JP2000136281A - Resin composition and use thereof - Google Patents

Resin composition and use thereof

Info

Publication number
JP2000136281A
JP2000136281A JP10310088A JP31008898A JP2000136281A JP 2000136281 A JP2000136281 A JP 2000136281A JP 10310088 A JP10310088 A JP 10310088A JP 31008898 A JP31008898 A JP 31008898A JP 2000136281 A JP2000136281 A JP 2000136281A
Authority
JP
Japan
Prior art keywords
resin composition
layer
weight
resin
evoh
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.)
Pending
Application number
JP10310088A
Other languages
Japanese (ja)
Inventor
Kenji Nimiya
賢二 仁宮
Tomoyuki Yamamoto
友之 山本
Hiroki Masumoto
博樹 増元
Yasushi Kita
康司 北
Masahiko Toyozumi
政彦 豊住
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.)
Nippon Synthetic Chemical Industry Co Ltd
Original Assignee
Nippon Synthetic Chemical Industry Co Ltd
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 by Nippon Synthetic Chemical Industry Co Ltd filed Critical Nippon Synthetic Chemical Industry Co Ltd
Priority to JP10310088A priority Critical patent/JP2000136281A/en
Publication of JP2000136281A publication Critical patent/JP2000136281A/en
Pending legal-status Critical Current

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B9/00—Making granules
    • B29B9/12—Making granules characterised by structure or composition
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B9/00—Making granules
    • B29B9/02—Making granules by dividing preformed material
    • B29B9/06—Making granules by dividing preformed material in the form of filamentary material, e.g. combined with extrusion

Landscapes

  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Packging For Living Organisms, Food Or Medicinal Products That Are Sensitive To Environmental Conditiond (AREA)
  • Laminated Bodies (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

PROBLEM TO BE SOLVED: To obtain the subject composition excellent in long-run moldability, gas barrier properties, retort resistance, etc., and useful for a packaged multilayered laminate, etc., for boiling sterilization or retort sterilization by including a saponified ethylene-vinyl acetate copolymer, an alcohol-soluble polyamide-based resin, etc. SOLUTION: This resin composition is obtained by including (A) a saponified ethylene-vinyl acetate copolymer having preferably 25-35 mol% ethylene content and >=99 mol% degree of saponification of the vinyl acetate, (B) an alcohol- soluble polyamide-based resin which is preferably a terpolymer, etc., of nylon 6, 66 and 610 and (C) a phoshoric salt such as dihydrogenmagnesium phosphate preferably in (99.9/0.1) to (50/50) weight ratio of the components A/B. The amount of the contained component C is 0.001-0.05 pt.wt. expressed in terms of phosphate radicals based on 100 pts.wt. of the component A. The composition is useful for applications such as films for packaging foods, medicines, agrochemicals or industrial chemicals.

Description

【発明の詳細な説明】DETAILED DESCRIPTION OF THE INVENTION

【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）を
主成分とする樹脂組成物およびその積層体に関し、更に
詳しくは、ロングラン成形性、ガスバリア性、耐レトル
ト性等に優れた樹脂組成物およびその積層体に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a resin composition containing a saponified ethylene-vinyl acetate copolymer (hereinafter abbreviated as EVOH) as a main component and a laminate thereof. The present invention relates to a resin composition excellent in gas barrier properties, retort resistance and the like, and a laminate thereof.

【０００２】[0002]

【従来の技術】従来より、ＥＶＯＨとポリアミド系樹脂
との組成物は、前者に基づくガスバリア性、耐油性、耐
溶剤性に、後者に基づく耐衝撃性、耐熱水性が付与され
た特性を有していることから、食品包装用のフィルム、
シート、容器等をはじめとする各種の包装用途に多用さ
れている。2. Description of the Related Art Heretofore, a composition of EVOH and a polyamide resin has characteristics of imparting gas barrier properties, oil resistance, and solvent resistance based on the former to impact resistance and hot water resistance based on the latter. From the film for food packaging,
It is widely used for various packaging applications such as sheets and containers.

【０００３】特に、該組成物層と他の熱可塑性樹脂層か
らなる積層体は、食品のボイル用或いはレトルト用の包
装材料として有用であることが知られている。しかしな
がら、該組成物は熱安定性に乏しいことから、溶融成形
を長時間にわたって連続して行えない、いわゆるロング
ラン成形性に劣るという欠点を有し、さらに耐レトルト
性（ボイル或いはレトルト処理後の成形体の外観性やガ
スバリア性の回復程度）についても改善の余地がある。
ロングラン成形性を改善する目的で、特開平４−３０４
２５３号公報には有機酸を配合する処方が、特開平７−
９７４９１号公報には２種のアルカリ土類金属塩を配合
する処方が、特開平８−２５９７５６号公報にはジアミ
ン化合物とカルボン酸により末端を変性されたポリアミ
ド系樹脂を使用する処方の記載がある。さらに、ボイル
或いはレトルト処理後の成形体の外観性を改善する目的
で、特開平１０−８０９８１号公報には、ＥＶＯＨ５５
〜９７重量部とポリアミド系樹脂４５〜３重量部からな
る樹脂組成物の層を最外層とし、内層に低透湿性の熱可
塑性樹脂が積層された多層包装体が、特開平４−１３１
２３７号公報には、ホウ酸化合物や酢酸塩等の金属化合
物を配合する処方が、特開平６−２３９２４号公報に
は、中間層に２種ＥＶＯＨとポリアミド系樹脂からなる
樹脂組成物を用いることが記載されている。[0003] In particular, it is known that a laminate comprising the composition layer and another thermoplastic resin layer is useful as a packaging material for boiling or retorting foods. However, since the composition has poor thermal stability, it has a drawback that melt molding cannot be continuously performed for a long time, that is, it is inferior in so-called long-run moldability, and further has retort resistance (forming after boiling or retort treatment). There is also room for improvement in the appearance of the body and the degree of recovery of gas barrier properties).
For the purpose of improving long-run formability, Japanese Patent Application Laid-Open No. 4-304
No. 253 discloses a formulation containing an organic acid.
Japanese Patent Application Laid-Open No. 97491/1990 describes a formulation for mixing two kinds of alkaline earth metal salts, and Japanese Patent Application Laid-Open No. 8-259756 describes a formulation for using a polyamide resin whose terminal is modified with a diamine compound and a carboxylic acid. . Further, for the purpose of improving the appearance of the molded product after the boiling or retorting treatment, JP-A-10-80981 discloses EVOH55.
Japanese Patent Application Laid-Open No. 4-131 discloses a multilayer package in which a layer of a resin composition comprising 97 parts by weight and 45 to 3 parts by weight of a polyamide resin is used as an outermost layer and an inner layer is laminated with a thermoplastic resin having low moisture permeability.
No. 237 discloses a formulation for mixing a metal compound such as a boric acid compound or an acetate, and Japanese Patent Application Laid-Open No. Hei 6-23924 discloses that a resin composition comprising two kinds of EVOH and a polyamide resin is used for an intermediate layer. Is described.

【０００４】[0004]

【発明が解決しようとする課題】しかしながら、本発明
者らが上記の各公報開示技術について、詳細に検討を行
った結果、特開平４−３０４２５３号公報や特開平７−
９７４９１号公報に開示の技術では、ロングラン成形性
の改善は見られるものの、ボイル或いはレトルト処理後
の成形体の外観性の改善については十分ではなく、ま
た、特開平１０−８０９８１号公報、特開平４−１３１
２３７号公報、特開平６−２３９２４号公報等に開示の
技術では、ボイル或いはレトルト処理後の成形体の外観
性の改善は見られるものの、ロングラン成形性の改善に
ついては十分ではなく、両者を同時に満足させることは
困難であり、更に特開平８−２５９７５６号公報の開示
技術についても、上記のロングラン成形性の改善やボイ
ル或いはレトルト処理後の成形体の外観性の改善は認め
られるものの、ボイル或いはレトルト処理後のガスバリ
ア性の回復という点で改善の余地が残るものであり、ロ
ングラン成形性、ガスバリア性、耐レトルト性等の全て
にバランスのとれた樹脂組成物が望まれるところであ
る。However, the inventors of the present invention have conducted detailed studies on the above-mentioned publications, and as a result, disclosed in Japanese Patent Application Laid-Open Nos. 4-304253 and 7-304.
Although the technology disclosed in Japanese Patent No. 97491 can improve the long-run moldability, it does not sufficiently improve the appearance of the molded product after the boiling or retort treatment. 4-131
In the techniques disclosed in Japanese Patent Application Laid-Open No. 237,237 and Japanese Patent Application Laid-Open No. Hei 6-23924, although the appearance of the molded body after boiling or retort treatment is improved, the improvement in long-run moldability is not sufficient. It is difficult to satisfy the requirements, and with the technology disclosed in Japanese Patent Application Laid-Open No. Hei 8-259756, although the improvement of the long-run formability and the improvement of the appearance of the molded product after the boil or retort treatment are recognized, There is room for improvement in terms of recovery of gas barrier properties after retort treatment, and a resin composition that balances all of long-run moldability, gas barrier properties, retort resistance, and the like is desired.

【０００５】[0005]

【課題を解決するための手段】そこで、本発明者らはか
かる問題を解決するため鋭意研究を重ねた結果、ＥＶＯ
Ｈ（Ａ）、アルコール可溶性ポリアミド系樹脂（Ｂ）及
びリン酸塩（Ｃ）を含有してなる樹脂組成物が、上記の
課題を解決できることを見出し、更にはホウ素化合物、
脂肪酸塩から選ばれる少なくとも１種（Ｄ）を配合する
ことにより、本発明の効果がより顕著に得られることを
見出し、本発明を完成するに至った。The inventors of the present invention have conducted intensive studies in order to solve such a problem and found that EVO
H (A), a resin composition containing an alcohol-soluble polyamide resin (B) and a phosphate (C) have been found to be able to solve the above-mentioned problems, and further have a boron compound,
It has been found that the effects of the present invention can be more remarkably obtained by blending at least one type (D) selected from fatty acid salts, and the present invention has been completed.

【０００６】[0006]

【発明の実施の形態】以下、本発明について具体的に説
明する。本発明に用いられるＥＶＯＨ（Ａ）としては、
特に限定されないが、エチレン含量２０〜６０モル％
（更には２０〜４５モル％、特に２５〜３５モル％）
で、酢酸ビニル成分のケン化度が９０モル％以上（更に
は９５モル％以上、特に９９モル％以上）のものが用い
られ、該エチレン含有量が２０モル％未満では高湿時の
ガスバリア性、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ア性が得られず、更にケン化度
が９０モル％未満ではガスバリア性、熱安定性、耐湿性
等が低下して好ましくない。特にＥＶＯＨ（Ａ）とし
て、エチレン含量が２５〜３５モル％で、かつ酢酸ビニ
ル成分のケン化度が９９モル％以上のものを用いた場合
に、本発明の効果を顕著に得ることができる。BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described specifically. EVOH (A) used in the present invention includes:
Although not particularly limited, an ethylene content of 20 to 60 mol%
(Furthermore, 20 to 45 mol%, especially 25 to 35 mol%)
A vinyl acetate component having a degree of saponification of 90 mol% or more (more preferably 95 mol% or more, particularly 99 mol% or more) is used. If the ethylene content is less than 20 mol%, the gas barrier property at high humidity is used. On the other hand, if it exceeds 60 mol%, sufficient gas barrier properties cannot be obtained, and if the saponification degree is less than 90 mol%, the gas barrier properties, heat stability, moisture resistance, etc. decrease, which is preferable. Absent. In particular, when the EVOH (A) has an ethylene content of 25 to 35 mol% and a degree of saponification of a vinyl acetate component of 99 mol% or more, the effect of the present invention can be remarkably obtained.

【０００７】また、ＥＶＯＨ（Ａ）のメルトインデック
ス（ＭＩ）は、０．５〜５０ｇ／１０分（２１０℃、２
１６０ｇ荷重）が好ましく、更には１〜３５ｇ／１０分
（同上）が好ましい。かかるＭＩが０．５ｇ／１０分
（同上）未満では、粘度が高くなり過ぎて溶融押出しが
困難となることがあり、逆に５０ｇ／１０分（同上）を
越えると、製膜性が不安定となることがあり好ましくな
い。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、溶液重合、懸
濁重合、エマルジョン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。The melt index (MI) of EVOH (A) is 0.5 to 50 g / 10 min (210 ° C., 2
160 g load), more preferably 1 to 35 g / 10 min (as above). If the MI is less than 0.5 g / 10 min (same as above), the viscosity may be too high and melt extrusion may be difficult. If the MI is more than 50 g / 10 min (same as above), the film forming property may be unstable. May be unfavorable. The EVOH (A) is obtained by saponifying an ethylene-vinyl acetate copolymer, and the ethylene-vinyl acetate copolymer can be produced by any known polymerization method, for example, solution polymerization, suspension polymerization, emulsion polymerization and the like. The saponification of the ethylene-vinyl acetate copolymer can also be performed by a known method.

【０００８】また、本発明では、本発明の効果を阻害し
ない範囲で共重合可能なエチレン性不飽和単量体を共重
合していてもよく、かかる単量体としては、プロピレ
ン、１−ブテン、イソブテン等のオレフィン類、アクリ
ル酸、メタクリル酸、クロトン酸、（無水）フタル酸、
（無水）マレイン酸、（無水）イタコン酸等の不飽和酸
類あるいはその塩あるいは炭素数１〜１８のモノまたは
ジアルキルエステル類、アクリルアミド、炭素数１〜１
８のＮ−アルキルアクリルアミド、Ｎ，Ｎ−ジメチルア
クリルアミド、２−アクリルアミドプロパンスルホン酸
あるいはその塩、アクリルアミドプロピルジメチルアミ
ンあるいはその酸塩あるいはその４級塩等のアクリルア
ミド類、メタクリルアミド、炭素数１〜１８のＮ−アル
キルメタクリルアミド、Ｎ，Ｎ−ジメチルメタクリルア
ミド、２−メタクリルアミドプロパンスルホン酸あるい
はその塩、メタクリルアミドプロピルジメチルアミンあ
るいはその酸塩あるいはその４級塩等のメタクリルアミ
ド類、Ｎ−ビニルピロリドン、Ｎ−ビニルホルムアミ
ド、Ｎ−ビニルアセトアミド等のＮ−ビニルアミド類、
アクリルニトリル、メタクリルニトリル等のシアン化ビ
ニル類、炭素数１〜１８のアルキルビニルエーテル、ヒ
ドロキシアルキルビニルエーテル、アルコキシアルキル
ビニルエーテル等のビニルエーテル類、塩化ビニル、塩
化ビニリデン、フッ化ビニル、フッ化ビニリデン、臭化
ビニル等のハロゲン化ビニル類、トリメトキシビニルシ
ラン等のビニルシラン類、酢酸アリル、塩化アリル、ア
リルアルコール、ジメチルアリルアルコール、トリメチ
ル−（３−アクリルアミド−３−ジメチルプロピル）−
アンモニウムクロリド、アクリルアミド−２−メチルプ
ロパンスルホン酸等が挙げられる。In the present invention, a copolymerizable ethylenically unsaturated monomer may be copolymerized as long as the effects of the present invention are not impaired. Examples of such a monomer include propylene and 1-butene. , Olefins such as isobutene, acrylic acid, methacrylic acid, crotonic acid, (anhydrous) phthalic acid,
Unsaturated acids such as (anhydride) maleic acid and (anhydride) itaconic acid or salts thereof, mono- or dialkyl esters having 1 to 18 carbon atoms, acrylamide, 1 to 1 carbon atoms
8, acrylamides such as N-alkylacrylamide, N, N-dimethylacrylamide, 2-acrylamidopropanesulfonic acid or a salt thereof, acrylamidopropyldimethylamine or an acid salt thereof or a quaternary salt thereof, methacrylamide, having 1 to 18 carbon atoms Methacrylamides such as N-alkyl methacrylamide, N, N-dimethyl methacrylamide, 2-methacrylamidopropanesulfonic acid or a salt thereof, methacrylamidopropyldimethylamine or an acid salt thereof or a quaternary salt thereof, N-vinylpyrrolidone N-vinylamides such as, N-vinylformamide and N-vinylacetamide;
Vinyl cyanides such as acrylonitrile and methacrylonitrile; vinyl ethers such as alkyl vinyl ethers having 1 to 18 carbon atoms, hydroxyalkyl vinyl ethers and alkoxyalkyl vinyl ethers; vinyl chloride, vinylidene chloride, vinyl fluoride, vinylidene fluoride and vinyl bromide And vinylsilanes such as trimethoxyvinylsilane, allyl acetate, allyl chloride, allyl alcohol, dimethylallyl alcohol, trimethyl- (3-acrylamido-3-dimethylpropyl)-
Examples thereof include ammonium chloride and acrylamide-2-methylpropanesulfonic acid.

【０００９】本発明に用いられるアルコール可溶性ポリ
アミド系樹脂（Ｂ）とは、メタノール、エタノールなど
の低級脂肪族アルコールに完全に均一に溶解するポリア
ミド系樹脂を意味し、これらのアルコールに可溶性のも
のであればいずれも使用可能である。代表的には、ドデ
シレンジアミン、ヘキサメチレンジアミン、ピペラジ
ン、テトラメチレンジアミン、トリメチレンジアミン、
エチレンジアミン、トリメチルヘキサメチレンジアミ
ン、ｍ−キシリレンジアミン、ｐ−キシリレンジアミン
等のジアミン成分と、γ−ブチロラクタム、δ−バレロ
ラクタム、ε−カプロラクタム、ω−ラウロラクタム、
ω−アミノウンデカン酸、ω−アミノドデカン酸、ω−
アミノヘプタン酸、ω−アミノノナン酸等のアミノカル
ボン酸成分と、テレフタル酸、イソフタル酸、ナフタリ
ンジカルボン酸、アゼライン酸、セバシン酸、ピメリン
酸、アジピン酸、グルタル酸、コハク酸、ドデカン二酸
等の多価カルボン酸成分を原料として得られる共重合ナ
イロンや、ナイロンにホルマリンとメタノールを作用さ
せたＮ−メトキシメチル変性ナイロン、分子中にエーテ
ル基、エステル基、スルホン酸誘導体、アンモニウム塩
などを有する変性ナイロン等が挙げられ、これらの１種
または２種以上が用いられ、ナイロン６・６６・６１０
の三元共重合体、ナイロン６・６６・６１０・１２又は
ナイロン６・６６・６１０・１１の四元共重合体からな
るポリアミド系樹脂が、ロングラン成形性と耐レトルト
性に優れている点で好適に用いられる。The alcohol-soluble polyamide resin (B) used in the present invention means a polyamide resin which is completely and uniformly dissolved in lower aliphatic alcohols such as methanol and ethanol, and is soluble in these alcohols. Any can be used. Typically, dodecylenediamine, hexamethylenediamine, piperazine, tetramethylenediamine, trimethylenediamine,
Diamine components such as ethylenediamine, trimethylhexamethylenediamine, m-xylylenediamine, p-xylylenediamine, and γ-butyrolactam, δ-valerolactam, ε-caprolactam, ω-laurolactam,
ω-aminoundecanoic acid, ω-aminododecanoic acid, ω-
Aminocarboxylic acid components such as aminoheptanoic acid and ω-aminononanoic acid; Nylon obtained by using a polycarboxylic acid component as a raw material, N-methoxymethyl-modified nylon obtained by allowing formalin and methanol to act on nylon, and modified nylon having an ether group, ester group, sulfonic acid derivative, ammonium salt, etc. in the molecule And one or more of these are used, and nylon 6, 66, 610 is used.
Polyamide resin consisting of a terpolymer of nylon 6,66,610,12 or a quaternary copolymer of nylon 6,66,610,11 is excellent in long-run moldability and retort resistance. It is preferably used.

【００１０】本発明においては、上記の如きＥＶＯＨ
（Ａ）およびアルコール可溶性ポリアミド系樹脂（Ｂ）
からなる樹脂組成物に、更に、リン酸塩（Ｃ）を配合し
たことを最大の特徴とするもので、かかる（Ｃ）成分が
配合されない場合は本発明の作用効果を得ることは困難
となる。かかるリン酸塩（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。In the present invention, the above-mentioned EVOH
(A) and alcohol-soluble polyamide resin (B)
The greatest feature of the present invention is that a phosphate (C) is further blended into the resin composition consisting of the above. If such a component (C) is not blended, it is difficult to obtain the effects of the present invention. . Examples of the phosphate (C) include sodium dihydrogen phosphate, disodium hydrogen phosphate, potassium dihydrogen phosphate, dipotassium hydrogen phosphate, tripotassium phosphate, calcium monohydrogen phosphate, and calcium dihydrogen phosphate , Tricalcium phosphate, magnesium phosphate, magnesium hydrogen phosphate, magnesium dihydrogen phosphate, zinc hydrogen phosphate, barium hydrogen phosphate, manganese hydrogen phosphate, and the like, preferably sodium dihydrogen phosphate. , Potassium dihydrogen phosphate, calcium dihydrogen phosphate, and magnesium dihydrogen phosphate are used.

【００１１】本発明の樹脂組成物は、上記の（Ａ）〜
（Ｃ）成分からなるものであるが、その配合割合は、特
に限定されないが、（Ａ）成分及び（Ｂ）成分について
は、Ａ／Ｂ＝９９．９／０．１〜５０／５０（更には９
９／１〜７０／３０、特に９８／２〜９０／１０）（重
量比）とすることが好ましく、かかる配合割合が９９．
９／０．１を越えるときは耐レトルト性が不十分とな
り、逆に５０／５０より少ないときはガスバリア性が不
足することとなって好ましくない。また、（Ｃ）成分の
配合割合も特に限定されないが、ＥＶＯＨ１００重量部
に対してリン酸根換算で０．０００１〜１重量部（更に
は０．０００５〜０．１重量部、特には０．００１〜
０．０５重量部）が好ましく、０．０００１重量部未満
ではロングラン成形性が十分ではなく、逆に１重量部を
越えると最終的に得られる成形物の外観性が低下して好
ましくない。[0011] The resin composition of the present invention comprises the above (A)
Although it is composed of the component (C), its mixing ratio is not particularly limited, but for the component (A) and the component (B), A / B = 99.9 / 0.1 to 50/50 (further, Is 9
9/1 to 70/30, especially 98/2 to 90/10) (weight ratio).
If it exceeds 9 / 0.1, the retort resistance becomes insufficient, and if it is less than 50/50, the gas barrier properties become insufficient, which is not preferable. The mixing ratio of the component (C) is not particularly limited, either, but is 0.0001 to 1 part by weight (further 0.0005 to 0.1 part by weight, particularly 0.001 to 1 part by weight) based on 100 parts by weight of EVOH. ~
0.05 parts by weight) is preferred. If the amount is less than 0.0001 parts by weight, the long-run moldability is not sufficient, and if it exceeds 1 part by weight, the appearance of the finally obtained molded product is undesirably deteriorated.

【００１２】本発明の樹脂組成物を得るには、上記の
（Ａ）〜（Ｃ）成分をブレンドすれば良いのであるが、
具体的には、（Ａ）〜（Ｃ）成分を一括で混合した後
に溶融混練する方法、（Ａ）成分及び（Ｂ）成分を溶
融混練した後に（Ｃ）成分を添加して更に溶融混練する
方法、（Ａ）成分に（Ｃ）成分を含有させた後に
（Ｂ）成分を溶融混練する方法、（Ｂ）成分に（Ｃ）
成分を含有させた後に（Ａ）成分を溶融混練する方法、
（Ａ）、（Ｂ）両成分にそれぞれ（Ｃ）成分を含有さ
せた後に両者を溶融混練する方法、（Ａ）〜（Ｃ）成
分を溶解可能な溶剤中で均一に溶解して混合した後に該
溶剤を除去する方法等を挙げることができ、好適には
の方法が用いられ、かかる方法について、更に詳細に説
明をするが、これに限定されるものではない。The resin composition of the present invention can be obtained by blending the above components (A) to (C).
Specifically, the components (A) to (C) are mixed at once and then melt-kneaded. The components (A) and (B) are melt-kneaded, then the component (C) is added and further melt-kneaded. A method in which the component (B) is melt-kneaded after the component (A) contains the component (C), and the component (B) is added to the component (B).
A method of melt-kneading the component (A) after the component is contained,
(A) and (B) a method in which both components contain the component (C) and then are melt-kneaded, and after the components (A) to (C) are uniformly dissolved and mixed in a solvent capable of being dissolved, A method for removing the solvent can be used, and a suitable method is used. Such a method will be described in more detail, but is not limited thereto.

【００１３】ＥＶＯＨ（Ａ）にリン酸塩（Ｃ）を含有さ
せるにあたっては、リン酸化合物（Ｃ）の水溶液にＥＶ
ＯＨ（Ａ）を接触させることで含有させることができ、
このときの該水溶液中のリン酸塩（Ｃ）の濃度は、０．
０００１〜１０重量％（更には０．０００５〜１重量
％、特には０．００１〜０．５重量部）が好ましく、
０．０００１重量％未満では所定量のリン酸塩を含有さ
せることが困難となり、逆に１０重量％を越えると最終
的に得られる成形物の外観性が低下して好ましくない。
かかる水溶液にＥＶＯＨ（Ａ）を接触させる方法として
は特に限定されないが、通常は該水溶液にペレット状に
成形されたＥＶＯＨ（Ａ）を投入して撹拌しながら、上
記のリン酸塩（Ｃ）を含有させることが好ましい。When the phosphate (C) is contained in the EVOH (A), EVOH (A) is added to an aqueous solution of the phosphate compound (C).
OH (A) can be contained by contacting
At this time, the concentration of the phosphate (C) in the aqueous solution was 0.1%.
0001 to 10% by weight (more preferably 0.0005 to 1% by weight, particularly 0.001 to 0.5% by weight),
If it is less than 0.0001% by weight, it becomes difficult to contain a predetermined amount of phosphate, and if it exceeds 10% by weight, the appearance of a finally obtained molded product is undesirably deteriorated.
The method of bringing EVOH (A) into contact with the aqueous solution is not particularly limited, but usually, the above-mentioned phosphate (C) is added to the aqueous solution while stirring the EVOH (A) formed into pellets and stirring. It is preferable to include them.

【００１４】尚、上記のＥＶＯＨペレットの調製（成
形）にあたっては、公知の方法を採用することができ、
例えば、ＥＶＯＨの水とアルコールの混合溶液等を凝固
液中にストランド状若しくはシート状に押出した後、得
られるストランドやシートをカットしてペレット状にす
ればよい。かかるペレット状のＥＶＯＨの形状として
は、円柱状、球状等のものが好ましく、円柱状の場合は
直径が１〜１０ｍｍ、長さが１〜１０ｍｍが好ましく、
球状の場合は直径が１〜１０ｍｍが好ましい。またかか
るＥＶＯＨは、直径が０．１〜１０μｍ程度の細孔が均
一に分布したミクロポーラスな内部構造をもつものが、
リン酸塩（Ｃ）を均一に含有させ得る点で好ましく、通
常ＥＶＯＨの溶液（水／アルコール混合溶媒等）を凝固
浴中に押し出すときに、ＥＶＯＨ溶液の濃度（２０〜８
０重量％）、押し出し温度（４５〜７０℃）、溶媒の種
類（水／アルコール混合重量比＝８０／２０〜５／９５
等）、凝固浴の温度（１〜２０℃）、滞留時間（０．２
５〜３０時間）、凝固浴中でのＥＶＯＨ量（０．０２〜
２重量％）などを任意に調節することで、該構造のＥＶ
ＯＨを得ることが可能となる。更には含水率２０〜８０
重量％のものが、上記の化合物等を均一にかつ迅速に含
有させることができて好ましい。また、化合物等の含有
量の調整にあたっては、特に限定されないが、前述の水
溶液との接触処理において、化合物等の水溶液濃度、接
触処理時間、接触処理温度、接触処理時の撹拌速度や処
理されるＥＶＯＨの含水率等をコントロールすることで
可能である。こうして上記の（Ｃ）成分を含有したペレ
ット状の含水ＥＶＯＨ樹脂組成物が得られるのである
が、通常は、上記の接触処理後に乾燥工程を経て、樹脂
組成物が得られるのである。In preparing (molding) the above-mentioned EVOH pellets, a known method can be adopted.
For example, after a mixed solution of EVOH water and alcohol is extruded into a coagulating liquid into a strand or a sheet, the resulting strand or sheet may be cut into pellets. As the shape of such a pellet-shaped EVOH, a columnar shape, a spherical shape, or the like is preferable, and in the case of a columnar shape, the diameter is preferably 1 to 10 mm, and the length is preferably 1 to 10 mm,
In the case of a spherical shape, the diameter is preferably 1 to 10 mm. Further, such EVOH has a microporous internal structure in which pores having a diameter of about 0.1 to 10 μm are uniformly distributed,
It is preferable in that the phosphate (C) can be uniformly contained. Usually, when the EVOH solution (water / alcohol mixed solvent or the like) is extruded into the coagulation bath, the concentration of the EVOH solution (20 to 8) is used.
0% by weight), extrusion temperature (45 to 70 ° C.), type of solvent (water / alcohol mixture weight ratio = 80/20 to 5/95)
Etc.), the temperature of the coagulation bath (1 to 20 ° C.), the residence time (0.2
5-30 hours), the amount of EVOH in the coagulation bath (0.02-
2% by weight) to adjust the EV of the structure.
OH can be obtained. Furthermore, the water content is 20 to 80
% By weight is preferable because the above-mentioned compounds and the like can be uniformly and rapidly contained. In addition, in adjusting the content of the compound and the like, although not particularly limited, in the contact treatment with the aqueous solution, the concentration of the aqueous solution of the compound and the like, the contact treatment time, the contact treatment temperature, the stirring speed during the contact treatment and the treatment are performed. It is possible by controlling the water content of EVOH and the like. In this way, a pellet-shaped water-containing EVOH resin composition containing the above-mentioned component (C) is obtained. Usually, the resin composition is obtained through a drying step after the above-mentioned contact treatment.

【００１５】かかる乾燥方法としては、種々の乾燥方法
を採用することが可能である。例えば、実質的にペレッ
ト状等の樹脂組成物が機械的にもしくは熱風により撹拌
分散されながら行われる流動乾燥や、実質的にペレット
状等の樹脂組成物が攪拌、分散などの動的な作用を与え
られずに行われる静置乾燥が挙げられ、流動乾燥を行う
ための乾燥器としては、円筒・溝型撹拌乾燥器、円筒乾
燥器、回転乾燥器、流動層乾燥器、振動流動層乾燥器、
円錐回転型乾燥器等が挙げられ、また、静置乾燥を行う
ための乾燥器として、材料静置型としては回分式箱型乾
燥器が、材料移送型としてはバンド乾燥器、トンネル乾
燥器、竪型乾燥器等を挙げることができるが、これらに
限定されるものではない。流動乾燥と静置乾燥を組み合
わせて行うことも可能である。As such a drying method, various drying methods can be adopted. For example, fluid drying is performed while the resin composition substantially in the form of pellets is stirred or dispersed by mechanical or hot air, or the resin composition substantially in the form of pellets has dynamic effects such as stirring and dispersion. Stationary drying performed without being given is mentioned. Examples of the dryer for performing fluidized drying include a cylindrical / groove type stirring dryer, a cylindrical dryer, a rotary dryer, a fluidized bed dryer, and a vibration fluidized bed dryer. ,
Conical rotary dryers, etc., and as a dryer for performing stationary drying, a batch box dryer as a material stationary type, a band dryer, a tunnel dryer, a vertical dryer as a material transfer type. Examples include, but are not limited to, a mold dryer. It is also possible to combine fluidized drying and standing drying.

【００１６】該乾燥処理時に用いられる加熱ガスとして
は空気または不活性ガス（窒素ガス、ヘリウムガス、ア
ルゴンガス等）が用いられ、該加熱ガスの温度として
は、４０〜１５０℃が、生産性と樹脂組成物の熱劣化防
止の点で好ましい。該乾燥処理の時間としては、樹脂組
成物の含水量やその処理量にもよるが、通常は１５分〜
７２時間程度が、生産性と樹脂組成物の熱劣化防止の点
で好ましい。 上記の条件で樹脂組成物が乾燥処理され
て、（Ａ）及び（Ｃ）からなる樹脂組成物が得られるの
であるが、該乾燥処理後の樹脂組成物の含水率は０．０
０１〜５重量％（更には０．０１〜２重量％、特には
０．１〜１重量部）になるようにするのが好ましく、該
含水率が０．００１重量％未満では、最終的に得られる
本発明の樹脂組成物のロングラン成形性が低下する傾向
にあり、逆に５重量％を越えると次のポリアミド系樹脂
との溶融混練時に発泡が発生しやすくなり好ましくな
い。Air or an inert gas (nitrogen gas, helium gas, argon gas, etc.) is used as the heating gas used in the drying process. The temperature of the heating gas is 40 to 150 ° C. It is preferable from the viewpoint of preventing thermal deterioration of the resin composition. The time for the drying treatment depends on the water content of the resin composition and the amount of the treatment, but is usually from 15 minutes to
About 72 hours is preferable in terms of productivity and prevention of thermal deterioration of the resin composition. The resin composition is dried under the above conditions to obtain a resin composition comprising (A) and (C). The water content of the resin composition after the drying treatment is 0.0%.
It is preferable that the content be from 0.01 to 5% by weight (furthermore, from 0.01 to 2% by weight, especially from 0.1 to 1% by weight). Long-run moldability of the obtained resin composition of the present invention tends to decrease. Conversely, if it exceeds 5% by weight, foaming is likely to occur during melt-kneading with the next polyamide resin, which is not preferable.

【００１７】かくして得られた（Ａ）及び（Ｃ）成分か
らなる樹脂組成物に、更にアルコール可溶性ポリアミド
系樹脂（Ｂ）を溶融混練するのであるが、かかる溶融混
練にあたっては、特に限定はなく、該組成物とアルコー
ル可溶性ポリアミド系樹脂が十分に溶融混練されればよ
く、公知の方法を採用することができる。例えば、ニー
ダールーダー、押出機、ミキシングロール、バンバリー
ミキサー、プラストミル等の公知の混練装置を用いるこ
とができ、通常は１５０〜３００℃（更には１８０〜２
８０℃）で、１分〜１時間程度溶融混練することが好ま
しく、工業的には単軸押出機、二軸押出機等の押出機を
用いることが有利であり、水分の脱揮のためにベント付
き押出機が好ましい。該溶融混練においては、固体状
の該樹脂組成物とポリアミド系樹脂を一括して混合して
溶融混練する方法、溶融状態の該樹脂組成物に固体状
のポリアミド系樹脂を投入して溶融混練する方法、溶
融状態のポリアミド系樹脂に固体状の該樹脂組成物を投
入して溶融混練する方法、溶融状態の該樹脂組成物と
ポリアミド系樹脂を混合して溶融混練する方法等を挙げ
ることができる。The alcohol-soluble polyamide resin (B) is further melt-kneaded with the resin composition comprising the components (A) and (C) thus obtained. The melt-kneading is not particularly limited. It is sufficient that the composition and the alcohol-soluble polyamide resin are sufficiently melt-kneaded, and a known method can be employed. For example, a known kneading device such as a kneader ruder, an extruder, a mixing roll, a Banbury mixer, a plastomill, or the like can be used.
(80 ° C.), it is preferable to melt and knead for about 1 minute to 1 hour, and it is advantageous to use an extruder such as a single screw extruder or a twin screw extruder industrially. Extruders with vents are preferred. In the melt kneading, a method in which the solid resin composition and the polyamide resin are collectively mixed and melt kneaded, and a solid polyamide resin is charged into the molten resin composition and melt kneaded. A method in which the solid resin composition is charged into a molten polyamide resin and melt-kneaded, and a method in which the molten resin composition and the polyamide resin are mixed and melt-kneaded. .

【００１８】本発明においては、かかる（Ａ）〜（Ｃ）
成分からなる樹脂組成物に、更にホウ素化合物、脂肪酸
塩から選ばれる少なくとも１種（Ｄ）が含有されている
ことも好ましく、かかるホウ素化合物としては、ホウ酸
またはその金属塩、例えばホウ酸カルシウム、ホウ酸コ
バルト、ホウ酸亜鉛（四ホウ酸亜鉛，メタホウ酸亜鉛
等）、ホウ酸アルミニウム・カリウム、ホウ酸アンモニ
ウム（メタホウ酸アンモニウム、四ホウ酸アンモニウ
ム、五ホウ酸アンモニウム、八ホウ酸アンモニウム
等）、ホウ酸カドミウム（オルトホウ酸カドミウム、四
ホウ酸カドミウム等）、ホウ酸カリウム（メタホウ酸カ
リウム、四ホウ酸カリウム、五ホウ酸カリウム、六ホウ
酸カリウム、八ホウ酸カリウム等）、ホウ酸銀（メタホ
ウ酸銀、四ホウ酸銀等）、ホウ酸銅（ホウ酸第２銅、メ
タホウ酸銅、四ホウ酸銅等）、ホウ酸ナトリウム（メタ
ホウ酸ナトリウム、二ホウ酸ナトリウム、四ホウ酸ナト
リウム、五ホウ酸ナトリウム、六ホウ酸ナトリウム、八
ホウ酸ナトリウム等）、ホウ酸鉛（メタホウ酸鉛、六ホ
ウ酸鉛等）、ホウ酸ニッケル（オルトホウ酸ニッケル、
二ホウ酸ニッケル、四ホウ酸ニッケル、八ホウ酸ニッケ
ル等）、ホウ酸バリウム（オルトホウ酸バリウム、メタ
ホウ酸バリウム、二ホウ酸バリウム、四ホウ酸バリウム
等）、ホウ酸ビスマス、ホウ酸マグネシウム（オルトホ
ウ酸マグネシウム、二ホウ酸マグネシウム、メタホウ酸
マグネシウム、四ホウ酸三マグネシウム、四ホウ酸五マ
グネシウム等）、ホウ酸マンガン（ホウ酸第１マンガ
ン、メタホウ酸マンガン、四ホウ酸マンガン等）、ホウ
酸リチウム（メタホウ酸リチウム、四ホウ酸リチウム、
五ホウ酸リチウム等）などの他、ホウ砂、カーナイト、
インヨーアイト、コトウ石、スイアン石、ザイベリ石等
のホウ酸塩鉱物などが挙げられ、好適にはホウ砂、ホウ
酸、ホウ酸ナトリウム（メタホウ酸ナトリウム、二ホウ
酸ナトリウム、四ホウ酸ナトリウム、五ホウ酸ナトリウ
ム、六ホウ酸ナトリウム、八ホウ酸ナトリウム等）が用
いられる。In the present invention, such (A) to (C)
It is also preferable that the resin composition composed of the components further contain at least one kind (D) selected from a boron compound and a fatty acid salt. Examples of the boron compound include boric acid or a metal salt thereof, such as calcium borate; Cobalt borate, zinc borate (zinc tetraborate, zinc metaborate, etc.), potassium aluminum borate, ammonium borate (ammonium metaborate, ammonium tetraborate, ammonium pentaborate, ammonium octaborate, etc.), Cadmium borate (cadmium orthoborate, cadmium tetraborate, etc.), potassium borate (potassium metaborate, potassium tetraborate, potassium pentaborate, potassium hexaborate, potassium octaborate, etc.), silver borate (metaborate Silver acid, silver tetraborate, etc.), copper borate (copper borate, copper metaborate, copper tetraborate, etc.) , Sodium borate (sodium metaborate, sodium diborate, sodium tetraborate, sodium pentaborate, sodium hexaborate, sodium octaborate, etc.), lead borate (lead metaborate, lead hexaborate, etc.) , Nickel borate (nickel orthoborate,
Nickel diborate, nickel tetraborate, nickel octaborate, etc., barium borate (barium orthoborate, barium metaborate, barium diborate, barium tetraborate, etc.), bismuth borate, magnesium borate (orthoborate) Magnesium borate, magnesium diborate, magnesium metaborate, trimagnesium tetraborate, pentamagnesium tetraborate, etc., manganese borate (manganese borate, manganese metaborate, manganese tetraborate, etc.), lithium borate (Lithium metaborate, lithium tetraborate,
Lithium pentaborate, etc.), borax, carnite,
Examples include borate minerals such as inyoite, dwarfite, zyanite, and ziberite, and preferably borax, boric acid, sodium borate (sodium metaborate, sodium diborate, sodium tetraborate, pentaborate) Sodium, sodium hexaborate, sodium octaborate, etc.) are used.

【００１９】また、脂肪酸塩としては、酢酸、プロピオ
ン酸、酪酸、ラウリル酸、ステアリン酸、オレイン酸、
ベヘニン酸等のアルカリ金属塩（ナトリウム塩、カリウ
ム塩等）やアルカリ土類金属塩（マグネシウム塩、カル
シウム塩、バリウム塩等）や亜鉛金属塩、マンガン金属
塩などを挙げることができ、好適には酢酸ナトリウム、
酢酸カリウム、酢酸カルシウム、酢酸マグネシウムが用
いられる。かかる（Ｄ）成分の含有割合も特に限定され
ないが、ホウ素化合物の場合は、ＥＶＯＨ１００重量部
に対してホウ素換算で０．００１〜１重量部（更には
０．００２〜０．５重量部、特には０．００５〜０．２
重量部）が好ましく、０．００１重量部未満ではロング
ラン成形性が十分ではなく、逆に１重量部を越えると最
終的に得られる成形物の外観性が低下して好ましくな
い。また、脂肪酸塩の場合は、ＥＶＯＨ１００重量部に
対して金属換算で０．０００５〜０．５重量部（更には
０．００１〜０．０５重量部、特には０．００２〜０．
０３重量）が好ましく、０．０００５重量部未満ではロ
ングラン成形性が十分ではなく、逆に０．５重量部を越
えると最終的に得られる成形物の外観性が低下して好ま
しくない。ホウ素化合物及び脂肪酸塩を併用する場合は
それぞれの含有量が上記の条件を満足することが好まし
い。The fatty acid salts include acetic acid, propionic acid, butyric acid, lauric acid, stearic acid, oleic acid,
Alkali metal salts such as behenic acid (sodium salt, potassium salt, etc.), alkaline earth metal salts (magnesium salt, calcium salt, barium salt, etc.), zinc metal salt, manganese metal salt and the like can be mentioned. Sodium acetate,
Potassium acetate, calcium acetate, and magnesium acetate are used. The content ratio of the component (D) is not particularly limited. In the case of a boron compound, 0.001 to 1 part by weight (furthermore, 0.002 to 0.5 part by weight, particularly Is 0.005 to 0.2
Parts by weight), and if it is less than 0.001 part by weight, the long-run formability is not sufficient, and if it exceeds 1 part by weight, the appearance of the finally obtained molded product is undesirably deteriorated. In the case of a fatty acid salt, 0.0005 to 0.5 parts by weight (furthermore, 0.001 to 0.05 parts by weight, particularly 0.002 to 0.
03 parts by weight), and if it is less than 0.0005 parts by weight, the long-run moldability is not sufficient. On the contrary, if it exceeds 0.5 parts by weight, the appearance of the finally obtained molded product is undesirably deteriorated. When a boron compound and a fatty acid salt are used in combination, it is preferable that the respective contents satisfy the above conditions.

【００２０】上記の（Ｄ）成分を含有するにあたって
は、上記の（Ｃ）成分の含有時に同様に行うことがで
き、このときの水溶液中のホウ素化合物や脂肪酸塩
（Ｄ）の濃度は、ホウ素化合物の場合は０．００１〜１
重量％（更には０．００３〜０．５重量％、特には０．
００５〜０．３重量）が好ましく、０．００１重量％未
満では所定量のホウ素化合物を含有させることが困難と
なり、逆に１重量％を越えると最終的に得られる成形物
の外観性が低下して好ましくない。また、脂肪酸塩の場
合は０．００１〜１重量％（更には０．０１〜０．５重
量％、特には０．０２〜０．３重量）が好ましく、０．
００１重量％未満では所定量の脂肪酸塩を含有させるこ
とが困難となり、逆に１重量％を越えると最終的に得ら
れる成形物の外観性が低下して好ましくない。ホウ素化
合物及び脂肪酸塩を併用する場合はそれぞれの濃度が上
記の条件を満足することが好ましい。The above-mentioned component (D) can be contained in the same manner as when the above-mentioned component (C) is contained. At this time, the concentration of the boron compound or the fatty acid salt (D) in the aqueous solution is adjusted to the boron concentration. 0.001 to 1 for compounds
% By weight (further 0.003 to 0.5% by weight, particularly 0.1% by weight).
005-0.3% by weight), and if it is less than 0.001% by weight, it becomes difficult to contain a predetermined amount of a boron compound. Conversely, if it exceeds 1% by weight, the appearance of a finally obtained molded product is deteriorated. Is not preferred. In the case of a fatty acid salt, the content is preferably 0.001 to 1% by weight (further preferably 0.01 to 0.5% by weight, particularly preferably 0.02 to 0.3% by weight).
If the amount is less than 001% by weight, it becomes difficult to contain a predetermined amount of a fatty acid salt. Conversely, if it exceeds 1% by weight, the appearance of a finally obtained molded product is undesirably deteriorated. When a boron compound and a fatty acid salt are used in combination, the respective concentrations preferably satisfy the above conditions.

【００２１】かくして、（Ａ）〜（Ｃ）或いは（Ａ）〜
（Ｄ）成分からなる本発明の樹脂組成物が得られるので
あるが、かかる組成物には、更に、必要に応じて、可塑
剤、滑剤、熱安定剤、紫外線吸収剤、酸化防止剤、ブロ
ッキング防止剤、スリップ剤、帯電防止剤、着色剤、抗
菌剤、乾燥剤、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（（Ｄ）以外）を添加することもできる。Thus, (A)-(C) or (A)-
The resin composition of the present invention comprising the component (D) is obtained. The composition may further contain a plasticizer, a lubricant, a heat stabilizer, an ultraviolet absorber, an antioxidant, a blocking agent, if necessary. It is also possible to use additives such as an inhibitor, a slip agent, an antistatic agent, a coloring agent, an antibacterial agent, a desiccant, a filler, and other resins. In particular, a hydrotalcite-based compound, a hindered phenol-based, a hindered amine-based heat stabilizer, and a metal salt of a higher aliphatic carboxylic acid (other than (D)) can also be added as a gel generation inhibitor.

【００２２】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、耐レトルト性を保持した
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。異なる
２種以上のＥＶＯＨの製造方法は特に限定されず、例え
ばケン化前のＥＶＡの各ペーストを混合後ケン化する方
法、ケン化後の各ＥＶＯＨのアルコールまたは水とアル
コールの混合溶液を混合後ペレット化する方法、各ＥＶ
ＯＨペレットを混合後溶融混練する方法などが挙げられ
る。It is also possible to use two or more different EVOHs as the EVOH (A). In this case, the ethylene content differs by 5 mol% or more and / or the saponification degree differs by 1 mol% or more. Use of the EVOH blend is useful because the stretchability at the time of high stretching and the secondary workability such as vacuum pressure forming and deep drawing are improved while maintaining gas barrier properties and retort resistance. The method for producing two or more different types of EVOH is not particularly limited. For example, a method in which each paste of EVA before saponification is mixed and then saponified, and a method in which an alcohol of each EVOH after saponification or a mixed solution of water and alcohol is mixed. Pelletizing method, each EV
A method of melting and kneading the OH pellets after mixing is exemplified.

【００２３】かくして得られた本発明の樹脂組成物は、
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
もでき、かかる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、１５０〜３００℃の範囲から選ぶ
ことが多い。The resin composition of the present invention thus obtained comprises:
It is often used for molded products, and pellets by melt molding etc.
It can be formed into films, sheets, containers, fibers, rods, tubes, various molded products, etc., and can also be subjected to melt molding again using these crushed products (such as when reused products) and pellets are used. As such a 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 300 ° C.

【００２４】また、本発明の樹脂組成物は、単層として
用いることができるが、特に積層体用途に供した時に本
発明の作用効果を十分に発揮することができ、具体的に
は該樹脂組成物からなる層の少なくとも片面に熱可塑性
樹脂層等を積層して多層積層体として用いることが有用
である。該積層体を製造するに当たっては、該樹脂組成
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、例えば該樹脂組成物のフィルム
や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樹脂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、
更には本発明の樹脂組成物のフィルムやシートと他の基
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ドライラミネートする方
法等が挙げられる。本発明の樹脂組成物は、前述のよう
にロングラン成形性に優れているので、特に共押出成形
に供した時に本発明の作用効果を十分に発揮することが
できる。Although the resin composition of the present invention can be used as a single layer, the effect of the present invention can be sufficiently exerted especially when used for a laminated body. It is useful to laminate a thermoplastic resin layer or the like on at least one side of a layer made of the composition and use it as a multilayer laminate. In producing the laminate, another substrate is laminated on one or both sides of the layer of the resin composition.As a lamination method, for example, a thermoplastic resin is used for a film or sheet of the resin composition. A method of melt-extrusion, a method of melt-extruding the resin composition on a substrate such as a thermoplastic resin,
A method of co-extruding the resin composition and another thermoplastic resin,
Further, a method of dry laminating a film or sheet of the resin composition of the present invention with a film or sheet of another substrate using a known adhesive such as an organic titanium compound, an isocyanate compound, a polyester compound, or a polyurethane compound. Is mentioned. Since the resin composition of the present invention has excellent long-run moldability as described above, the effect of the present invention can be sufficiently exerted particularly when subjected to coextrusion molding.

【００２５】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、ポリカーボネート、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、ポリケトン、ポリアルコール等が挙げられ
る。ＥＶＯＨ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、ポ
リカーボネート、ＰＥＴ、ＰＥＮが好ましく用いられ
る。In the case of coextrusion, the mating resin may be a 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, polycarbonate, vinyl ester resin, polyester elastomer, polyurethane elastomer, chlorinated polyethylene, chlorinated polypropylene, polyketone, polyalcohol And the like. EVOH can also be co-extruded. Among the above, polypropylene, polyamide, polyethylene, ethylene-vinyl acetate copolymer, polystyrene, polycarbonate, PET, and PEN are preferably used from the viewpoint of easiness of coextrusion film formation and practicality of film physical properties (particularly strength). Can be

【００２６】更に、本発明の樹脂組成物から一旦フィル
ムや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、無延伸、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。Further, a molded product such as a film or a sheet is once obtained from the resin composition of the present invention, and another substrate is extrusion-coated thereon, or a film or sheet of another substrate is formed by using an adhesive. When laminating, any substrate (paper, metal foil, non-stretched, uniaxially or biaxially stretched plastic film or sheet, woven fabric, nonwoven fabric, metal flocculent, woody, etc.) other than the above-mentioned thermoplastic resin can be used. is there.

【００２７】積層体の層構成は、本発明の樹脂組成物の
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、ｂ1／ｂ2／ａ／ｂ
3／ｂ4、ａ1／ｂ1／ａ2／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。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、延伸容器、延伸ボトル等が得られる。The layer structure of the laminate is such that a layer of the resin composition of the present invention is a (a 1 , a 2 ,...) And another base material, for example, a thermoplastic resin layer is b (b 1 , b 2) when the...), a film, a sheet, if a bottle shape, not only the double layer structure of a / b, b / a / b, a / b / a, a 1 / a 2 / b, a /
b 1 / b 2, b 2 / b 1 / a / b 1 / b 2, b 1 / b 2 / a / b
3 / b 4, a 1 / b 1 / a 2 / b 2 etc. are possible any combination, in filamentous a, b 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. The laminate is used for various shapes as it is, but it is also preferable to perform a stretching treatment in order to further improve the physical properties of the laminate. For such stretching, either uniaxial stretching or biaxial stretching is used. Stretching may be carried out, and it is better to perform stretching at as high a magnification as possible in terms of physical properties, and a stretched film, stretched sheet, stretched container, stretched bottle, or the like that does not generate pinholes, cracks, stretch unevenness, delamination, etc. during stretching can be obtained. .

【００２８】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、真空圧空成形等のうち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
６０〜１７０℃、好ましくは８０〜１６０℃程度の範囲
から選ばれる。延伸が終了した後、次いで熱固定を行う
ことも好ましい。。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８０〜１
７０℃、好ましくは１００〜１６０℃で２〜６００秒間
程度熱処理を行う。The stretching method includes a roll stretching method, a tenter stretching method, a tubular stretching method, a stretching blow method, and the like.
Among the deep drawing forming, vacuum press forming and the like, those having a high stretching ratio can be employed. In the case of biaxial stretching, any of a simultaneous biaxial stretching method and a sequential biaxial stretching method can be adopted. The stretching temperature is selected from the range of 60 to 170 ° C, preferably about 80 to 160 ° C. After completion of the stretching, it is also preferable to perform heat setting. . The heat setting can be carried out by a known means, and the stretched film is kept at a tension of 80 to 1 while being kept in tension.
Heat treatment is performed at 70 ° C., preferably 100 to 160 ° C. for about 2 to 600 seconds.

【００２９】また、生肉、加工肉、チーズ等の熱収縮包
装用途に用いる場合には、延伸後の熱固定は行わずに製
品フィルムとし、上記の生肉、加工肉、チーズ等を該フ
ィルムに収納した後、５０〜１３０℃、好ましくは７０
〜１２０℃で、２〜３００秒程度の熱処理を行って、該
フィルムを熱収縮させて密着包装をする。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、得られる積層
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。When used for heat shrink wrapping of raw meat, processed meat, cheese, etc., the product is not heat-set after stretching but is used as a product film, and the above-mentioned raw meat, processed meat, cheese, etc. are stored in the film. After that, 50-130 ° C., preferably 70
The film is subjected to a heat treatment at about 120 ° C. for about 2 to 300 seconds to thermally shrink the film, thereby performing tight packaging. 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 treatment, if necessary,
Bag making, deep drawing, box processing, tube processing, split processing, and the like can be performed.

【００３０】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が、本発明においては、ボイル殺
菌用またはレトルト殺菌用の包装多層積層体に用いるこ
とが好ましく、かかる積層体について、詳細に説明す
る。かかる積層体の層構成としては、［外層側］熱可塑
性樹脂層／（接着性樹脂層）／本発明の樹脂組成物の層
／（接着性樹脂層）／熱可塑性樹脂層［内層側］、［外
層側］本発明の樹脂組成物の層／（接着性樹脂層）／熱
可塑性樹脂層［内層側］、［外層側］本発明の樹脂組成
物の層／（接着性樹脂層）／熱可塑性樹脂層／（接着性
樹脂層）／本発明の樹脂組成物の層／（接着性樹脂層）
／熱可塑性樹脂層［内層側］等が挙げられ、必要に応じ
て回収層を設けたり、熱可塑性樹脂層を異なる２種の多
層構成としたり、熱可塑性樹脂層に有機・無機の蒸着処
理を施すことも可能である。The film, sheet or container obtained as described above is useful as various packaging materials such as foods, pharmaceuticals, industrial chemicals and agricultural chemicals. In the present invention, the packaging multilayer for sterilizing boil or retort is used. It is preferably used for a laminate, and such a laminate will be described in detail. Examples of the layer structure of such a laminate include [outer layer side] thermoplastic resin layer / (adhesive resin layer) / layer of resin composition of the present invention / (adhesive resin layer) / thermoplastic resin layer [inner layer side], [Outer layer side] layer of resin composition of the present invention / (adhesive resin layer) / thermoplastic resin layer [inner layer side], [outer layer side] layer of resin composition of the present invention / (adhesive resin layer) / heat Plastic resin layer / (adhesive resin layer) / layer of resin composition of the present invention / (adhesive resin layer)
/ A thermoplastic resin layer [inner layer side] and the like. A recovery layer may be provided as necessary, the thermoplastic resin layer may have two different multilayer structures, or an organic / inorganic vapor deposition treatment may be performed on the thermoplastic resin layer. It is also possible to apply.

【００３１】熱可塑性樹脂層としては前述の樹脂一覧の
中から選択すればよく、特に限定されないが、好適に
は、外層側の熱可塑性樹脂層としてはポリプロピレン、
エチレン−プロピレン共重合体、ポリアミド、共重合ポ
リアミド、ポリカーボネート、ＰＥＴが、内層側の熱可
塑性樹脂層としてはポリプロピレン、エチレン−プロピ
レン共重合体、プロピレン−α−オレフィン共重合体、
各種ポリエチレンが用いられる。また、上記の各層の厚
みとしては、積層体の形態により異なるなるので一概に
は言えないが、フィルム包材として蓋材、パウチ類、真
空包装、スキンパック、絞り包装、ピロー包装、ロケッ
ト包装に使用される場合には、外層側の熱可塑性樹脂層
は５〜３００μｍ（更に１０〜１５０μｍ）、本発明の
樹脂組成物の層は５〜２５０μｍ（更に８〜１００μ
ｍ）、内層側の熱可塑性樹脂層は１０〜５００μｍ（更
に１５〜３００μｍ）、接着性樹脂層は１〜２００μｍ
（更に７〜８０μｍ）が好ましく、また積層体全体の厚
みとしては、２０〜１０００μｍ（更に２５〜５００μ
ｍ）が好ましい。特に、［外層側］熱可塑性樹脂層／
（接着性樹脂層）／本発明の樹脂組成物の層／（接着性
樹脂層）／熱可塑性樹脂層［内層側］の層構成とした場
合には、外層側の熱可塑性樹脂層／（接着性樹脂層）の
厚みをＴｏ、内層側の（接着性樹脂層）／熱可塑性樹脂
層の厚みをＴｉとすると、Ｔｏ／Ｔｉ≦１とすることに
より、ボイル処理あるいはレトルト処理後のガスバリア
性の回復に優れる点で好ましい。The thermoplastic resin layer may be selected from the above-mentioned resin list, and is not particularly limited. Preferably, the thermoplastic resin layer on the outer layer side is polypropylene,
Ethylene-propylene copolymer, polyamide, copolymerized polyamide, polycarbonate, PET, as the thermoplastic resin layer on the inner layer side, polypropylene, ethylene-propylene copolymer, propylene-α-olefin copolymer,
Various polyethylenes are used. In addition, the thickness of each of the above-mentioned layers is different depending on the form of the laminated body, so it cannot be said unconditionally. However, as a film packaging material, a lid material, a pouch, a vacuum package, a skin pack, a drawing package, a pillow package, a rocket package, and the like. When used, the thermoplastic resin layer on the outer layer side is 5 to 300 μm (further 10 to 150 μm), and the layer of the resin composition of the present invention is 5 to 250 μm (further 8 to 100 μm).
m), the thermoplastic resin layer on the inner layer side is 10 to 500 μm (further 15 to 300 μm), and the adhesive resin layer is 1 to 200 μm.
(More preferably 7 to 80 μm), and the total thickness of the laminate is 20 to 1000 μm (further 25 to 500 μm).
m) is preferred. In particular, the [outer layer side] thermoplastic resin layer /
In the case of a layer structure of (adhesive resin layer) / layer of the resin composition of the present invention / (adhesive resin layer) / thermoplastic resin layer [inner layer side], thermoplastic resin layer on outer layer side / (adhesion Assuming that the thickness of the thermoplastic resin layer) is To and the thickness of the (adhesive resin layer) / thermoplastic resin layer on the inner layer side is Ti, by setting To / Ti ≦ 1, the gas barrier property after the boil treatment or the retort treatment is obtained. It is preferable because it is excellent in recovery.

【００３２】本発明の積層体は、フィルム包材以外に
も、カップ、トレー、ボトル型の容器としても優れた性
能を発揮する。また、積層体を製造するに当たっても特
に限定されず、前述の各種積層法を用いることが可能で
ある。本発明のボイル殺菌処理またはレトルト殺菌処理
方法としては公知の熱水加熱処理方法および条件を採用
することができる。レトルト処理は回収式、置換式、蒸
気式、シャワー式、スプレー式等各種の方法が採用され
る。The laminate of the present invention exhibits excellent performance not only as a film packaging material but also as a cup, tray or bottle type container. Further, there is no particular limitation on the production of the laminate, and the above-described various lamination methods can be used. As the boil sterilization treatment or the retort sterilization treatment method of the present invention, known hot water heating treatment methods and conditions can be adopted. For the retort treatment, various methods such as a recovery method, a displacement method, a steam method, a shower method, and a spray method are employed.

【００３３】[0033]

【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。また、実施例中の（Ｃ）ま
たは（Ｄ）成分の含有量は下記の方法で分析した。 ・リン酸塩：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した。 ・ホウ素化合物：樹脂組成物をアルカリ溶融してＩＣＰ
発光分光分析法によりホウ素を定量した。 ・脂肪酸塩：樹脂組成物を灰化後、塩酸水溶液に溶解し
原子吸光分析法により金属を定量した。The present invention will be specifically described below with reference to examples. In the examples, “parts” and “%” are based on weight unless otherwise specified. The content of the component (C) or (D) in the examples was analyzed by the following method. Phosphate: The resin composition was extracted with warm diluted sulfuric acid, and the phosphate group was quantified by an absorption spectrophotometric method (molybdenum blue). -Boron compound: ICP by melting the resin composition with alkali
Boron was quantified by emission spectroscopy. -Fatty acid salt: After the resin composition was ashed, it was dissolved in an aqueous hydrochloric acid solution and the metal was quantified by atomic absorption spectrometry.

【００３４】実施例１ ＥＶＯＨ［エチレン含有量３４モル％、ケン化度９９．
５モル％、ＭＩ８ｇ／１０分（２１０℃、荷重２１６０
ｇ）］（Ａ）の水／メタノール（水／メタノール＝４０
／６０混合重量比）溶液（６０℃、ＥＶＯＨ濃度４５
％）を５℃に維持された水槽にストランド状に押し出し
て凝固させた後、カッターで切断してペレット状（直径
４ｍｍ、長さ４ｍｍ）のＥＶＯＨを得て、更に該ＥＶＯ
Ｈを３０℃の温水で洗浄後、酢酸水溶液中に投入して、
約２時間撹拌を行って含水率５０％の多孔性析出物を得
た。次いで、得られた多孔性析出物を０．０６％のリン
酸二水素マグネシウム（Ｃ）水溶液に投入し、３５℃で
約４時間撹拌して、ＥＶＯＨ（Ａ）及びリン酸二水素マ
グネシウム（Ｃ）からなる樹脂組成物を得た。Example 1 EVOH [Ethylene content 34 mol%, saponification degree 99.
5 mol%, MI 8 g / 10 min (210 ° C., load 2160
g)] water / methanol of (A) (water / methanol = 40)
/ 60 mixture weight ratio) solution (60 ° C, EVOH concentration 45
%) Was extruded into a water tank maintained at 5 ° C. in the form of a strand and solidified, and then cut with a cutter to obtain a pellet-shaped (4 mm in diameter, 4 mm in length) EVOH.
After H was washed with warm water of 30 ° C., it was thrown into acetic acid aqueous solution,
The mixture was stirred for about 2 hours to obtain a porous precipitate having a water content of 50%. Next, the obtained porous precipitate was poured into a 0.06% aqueous solution of magnesium dihydrogen phosphate (C), and the mixture was stirred at 35 ° C. for about 4 hours to obtain EVOH (A) and magnesium dihydrogen phosphate (C). ) Was obtained.

【００３５】得られた樹脂組成物を下記の方法により乾
燥処理を行った。 ＜流動乾燥工程＞上記で得られた樹脂組成物を回分式流
動層乾燥器（塔型）を用いて、７５℃の窒素ガスを流動
させながら、約３時間乾燥を行って含水率２０％の樹脂
組成物を得た。 ＜静置乾燥工程＞次いで、流動乾燥処理後の樹脂組成物
を回分式箱型乾燥器（通気式）を用いて、１２５℃の窒
素ガスで、約１８時間乾燥を行って、含水率０．３％の
樹脂組成物［ＥＶＯＨ（Ａ）１００重量部に対して、リ
ン酸化合物（Ｃ）をリン酸根換算で０．０１２重量部含
有］を得た。該樹脂組成物（Ａ＋Ｃ）９５部とナイロン
６・６６・６１０の三元共重合体（Ｂ）［ＤｕＰｏｎｔ
社製「エルバミド８０６１」］５部を、二軸押出機（３
０ｍｍΦ、Ｌ／Ｄ＝３０）に供給し、温度２３０℃で溶
融混練を行って、本発明の樹脂組成物を得た。The obtained resin composition was dried by the following method. <Flow drying step> The resin composition obtained above was dried for about 3 hours while flowing nitrogen gas at 75 ° C using a batch type fluidized bed dryer (tower type) to obtain a water content of 20%. A resin composition was obtained. <Standing Drying Step> Next, the resin composition after the fluidized drying treatment was dried for about 18 hours with nitrogen gas at 125 ° C. using a batch-type box dryer (ventilated) to obtain a water content of 0.1%. 3% of a resin composition [containing 0.012 parts by weight of a phosphoric acid compound (C) in terms of a phosphate group per 100 parts by weight of EVOH (A)] was obtained. Terpolymer (B) of 95 parts of the resin composition (A + C) and nylon 6,66,610 [DuPont
5 parts of "Elvamide 8061" manufactured by
0 mmΦ, L / D = 30) and melt-kneaded at a temperature of 230 ° C. to obtain a resin composition of the present invention.

【００３６】得られた樹脂組成物、ポリプロピレン、接
着性樹脂（無水マレイン酸変性ポリプロピレン）を３種
５層の共押出製膜装置（成形温度２３０℃）に供給し
て、ポリプロピレン層／接着性樹脂層／樹脂組成物層／
接着性樹脂層／ポリプロピレン層［厚み構成：３５／１
０／１０／１０／３５（μｍ）］からなる積層体の製造
を行って、以下の評価を行った。The obtained resin composition, polypropylene, and adhesive resin (maleic anhydride-modified polypropylene) were supplied to a co-extrusion film forming apparatus having three types and five layers (forming temperature: 230 ° C.) to obtain a polypropylene layer / adhesive resin. Layer / resin composition layer /
Adhesive resin layer / polypropylene layer [Thickness composition: 35/1
0/10/10/10/35 (μm)], and the following evaluation was performed.

【００３７】（ロングラン成形性）上記の積層体の製造
を連続して１０日間行い、積層体の経日の外観を目視観
察して、以下の通り評価した。 ◎ −−− 製膜開始後、１０日間経過しても異物、ゲ
ルまたはサージングの発生はほとんど認められない ○ −−− 製膜開始後、７日間経過しても異物、ゲル
またはサージングの発生はほとんど認められない △ −−− 製膜開始後、３〜６日で異物、ゲルまたは
サージングが発生した × −−− 製膜開始後、３日以内で異物、ゲルまたは
サージングが発生した(Long-run moldability) The above-mentioned laminate was manufactured continuously for 10 days, and the appearance of the laminate over time was visually observed and evaluated as follows. ◎ −−− Almost no occurrence of foreign matter, gel or surging even after 10 days from the start of film formation ○ −−− No occurrence of foreign matter, gel or surging even after 7 days after start of film formation Hardly observed △ −−− Foreign matter, gel or surging occurred 3 to 6 days after the start of film formation × −−− Foreign matter, gel or surging occurred within 3 days after the start of film formation

【００３８】（ガスバリア性）得られた積層体の酸素透
過度を２３℃、５０％ＲＨで、酸素透過度測定装置（Ｍ
ＯＣＯＮ社製「ＯＸＴＲＡＮ１０／５０」）を用いて測
定した。 （レトルト適性−ガスバリア性）得られた積層体をレ
トルト装置（ヤマト科学社製「オートクレーブＳＭ−３
１」）を用いて、１２１℃水蒸気雰囲気中で３０分間レ
トルト殺菌処理を行った後、２３℃、５０％ＲＨで、２
４時間放置後に上記の方法にて酸素透過度を測定した。
また９６時間放置後の酸素透過度も測定した。 （レトルト適性−透明性）得られた積層体を上記と同
様のレトルト殺菌処理を行った後、２３℃、５０％ＲＨ
で、３０分間放置したときの積層体の外観を目視観察し
て、以下の通り評価した。 ○ −−− 外観に異常は認められなかった × −−− 白化が認められた(Gas Barrier Property) The oxygen permeability of the obtained laminate was measured at 23 ° C. and 50% RH using an oxygen permeability measuring apparatus (M
The measurement was performed using "OXTRAN10 / 50" manufactured by OCON. (Appropriate retort-gas barrier property) The obtained laminate was subjected to a retort apparatus ("Autoclave SM-3" manufactured by Yamato Scientific Co., Ltd.).
1)), subjected to a retort sterilization treatment in a steam atmosphere of 121 ° C. for 30 minutes, and then heated at 23 ° C. and 50% RH for 2 minutes.
After leaving for 4 hours, the oxygen permeability was measured by the above method.
The oxygen permeability after 96 hours of standing was also measured. (Retort suitability-transparency) After the obtained laminate was subjected to the same retort sterilization treatment as above, at 23 ° C and 50% RH.
The appearance of the laminate when left for 30 minutes was visually observed and evaluated as follows. ○ −−− No abnormal appearance was observed × −−− Whitening was observed

【００３９】実施例２ ＥＶＯＨ［エチレン含有量２９モル％、ケン化度９９．
６モル％、ＭＩ６ｇ／１０分（２１０℃、荷重２１６０
ｇ）］（Ａ）の水／メタノール（水／メタノール＝５０
／５０混合重量比）溶液（６０℃、ＥＶＯＨ濃度４０
％）を５℃に維持された水槽にストランド状に押し出し
て凝固させた後、カッターで切断してペレット状（直径
４ｍｍ、長さ５ｍｍ）のＥＶＯＨを得て、更に該ＥＶＯ
Ｈを３０℃の温水で洗浄後、酢酸水溶液中に投入して、
約２時間撹拌を行って含水率５０％の多孔性析出物を得
た。次いで、得られた多孔性析出物を０．０３％のリン
酸二水素ナトリウム（Ｃ）水溶液に投入し、３０℃で約
５時間撹拌して、ＥＶＯＨ（Ａ）及びリン酸二水素ナト
リウム（Ｃ）からなる樹脂組成物を得た。Example 2 EVOH [Ethylene content 29 mol%, saponification degree 99.
6 mol%, MI 6 g / 10 min (210 ° C., load 2160
g)] water / methanol of (A) (water / methanol = 50)
/ 50 mixture weight ratio) solution (60 ° C, EVOH concentration 40
%) Was extruded into a water tank maintained at 5 ° C. in the form of a strand and solidified, and then cut with a cutter to obtain pellet-shaped (diameter 4 mm, length 5 mm) EVOH.
After H was washed with warm water of 30 ° C., it was thrown into acetic acid aqueous solution,
The mixture was stirred for about 2 hours to obtain a porous precipitate having a water content of 50%. Next, the obtained porous precipitate is poured into a 0.03% aqueous solution of sodium dihydrogen phosphate (C), and the mixture is stirred at 30 ° C. for about 5 hours to obtain EVOH (A) and sodium dihydrogen phosphate (C). ) Was obtained.

【００４０】得られた樹脂組成物を実施例１と同様の方
法により乾燥処理を行って、含水率０．３％の樹脂組成
物［ＥＶＯＨ（Ａ）１００重量部に対して、リン酸二水
素ナトリウム（Ｃ）をリン酸根換算で０．００９重量部
含有］を得た。該組成物（Ａ＋Ｃ）９６部とナイロン６
・６６・６１０・１２の四元共重合体（Ｂ）［東レ社製
「アミランＣＭ８０００」］４部を、実施例１と同様に
二軸押出機で溶融混練を行って、本発明の樹脂組成物を
得た。更に実施例１と同様にして、得られた樹脂組成
物、ポリプロピレン、接着性樹脂（無水マレイン酸変性
ポリプロピレン）を３種５層の共押出製膜装置（成形温
度２３０℃）に供給して、ポリプロピレン層／接着性樹
脂層／樹脂組成物層／接着性樹脂層／ポリプロピレン層
［厚み構成：３５／１０／１０／１０／３５（μｍ）］
からなる積層体の製造を行って、実施例１と同様の評価
を行った。The obtained resin composition was subjected to a drying treatment in the same manner as in Example 1 to obtain a resin composition having a water content of 0.3% [EVOH (A) 100 parts by weight and dihydrogen phosphate Sodium (C) containing 0.009 parts by weight in terms of phosphate group]. 96 parts of the composition (A + C) and nylon 6
4 parts of a 66.610.12 quaternary copolymer (B) [“Amilan CM8000” manufactured by Toray Industries, Inc.] were melt-kneaded with a twin-screw extruder in the same manner as in Example 1 to obtain a resin composition of the present invention. I got something. Further, in the same manner as in Example 1, the obtained resin composition, polypropylene, and adhesive resin (maleic anhydride-modified polypropylene) were supplied to a three-type, five-layer co-extrusion film forming apparatus (forming temperature: 230 ° C.) Polypropylene layer / adhesive resin layer / resin composition layer / adhesive resin layer / polypropylene layer [Thickness composition: 35/10/10/10/35 (μm)]
Was manufactured, and the same evaluation as in Example 1 was performed.

【００４１】実施例３ 実施例１において、ＥＶＯＨ（Ａ）１００重量部に対し
て、リン酸化合物（Ｃ）としてリン酸二水素カルシウム
をリン酸根換算で０．００７重量部、ホウ素化合物
（Ｄ）としてホウ酸をホウ素換算で０．０３重量部含有
する組成物（Ａ＋Ｃ＋Ｄ）を得た以外は同様に、アルコ
ール可溶性ポリアミド系樹脂（Ｂ）を溶融混練して本発
明の樹脂組成物を得て、同様にポリプロピレン層／接着
性樹脂層／樹脂組成物層／接着性樹脂層／ポリプロピレ
ン層［厚み構成：３０／１０／１５／１０／３０（μ
ｍ）］からなる積層体の製造を行って、実施例１と同様
の評価を行った。Example 3 In Example 1, 0.007 parts by weight of calcium dihydrogen phosphate as the phosphoric acid compound (C) was added to 100 parts by weight of EVOH (A), and the boron compound (D) was used. Similarly, except that a composition (A + C + D) containing 0.03 parts by weight of boric acid in terms of boron was obtained, an alcohol-soluble polyamide-based resin (B) was melt-kneaded to obtain a resin composition of the present invention. Similarly, a polypropylene layer / adhesive resin layer / resin composition layer / adhesive resin layer / polypropylene layer [thickness configuration: 30/10/15/10/30 (μ
m)], and the same evaluation as in Example 1 was performed.

【００４２】実施例４ 実施例２において、ＥＶＯＨ（Ａ）１００重量部に対し
て、リン酸化合物（Ｃ）としてリン酸二水素カルシウム
をリン酸根換算で０．００５重量部と、脂肪酸塩（Ｄ）
として酢酸ナトリウムをナトリウム換算で０．０１５重
量部含有する組成物（Ａ＋Ｃ＋Ｄ）を得た以外は同様
に、アルコール可溶性ポリアミド系樹脂（Ｂ）を溶融混
練して本発明の樹脂組成物を得て、同様にポリプロピレ
ン層／接着性樹脂層／樹脂組成物層／接着性樹脂層／ポ
リプロピレン層［厚み構成：３５／１０／１０／１０／
３５（μｍ）］からなる積層体の製造を行って、実施例
１と同様の評価を行った。Example 4 In Example 2, 0.005 parts by weight of calcium dihydrogen phosphate as a phosphate compound (C) was added to 100 parts by weight of EVOH (A) in terms of a phosphate group, and a fatty acid salt (D )
Similarly, an alcohol-soluble polyamide-based resin (B) was melt-kneaded to obtain a resin composition of the present invention, except that a composition (A + C + D) containing 0.015 parts by weight of sodium acetate as sodium was obtained. Similarly, a polypropylene layer / adhesive resin layer / resin composition layer / adhesive resin layer / polypropylene layer [thickness configuration: 35/10/10/10 //
35 (μm)], and the same evaluation as in Example 1 was performed.

【００４３】比較例１ 実施例１において、（Ｃ）成分を配合しなかった以外は
同様に行って、ポリプロピレン層／接着性樹脂層／樹脂
組成物層／接着性樹脂層／ポリプロピレン層［厚み構
成：３５／１０／１０／１０／３５（μｍ）］からなる
積層体の製造を行って、実施例１と同様の評価を行っ
た。Comparative Example 1 The procedure of Example 1 was repeated, except that the component (C) was not added, to obtain a polypropylene layer / adhesive resin layer / resin composition layer / adhesive resin layer / polypropylene layer [thickness structure]. : 35/10/10/10/35 (μm)], and the same evaluation as in Example 1 was performed.

【００４４】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。Table 1 shows the evaluation results of the examples and comparative examples.

【表１】 ロンク゛ラン成形性 カ゛スハ゛リア性* レトルト適性* レトルト適性 ２４時間 ９６時間 実施例１ ○ １．４ ２２ １．４ ○ 〃 ２ ○ ０．６ １７ ０．６ ○ 〃 ３ ◎ ０．９ １５ ０．９ ○ 〃 ４ ◎ ０．６ １６ ０．６ ○ 比較例１ × １．４ ４０ １．４ × ＊単位は、ｃｃ／ｍ2・ｄａｙ・ａｔｍ[Table 1] Longcuran moldability Gas porosity * Retort suitability * Retort suitability 24 hours 96 hours Example 1 ○ 1.4 22 1.4 ○ ○ 2 ○ 0.6 17 0.6 ○ ○ 3 ◎ 0.9 150 ９ 9 〃 4 ◎ 0.6 16 0.6 0.6 比較 Comparative Example 1 × 1.4 40 1.4 × * Unit is cc / m 2 · day · atm

【００４５】[0045]

【発明の効果】本発明の樹脂組成物は、上記の如き
（Ａ）〜（Ｃ）又は（Ａ）〜（Ｄ）成分からなるため、
ロングラン成形性、ガスバリア性、耐レトルト性等に優
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、ボトル、カップやトレーなどの容器等の用途に非常
に有用で、特に、ボイル殺菌用またはレトルト殺菌用の
包装多層積層体に好適に用いることができる。The resin composition of the present invention comprises the components (A) to (C) or (A) to (D) as described above.
Excellent in long-run formability, gas barrier properties, retort resistance, etc., can be made into various laminates, films, sheets, tubes for packaging foods, pharmaceuticals, agricultural chemicals, industrial chemicals,
It is very useful for applications such as bags, bottles, containers such as cups and trays, and can be particularly suitably used for packaging multilayer laminates for boiling sterilization or retort sterilization.

───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.7 識別記号 ＦＩ テーマコート゛(参考） Ｃ０８Ｋ 5/098 Ｃ０８Ｋ 5/098 Ｃ０８Ｌ 23/26 Ｃ０８Ｌ 23/26 77/00 77/00 (72)発明者 北 康司 岡山県倉敷市松江４丁目８番１号 日本合 成化学工業株式会社水島事業所内 (72)発明者 豊住 政彦 岡山県倉敷市松江４丁目８番１号 日本合 成化学工業株式会社水島事業所内 Ｆターム(参考） 3E035 AA20 BA02 BA05 BA08 BC02 BD02 BD04 BD06 CA07 DA01 4F100 AA04C AA04H AA31C AA31H AH02C AH02H AH08C AH08H AK01A AK01B AK07 AK46C AK48C AK48K AK69C AL01C AL05C BA02 BA03 BA06 BA10A BA10B CA23C CB00 EH20 JB07C JB16A JB16B JC00 JD02 JL00 JL01 JN01 YY00C 4J002 BB221 BE031 CL052 DE046 DH036 DK007 EG027 EG037 FD036 FD037 GF00 GG00──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. 7 Identification symbol FI Theme coat ゛ (Reference) C08K 5/098 C08K 5/098 C08L 23/26 C08L 23/26 77/00 77/00 (72) Inventor Koji Kita 4-81-1, Matsue, Kurashiki-shi, Okayama Pref. Inside the Mizushima Plant of Nippon Gosei Chemical Industry Co., Ltd. (72) Inventor Masahiko Toyozumi 4-81-1, Matsue, Kurashiki-shi, Okayama Pref. In-house F-term (Reference) 3E035 AA20 BA02 BA05 BA08 BC02 BD02 BD04 BD06 CA07 DA01 4F100 AA04C AA04H AA31C AA31H AH02C AH02H AH08C AH08H AK01C JAKA BACBACBACBACBACBACBACBACBACBACBACBACBACBACBAC JN01 YY00C 4J002 BB221 BE031 CL052 DE046 DH036 DK007 EG027 EG037 FD036 FD037 GF00 GG00

Claims (7)

【特許請求の範囲】[Claims] 【請求項１】 エチレン−酢酸ビニル共重合体ケン化物
（Ａ）、アルコール可溶性ポリアミド系樹脂（Ｂ）及び
リン酸塩（Ｃ）を含有してなることを特徴とする樹脂組
成物。1. A resin composition comprising a saponified ethylene-vinyl acetate copolymer (A), an alcohol-soluble polyamide resin (B) and a phosphate (C). 【請求項２】 更に、ホウ素化合物、脂肪酸塩から選ば
れる少なくとも１種（Ｄ）を含有してなることを特徴と
する請求項１記載の樹脂組成物。2. The resin composition according to claim 1, further comprising at least one (D) selected from a boron compound and a fatty acid salt. 【請求項３】 アルコール可溶性ポリアミド系樹脂
（Ｂ）がナイロン６・６６・６１０の三元共重合体、ナ
イロン６・６６・６１０・１２又はナイロン６・６６・
６１０・１１の四元共重合体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または２記載の樹脂
組成物。3. The ternary copolymer of an alcohol-soluble polyamide resin (B) of nylon 66.610, nylon 66.610.12 or nylon 66.66.
At least one selected from 610 and 11 quaternary copolymers
3. The resin composition according to claim 1, which is a seed. 【請求項４】 エチレン−酢酸ビニル共重合体ケン化物
（Ａ）およびアルコール可溶性ポリアミド系樹脂（Ｂ）
の配合割合がＡ／Ｂ＝９９．９／０．１〜５０／５０
（重量比）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。4. A saponified ethylene-vinyl acetate copolymer (A) and an alcohol-soluble polyamide resin (B)
A / B = 99.9 / 0.1 to 50/50
The resin composition according to any one of claims 1 to 3, which is (weight ratio). 【請求項５】 請求項１〜４いずれか記載の樹脂組成物
の層と少なくとも熱可塑性樹脂層が積層されたことを特
徴とする積層体。5. A laminate comprising a layer of the resin composition according to claim 1 and at least a thermoplastic resin layer. 【請求項６】 樹脂組成物の層を中間層として両外層に
熱可塑性樹脂層を積層したことを特徴とする請求項５記
載の積層体。6. The laminate according to claim 5, wherein a thermoplastic resin layer is laminated on both outer layers with the resin composition layer being an intermediate layer. 【請求項７】 ボイル殺菌用またはレトルト殺菌用に用
いることを特徴とする請求項５または６記載の積層体。7. The laminate according to claim 5, wherein the laminate is used for sterilizing boiling or retort.
JP10310088A 1998-10-30 1998-10-30 Resin composition and use thereof Pending JP2000136281A (en)

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