかなように本発
明の熱収縮性フイルムは延伸性にすぐれ、共押出
性もよいので製造が容易であり、しかも得られた
フイルムは適度なフイルム剛性を有するため包装
時の作業性が優れている。比較例１は共押出性は
よいがポリアミドもしくは熱可塑性ポリエステル
を含まないため、フイルム剛性が劣り作業性が不
良となる。又比較例２はポリアミドを内層に有し
ているもののPVDC層があまりに薄いため共押出
時にPVDCの分解を生じ積層フイルムを得ること
ができない。更に比較例３は熱可塑性ポリエステ
ル層が全層の厚みに対し45％と厚いため共押出性
が劣りPVDCが分解気味となり延伸性も不良で良
好な積層フイルムを得ることができない。
【図面の簡単な説明】
第１図は環状ダイスの模式図で全層の会合部分
を示した説明図である。 １，６……オレフイン樹脂流路、２……PVDC
流路、４……ポリアミド又は熱可塑性ポリエステ
ル流路、７……複合流、３，５……断熱空間。

Claims (1)

  1. 【特許請求の範囲】 １ ガスバリヤー層が6μ以上で全層の厚みに対
    して30％以下の塩化ビニリデン系樹脂、両外層が
    オレフイン系樹脂からなり、内層に全層の厚みに
    対して５〜40％の厚みをもつ少くとも１層の結晶
    融点が240℃以下を有するポリアミドもしくは熱
    可塑性ポリエステルを有し、且つ夫々の層間に接
    着剤層をもつことからなる熱収縮性筒状積層フイ
    ルム。 ２ 外層の少くとも１層が、80〜103℃の結晶融
    点を有するエチレン−酢酸ビニル共重合体からな
    る特許請求の範囲第１項記載の熱収縮性筒状積層
    フイルム。 ３ 外層の１層が、結晶融点110〜130℃を有する
    線状低密度ポリエチレン又は該線状低密度ポリエ
    チレン40重量％以下と80〜103℃の結晶融点を有
    するエチレン−酢酸ビニル共重合体60重量％以上
    とからなる混合物である特許請求の範囲第２項記
    載の熱収縮性筒状積層フイルム。
JP58228116A 1983-12-02 1983-12-02 熱収縮性筒状積層フイルム Granted JPS60120050A (ja)

Priority Applications (5)

Application Number Priority Date Filing Date Title
JP58228116A JPS60120050A (ja) 1983-12-02 1983-12-02 熱収縮性筒状積層フイルム
US06/675,307 US4732795A (en) 1983-12-02 1984-11-27 Heat-shrinkable laminate tubular film
EP84308302A EP0149321B1 (en) 1983-12-02 1984-11-29 Heat-shrinkable laminate tubular film and process for producing it
DE8484308302T DE3472655D1 (en) 1983-12-02 1984-11-29 Heat-shrinkable laminate tubular film and process for producing it
US07/130,528 US4883693A (en) 1983-12-02 1987-12-09 Heat-shrinkable laminate tubular film

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP58228116A JPS60120050A (ja) 1983-12-02 1983-12-02 熱収縮性筒状積層フイルム

Publications (2)

Publication Number Publication Date
JPS60120050A JPS60120050A (ja) 1985-06-27
JPS6410183B2 true JPS6410183B2 (ja) 1989-02-21

Family

ID=16871450

Family Applications (1)

Application Number Title Priority Date Filing Date
JP58228116A Granted JPS60120050A (ja) 1983-12-02 1983-12-02 熱収縮性筒状積層フイルム

Country Status (4)

Country Link
US (2) US4732795A (ja)
EP (1) EP0149321B1 (ja)
JP (1) JPS60120050A (ja)
DE (1) DE3472655D1 (ja)

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US4883693A (en) 1989-11-28
US4732795A (en) 1988-03-22
EP0149321B1 (en) 1988-07-13
JPS60120050A (ja) 1985-06-27
DE3472655D1 (en) 1988-08-18
EP0149321A1 (en) 1985-07-24

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