JPS602984B2 - Manufacturing method for resin laminates - Google Patents
Manufacturing method for resin laminatesInfo
- Publication number
- JPS602984B2 JPS602984B2 JP52112120A JP11212077A JPS602984B2 JP S602984 B2 JPS602984 B2 JP S602984B2 JP 52112120 A JP52112120 A JP 52112120A JP 11212077 A JP11212077 A JP 11212077A JP S602984 B2 JPS602984 B2 JP S602984B2
- Authority
- JP
- Japan
- Prior art keywords
- resin
- eva
- weight
- acid
- ethylene
- 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
Links
Landscapes
- Containers Having Bodies Formed In One Piece (AREA)
- Laminated Bodies (AREA)
- Extrusion Moulding Of Plastics Or The Like (AREA)
Description
【発明の詳細な説明】
本発明は、塩化ビニリデソ樹脂、熱可塑性ポリエステル
樹脂、ポリアミド樹脂、又はエチレン・酢酸ビニル共重
合体の鹸化物より選ばれたガスバリャー性樹脂と剛性の
優れたポリェスチレン系樹脂を基体として用いた耐油性
、ガスバリャー性に優れかつ強度の高い積層物を製造す
る方法に関する。Detailed Description of the Invention The present invention uses a gas barrier resin selected from vinylideso chloride resin, thermoplastic polyester resin, polyamide resin, or saponified product of ethylene/vinyl acetate copolymer and polystyrene resin with excellent rigidity. This invention relates to a method for producing a laminate that is used as a substrate and has excellent oil resistance, gas barrier properties, and high strength.
従来、塩化ビニリデン樹脂、熱可塑性ポリエステル樹脂
、ポリアミド樹脂、エチレン・酢酸ビニル共重合体の鹸
化物(以下「鹸化EVA」と称す)は、ガスバリャー性
、耐油性、機械的強度等の点で著しく良好な性質を有す
るが、価格が著しく高く、また水の透過性が大きいため
食品業界、自動車業界等においては単一材料としては使
用しにくい欠点があった。Conventionally, saponified products of vinylidene chloride resin, thermoplastic polyester resin, polyamide resin, and ethylene/vinyl acetate copolymer (hereinafter referred to as "saponified EVA") have been extremely good in terms of gas barrier properties, oil resistance, mechanical strength, etc. However, it is extremely expensive and has high water permeability, making it difficult to use as a single material in the food industry, automobile industry, etc.
一方、耐衝撃性ポリスチレン、A斑樹脂等の剛性の高い
ポリスチレン系樹脂は、その低価格性に加え、良好な機
械的強度、真空成形性あるし、は押出成形性及び衛生性
等の見地から広い用途に用いられている。On the other hand, highly rigid polystyrene resins such as high-impact polystyrene and A-spot resin are not only inexpensive, but also have good mechanical strength, vacuum formability, extrusion moldability, and hygiene. It is used for a wide range of purposes.
しかしながら、かかる高剛性のポリスチレン系樹脂はガ
スバリャー性、耐油性が不良であるために、マヨネーズ
や醤油等の食品容器として使用した場合、食品の長期保
存が不可能であり、又、ガソリン容器として使用した場
合、ガソリンが大量に透失したり、容器が勝潤して変形
したりする欠点があった。ポリスチレン系樹脂のかかる
欠点を改善するために従来から種々の提案がなされてい
るが、製造工程が複雑になったり、コストが高くなった
.り、用途デザインが限定される等の制約を受けて満足
なる結果が得られていない。However, such highly rigid polystyrene resin has poor gas barrier properties and oil resistance, so when used as containers for foods such as mayonnaise and soy sauce, it is impossible to preserve food for a long time, and when used as containers for gasoline. When this happens, there are drawbacks such as a large amount of gasoline being lost and the container becoming wet and deformed. Various proposals have been made to improve the drawbacks of polystyrene resins, but these have complicated the manufacturing process and increased costs. Satisfactory results have not been obtained due to constraints such as limited application design.
この解決法の一つとしては、上述したポリスチレン系樹
脂の欠点を補うような性質を持つ熱可塑性ポリエステル
、ポリアミド、鹸化EVA等の樹脂と積層することが考
慮されるが、本来、ポリスチレン系樹脂はその化学的構
造から考えられるように無極性であり、上記3種の樹脂
との親和性は小さく、単に両樹脂を溶融圧着した場合簡
単に剥離してしまう欠点があった。One solution to this problem is to consider laminating it with resins such as thermoplastic polyester, polyamide, and saponified EVA, which have properties that compensate for the drawbacks of polystyrene resins, but originally polystyrene resins As expected from its chemical structure, it is non-polar and has a low affinity with the three resins mentioned above, which has the disadvantage that it easily peels off when both resins are simply melted and pressed together.
これら両樹脂層の間に接着層を設けるという提案もある
が、このためには接着剤塗布の工程を別に設けなければ
ならず、製造工程が複雑になる欠点があった。本発明の
目的は、ガスバリャー性、耐水性、低コストの長所を兼
ね備え、しかも両樹脂層が接着剤ないこ強固に結合され
ている積層物を製造する方法を提供することにある。Although there has been a proposal to provide an adhesive layer between these two resin layers, this requires a separate adhesive coating process, which has the disadvantage of complicating the manufacturing process. An object of the present invention is to provide a method for producing a laminate that has the advantages of gas barrier properties, water resistance, and low cost, and in which both resin layers are firmly bonded with an adhesive.
本発明は、上記の目的を達成せんとするものであって、
風 耐衝撃性ポリスチレン、A斑樹脂より選ばれたポリ
スチレン系樹脂‘B} エチレン−酢酸ビニル共重合体
の鹸化物、ポリァミド樹脂、塩化ビニリデン樹脂、熱可
塑性ポリエステル樹脂より選ばれたガスバリャ−性樹脂
に’不飽和カルボン酸またはその酸無水物の成分濃度が
0.001−10重量%である変性エチレン−酢酸ビニ
ル共重合体上記凶とtB〕の樹脂を{qの接着性樹脂を
介して溶融共押出することを特徴とする樹脂積層物の製
造法を提供するものである。The present invention aims to achieve the above object,
Wind: Polystyrene resin 'B' selected from impact-resistant polystyrene, mottled resin A, gas barrier resin selected from saponified ethylene-vinyl acetate copolymer, polyamide resin, vinylidene chloride resin, and thermoplastic polyester resin. 'Modified ethylene-vinyl acetate copolymer having a component concentration of unsaturated carboxylic acid or its acid anhydride of 0.001-10% by weight. The present invention provides a method for producing a resin laminate characterized by extrusion.
本発明に用いる凶の樹脂の耐衝撃性ポリスチレン(以下
「HIPS」という。The most important resin used in the present invention is high impact polystyrene (hereinafter referred to as "HIPS").
)、A茂樹脂は、広く業界に知られて、HIPSは例え
ば5〜2の重量%のブタジエンースチレンラバ−をスチ
レンモノマー90〜8の重量%に溶融させ、この溶液に
水および懸濁剤を配合し、塊状重合、溶液重合、懸濁重
合等の重合法で製造することにより得られる配合ポリス
チレン樹脂である。またABS樹脂はスチレン70〜8
の重量部に対しアクロニトリル30〜2の重量部を魂重
合または懸濁重合して得られる樹脂「SAN樹脂」95
〜70重量部に、ブタジェンーアクリロニトリルゴム(
ブタジェン80〜6の重量%、アクリロニトリル20〜
4の重量%)を5〜3の重量部配合したブレンドタイプ
のもの或いはポリブタジェン10〜4の重量部をスチレ
ン、アクリロニトリルの混合モノマ−10の重量部に溶
解させ、懸濁童合することにより得られる重合タイプの
ものが挙げられる。), Amo resin is widely known in the industry, and HIPS is, for example, by melting 5-2% by weight of butadiene-styrene rubber into 90-8% by weight of styrene monomer, adding water and a suspending agent to this solution. It is a blended polystyrene resin obtained by blending and manufacturing by a polymerization method such as bulk polymerization, solution polymerization, or suspension polymerization. Also, ABS resin is styrene 70-8
Resin "SAN resin" obtained by polymerization or suspension polymerization of 30 to 2 parts by weight of acronitrile to 95 parts by weight
~70 parts by weight of butadiene-acrylonitrile rubber (
Butadiene 80-6% by weight, acrylonitrile 20-6%
A blend type containing 5 to 3 parts by weight of 4% by weight), or a blend type obtained by dissolving 10 to 4 parts by weight of polybutadiene in 10 parts by weight of a mixed monomer of styrene and acrylonitrile and suspending the mixture. Examples include polymerization types.
本発明に使用される‘81の樹脂のエチレン−酢酸ビニ
ル共重合体の鹸化物(鹸化EVA)としては、その化学
組成を限定するものではないが、ガスバリャー性、耐油
性、水蒸気透過性から考えてエチレン含量が25〜50
モル%のエチレン−酢酸ビニル共重合体を、その鹸化度
が93%以上好ましくは96%以上となるように鹸化す
ることにより得られるものが好ましい。Although the chemical composition of the saponified ethylene-vinyl acetate copolymer (saponified EVA) used in the '81 resin is not limited, it is considered from the viewpoint of gas barrier properties, oil resistance, and water vapor permeability. and the ethylene content is 25-50
It is preferable to use one obtained by saponifying mol% of ethylene-vinyl acetate copolymer so that the degree of saponification becomes 93% or more, preferably 96% or more.
ポリアミド樹脂は、‘a}ジァミンとジカルボン酸の縮
合、{b)アミノ酸の縮合及び{cーラクタムの関環に
より得られる酸アミド結合を有する線状合成高分子で、
例えばナイロン6(ポリカプロアミド)、ナイロン61
6(ポリへキサメチレンアデイフアミド)、ナイロン6
・10(ポリへキサメチレンセバカミド)、ナイロン1
1(ポリウンデカミド)、ナイロン12等が使用できる
。Polyamide resin is a linear synthetic polymer having an acid amide bond obtained by condensation of 'a} diamine and dicarboxylic acid, {b) condensation of amino acid, and {condensation of c-lactam,
For example, nylon 6 (polycaproamide), nylon 61
6 (polyhexamethylene adefamide), nylon 6
・10 (polyhexamethylene sebamide), nylon 1
1 (polyundecamide), nylon 12, etc. can be used.
熱可塑性ポリエステル樹脂は飽和二塩基酸とグリコール
類の縮合により得られるものであり、例えばエチレング
リコールとテレフタル酸より得られるポリエチレンテレ
フタレート、フタル酸、ィンフタル酸、セパシン酸、ア
ジピン酸、アゼラィン酸、グルタル酸、コハク酸、シュ
ウ酸などの飽和二塩基酸を共重合体成分としたポリエチ
レンテレフタレート共重合体、およびジオール成分とし
て1・4ーシクロヘキサンジメタノール、ジエチレング
リコール、プロピレングリコールなどを英重合体成分と
したポリエチレンテレフタレート共重合体またはポリプ
チレンあるいはこれらのブレンド品である。Thermoplastic polyester resins are obtained by condensation of saturated dibasic acids and glycols, such as polyethylene terephthalate obtained from ethylene glycol and terephthalic acid, phthalic acid, phthalic acid, cepacic acid, adipic acid, azelaic acid, and glutaric acid. , polyethylene terephthalate copolymers containing saturated dibasic acids such as succinic acid and oxalic acid as copolymer components, and polyethylene containing 1,4-cyclohexanedimethanol, diethylene glycol, propylene glycol, etc. as diol components as polymer components. It is a terephthalate copolymer, polybutylene, or a blend thereof.
塩化ビニリデン樹脂としては、塩化ビニリデンモノマー
75〜85重量部を塩化ビニルモノマ−あるいはアクリ
ロニトルモノマ‐またはこれらの混合物25〜15重量
部を共重合(乳化重合、懸濁重合)させて得られたもの
である。The vinylidene chloride resin is obtained by copolymerizing 75 to 85 parts by weight of vinylidene chloride monomer with 25 to 15 parts by weight of vinyl chloride monomer or acrylonitrile monomer or a mixture thereof (emulsion polymerization, suspension polymerization). It is.
次に‘C}の接着剤樹脂としての変性EVAは、メルト
ィンデックス0.5〜20、酢酸ビニル含量5〜70重
量%以下のエチレン−酢酸ビニル共重合体(以下「EV
A」という)に不飽和カルポン酸またはその酸無水物を
グラフト重合させたものであり、不飽和カルボン酸又は
その無水物(以下「不飽和カルボン酸」で両者を示す。Next, the modified EVA used as the adhesive resin 'C} is an ethylene-vinyl acetate copolymer (hereinafter referred to as "EV") having a melt index of 0.5 to 20 and a vinyl acetate content of 5 to 70% by weight.
It is obtained by graft polymerizing an unsaturated carboxylic acid or its acid anhydride to an unsaturated carboxylic acid or its anhydride (hereinafter referred to as "unsaturated carboxylic acid").
)としては、アクリル酸、マレィン酸、フマール酸、イ
タコン酸、ハィミック酸又はそれらの無水物等があげら
れる。中でもアクリル酸又は無水マレィン酸が望ましい
。上記EVAの変性の手法としては、上記不飽和カルボ
ン酸又はその無水物をEVAにグラフト重合させること
である。) include acrylic acid, maleic acid, fumaric acid, itaconic acid, himic acid, or anhydrides thereof. Among these, acrylic acid or maleic anhydride is preferred. A method for modifying the EVA is to graft-polymerize the unsaturated carboxylic acid or its anhydride to EVA.
グラフト重合させる手法としては、EVA、グラフト用
不飽和カルボン酸および触媒を押出機中で溶融混線する
方法又は、適当な溶媒中に懸濁しているEVA樹脂粒子
にグラフト用不飽和カルボン酸および触媒を添加して加
熱櫨拝する方法等がある。変性EVA中に占める不飽和
カルボン酸の単位濃度は0.001〜1の重量%である
。Graft polymerization can be carried out by melting and mixing EVA, an unsaturated carboxylic acid for grafting, and a catalyst in an extruder, or by adding an unsaturated carboxylic acid for grafting and a catalyst to EVA resin particles suspended in an appropriate solvent. There are methods such as adding it and heating it. The unit concentration of unsaturated carboxylic acid in the modified EVA is from 0.001 to 1% by weight.
これら接着性樹脂は単独で或いは成形性を向上させる為
低密度ポリエチレン、EVA、エチレンーァクリル酸共
重合体、エチレンーメタクリル酸共重合体、エチレンー
メタクリレート共重合体、エチレンーアクリル酸エチル
共重合体又はそれらのNa、K、Ag、Cu、Ba、Z
n等の金属塩を1〜8の重量%含有させてもよい、また
、接着性を向上させる為、ポリアミド樹脂、ポリエステ
ル樹脂、鹸化EVAを0.3〜5重量%、或いはエチレ
ンープロピレンラバー、スチレンーブタジエンラバー、
ブタジエンラバ−、エチレンープロピレンーターポリマ
ー等のゴム質を3〜35重量%含有させてもよい。These adhesive resins may be used alone or in combination with low density polyethylene, EVA, ethylene-acrylic acid copolymer, ethylene-methacrylic acid copolymer, ethylene-methacrylate copolymer, ethylene-ethyl acrylate copolymer, etc. Polymers or their Na, K, Ag, Cu, Ba, Z
It may contain 1 to 8% by weight of metal salts such as n, etc. Also, to improve adhesiveness, 0.3 to 5% by weight of polyamide resin, polyester resin, saponified EVA, or ethylene-propylene rubber, Styrene-butadiene rubber,
A rubber material such as butadiene rubber or ethylene-propylene terpolymer may be contained in an amount of 3 to 35% by weight.
変性EVAの代りに、EVAと同種のポリプロピレン、
低密度ポリエチレン、高密度ポリエチレン等のポリオレ
フィンの不飽和カルボン酸グラフト化物は、ガスバリャ
ー性樹脂とは強固な接着力を得るが、ポリスチレン系樹
脂とは、得られる積層物、例えばバリソンあるいはシー
トを中空成形でブローする場合または真空成形、プレス
成形、圧空成形等で延展させる場合にポリスチレン系樹
脂と接着剤の層が剥離を生じるので実用的でない。Instead of modified EVA, polypropylene of the same type as EVA,
Unsaturated carboxylic acid grafted products of polyolefins such as low-density polyethylene and high-density polyethylene have strong adhesive strength with gas barrier resins, but with polystyrene resins, the resulting laminate, such as balisong or sheet, can be blow-molded. This is not practical because the polystyrene resin and adhesive layer will peel off when blowing or spreading using vacuum forming, press forming, pressure forming, etc.
本発明で変性EVAを介してポリスチレン系樹脂とポリ
エステル樹脂、ポリアミド樹脂、鹸化EVA、塩化ビニ
リデン樹脂を溶融共押出して積層する方法としては、ダ
ィ内ラミネート法、ダィ外ラミネート法があるが、ダィ
内ラミネートの方がより強固な接着を得ることができる
。以下、本発明を具体的に説明するため実施例を示す。In the present invention, methods for melt-coextruding and laminating polystyrene resin, polyester resin, polyamide resin, saponified EVA, and vinylidene chloride resin via modified EVA include an in-die lamination method and an outside-die lamination method. In-die laminate provides stronger adhesion. Examples are shown below to specifically explain the present invention.
実施例 1
三菱油化製エチレン−酢酸ビニル共重合体“ュカロン
ェバ 41H”(肌2、比重0.938、VA含量15
重量%)10の重量部に無水マレィン酸1重量部、2・
5−ジメチルヘキサン−2・5−ジ/・ィドロパーオキ
サィド0.5重量部を添加後、ヘンシェルミキサ−にて
混合し、径100ぐ、L/D28の押出機にて220q
oで押出し、水袷後べレット化した。Example 1 Ethylene-vinyl acetate copolymer “Cucalon” manufactured by Mitsubishi Yuka Co., Ltd.
Eva 41H” (skin 2, specific gravity 0.938, VA content 15
(wt%) 10 parts by weight, 1 part by weight of maleic anhydride, 2.
After adding 0.5 parts by weight of 5-dimethylhexane-2,5-di/·hydroperoxide, it was mixed in a Henschel mixer, and 220q was added in an extruder with a diameter of 100 g and L/D of 28.
It was extruded at 100 ml, and made into pellets after being covered with water.
(この変性EVAを沸騰したキシレンに溶解して大量の
アセトンにて再沈させた後、赤外線吸収スペクトル分析
法で変性EVA中に占める無水マレィン酸濃度を測定し
たところ、0.$重量%であった。)この変性EVAを
接着剤として、クラレ■製の鹸化EVA、(EVAL、
鹸価度鱗モル%、エチレン含量$重量%、酢酸ビニル含
量1重量%、ビニルアルコール含量41重量%)と三菱
モンサント製耐衝撃性ポリスチレンHT88−5をTダ
イを用いてダィ内ラミネートし、ついで冷却し、4層構
造(変性EVA/鹸化EVA/変性EVA/m鷲;肉厚
20ム/20〃/20仏ノ40山)の積層シートを得た
。(After dissolving this modified EVA in boiling xylene and reprecipitating it in a large amount of acetone, the concentration of maleic anhydride in the modified EVA was measured using infrared absorption spectroscopy, and it was found to be 0.0% by weight. ) Using this modified EVA as an adhesive, saponified EVA (EVAL,
(saponency scale mol%, ethylene content $wt%, vinyl acetate content 1wt%, vinyl alcohol content 41wt%) and impact-resistant polystyrene HT88-5 manufactured by Mitsubishi Monsanto were laminated in the die using a T-die, The mixture was then cooled to obtain a laminate sheet having a four-layer structure (modified EVA/saponified EVA/modified EVA/m2; wall thickness 20 mm/20 mm/20 mm/40 mm).
そのラミネート時の各樹脂の押出温度は、変性EVA1
80℃、鹸化EVA210℃、HmS21000である
。縛られたシートの剥離強度は、変性EVA/鹸化EV
A間で0.8k9/弧、変性EVA/HmS間で0.5
k9′伽であった。The extrusion temperature of each resin during lamination is modified EVA1
80°C, saponified EVA 210°C, HmS 21000. The peel strength of the tied sheet is the same as that of modified EVA/saponified EV.
0.8k9/arc between A, 0.5 between modified EVA/HmS
It was k9′.
この幅100仇帆の積層シート及び多数個取り(12コ
×12コ)金型を用いて、プラグアシスト真空成形を2
20qoの温度で行い、径6仇帆、深さ40側のカップ
を得た。Using this 100mm wide laminated sheet and a multi-cavity (12 x 12) mold, two plug-assisted vacuum forming operations were performed.
The process was carried out at a temperature of 20 qo to obtain a cup with a diameter of 6 mm and a depth of 40 mm.
このカップの各樹脂層の間の剥離はなかった。There was no peeling between the resin layers of this cup.
実施例 2実施例1で用いた変性EVA5の重量部にュ
カロンェバ日41を4力量量部、スチレンーブタジェン
ラバー3重量部を配合したものを接着剤樹脂として、H
mSの代りに三菱モンサント製のABS樹脂TFX76
1を用いる他は、実施例1と同様にして積層シートを得
た。Example 2 A mixture of the modified EVA 5 used in Example 1, 4 parts by weight of Cucarone Eva Day 41, and 3 parts by weight of styrene-butadiene rubber was used as an adhesive resin.
Mitsubishi Monsanto ABS resin TFX76 instead of mS
A laminated sheet was obtained in the same manner as in Example 1, except that Example 1 was used.
各樹脂層間の剥離強度はABS/接着剤層0.5k9/
伽、鹸化EVA/接着剤層0.7k9′肌であり、この
積層シートを真空成形しても各樹脂の層間剥離はなかつ
た。The peel strength between each resin layer is ABS/adhesive layer 0.5k9/
The saponified EVA/adhesive layer had a thickness of 0.7k9', and even when this laminated sheet was vacuum formed, there was no interlayer separation of the resins.
実施例 3
実施例1で用いた変性EVA5の重量部にュカロン ェ
バ 日41 49.5重量部、ナイロン6 0.5重量
部配合したものを接着剤層として、ポリエチレンテレフ
タレート(AKZO社製amite A 200)を内
層に及びHI凶(HT磯‐5)を外層にしてダィ内ラミ
ネートブロー成形法にて内層20ム、接着層20r、外
層1肌の3層構造の複数ピンを作った。Example 3 A mixture of 49.5 parts by weight of Cucaron EVA 41 and 0.5 parts by weight of Nylon 6 in the modified EVA 5 used in Example 1 was used as an adhesive layer, and polyethylene terephthalate (Amite A manufactured by AKZO) was used as an adhesive layer. 200) as the inner layer and HI Kyo (HT Iso-5) as the outer layer, multiple pins with a three-layer structure of 20 mm inner layer, 20 r adhesive layer, and 1 skin outer layer were made by in-die lamination blow molding method.
成形時の樹脂温度は、外層の温度200℃、接着剤層1
80℃、内層270つ○で、ラミネート部の樹脂圧はダ
イのゲージ圧で5k9/仇であった。The resin temperature during molding was 200°C for the outer layer and 1 for the adhesive layer.
The temperature was 80° C., the inner layer was 270 ○, and the resin pressure in the laminated portion was 5k9/m in gauge pressure of the die.
得られた中空瓶の各樹脂の層間剥離強度は接着剤層とポ
リエチレンテレフタレートとの間は1.0k9′凧、接
着剤層とm塔との間は0.5k9/仇であって、実用上
問題はなかった。The interlayer peel strength of each resin in the obtained hollow bottle was 1.0k9/kite between the adhesive layer and polyethylene terephthalate, and 0.5k9/kite between the adhesive layer and the m tower, which is practically acceptable. There were no problems.
実施例 4
ポリエチレンテレフタレートの代りにポリ塩化ビニリデ
ンを用い、内層の樹脂温度を210℃とする他は実施例
4と同様にして中空瓶を成形した。Example 4 A hollow bottle was molded in the same manner as in Example 4, except that polyvinylidene chloride was used instead of polyethylene terephthalate and the resin temperature of the inner layer was set to 210°C.
ポリ塩化ビニリデンと接着剤層との剥離強度は0.5k
9/抑、接着剤層とH把Sとの剥離強度は0.5k9′
肌であり、実用上問題はなかった。◎剥離強度:T−ビ
ール剥離
幅1伽、引張速度5仇岬/分
なお、本発明の積層構造物に於て、耐油性が要求される
ものは、内層をガスバリャー性樹脂とするのが好ましく
、また耐薬品性が要求されるものは、実施例1のように
ガスバリャー性樹脂層を変性EVAでコーティングし、
これを内層とするのがよい。Peel strength between polyvinylidene chloride and adhesive layer is 0.5k
9/ Peel strength between adhesive layer and H grip S is 0.5k9'
skin, and there were no practical problems. ◎Peel strength: T-beer Peel width 1.5cm, tensile speed 5cm/min.In addition, in the laminated structure of the present invention that requires oil resistance, it is preferable that the inner layer is made of gas barrier resin. In addition, for those requiring chemical resistance, the gas barrier resin layer is coated with modified EVA as in Example 1,
It is best to use this as the inner layer.
実施例 5
実施例1で用いた変性EVA7の重量部に、スチレンー
ブタジェンゴム(シェル社製カリフレックスTRII0
2)3の重量部を配合したものを接着剤樹脂とし、耐衝
撃性ポリスチレン(フィリップ社製K−レジンKR−0
1)を用いる他は、実施例1と同様にして積層シートを
得た。Example 5 Styrene-butadiene rubber (Califlex TRII0 manufactured by Shell Co., Ltd.) was added to the weight part of the modified EVA7 used in Example 1.
2) An adhesive resin containing 3 parts by weight was used as an adhesive resin, and impact-resistant polystyrene (K-Resin KR-0 manufactured by Philips Co., Ltd.) was used as an adhesive resin.
A laminated sheet was obtained in the same manner as in Example 1, except that Example 1) was used.
各樹脂眉間の剥離強度はH花S/接着剤層0.7k9′
伽、ケン化EVA/接着剤層0.8k9/肌であり、こ
の積層シートを真空成形しても各樹脂の層間剥離はなか
った。The peel strength between each resin eyebrow is H flower S/adhesive layer 0.7k9'
The composition was saponified EVA/adhesive layer 0.8k9/skin, and even when this laminated sheet was vacuum formed, there was no delamination between the resin layers.
比較例 1
実施例1で用いた未変性EVA(M12、比重0,93
入VA含量14重量%)を用いる他は、実施例1と同様
にして積層シートを得た。Comparative Example 1 Unmodified EVA used in Example 1 (M12, specific gravity 0.93
A laminated sheet was obtained in the same manner as in Example 1, except that the VA content was 14% by weight.
各樹脂間の剥離強度は、HmS/接着剤層0.1k9′
功、ケン化EVA/接着剤層0.2k9/弧であり、こ
の積層シートを真空成形した所、各層間で剥離を生じ、
実用に耐えないものであった。The peel strength between each resin is HmS/adhesive layer 0.1k9'
It was saponified EVA/adhesive layer 0.2k9/arc, and when this laminated sheet was vacuum formed, peeling occurred between each layer,
It was impractical.
Claims (1)
ばれたポリスチレン系樹脂(B) エチレン−酢酸ビニ
ル共重合体の鹸化物、ポリアミド樹脂、塩化ビニリデン
樹脂、熱可塑性ポリエステル樹脂より選ばれたガスバリ
ヤー性樹脂(C) 不飽和カルボン酸またはその酸無水
物の成分濃度が0.001〜10重量%である変性エチ
レン−酢酸ビニル共重合体 上記(A)と(B)の樹脂
を(C)の接着性樹脂を介して溶融共押出することを特
徴とする樹脂積層物の製造法。1 (A) Polystyrene resin selected from impact-resistant polystyrene and ABS resin (B) Gas barrier property selected from saponified ethylene-vinyl acetate copolymer, polyamide resin, vinylidene chloride resin, and thermoplastic polyester resin Resin (C) Modified ethylene-vinyl acetate copolymer having a component concentration of unsaturated carboxylic acid or its acid anhydride from 0.001 to 10% by weight Adhesion of resins (A) and (B) above to (C) 1. A method for producing a resin laminate, characterized by melt coextrusion through a plastic resin.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP52112120A JPS602984B2 (en) | 1977-09-20 | 1977-09-20 | Manufacturing method for resin laminates |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP52112120A JPS602984B2 (en) | 1977-09-20 | 1977-09-20 | Manufacturing method for resin laminates |
Publications (2)
Publication Number | Publication Date |
---|---|
JPS5446281A JPS5446281A (en) | 1979-04-12 |
JPS602984B2 true JPS602984B2 (en) | 1985-01-25 |
Family
ID=14578674
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP52112120A Expired JPS602984B2 (en) | 1977-09-20 | 1977-09-20 | Manufacturing method for resin laminates |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPS602984B2 (en) |
Families Citing this family (15)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS55160070A (en) * | 1979-05-30 | 1980-12-12 | Seiko Epson Corp | Fluid ink for printer |
JPS58203041A (en) * | 1982-05-21 | 1983-11-26 | 大日本印刷株式会社 | Laminate |
JPS5924665A (en) * | 1982-07-31 | 1984-02-08 | 大日本印刷株式会社 | Laminate |
JPS5957747A (en) * | 1982-09-29 | 1984-04-03 | 出光興産株式会社 | Laminate |
JPS59109361A (en) * | 1982-12-14 | 1984-06-25 | 日本石油化学株式会社 | Multilayer structure |
JPS59152852A (en) * | 1983-02-22 | 1984-08-31 | 株式会社クラレ | Laminate and manufacture thereof |
JPS59215864A (en) * | 1983-05-25 | 1984-12-05 | 株式会社ジェイエスピー | Manufacture of multilayer structure material |
JPS6026072A (en) * | 1983-07-22 | 1985-02-08 | Takeda Chem Ind Ltd | Adhesive comprising modified ethylene/vinyl acetate copolymer and molding bonded with said adhesive |
JPS60107337A (en) * | 1983-11-17 | 1985-06-12 | 東洋製罐株式会社 | Sheet molding laminated plastic vessel |
JPS60212350A (en) * | 1984-04-06 | 1985-10-24 | 旭化成株式会社 | Polyvinylidene chloride coated polystyrene film or sheet |
JPS6160436A (en) * | 1984-08-23 | 1986-03-28 | 東洋製罐株式会社 | Multilayer gas barrier property oriented polyester vessel |
US5089353A (en) * | 1988-10-14 | 1992-02-18 | Kuraray Co., Ltd. | Multi-layer material having gas barrier properties |
US5091467A (en) * | 1991-03-29 | 1992-02-25 | The Goodyear Tire & Rubber Company | Controlled morphology barrier elastomers made from blends of syndiotactic 1,2-polybutadiene and ethylene-vinyl acetate-vinyl alcohol terpolymers |
US5153262A (en) * | 1991-03-29 | 1992-10-06 | The Goodyear Tire & Rubber Company | Controlled morphology barrier elastomers made from blends of syndiotactic 1,2-polybutadiene and ethylene-vinyl acetate-vinyl alcohol terpolymers |
JP5860585B2 (en) * | 2010-09-30 | 2016-02-16 | 積水化成品工業株式会社 | Polystyrene resin sheet |
-
1977
- 1977-09-20 JP JP52112120A patent/JPS602984B2/en not_active Expired
Also Published As
Publication number | Publication date |
---|---|
JPS5446281A (en) | 1979-04-12 |
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