JPH0411788Y2 - - Google Patents

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Publication number
JPH0411788Y2
JPH0411788Y2 JP12092986U JP12092986U JPH0411788Y2 JP H0411788 Y2 JPH0411788 Y2 JP H0411788Y2 JP 12092986 U JP12092986 U JP 12092986U JP 12092986 U JP12092986 U JP 12092986U JP H0411788 Y2 JPH0411788 Y2 JP H0411788Y2
Authority
JP
Japan
Prior art keywords
resin
copolymer
styrene
layer
laminate
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
JP12092986U
Other languages
Japanese (ja)
Other versions
JPS6327319U (en
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed filed Critical
Priority to JP12092986U priority Critical patent/JPH0411788Y2/ja
Publication of JPS6327319U publication Critical patent/JPS6327319U/ja
Application granted granted Critical
Publication of JPH0411788Y2 publication Critical patent/JPH0411788Y2/ja
Expired legal-status Critical Current

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Description

【考案の詳細な説明】 〔産業上の利用分野〕 本考案は層間接着性に優れ、酸素および水分の
遮断性に優れた、かつ熱成形が容易な積層体に関
するものである。 〔従来技術〕 一般にいわゆる合成樹脂成形品特にフイルム、
瓶状容器等の成形品を積層させる為の研究は古く
より行なわれている。その目的とするところは、
各種の合成樹脂を積層することによつて、各々の
樹脂が単層の場合における夫々の長所を活用し、
かつ夫々の短所を補なわんとするにある。具体的
には、耐熱性、水蒸気やガス透過性、油や化学薬
品に対する抵抗性、耐衝撃性、機械的強度、腰の
強さ、ヒートシール性、経済性、の改良である。 従来、塩化ビニリデン系共重合体より成るフイ
ルムは気体遮断性、強度、透明性、等包装材料と
しての適性が優秀で特に食品包装用途に広く普及
している。しかし反面において高価であること低
温可撓性、ヒートシール性に乏しいこととまた内
容物が油性のものであるときはフイルム中の可塑
剤が抽出されて内容物を汚染する等の欠点を併有
する。 また、スチレン系樹脂シール及びフイルムは他
の樹脂シートフイルムに比べ、腰が強く、また成
形が容易であるという点で広く食品包装用途に使
されているが、水蒸気、酸素、等の気体遮断性に
乏しく、長期の食品保存用途では内容物の食品を
変質させてしまうという欠点をもつていた。 これらの欠点を補う為に特開昭49−9886号にみ
られるが如き、塩化ビニリデン系樹脂とスチレン
系樹脂とが接着性樹脂を介して積層されたフイル
ムが考案されたがこれらのシートの層間接着強度
が強くなく、成形時あるいは、成形品打ち抜き
時、開封時に層間に剥離が生じ包装容器として実
用的な積層体とはいえない、またスチレン系樹脂
を外層に用いる為、オレフイン系の外層樹脂を用
いるのに比べて、耐衝撃性に劣るという欠点をも
つていた。 このため層間接着力に優れ耐衝撃性の優れた積
層体が要望されていた。 〔考案の目的〕 本考案は、上述の問題について鋭意研究の結
果、外層のスチレン系樹脂層と芯層の塩化ビニリ
デン樹脂層を、それぞれと強い接着性を有する接
着性樹脂とで結びつけることで強い層間接着を得
られるという知見を得、更にこの知見に基づき
種々研究を進め本考案を完成するに至つたもので
ある。 〔考案の構成〕 すなわち、本考案は塩化ビニリデン系共重合体
層A、とスチレン系樹脂層B、とブタジエン−ス
チレン系共重合体層C、接着性樹脂層D、とがB
−C−D−A−D−C−Bの順に積層され、これ
を特徴とする積層体に関するものである。 以下、本考案を詳細に説明する。 本考案に使用する塩化ビニリデン系共重合体
は、塩化ビニリデンを主体として、これと塩化ビ
ニル、アルキルアクリレート、アクリル酸、アク
リロニトリルその他の共重合成分とを共重合した
二元又は多元の共重合物である。更に塩化ビニリ
デン共重合体に公知の添加剤例えばジブチルセバ
ケート、エポキシ大豆油等が含有されていてもよ
い。 各層に用いるスチレン系樹脂としては、GPス
チレン樹脂、Hiスチレン樹脂、スチレン−メタ
アクリル酸共重合体及びそれらを混合したものを
用いることができる。 本考案に用いる接着性樹脂C、とは,スチレン
系樹脂と強固な接着性を有する熱可塑性樹脂であ
り、ここにブタジエン−スチレン系共重合体を用
いる。 また接着性を損なわない範囲で、スチレン系樹
脂、エチレン酢酸ビニル共重合体を混合すること
ができる,また接着性樹脂Dとは、塩化ビニリデ
ン系共重合体との接着性のある熱可塑性樹脂であ
り、エチレン酢酸ビニル共重合体、エチレンアク
リル酸エステル共重合、もしくは変性オレフイン
樹脂およびブタジエン比率の高いブタジエン−ス
チレン系共重合体およびそれらの混合物を指す。 本考案の積層体の製造方法としては積層時の接
着強度が良好である共押出法が望ましいが、押出
ラミネート法によつても成膜する事ができる。 〔考案の効果〕 本考案は、従来の外層のスチレン系樹脂と芯層
の塩化ビニリデン系共重合体をひとつの接着性樹
脂層とで積層された積層体では接着力が弱く各層
の剥離が生じる問題があつたのに対して、塩化ビ
ニリデン系共重合体、スチレン系樹脂双方に対し
て、ブタジエン−スチレン共重合体樹脂層を作る
事により、安定した接着性を与える事ができる、
またブタジエン−スチレン系共重合体が一層加う
ることにより、成形品の耐衝撃性が向上した積層
体を得ることができる。 〔実施例〕 以下実施例によつて説明する。 第1表に示す、寸法、組成をもつた、実施例、
比較例の積層体を各樹脂を4台もしくは、5台の
押出機で別々に押出し、溶融された樹脂をT−ダ
イに導く共押出法により、第1図のように積層体
を作成した。 層間接着力は積層体を15mm巾に切断した試料を
島津オートグラフによる180°剥離試験を行つた。 また、実用試験として連続真空成形機により、
各積層体で成形品を作成し、中に水を充填し、ア
ルミニウム箔を蓋としてシールした後打ち抜き刃
により成形品一個ずつに打ち抜き、その外観を比
較した後、地上より1m高さより落下させ、その
損傷の程度を調べることにより、耐衝撃性を比較
した。 ○……容器は損傷を受けず、内容物は保護されて
いた。 ×……容器は損傷を受け、内容物の水が外部に流
出した。 実施例1〜4、比較例1〜2をみると、本考案
による積層体は、従来のものに比べて強固な接着
力を有しておることがわかつた。 【表】
[Detailed Description of the Invention] [Industrial Field of Application] The present invention relates to a laminate that has excellent interlayer adhesion, excellent oxygen and moisture barrier properties, and is easy to thermoform. [Prior art] Generally, so-called synthetic resin molded products, especially films,
Research into laminating molded products such as bottle-shaped containers has been conducted for a long time. Its purpose is to
By laminating various synthetic resins, we can take advantage of the advantages of each resin when it is a single layer.
At the same time, the aim is to compensate for the shortcomings of each. Specifically, improvements include heat resistance, water vapor and gas permeability, resistance to oil and chemicals, impact resistance, mechanical strength, stiffness, heat sealability, and economic efficiency. Conventionally, films made of vinylidene chloride copolymers have excellent suitability as packaging materials, such as gas barrier properties, strength, and transparency, and have been widely used, particularly in food packaging applications. However, on the other hand, it has the disadvantages of being expensive, having poor low-temperature flexibility and heat sealability, and if the content is oil-based, the plasticizer in the film may be extracted and contaminate the content. . In addition, styrene resin seals and films are widely used for food packaging because they are stronger and easier to mold than other resin sheet films, but they also have good barrier properties against gases such as water vapor and oxygen. However, when used for long-term food preservation, it has the disadvantage of deteriorating the quality of the food contained therein. In order to compensate for these drawbacks, a film was devised in which vinylidene chloride resin and styrene resin were laminated with an adhesive resin in between, as shown in Japanese Patent Application Laid-Open No. 49-9886. The adhesive strength is not strong, and the layers peel when molded, punched out, or opened, making the laminate unsuitable for use as a packaging container.Also, since styrene resin is used for the outer layer, olefin-based outer layer resin is used. It had the disadvantage of being inferior in impact resistance compared to using . For this reason, there has been a demand for a laminate with excellent interlayer adhesion and impact resistance. [Purpose of the invention] As a result of intensive research on the above-mentioned problems, the present invention has been developed by combining the outer styrene resin layer and the core vinylidene chloride resin layer with adhesive resin that has strong adhesive properties. We obtained the knowledge that interlayer adhesion could be obtained, and based on this knowledge, we proceeded with various studies and completed the present invention. [Structure of the invention] That is, the invention consists of a vinylidene chloride copolymer layer A, a styrene resin layer B, a butadiene-styrene copolymer layer C, an adhesive resin layer D, and a B layer.
The present invention relates to a laminate characterized by being laminated in the order of -C-D-A-D-C-B. The present invention will be explained in detail below. The vinylidene chloride copolymer used in the present invention is a binary or multi-component copolymer consisting mainly of vinylidene chloride and copolymerized with vinyl chloride, alkyl acrylate, acrylic acid, acrylonitrile, and other copolymer components. be. Furthermore, the vinylidene chloride copolymer may contain known additives such as dibutyl sebacate and epoxy soybean oil. As the styrene resin used for each layer, GP styrene resin, Hi styrene resin, styrene-methacrylic acid copolymer, and mixtures thereof can be used. The adhesive resin C used in the present invention is a thermoplastic resin that has strong adhesion to styrene resin, and a butadiene-styrene copolymer is used here. In addition, styrene resin and ethylene vinyl acetate copolymer can be mixed as long as the adhesiveness is not impaired.Adhesive resin D is a thermoplastic resin that has adhesive properties with vinylidene chloride copolymer. It refers to ethylene vinyl acetate copolymer, ethylene acrylate copolymer, or modified olefin resin, butadiene-styrene copolymer with a high butadiene ratio, and mixtures thereof. As a method for manufacturing the laminate of the present invention, a coextrusion method is preferable because it provides good adhesive strength during lamination, but the film can also be formed by an extrusion lamination method. [Effects of the invention] This invention has the advantage that a conventional laminate in which a styrene resin for the outer layer and a vinylidene chloride copolymer for the core layer are laminated with one adhesive resin layer has weak adhesion and causes peeling of each layer. However, by creating a butadiene-styrene copolymer resin layer for both vinylidene chloride copolymer and styrene resin, stable adhesion can be achieved.
Furthermore, by adding more butadiene-styrene copolymer, it is possible to obtain a laminate with improved impact resistance of the molded article. [Example] The following is an explanation based on an example. Examples having the dimensions and composition shown in Table 1,
A laminate as shown in FIG. 1 was prepared by a coextrusion method in which each resin was separately extruded using four or five extruders and the molten resin was introduced into a T-die for the laminate of the comparative example. The interlayer adhesion strength was determined by performing a 180° peel test using a Shimadzu Autograph on a 15 mm wide sample of the laminate. In addition, as a practical test, a continuous vacuum forming machine was used to
A molded product was created from each laminate, filled with water, sealed with aluminum foil as a lid, and then punched out one by one using a punching blade. After comparing the appearance, the molded product was dropped from a height of 1 m above the ground. The impact resistance was compared by examining the degree of damage. ○...The container was not damaged and the contents were protected. ×...The container was damaged and the water content leaked outside. Looking at Examples 1 to 4 and Comparative Examples 1 to 2, it was found that the laminates according to the present invention had stronger adhesive strength than the conventional ones. 【table】

【図面の簡単な説明】[Brief explanation of the drawing]

第1図は実施例1の積層体の断面図を示す。 FIG. 1 shows a cross-sectional view of the laminate of Example 1.

Claims (1)

【実用新案登録請求の範囲】[Scope of utility model registration request] 塩化ビニリデン系共重合体層A、スチレン系樹
脂層B、ブタジエン−スチレン系共重合体を主体
とする樹脂C、エチレン酢酸ビニル共重合体、エ
チレンアクリル酢酸エステル共重合体、変性オレ
フイン樹脂、ブタジエン−スチレン系共重合体も
しくは、それらの混合物からなる接着性樹脂層
D、とがB−C−D−A−D−C−Bの順に積層
されてなることを特徴とする積層体。
Vinylidene chloride copolymer layer A, styrene resin layer B, resin C mainly composed of butadiene-styrene copolymer, ethylene vinyl acetate copolymer, ethylene acrylic acetate copolymer, modified olefin resin, butadiene- A laminate characterized in that an adhesive resin layer D made of a styrene copolymer or a mixture thereof is laminated in the order of B-C-D-A-D-C-B.
JP12092986U 1986-08-08 1986-08-08 Expired JPH0411788Y2 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP12092986U JPH0411788Y2 (en) 1986-08-08 1986-08-08

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP12092986U JPH0411788Y2 (en) 1986-08-08 1986-08-08

Publications (2)

Publication Number Publication Date
JPS6327319U JPS6327319U (en) 1988-02-23
JPH0411788Y2 true JPH0411788Y2 (en) 1992-03-24

Family

ID=31009713

Family Applications (1)

Application Number Title Priority Date Filing Date
JP12092986U Expired JPH0411788Y2 (en) 1986-08-08 1986-08-08

Country Status (1)

Country Link
JP (1) JPH0411788Y2 (en)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH07112729B2 (en) * 1989-10-13 1995-12-06 出光興産株式会社 Container

Also Published As

Publication number Publication date
JPS6327319U (en) 1988-02-23

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