JPH11116758A - Preparation of resin composition - Google Patents
Preparation of resin compositionInfo
- Publication number
- JPH11116758A JPH11116758A JP9293415A JP29341597A JPH11116758A JP H11116758 A JPH11116758 A JP H11116758A JP 9293415 A JP9293415 A JP 9293415A JP 29341597 A JP29341597 A JP 29341597A JP H11116758 A JPH11116758 A JP H11116758A
- Authority
- JP
- Japan
- Prior art keywords
- acetic acid
- weight
- resin composition
- evoh
- parts
- 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.)
- Granted
Links
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- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
【0001】[0001]
【発明の属する技術分野】本発明は、エチレン−酢酸ビ
ニル共重合体ケン化物(以下、EVOHと略記する)樹
脂組成物の製造法に関し、更に詳しくは熱安定性、ロン
グラン成形性等に優れたEVOH樹脂組成物の製造法に
関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a saponified ethylene-vinyl acetate copolymer (hereinafter abbreviated as EVOH) resin composition, and more particularly, to a method having excellent heat stability and long-run moldability. The present invention relates to a method for producing an EVOH resin composition.
【0002】[0002]
【従来の技術】一般に、EVOHはその透明性、ガスバ
リヤー性、保香性、耐溶剤性、耐油性などに優れてお
り、かかる特性を生かして、食品包装材料、医薬品包装
材料、工業薬品包装材料、農薬包装材料等のフィルムや
シート、或いはボトル等の容器等に成形されて利用され
ている。かかる成形にあたっては、通常溶融成形が行わ
れ、かかる成形により、フィルム状、シート状、ボトル
状、カップ状、チューブ状、パイプ状等の形状に加工さ
れて実用に供されており、その加工性(成形性)は大変
重要であり、かかる成形性を向上させるために、EVO
Hにリン酸化合物を配合することが試みられており、本
出願人も熱安定性や溶融成形性(フィッシュアイやゲル
の抑制等)の改善のためにEVOHをリン酸化合物で処
理する方法を提案した(特開昭62−143954号公
報)。2. Description of the Related Art In general, EVOH is excellent in transparency, gas barrier property, fragrance retention, solvent resistance, oil resistance and the like. It is used after being formed into materials, films and sheets of packaging materials for agricultural chemicals, containers such as bottles, and the like. In such molding, usually, melt molding is performed, and by such molding, it is processed into a shape such as a film shape, a sheet shape, a bottle shape, a cup shape, a tube shape, a pipe shape, and is provided for practical use. (Moldability) is very important, and in order to improve such moldability, EVO
Attempts have been made to incorporate a phosphoric acid compound into H. The present applicant has also proposed a method of treating EVOH with a phosphoric acid compound in order to improve thermal stability and melt moldability (such as suppression of fish eyes and gels). It has been proposed (Japanese Patent Application Laid-Open No. 62-143954).
【0003】[0003]
【発明が解決しようとする課題】しかしながら、昨今の
新たなる成形物への要求性能の高まりに対応すべく、上
記の技術について、詳細に検討を重ねた結果、直径が
0.1mm以上のフィッシュアイやゲル等の改善は認め
られるものの、0.1mm未満の小さなものについて
は、上記の技術では必ずしも解決できるものではなく、
成形条件等により0.1mm未満のフィッシュアイ等が
発生する恐れがあり、新たなる改良が望まれることが判
明した。However, in order to cope with the recent increase in performance required for a new molded product, the above-mentioned technology has been studied in detail, and as a result, a fisheye having a diameter of 0.1 mm or more has been obtained. Although improvements such as gels and the like are recognized, small ones of less than 0.1 mm are not necessarily solvable with the above technology,
Fish eyes or the like having a diameter of less than 0.1 mm may be generated depending on molding conditions and the like, and it has been found that a new improvement is desired.
【0004】[0004]
【課題を解決するための手段】そこで、本発明者は、か
かる現況に鑑みて鋭意研究を重ねた結果、エチレン−酢
酸ビニル共重合体ケン化物(A)、酢酸(B)およびリ
ン酸化合物(C)を含有してなる樹脂組成物を製造する
にあたり、酢酸(B)水溶液にリン酸化合物(C)を仕
込んで溶解させた混合液(I)に、エチレン−酢酸ビニ
ル共重合体ケン化物(A)を接触せしめることにより、
溶融成形性に優れ、特に直径が0.1mm未満のフィッ
シュアイ等の発生を抑制することができ、かつロングラ
ン成形時においても良好であるEVOHの樹脂組成物が
得られることを見出し、本発明を完成するに至った。Accordingly, the present inventor has conducted intensive studies in view of the present situation, and as a result, has found that a saponified ethylene-vinyl acetate copolymer (A), acetic acid (B) and a phosphoric acid compound ( In producing the resin composition containing (C), a mixture of a phosphoric acid compound (C) and an aqueous solution of acetic acid (B) dissolved therein is mixed with a saponified ethylene-vinyl acetate copolymer (I). By bringing A) into contact,
It has been found that a resin composition of EVOH which is excellent in melt moldability, in particular, can suppress generation of fish eyes having a diameter of less than 0.1 mm, and is excellent even in long-run molding can be obtained. It was completed.
【0005】[0005]
【発明の実施の形態】以下に、本発明を詳細に述べる。
本発明のEVOH(A)としては、特に限定されない
が、エチレン含有量が20〜60モル%(更には25〜
55モル%)、ケン化度が90モル%以上(更には95
モル%以上)のものが用いられ、該エチレン含有量が2
0モル%未満では高湿時のガスバリヤー性、溶融成形性
が低下し、逆に60モル%を越えると充分なガスバリヤ
ー性が得られず、更にケン化度が90モル%未満ではガ
スバリヤー性、熱安定性、耐湿性等が低下して、好まし
くない。また、EVOH(A)は、メルトインデックス
(MI)(210℃、荷重2160g)が0.1〜10
0g/10分(更には0.5〜50g/10分)のもの
が好ましく、該メルトインデックスが該範囲よりも小さ
い場合には、成形時に押出機内が高トルク状態となって
押出加工が困難となり、また該範囲よりも大きい場合に
は、溶融成形性が低下して好ましくない。BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.
The EVOH (A) of the present invention is not particularly limited, but has an ethylene content of 20 to 60 mol% (furthermore, 25 to 60 mol%).
55 mol%), and the degree of saponification is 90 mol% or more (furthermore, 95 mol%).
Mol% or more) and the ethylene content is 2
If it is less than 0 mol%, the gas barrier properties and melt moldability at high humidity will be reduced. Conversely, if it exceeds 60 mol%, sufficient gas barrier properties will not be obtained. The properties, thermal stability, moisture resistance and the like are undesirably reduced. EVOH (A) has a melt index (MI) (210 ° C., load 2160 g) of 0.1 to 10;
The melt index is preferably 0 g / 10 min (more preferably 0.5 to 50 g / 10 min). If the melt index is smaller than the above range, the inside of the extruder will be in a high torque state during molding and extrusion processing will be difficult. If it is larger than the above range, the melt moldability is undesirably reduced.
【0006】該EVOH(A)は、エチレン−酢酸ビニ
ル共重合体のケン化によって得られ、該エチレン−酢酸
ビニル共重合体は、公知の任意の重合法、例えば懸濁重
合、エマルジョン重合、溶液重合などにより製造され、
エチレン−酢酸ビニル共重合体のケン化も公知の方法で
行い得る。該EVOHは、少量であればα−オレフィ
ン、不飽和カルボン酸系化合物、不飽和スルホン酸系化
合物、(メタ)アクリロニトリル、(メタ)アクリルア
ミド、ビニルエーテル、ビニルシラン化合物、塩化ビニ
ル、スチレンなどの他のコモノマーで「共重合変性」さ
れても差し支えない。又、本発明の趣旨を損なわない範
囲で、ウレタン化、アセタール化、シアノエチル化など
「後変性」されても差し支えない。The EVOH (A) is obtained by saponifying an ethylene-vinyl acetate copolymer. The ethylene-vinyl acetate copolymer can be produced by any known polymerization method, for example, suspension polymerization, emulsion polymerization, solution polymerization, and the like. Manufactured by polymerization, etc.
Saponification of the ethylene-vinyl acetate copolymer can also be performed by a known method. If EVOH is used in a small amount, other comonomers such as α-olefin, unsaturated carboxylic acid compound, unsaturated sulfonic acid compound, (meth) acrylonitrile, (meth) acrylamide, vinyl ether, vinyl silane compound, vinyl chloride and styrene And may be "copolymerized". Also, "post-modified" such as urethanization, acetalization, and cyanoethylation may be used as long as the gist of the present invention is not impaired.
【0007】上記のEVOH(A)と同時に含有される
のは、酢酸(B)およびリン酸化合物(C)で、かかる
リン酸化合物(C)としては、リン酸二水素ナトリウ
ム、リン酸水素二ナトリウム、リン酸二水素カリウム、
リン酸水素二カリウム、リン酸三カリウム、リン酸一水
素カルシウム、リン酸二水素カルシウム、リン酸三カル
シウム、リン酸マグネシウム、リン酸水素マグネシウ
ム、リン酸二水素マグネシウム、リン酸水素亜鉛、リン
酸水素バリウム、リン酸水素マンガン等を挙げることが
でき、好適にはリン酸二水素ナトリウム、リン酸二水素
カリウム、リン酸二水素カルシウム、リン酸二水素マグ
ネシウムが用いられる。Acetic acid (B) and a phosphoric acid compound (C) are contained at the same time as the EVOH (A). The phosphoric acid compound (C) includes sodium dihydrogen phosphate and dihydrogen hydrogen phosphate. Sodium, potassium dihydrogen phosphate,
Dipotassium hydrogen phosphate, tripotassium phosphate, calcium monohydrogen phosphate, calcium dihydrogen phosphate, tricalcium phosphate, magnesium phosphate, magnesium hydrogen phosphate, magnesium dihydrogen phosphate, zinc hydrogen phosphate, phosphoric acid Examples thereof include barium hydrogen and manganese hydrogen phosphate, and preferably, sodium dihydrogen phosphate, potassium dihydrogen phosphate, calcium dihydrogen phosphate, and magnesium dihydrogen phosphate are used.
【0008】本発明においては、上記の(A)〜(C)
を配合するにあたり、予め酢酸(B)水溶液にリン酸化
合物(C)を仕込んで溶解させた混合液(I)を調製し
ておき、かかる混合液(I)にEVOH(A)を接触せ
しめて樹脂組成物を得ることを最大の特徴とするもので
あり、その方法について詳細に説明する。酢酸(B)水
溶液は、0.001〜0.1重量%程度のメタノール、
エタノール、プロパノール、酢酸メチル、酢酸エチル等
を含有していても差し支えない。酢酸(B)水溶液中の
酢酸濃度は、0.005〜1重量%が好ましく、更には
0.01〜0.8重量%が好ましく、かかる濃度が0.
005重量%未満では、酢酸の効力が発揮されなくな
り、逆に1重量%を越えると混合するリン酸化合物の効
力が発揮されなくなって好ましくない。In the present invention, the above (A) to (C)
Is prepared by mixing a phosphoric acid compound (C) into an aqueous acetic acid (B) solution to prepare a mixed solution (I), and contacting the mixed solution (I) with EVOH (A). The greatest feature of the present invention is to obtain a resin composition, and the method will be described in detail. Acetic acid (B) aqueous solution contains about 0.001 to 0.1% by weight of methanol,
Ethanol, propanol, methyl acetate, ethyl acetate and the like may be contained. The acetic acid concentration in the acetic acid (B) aqueous solution is preferably 0.005 to 1% by weight, more preferably 0.01 to 0.8% by weight.
If the amount is less than 005% by weight, the effect of acetic acid is not exhibited, and if it exceeds 1% by weight, the effect of the phosphoric acid compound to be mixed is not exhibited, which is not preferable.
【0009】次いで、得られた酢酸(B)水溶液にリン
酸化合物(C)を溶解させて混合液(I)を得るのであ
るが、このときのリン酸化合物(C)の溶解量(含有
量)は混合液(I)中に0.0001〜0.5重量%含
有することが好ましく、更には0.001〜0.3重量
%が好ましく、かかる濃度が0.0001重量%未満で
は、リン酸化合物の効力が発揮されなくなり、逆に0.
5重量%を越えると酢酸の効力が発揮されなくなって好
ましくない。かかるリン酸化合物(C)の溶解は、20
〜40℃程度で行うことが好ましい。また、上記の混合
液(I)を調製するにあたっては、あらかじめ酢酸
(B)濃度1〜10重量%(更には3〜9重量%)の水
溶液を作っておき、該水溶液にリン酸化合物(C)を溶
解させた後、水希釈して上記のリン酸化合物(C)の含
有量となるように調製することが、フィッシュアイの低
減化の点で好ましい。Next, the phosphoric acid compound (C) is dissolved in the obtained aqueous solution of acetic acid (B) to obtain a mixed solution (I). The dissolved amount (content) of the phosphoric acid compound (C) at this time is obtained. ) Is preferably contained in the mixture (I) in an amount of 0.0001 to 0.5% by weight, more preferably 0.001 to 0.3% by weight. The acid compound is no longer effective,
If it exceeds 5% by weight, the effect of acetic acid is not exhibited, which is not preferable. The dissolution of the phosphate compound (C) is 20
It is preferable to carry out at about 40 ° C. In preparing the above mixture (I), an aqueous solution of acetic acid (B) having a concentration of 1 to 10% by weight (furthermore, 3 to 9% by weight) is prepared in advance, and a phosphate compound (C) is added to the aqueous solution. ) Is dissolved and then diluted with water to prepare the above-mentioned content of the phosphoric acid compound (C), from the viewpoint of reducing fish eyes.
【0010】最後に、得られた混合液(I)にEVOH
(A)を接触せしめて、樹脂組成物を得るのであるが、
最終的には混合液(I)にEVOH(A)を接触させ
て、EVOH(A)に上記の(B)および(C)を含有
させればよく、かかる方法としては、特に限定されず、
混合液(I)中に直接EVOH(A)のペレットや粉
体等を浸漬させて含有させる方法、EVOH(A)の
水/アルコール混合溶液の多孔性析出物を混合液(I)
中に浸漬させて含有させる方法、EVOH(A)の水
/アルコール混合溶液に混合液(I)を添加後、(凝固
槽等で)析出させて含有させる方法、溶融状態のEV
OH(A)に混合液(I)を添加して含有させる方法等
が挙げられるが、(B)および(C)をより均一に効率
良く含有させるという点では、やの方法が好適に用
いられる。Finally, EVOH is added to the obtained mixture (I).
(A) is brought into contact to obtain a resin composition,
Finally, EVOH (A) may be brought into contact with the mixed solution (I) so that the above-mentioned (B) and (C) are contained in the EVOH (A). Such a method is not particularly limited.
A method in which pellets or powders of EVOH (A) are directly immersed and contained in the mixed solution (I), and a porous precipitate of a water / alcohol mixed solution of EVOH (A) is mixed with the mixed solution (I).
A method in which a mixed solution (I) is added to a water / alcohol mixed solution of EVOH (A) and then precipitated (in a coagulation tank or the like) to contain the EVOH (A);
A method of adding the mixed solution (I) to the OH (A) and containing the mixed solution may be mentioned, but the method is more preferably used in that the (B) and (C) are more uniformly and efficiently contained. .
【0011】上記の方法により目的とする樹脂組成物が
得られるのであるが、EVOH(A)に含有される
(B)および(C)の量は特に限定されないが、酢酸
(B)の含有量としては、(A)100重量部に対して
0.05重量部以下が好ましく、更に好ましくは0.0
005〜0.03重量部、特に好ましくは0.0005
〜0.01重量部で、かかる(B)の含有量が0.05
重量部を越えると成形時のロングラン成形性が低下して
好ましくない。また、リン酸化合物(C)の含有量とし
ては、リン酸根換算で(A)100重量部に対して0.
0005〜0.05重量部が好ましく、更に好ましくは
0.001〜0.04重量部、特に好ましくは0.00
2〜0.03重量部で、かかる(C)の含有量がリン酸
根換算で0.0005重量部未満ではロングラン成形性
が低下し、逆に0.05重量部を越えると成形物の外観
性が低下して好ましくない。The desired resin composition is obtained by the above method. The amounts of (B) and (C) contained in EVOH (A) are not particularly limited, but the content of acetic acid (B) is not limited. Is preferably 0.05 part by weight or less, more preferably 0.0 part by weight, per 100 parts by weight of (A).
005 to 0.03 parts by weight, particularly preferably 0.0005
To 0.01 parts by weight, and the content of (B) is 0.05
Exceeding the weight part is undesirable because the long-run moldability during molding decreases. In addition, the content of the phosphoric acid compound (C) is 0.1 wt.
0005 to 0.05 parts by weight, more preferably 0.001 to 0.04 parts by weight, particularly preferably 0.005 to 0.05 parts by weight.
When the content of (C) is less than 0.0005 parts by weight in terms of phosphate group, the long-run moldability is reduced. Is undesirably reduced.
【0012】上記の(B)および(C)の含有量を調整
するには、混合液(I)のそれぞれの含有量やEVOH
(A)との接触時間、温度、撹拌速度、接触後の乾燥条
件等をコントロールすればよく、特に限定はされない。
尚、上記の(B)および(C)の含有量の測定にあたっ
ては、以下の方法によって測定することができる。 (B):樹脂組成物を熱水抽出して、抽出液をアルカリ
で中和滴定して酢酸量を定量 (C):樹脂組成物を温希硫酸抽出して、吸光光度法
(モリブデン青)により、リン酸根を定量(JIS K
0102に準拠)To adjust the contents of the above (B) and (C), the respective contents of the mixed solution (I) and the EVOH
The contact time with the (A), the temperature, the stirring speed, the drying conditions after the contact and the like may be controlled, and there is no particular limitation.
In measuring the contents of (B) and (C), the contents can be measured by the following method. (B): Extraction of the resin composition with hot water, neutralization titration of the extract with alkali to determine the amount of acetic acid (C): Extraction of the resin composition with warm dilute sulfuric acid, and spectrophotometry (molybdenum blue) Quantifies phosphate groups by JIS K
0102)
【0013】上記の如き本発明の方法により、熱安定性
やロングラン成形性等に優れた樹脂組成物が得られるわ
けであるが、かかる樹脂組成物には、更に、必要に応じ
て、可塑剤、熱安定化剤、紫外線吸収剤、酸化防止剤、
着色剤、抗菌剤、フィラー、他樹脂などの添加剤を使用
することも可能である。特にゲル発生防止剤として、ハ
イドロタルサイト系化合物、ヒンダードフェノール系、
ヒンダードアミン系熱安定剤、高級脂肪族カルボン酸の
金属塩を添加することもできる。また、EVOH(A)
として、異なる2種以上のEVOHを用いることも可能
で、このときは、エチレン含有量が5モル%以上異な
り、及び/又はケン化度が1モル%以上異なるEVOH
のブレンド物を用いることにより、ガスバリヤー性を保
持したまま、更に高延伸時の延伸性、真空圧空成形や深
絞り成形などの2次加工性が向上するので有用である。According to the method of the present invention as described above, a resin composition having excellent heat stability and long run moldability can be obtained. However, if necessary, a plasticizer may be added to the resin composition. , Heat stabilizer, UV absorber, antioxidant,
It is also possible to use additives such as coloring agents, antibacterial agents, fillers and other resins. In particular, hydrotalcite-based compounds, hindered phenol-based compounds,
A hindered amine heat stabilizer and a metal salt of a higher aliphatic carboxylic acid can also be added. Also, EVOH (A)
It is also possible to use two or more different EVOHs, in which case the EVOHs differ in ethylene content by 5 mol% or more and / or the saponification degrees differ by 1 mol% or more.
Use of the blend of (1) is useful because the stretchability at the time of high stretching and the secondary workability such as vacuum pressure forming and deep drawing are further improved while maintaining gas barrier properties.
【0014】かくして本発明の方法で得られた樹脂組成
物は、成形物の用途に多用され、溶融成形等によりペレ
ット、フィルム、シート、容器、繊維、棒、管、各種成
形品等に成形され、又、これらの粉砕品(回収品を再使
用する時など)やペレットを用いて再び溶融成形に供す
ることも多い。溶融成形方法としては、押出成形法(T
−ダイ押出、インフレーション押出、ブロー成形、溶融
紡糸、異型押出等)、射出成形法が主として採用され
る。溶融成形温度は、150〜250℃の範囲から選ぶ
ことが多い。The resin composition thus obtained by the method of the present invention is frequently used for molded articles, and is formed into pellets, films, sheets, containers, fibers, rods, tubes, various molded articles, etc. by melt molding or the like. In addition, these pulverized products (for example, when a recovered product is reused) or pellets are often used for melt molding again. As the melt molding method, an extrusion molding method (T
-Die extrusion, inflation extrusion, blow molding, melt spinning, profile extrusion, etc.), and injection molding. The melt molding temperature is often selected from the range of 150 to 250 ° C.
【0015】本発明の方法で得られた樹脂組成物は、上
述の如き成形物に用いることができるが、特に該樹脂組
成物からなる層の少なくとも片面に熱可塑性樹脂層を積
層してなる積層体として用いることが好ましく、実用に
適した積層体が得られる。The resin composition obtained by the method of the present invention can be used for a molded product as described above. In particular, a laminate comprising a thermoplastic resin layer laminated on at least one surface of a layer made of the resin composition It is preferably used as a body, and a laminated body suitable for practical use is obtained.
【0016】該積層体を製造するに当たっては、本発明
の方法で得られた樹脂組成物の層の片面又は両面に他の
基材を積層するのであるが、積層方法としては、例えば
該組成物のフィルム、シートに熱可塑性樹脂を溶融押出
する方法、逆に熱可塑性樹脂等の基材に該組成物を溶融
押出する方法、該樹脂組成物と他の熱可塑性樹脂とを共
押出する方法、更には本発明で得られたEVOH組成物
のフィルム、シートと他の基材のフィルム、シートとを
有機チタン化合物、イソシアネート化合物、ポリエステ
ル系化合物、ポリウレタン化合物等の公知の接着剤を用
いてラミネートする方法等が挙げられる。In producing the laminate, another substrate is laminated on one side or both sides of the resin composition layer obtained by the method of the present invention. A method of melt-extruding a thermoplastic resin into a film or sheet, a method of melt-extruding the composition on a substrate such as a thermoplastic resin, a method of co-extruding the resin composition with another thermoplastic resin, Further, the EVOH composition film and sheet obtained in the present invention and the film and sheet of another substrate are laminated with a known adhesive such as an organic titanium compound, an isocyanate compound, a polyester compound, or a polyurethane compound. Method and the like.
【0017】共押出の場合の相手側樹脂としては直鎖状
低密度ポリエチレン、低密度ポリエチレン、中密度ポリ
エチレン、高密度ポリエチレン、エチレン−酢酸ビニル
共重合体、アイオノマー、エチレン−プロピレン共重合
体、エチレン−アクリル酸エステル共重合体、ポリプロ
ピレン、プロピレン−α−オレフィン(炭素数4〜20
のα−オレフィン)共重合体、ポリブテン、ポリペンテ
ン等のオレフィンの単独又は共重合体、或いはこれらの
オレフィンの単独又は共重合体を不飽和カルボン酸又は
そのエステルでグラフト変性したものなどの広義のポリ
オレフィン系樹脂、ポリエステル、ポリアミド、共重合
ポリアミド、ポリ塩化ビニル、ポリ塩化ビニリデン、ア
クリル系樹脂、ポリスチレン、ビニルエステル系樹脂、
ポリエステルエラストマー、ポリウレタンエラストマ
ー、塩素化ポリエチレン、塩素化ポリプロピレン等が挙
げられる。エチレン−酢酸ビニル共重合体ケン化物も共
押出可能である。上記のなかでも、共押出製膜の容易
さ、フィルム物性(特に強度)の実用性の点から、ポリ
プロピレン、ポリアミド、ポリエチレン、エチレン−酢
酸ビニル共重合体、ポリスチレン、PETが好ましく用
いられる。In the case of co-extrusion, the mating resin includes linear low-density polyethylene, low-density polyethylene, medium-density polyethylene, high-density polyethylene, ethylene-vinyl acetate copolymer, ionomer, ethylene-propylene copolymer, ethylene -Acrylate copolymer, polypropylene, propylene-α-olefin (having 4 to 20 carbon atoms)
Α-olefins) copolymers, polyolefins such as polybutenes and polypentenes, or polyolefins in a broad sense, such as homo- or copolymers of these olefins, or graft-modified homo- or copolymers of these olefins with unsaturated carboxylic acids or esters thereof Resin, polyester, polyamide, copolymerized polyamide, polyvinyl chloride, polyvinylidene chloride, acrylic resin, polystyrene, vinyl ester resin,
Examples thereof include polyester elastomer, polyurethane elastomer, chlorinated polyethylene, and chlorinated polypropylene. Saponified ethylene-vinyl acetate copolymer can also be coextruded. Among these, polypropylene, polyamide, polyethylene, ethylene-vinyl acetate copolymer, polystyrene, and PET are preferably used from the viewpoint of ease of coextrusion film formation and practicality of film physical properties (particularly strength).
【0018】更に、本発明の方法で得られた樹脂組成物
から一旦フィルム、シート等の成形物を得、これに他の
基材を押出コートしたり、他の基材のフィルム、シート
等を接着剤を用いてラミネートする場合、前記の熱可塑
性樹脂以外に任意の基材(紙、金属箔、一軸又は二軸延
伸プラスチックフィルム又はシート、織布、不織布、金
属綿状、木質等)が使用可能である。積層体の層構成
は、本発明の方法で得られた樹脂組成物の層をa
(a1、a2、・・・)、他の基材、例えば熱可塑性樹脂
層をb(b1、b2、・・・)とするとき、フィルム、シ
ート、ボトル状であれば、a/bの二層構造のみなら
ず、b/a/b、a/b/a、a1/a2/b、a/b1
/b2、b2/b1/a/b1/b2等任意の組み合わせが
可能であり、フィラメント状ではa、bがバイメタル
型、芯(a)−鞘(b)型、芯(b)−鞘(a)型、或
いは偏心芯鞘型等任意の組み合わせが可能である。Further, a molded product such as a film or a sheet is once obtained from the resin composition obtained by the method of the present invention, and another substrate is extrusion-coated thereon, or a film or sheet of another substrate is formed. When laminating using an adhesive, any substrate (paper, metal foil, uniaxially or biaxially stretched plastic film or sheet, woven fabric, nonwoven fabric, metallic cotton, woody, etc.) is used in addition to the above-mentioned thermoplastic resin. It is possible. The layer structure of the laminate is such that the layer of the resin composition obtained by the method of the present invention is a
(A 1 , a 2 ,...), Other substrates, for example, a thermoplastic resin layer b (b 1 , b 2 ,. not only double layer structure of / b, b / a / b , a / b / a, a 1 / a 2 / b, a / b 1
Any combination such as / b 2 , b 2 / b 1 / a / b 1 / b 2 is possible. In the filament form, a and b are bimetal type, core (a) -sheath (b) type, core (b) Any combination such as a) -sheath (a) type or an eccentric core-sheath type is possible.
【0019】又、共押出の場合、aにb、bにaをブレ
ンドしたり、aやbの少なくとも一方に両層面の密着性
を向上させる樹脂を配合することもある。該積層体は、
そのまま各種形状のものに使用されるが、更に該積層体
の物性を改善するためには延伸処理を施すことも好まし
く、かかる延伸については、一軸延伸、二軸延伸のいず
れであってもよく、できるだけ高倍率の延伸を行ったほ
うが物性的に良好で、延伸時にピンホールやクラック、
延伸ムラ、デラミ等の生じない延伸フィルムや延伸シー
ト等が得られる。In the case of co-extrusion, a may be blended with b and b may be blended with a, or at least one of a and b may be blended with a resin which improves the adhesion between the two layers. The laminate is
It is used as it is for various shapes, it is also preferable to perform a stretching treatment to further improve the physical properties of the laminate, and such stretching may be any of uniaxial stretching and biaxial stretching, Stretching as high as possible is better in physical properties, and pinholes, cracks,
A stretched film, a stretched sheet, or the like free from stretching unevenness and delamination can be obtained.
【0020】延伸方法としては、ロール延伸法、テンタ
ー延伸法、チューブラー延伸法、延伸ブロー法等の他、
深絞成形、真空成形等の延伸倍率の高いものも採用でき
る。二軸延伸の場合は同時二軸延伸方式、逐次二軸延伸
方式のいずれの方式も採用できる。延伸温度は80〜1
70℃、好ましくは100〜160℃程度の範囲から選
ばれる。The stretching method includes a roll stretching method, a tenter stretching method, a tubular stretching method, a stretching blow method, and the like.
Those having a high draw ratio such as deep drawing and vacuum forming can also be used. In the case of biaxial stretching, any of a simultaneous biaxial stretching method and a sequential biaxial stretching method can be adopted. Stretching temperature is 80-1
70 ° C, preferably selected from the range of about 100 to 160 ° C.
【0021】かくして延伸が終了した後、次いで熱固定
を行う。熱固定は周知の手段で実施可能であり、上記延
伸フィルムを緊張状態を保ちながら80〜170℃、好
ましくは100〜160℃で2〜600秒間程度熱処理
を行う。又、得られた延伸フィルムは必要に応じ、冷却
処理、圧延処理、印刷処理、ドライラミネート処理、溶
液又は溶融コート処理、製袋加工、深しぼり加工、箱加
工、チューブ加工、スプリット加工等を行うことができ
る。After the completion of the stretching, heat setting is performed. The heat setting can be performed by a well-known means, and heat treatment is performed at 80 to 170 ° C., preferably 100 to 160 ° C. for about 2 to 600 seconds while keeping the stretched film in a tensioned state. In addition, the obtained stretched film is subjected to a cooling process, a rolling process, a printing process, a dry laminating process, a solution or melt coating process, a bag making process, a deep squeezing process, a box process, a tube process, a split process, etc., as necessary. be able to.
【0022】かくして得られた積層体の形状としては任
意のものであってよく、フィルム、シート、テープ、ボ
トル、パイプ、フィラメント、異型断面押出物等が例示
される。又、得られた積層体は必要に応じ、熱処理、冷
却処理、圧延処理、印刷処理、ドライラミネート処理、
溶液又は溶融コート処理、製袋加工、深絞り加工、箱加
工、チューブ加工、スプリット加工等を行うことができ
る。上記の如く得られたフィルム、シート或いは容器等
は食品、医薬品、工業薬品、農薬等各種の包装材料とし
て有用である。The shape of the thus obtained laminate may be any shape, and examples thereof include a film, a sheet, a tape, a bottle, a pipe, a filament, and an extrudate having a modified cross section. In addition, the obtained laminate is subjected to heat treatment, cooling treatment, rolling treatment, printing treatment, dry lamination treatment,
Solution or melt coating processing, bag making processing, deep drawing processing, box processing, tube processing, split processing, and the like can be performed. The films, sheets, containers and the like obtained as described above are useful as various packaging materials for foods, pharmaceuticals, industrial chemicals, agricultural chemicals and the like.
【0023】[0023]
【実施例】以下、実施例を挙げて本発明を具体的に説明
する。尚、実施例中「部」、「%」とあるのは特に断り
のない限り重量基準を示す。 実施例1 [混合液(I)の調製]6%の酢酸(B)水溶液に、リ
ン酸二水素カルシウム(C)を0.35%となる様に溶
解させ、更にこれを50倍の水で希釈して、最終的に
0.12%の酢酸(B)及び0.007%のリン酸二水
素カルシウム(C)を含有する混合液(I)を得た。エ
チレン含有量35モル%、ケン化度99.5モル%、M
I20g/10分(210℃、荷重2160g)のEV
OH(A)のケン化後の水/メタノール溶液の多孔性析
出物(EVOH(A)100部に対して水100部含
有)を水で洗浄後、上記の混合液(I)に投入し、30
℃で5時間撹拌した後、110℃で8時間乾燥を行っ
て、EVOH(A)100重量部に対して、酢酸(B)
およびリン酸二水素カルシウム(C)をそれぞれ0.0
09重量部および0.005重量部(リン酸根換算)含
有する樹脂組成物を得た。次いで、得られた樹脂組成物
をTダイを備えた単軸押出機に供給し、下記の条件で、
厚さ120μmのEVOHフィルムの成形を行って、下
記の要領で直径が0.1mm未満の微細なフィッシュア
イの発生およびロングラン成形性の評価を行った。The present invention will be specifically described below with reference to examples. In the examples, “parts” and “%” are based on weight unless otherwise specified. Example 1 [Preparation of mixed solution (I)] Calcium dihydrogen phosphate (C) was dissolved in a 6% aqueous solution of acetic acid (B) so as to have a concentration of 0.35%. Upon dilution, a mixture (I) containing 0.12% acetic acid (B) and 0.007% calcium dihydrogen phosphate (C) was finally obtained. Ethylene content 35 mol%, degree of saponification 99.5 mol%, M
EV of 20g / 10 minutes (210 ° C, load 2160g)
After washing the porous precipitate of the water / methanol solution after saponification of OH (A) (containing 100 parts of water with respect to 100 parts of EVOH (A)) with water, the mixture is poured into the above mixed solution (I), 30
After stirring at 5 ° C. for 5 hours, drying was performed at 110 ° C. for 8 hours, and acetic acid (B) was added to 100 parts by weight of EVOH (A).
And calcium dihydrogen phosphate (C) each in 0.0
A resin composition containing 09 parts by weight and 0.005 parts by weight (in terms of phosphate group) was obtained. Next, the obtained resin composition is supplied to a single screw extruder equipped with a T die, and under the following conditions,
An EVOH film having a thickness of 120 μm was formed, and generation of fine fish eyes having a diameter of less than 0.1 mm and evaluation of long-run formability were performed in the following manner.
【0024】 [単軸押出機による製膜条件] スクリュー内径 40mm L/D 28 スクリュー圧縮比 3.2 Tダイ コートハンガータイプ ダイ巾 450mm 押出温度 C1:180℃、 H:210℃ C2:200℃、 D:210℃ C3:220℃、 C4:220℃[Film forming conditions by single screw extruder] Screw inner diameter 40 mm L / D 28 Screw compression ratio 3.2 T die Coat hanger type Die width 450 mm Extrusion temperature C1: 180 ° C, H: 210 ° C C2: 200 ° C, D: 210 ° C C3: 220 ° C, C4: 220 ° C
【0025】(フィッシュアイ)上記の成形直後のフィ
ルム(10cm×10cm)について、直径が0.01
mm以上で0.1mm未満のフィッシュアイの発生状況
を目視観察して、以下のとおり評価とした。 ◎ −−− 0〜 3個 ○ −−− 4〜10個 △ −−− 11〜50個 × −−− 51個以上 (ロングラン成形性)また、上記の成形を10日間連続
に行って、その時の成形フィルムについて、同様にフィ
ッシュアイの増加状況を目視観察して、以下のとおり評
価した。 ○ −−− 増加は認められなかった △ −−− 若干の増加が認められた × −−− 著しい増加が認められた(Fish Eye) The film (10 cm × 10 cm) immediately after molding has a diameter of 0.01
The occurrence of fish eyes of not less than 0.1 mm and less than 0.1 mm was visually observed and evaluated as follows. ◎ −−− 0 to 3 pieces ○ −−− 4 to 10 pieces △ −−− 11 to 50 pieces × −−− 51 or more (long-run moldability) In the same manner, the increase in the number of fish eyes was visually observed with respect to the formed film, and evaluated as follows. ○ −−− No increase was observed △ −−− A slight increase was observed × −−− A remarkable increase was observed
【0026】実施例2 [混合液(I)の調製]0.15%の酢酸(B)水溶液
に、リン酸二水素カリウム(C)を混合液(I)中に
0.057%となる様に溶解させて混合液(I)を得
た。次いで、上記の混合液(I)に、エチレン含有量4
0モル%、ケン化度99モル%、MI6g/10分(2
10℃、荷重2160g)のEVOH(A)を投入し
て、30℃で4時間撹拌した後、110℃で9時間乾燥
を行って、EVOH(A)100重量部に対して、酢酸
(B)およびリン酸二水素カリウム(C)をそれぞれ
0.01重量部および0.02重量部(リン酸根換算)
含有するEVOH組成物を得て、実施例1と同様に評価
を行った。Example 2 [Preparation of mixture (I)] Potassium dihydrogen phosphate (C) was added to a 0.15% aqueous acetic acid (B) solution so that the mixture (I) became 0.057%. To give a mixture (I). Next, an ethylene content of 4 was added to the mixture (I).
0 mol%, saponification degree 99 mol%, MI 6 g / 10 min (2
After charging EVOH (A) at 10 ° C. and a load of 2160 g), stirring at 30 ° C. for 4 hours, drying at 110 ° C. for 9 hours, acetic acid (B) was added to 100 parts by weight of EVOH (A). 0.01 parts by weight and 0.02 parts by weight of potassium dihydrogen phosphate (C) (in terms of phosphate radical)
An EVOH composition was obtained and evaluated in the same manner as in Example 1.
【0027】実施例3 実施例1において、6%の酢酸(B)水溶液に、0.9
2%のリン酸二水素マグネシウム(C)を仕込んで溶解
させた後、50倍の水で希釈して混合液(I)を調製し
た以外は同様に行って、EVOH(A)100重量部に
対して、酢酸(B)およびリン酸二水素マグネシウム
(C)をそれぞれ0.009重量部および0.018重
量部(リン酸根換算)含有するEVOH組成物を得て、
同様に評価を行った。Example 3 In Example 1, 0.9% aqueous solution of acetic acid (B) was added in 0.9%.
2% magnesium dihydrogen phosphate (C) was charged and dissolved, and the same procedure was repeated except that the mixture was diluted with 50-fold water to prepare a mixed solution (I). On the other hand, an EVOH composition containing 0.009 parts by weight and 0.018 parts by weight (in terms of phosphate radical) of acetic acid (B) and magnesium dihydrogen phosphate (C) respectively was obtained,
Evaluation was performed similarly.
【0028】実施例4 実施例1において、4%の酢酸(B)水溶液に、0.0
8%のリン酸二水素ナトリウム(C)を仕込んで溶解さ
せた後、50倍の水で希釈して混合液(I)を調製した
以外は同様に行って、EVOH(A)100重量部に対
して、酢酸(B)およびリン酸二水素ナトリウム(C)
をそれぞれ0.006重量部および0.008重量部
(リン酸根換算)含有するEVOH組成物を得て、同様
に評価を行った。Example 4 In Example 1, 0.0% aqueous solution of 4% acetic acid (B) was added.
8% sodium dihydrogen phosphate (C) was charged and dissolved, and the same procedure was repeated except that the mixture was diluted with 50-fold water to prepare a mixed solution (I). On the other hand, acetic acid (B) and sodium dihydrogen phosphate (C)
Was obtained in the same manner as above, and the same evaluation was performed.
【0029】実施例5 実施例1において、EVOH(A)として、エチレン含
有量30モル%、ケン化度99.5モル%、MI20g
/10分(210℃、荷重2160g)のEVOH(A
1)とエチレン含有量42モル%、ケン化度99.6モ
ル%、MI15g/10分(210℃、荷重2160
g)のEVOH(A2)の混合物(A1/A2の混合重量比が
70/30)を用いた以外は同様に行って、EVOH
(A)100重量部に対して、酢酸(B)およびリン酸
二水素カルシウム(C)をそれぞれ0.009重量部お
よび0.005重量部(リン酸根換算)含有するEVO
H組成物を得て、同様に評価を行った。Example 5 In Example 1, as EVOH (A), ethylene content was 30 mol%, saponification degree was 99.5 mol%, and MI was 20 g.
EVOH (A) for 10 minutes (210 ° C., load 2160 g)
1) and ethylene content of 42 mol%, saponification degree of 99.6 mol%, MI of 15 g / 10 min (210 ° C., load of 2160
g), except that a mixture of EVOH (A2) (mixing weight ratio of A1 / A2 is 70/30) was used.
(A) EVO containing 0.009 parts by weight and 0.005 parts by weight (in terms of phosphate radical) of acetic acid (B) and calcium dihydrogen phosphate (C) with respect to 100 parts by weight, respectively.
An H composition was obtained and evaluated similarly.
【0030】実施例6 実施例1において、EVOH(A)として、エチレン含
有量30モル%、ケン化度99.5モル%、MI20g
/10分(210℃、荷重2160g)のEVOH(A
1)とエチレン含有量47モル%、ケン化度97モル
%、MI35g/10分(210℃、荷重2160g)
のEVOH(A2)の混合物(A1/A2の混合重量比が80
/20)を用いた以外は同様に行って、EVOH(A)
100重量部に対して、酢酸(B)およびリン酸二水素
カルシウム(C)をそれぞれ0.009重量部および
0.005重量部(リン酸根換算)含有するEVOH組
成物を得て、同様に評価を行った。Example 6 In Example 1, as EVOH (A), ethylene content was 30 mol%, saponification degree was 99.5 mol%, and MI was 20 g.
EVOH (A) for 10 minutes (210 ° C., load 2160 g)
1) and ethylene content 47 mol%, saponification degree 97 mol%, MI 35 g / 10 min (210 ° C., load 2160 g)
Of EVOH (A2) (A1 / A2 mixture weight ratio of 80
/ 20), except that EVOH (A) was used.
An EVOH composition containing 0.009 parts by weight and 0.005 parts by weight (in terms of phosphate radical) of acetic acid (B) and calcium dihydrogen phosphate (C) with respect to 100 parts by weight, respectively, was obtained and evaluated similarly. Was done.
【0031】実施例7 0.6%の酢酸(B)水溶液に、リン酸二水素カルシウ
ム(C)を混合液(I)中に0.2%となる様に仕込ん
で溶解させて混合液(I)を得た。次いで、上記の混合
液をエチレン含有量40モル%、ケン化度99モル%、
MI6g/10分(210℃、荷重2160g)のEV
OH(A)のケン化後の水/メタノール溶液に練り込
み、多孔性析出物(ペレット)とした後、水で洗浄し、
110℃で9時間乾燥を行って、EVOH(A)100
重量部に対して、酢酸(B)およびリン酸二水素カルシ
ウム(C)をそれぞれ0.01重量部および0.022
重量部(リン酸根換算)含有するEVOH組成物を得
て、同様の評価を行った。Example 7 A mixture of calcium dihydrogen phosphate (C) was dissolved in a 0.6% aqueous solution of acetic acid (B) so as to be 0.2% in the mixture (I). I got. Next, the above mixture was subjected to an ethylene content of 40 mol%, a saponification degree of 99 mol%,
EV of MI 6g / 10min (210 ° C, load 2160g)
Kneaded into a water / methanol solution after saponification of OH (A) to form a porous precipitate (pellet), and then washed with water,
After drying at 110 ° C. for 9 hours, EVOH (A) 100
Acetic acid (B) and calcium dihydrogen phosphate (C) were added in an amount of 0.01 part by weight and 0.022 part by weight, respectively.
An EVOH composition containing parts by weight (in terms of phosphate groups) was obtained and subjected to the same evaluation.
【0032】実施例8 8%の酢酸(B)水溶液に、リン酸二水素マグネシウム
(C)を0.75%となる様に仕込んで溶解させ、更に
これを25倍の水で希釈して、最終的に0.32%の酢
酸(B)及び0.03%のリン酸二水素マグネシウム
(C)を含有する混合液(I)を得た。次いで、上記の
混合液をエチレン含有量35モル%、ケン化度99.5
モル%、MI20g/10分(210℃、荷重2160
g)のEVOH(A)のケン化後の水/メタノール溶液
に練り込み、多孔性析出物(ペレット)とした後、水で
洗浄し、110℃で8時間乾燥を行って、EVOH
(A)100重量部に対して、酢酸(B)およびリン酸
二水素マグネシウム(C)をそれぞれ0.01重量部お
よび0.007重量部(リン酸根換算)含有するEVO
H組成物を得て、同様の評価を行った。Example 8 Magnesium dihydrogen phosphate (C) was charged and dissolved in an 8% aqueous acetic acid (B) solution to a concentration of 0.75%, and this was further diluted with 25-fold water. Finally, a mixture (I) containing 0.32% acetic acid (B) and 0.03% magnesium dihydrogen phosphate (C) was obtained. Then, the mixture was treated with an ethylene content of 35 mol% and a saponification degree of 99.5.
Mol%, MI 20 g / 10 min (210 ° C., load 2160
g) into a water / methanol solution after saponification of EVOH (A) to form a porous precipitate (pellet), followed by washing with water and drying at 110 ° C. for 8 hours to obtain EVOH.
(A) EVO containing 0.01 parts by weight and 0.007 parts by weight (in terms of phosphate radical) of acetic acid (B) and magnesium dihydrogen phosphate (C) with respect to 100 parts by weight, respectively.
An H composition was obtained and the same evaluation was performed.
【0033】比較例1 実施例1のEVOH(A)のケン化後の水/メタノール
溶液の多孔性析出物(EVOH(A)100部に対して
水100部含有)100部に水500部を混合してスラ
リー化し、更に1%酢酸(B)水溶液50部および0.
3%リン酸二水素カルシウム(C)水溶液50部を同時
に加えて、30℃で5時間撹拌した後、110℃で8時
間乾燥を行って、EVOH(A)100重量部に対し
て、酢酸(B)およびリン酸二水素カルシウム(C)を
それぞれ0.01重量部および0.01重量部(リン酸
根換算)含有する樹脂組成物を得て、実施例1と同様に
評価を行った。実施例、比較例のそれぞれの評価結果を
表1にまとめて示す。Comparative Example 1 500 parts of water was added to 100 parts of the porous precipitate of the water / methanol solution after saponification of EVOH (A) of Example 1 (containing 100 parts of water with respect to 100 parts of EVOH (A)). The mixture was slurried, and 50 parts of a 1% aqueous acetic acid (B) solution and 0.1 part of a 0.1% aqueous acetic acid (B) solution were added.
50 parts of a 3% aqueous solution of calcium dihydrogen phosphate (C) were simultaneously added thereto, and the mixture was stirred at 30 ° C. for 5 hours, and then dried at 110 ° C. for 8 hours. A resin composition containing B) and 0.01 parts by weight (calculated as phosphate radicals) of calcium dihydrogen phosphate (C) was obtained, and was evaluated in the same manner as in Example 1. Table 1 shows the evaluation results of the examples and comparative examples.
【0034】[0034]
【表1】 フィッシュアイ ロングラン成形性 実施例1 ◎ ○ 〃 2 ○ ○ 〃 3 ◎ ○ 〃 4 ◎ ○ 〃 5 ◎ ○ 〃 6 ◎ ○ 〃 7 ○ ○ 〃 8 ◎ ○ 比較例1 × △ TABLE 1 fisheye long-run moldability Example 1 ◎ ○ 〃 2 ○ ○ 〃 3 ◎ ○ 〃 4 ◎ ○ 〃 5 ◎ ○ 〃 6 ◎ ○ 〃 7 ○ ○ 〃 8 ◎ ○ Comparative Example 1 × △
【0035】[0035]
【発明の効果】本発明の方法で得られた樹脂組成物は、
直径が0.1mm未満の微細なフィッシュアイの発生が
なく、かつロングラン成形性にも優れ、各種の積層体と
することができ、食品や医薬品、農薬品、工業薬品包装
用のフィルム、シート、チューブ、袋、容器等の用途に
非常に有用で、延伸を伴う二次加工製品等にも好適に用
いることができる。The resin composition obtained by the method of the present invention comprises:
There is no generation of fine fish eyes with a diameter of less than 0.1 mm, and it has excellent long-run moldability, and can be used as various types of laminates. Films and sheets for packaging foods, pharmaceuticals, agricultural chemicals, industrial chemicals, It is very useful for applications such as tubes, bags, and containers, and can be suitably used for secondary processed products that involve stretching.
Claims (6)
(A)、酢酸(B)およびリン酸化合物(C)を含有し
てなる樹脂組成物を製造するにあたり、酢酸(B)水溶
液にリン酸化合物(C)を仕込んで溶解させた混合液
(I)に、エチレン−酢酸ビニル共重合体ケン化物
(A)を接触せしめることを特徴とする樹脂組成物の製
造法。In producing a resin composition containing a saponified ethylene-vinyl acetate copolymer (A), acetic acid (B) and a phosphoric acid compound (C), phosphoric acid is added to an aqueous solution of acetic acid (B). A method for producing a resin composition, comprising bringing a saponified ethylene-vinyl acetate copolymer (A) into contact with a mixture (I) in which a compound (C) has been charged and dissolved.
005〜1重量%であることを特徴とする請求項1記載
の樹脂組成物の製造法。2. The acetic acid (B) concentration in the mixture (I) is 0.
The method for producing a resin composition according to claim 1, wherein the amount is from 005 to 1% by weight.
度が0.0001〜0.5重量%であることを特徴とす
る請求項1または2記載の樹脂組成物の製造法。3. The method for producing a resin composition according to claim 1, wherein the concentration of the phosphoric acid compound (C) in the mixture (I) is 0.0001 to 0.5% by weight.
濃度1〜10重量%の水溶液にリン酸化合物(C)を仕
込んで溶解させた後、水希釈して調製されたものである
ことを特徴とする請求項1〜3いずれか記載の樹脂組成
物の製造法。4. The mixed solution (I) is preliminarily prepared with acetic acid (B).
The resin composition according to any one of claims 1 to 3, which is prepared by dissolving a phosphoric acid compound (C) in an aqueous solution having a concentration of 1 to 10% by weight, and then diluting with water. Manufacturing method.
リウム、リン酸二水素カリウム、リン酸二水素カルシウ
ム、リン酸二水素マグネシウムから選ばれる少なくとも
1種であることを特徴とする請求項1〜4いずれか記載
の樹脂組成物の製造法。5. The phosphoric acid compound (C) is at least one selected from sodium dihydrogen phosphate, potassium dihydrogen phosphate, calcium dihydrogen phosphate, and magnesium dihydrogen phosphate. 5. The method for producing the resin composition according to any one of 1 to 4.
100重量部に対して0.05重量部以下、(C)の含
有量をリン酸根換算で(A)100重量部に対して0.
0005〜0.05重量部とすることを特徴とする請求
項1〜5いずれか記載の樹脂組成物の製造法。6. The resin composition according to claim 1, wherein the content of (B) is (A)
0.05 parts by weight or less based on 100 parts by weight, and the content of (C) is 0.1% based on 100 parts by weight of (A) in terms of phosphate group.
The method for producing a resin composition according to any one of claims 1 to 5, wherein the amount is from 0005 to 0.05 part by weight.
Priority Applications (7)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP29341597A JP3841941B2 (en) | 1997-10-09 | 1997-10-09 | Production method of resin composition |
EP98933923A EP0930339B1 (en) | 1997-07-25 | 1998-07-24 | Resin composition, process for preparing the same, and laminate containing layer of said resin composition |
PCT/JP1998/003310 WO1999005213A1 (en) | 1997-07-25 | 1998-07-24 | Resin composition, process for preparing the same, and laminate containing layer of said resin composition |
US09/269,222 US6174949B1 (en) | 1997-07-25 | 1998-07-24 | Resin composition, process for preparing the same, and laminate containing layer of said resin composition |
AU83576/98A AU741372B2 (en) | 1997-07-25 | 1998-07-24 | Resin composition, process for preparing the same, and laminate containing layer of said resin composition |
DE69821905T DE69821905T2 (en) | 1997-07-25 | 1998-07-24 | RESIN COMPOSITION, METHOD FOR THE PRODUCTION THEREOF AND LAMINATES CONTAINING A LAYER OF THIS RESIN COMPOSITION |
CA002267756A CA2267756C (en) | 1997-07-25 | 1998-07-24 | Resin composition, production thereof, and laminate comprising a layer composed of said resin composition |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP29341597A JP3841941B2 (en) | 1997-10-09 | 1997-10-09 | Production method of resin composition |
Publications (2)
Publication Number | Publication Date |
---|---|
JPH11116758A true JPH11116758A (en) | 1999-04-27 |
JP3841941B2 JP3841941B2 (en) | 2006-11-08 |
Family
ID=17794483
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP29341597A Expired - Fee Related JP3841941B2 (en) | 1997-07-25 | 1997-10-09 | Production method of resin composition |
Country Status (1)
Country | Link |
---|---|
JP (1) | JP3841941B2 (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2005538243A (en) * | 2003-06-20 | 2005-12-15 | 長春石油化學股▲分▼有限公司 | Method for enhancing processing heat resistance of ethylene-vinyl alcohol copolymer |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP4164151B2 (en) * | 1998-04-08 | 2008-10-08 | 日本合成化学工業株式会社 | Manufacturing method of resin composition |
JP4125417B2 (en) * | 1998-04-08 | 2008-07-30 | 日本合成化学工業株式会社 | Manufacturing method of resin composition |
JP4082780B2 (en) * | 1998-04-08 | 2008-04-30 | 日本合成化学工業株式会社 | Manufacturing method of resin composition |
-
1997
- 1997-10-09 JP JP29341597A patent/JP3841941B2/en not_active Expired - Fee Related
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2005538243A (en) * | 2003-06-20 | 2005-12-15 | 長春石油化學股▲分▼有限公司 | Method for enhancing processing heat resistance of ethylene-vinyl alcohol copolymer |
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JP3841941B2 (en) | 2006-11-08 |
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