JP4580627B2 - Ethylene-vinyl acetate copolymer saponified pellets and uses thereof - Google Patents

Ethylene-vinyl acetate copolymer saponified pellets and uses thereof Download PDF

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JP4580627B2
JP4580627B2 JP2003275196A JP2003275196A JP4580627B2 JP 4580627 B2 JP4580627 B2 JP 4580627B2 JP 2003275196 A JP2003275196 A JP 2003275196A JP 2003275196 A JP2003275196 A JP 2003275196A JP 4580627 B2 JP4580627 B2 JP 4580627B2
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vinyl acetate
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邦芳 浅野
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Nippon Synthetic Chemical Industry Co Ltd
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    • 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
    • B29B9/16—Auxiliary treatment of granules
    • 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

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  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)
  • Processing And Handling Of Plastics And Other Materials For Molding In General (AREA)
  • Laminated Bodies (AREA)

Description

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）のペレット群及びそれを用いた積層体に関し、さらに詳しくは、成形時にＥＶＯＨ層界面での乱れに起因するゲルの発生が抑制された成形性に優れたＥＶＯＨペレット群及びそれを用いた積層体に関する。   The present invention relates to a group of pellets of a saponified ethylene-vinyl acetate copolymer (hereinafter abbreviated as EVOH) and a laminate using the same, and more specifically, the gel caused by disturbance at the EVOH layer interface during molding. The present invention relates to a group of EVOH pellets excellent in moldability with suppressed generation and a laminate using the EVOH pellet group.

一般にＥＶＯＨは、透明性、ガスバリア性、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などに成形されて利用されている。   In general, EVOH is excellent in transparency, gas barrier properties, fragrance retention, solvent resistance, oil resistance, etc., making use of such properties, such as food packaging materials, pharmaceutical packaging materials, industrial chemical packaging materials, agricultural chemical packaging materials, etc. It is used by being formed into a film, a sheet, or a container such as a bottle.

そして、かかるＥＶＯＨを溶融成形して各種成形品に加工するにあたっては、その成形時にＥＶＯＨのゲルや焼けが発生して成形物（特にフィルムやシート等）のロングラン性や外観性が低下することがある。
かかる対策として、ＥＶＯＨに金属塩を配合することが試みられている。例えば、ＥＶＯＨに周期律表第２属の金属塩とｐｋａ３．５以上で定圧下の沸点が１２０℃以下の酸性物質を特定量配合して、ＥＶＯＨの粘度挙動をコントロールする方法（例えば、特許文献１参照。）やＥＶＯＨにホウ酸、酢酸ナトリウム及び酢酸マグネシウムを特定量含有させる方法（例えば、特許文献２参照。）等があり、また、一方では、ホウ酸カリウムやホウ酸カルシウムなどのホウ酸化合物をＥＶＯＨに配合することも検討されている（例えば、特許文献３参照。）。 When such EVOH is melt-molded and processed into various molded products, EVOH gels and burns may occur during the molding, and the long-run property and appearance of the molded product (especially films and sheets) may deteriorate. is there.
As such a measure, an attempt has been made to add a metal salt to EVOH. For example, a method of controlling the viscosity behavior of EVOH by blending EVOH with a specific amount of a metal salt belonging to Group 2 of the periodic table and an acidic substance having a boiling point of 120 ° C. or lower at a constant pressure of 3.5 or higher (for example, patent document) 1) and EVOH containing specific amounts of boric acid, sodium acetate and magnesium acetate (see, for example, Patent Document 2), and boric acids such as potassium borate and calcium borate. Mixing the compound with EVOH has also been studied (for example, see Patent Document 3).

特開昭６４−６６２６２号公報JP-A 64-66262 特開平１１−６０８７４号公報Japanese Patent Laid-Open No. 11-60874 特開平１１−４３５７２号公報JP 11-43572 A

しかしながら、上記の特許文献１〜３に開示の方法では、溶融したＥＶＯＨの熱安定性は改善されてロングラン成形により発生するゲルや焼けについては抑制されるものの、各種積層体に適用したときには押出機へのフィードの不安定性等によりＥＶＯＨ層の界面での乱れに起因するゲル等が発生する恐れがあることが判明した。   However, in the methods disclosed in the above Patent Documents 1 to 3, although the thermal stability of the melted EVOH is improved and the gel and scorch generated by the long run molding are suppressed, the extruder is used when applied to various laminates. It has been found that there is a possibility that gel or the like may be generated due to disturbance at the interface of the EVOH layer due to instability of feed to the surface.

そこで、本発明者は、かかる現況に鑑みてＥＶＯＨペレットのフィード部分での挙動について鋭意研究を重ねた結果、３２メッシュ（目開き５００μ）篩を通過する微紛の含有量が０．１重量％以下であるＥＶＯＨペレット群が上記のようなゲルの発生を抑制できることを見出して本発明を完成するに至った。
なお、本発明においては、ＥＶＯＨがホウ素化合物を含有していること、また、ＥＶＯＨが融点２００℃以下の酸性物質（Ａ）及びアルカリ金属（Ｂ）を含有し、かつその含有重量比（Ａ／Ｂ）が１〜５０であること等が好ましい実施態様である。 In view of the present situation, the present inventor has conducted extensive research on the behavior of EVOH pellets at the feed portion, and as a result, the content of fine particles passing through a 32 mesh (aperture 500 μ) sieve is 0.1% by weight. The present inventors have found that the following EVOH pellet group can suppress the generation of the gel as described above and have completed the present invention.
In the present invention, EVOH contains a boron compound, EVOH contains an acidic substance (A) and an alkali metal (B) having a melting point of 200 ° C. or less, and the weight ratio (A / A preferred embodiment is that B) is from 1 to 50.

本発明の、ＥＶＯＨペレット群は特定の微紛を特定量以下に押さえているため、成形物に溶融成形したときにＥＶＯＨ層界面での乱れに起因するゲルの発生がなく、良好な成形物が得られ、多層フィルムとして有用で、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、容器等の用途をはじめとして、各種成形用途に非常に有用である。   Since the EVOH pellet group of the present invention keeps specific fine powder below a specific amount, there is no generation of gel due to disturbance at the EVOH layer interface when melt-molded into a molded product, and a good molded product is obtained. It is obtained and useful as a multilayer film, and is very useful for various molding applications including foods, pharmaceuticals, agricultural chemicals, films for industrial chemical packaging, sheets, tubes, bags, containers and the like.

以下に、本発明を詳細に説明する。
本発明のＥＶＯＨペレット群は、３２メッシュ（目開き５００μ）篩を通過する微紛の含有量が０．１重量％以下であることが必要で、かかる含有量が０．１重量％を越えるときには本発明の目的を達成することができないもので、かかるＥＶＯＨペレットに成形されるＥＶＯＨとしては、エチレン含有量が５〜７０モル％（さらには１５〜６０モル％、特には２０〜５５モル％、殊に２５〜５０モル％）のものが好ましく、かかるエチレン含有量が５モル％未満では高湿時のガスバリア性が低下する傾向にあり、逆に７０モル％を越えると通常のガスバリア性や耐油性・耐薬品性等が低下する傾向にあり好ましくない。 The present invention is described in detail below.
The EVOH pellet group of the present invention requires that the content of fine powder passing through a 32 mesh (aperture 500 μ) sieve be 0.1% by weight or less, and when such content exceeds 0.1% by weight. The EVOH that cannot achieve the object of the present invention and is molded into such EVOH pellets has an ethylene content of 5 to 70 mol% (further 15 to 60 mol%, particularly 20 to 55 mol%, In particular, those having an ethylene content of less than 5 mol% tend to lower the gas barrier properties at high humidity, and conversely, if it exceeds 70 mol%, ordinary gas barrier properties and oil resistance It is not preferable because the property and chemical resistance tend to be lowered.

また、該ＥＶＯＨのケン化度は９０モル％以上（さらには９４モル％以上、特には９６モル％以上、殊に９８モル％以上）が好ましく、かかるケン化度が９０モル％未満では、高湿時のガスバリア性が低下して好ましくない。   The saponification degree of the EVOH is preferably 90 mol% or more (more preferably 94 mol% or more, particularly 96 mol% or more, particularly 98 mol% or more). When the saponification degree is less than 90 mol%, the saponification degree is high. It is not preferable because the gas barrier property when wet is lowered.

さらに、該ＥＶＯＨのメルトフローレート（ＭＦＲ）は、０．１〜１００ｇ／１０分（２１０℃、荷重２１６０ｇで測定。以下同様）（さらには１〜５０ｇ／１０分、特には１．５〜３５ｇ／１０分、殊に２〜３０ｇ／１０分）が好ましく、該ＭＦＲが０．１ｇ／１０分未満で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、逆に１００ｇ／１０分を越えると低トルクとなって押出加工性が不安定となり好ましくない。   Furthermore, the melt flow rate (MFR) of the EVOH is 0.1 to 100 g / 10 min (measured at 210 ° C. and a load of 2160 g. The same applies hereinafter) (further, 1 to 50 g / 10 min, particularly 1.5 to 35 g. / 10 minutes, in particular 2 to 30 g / 10 minutes), and if the MFR is less than 0.1 g / 10 minutes, the inside of the extruder is in a high torque state during molding, making extrusion difficult, and conversely 100 g / 10 minutes. Exceeding this is undesirable because the torque becomes low and the extrusion processability becomes unstable.

該ＥＶＯＨ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 EVOH is obtained by saponification of an ethylene-vinyl acetate copolymer, and the ethylene-vinyl acetate copolymer is produced by any known polymerization method such as 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.

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１〜１８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。また、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、シアノエチル化等、後変性されても差し支えない。さらには、特開昭６０−１４４３０４号公報に記載の如きケイ素を含有したＥＶＯＨを用いることも可能である。   In the present invention, an ethylenically unsaturated monomer that can be copolymerized within a range that does not impair the effects of the present invention may be copolymerized. Examples of such a monomer include propylene, 1-butene, and isobutene. Olefins, acrylic acid, methacrylic acid, crotonic acid, (anhydrous) phthalic acid, (anhydrous) maleic acid, (anhydrous) itaconic acid and other unsaturated acids or salts thereof, or mono- or dialkyl esters having 1 to 18 carbon atoms Acrylamide, acrylamide such as C1-C18 N-alkylacrylamide, N, N-dimethylacrylamide, 2-acrylamidepropanesulfonic acid or its salt, acrylamidepropyldimethylamine or its acid salt or its quaternary salt, methacryl Amides, N-alkyl methacrylamides having 1 to 18 carbon atoms, N, N- Methacrylamide such as methylmethacrylamide, 2-methacrylamidepropanesulfonic acid or its salt, methacrylamideamidopropylamine or its acid salt or its quaternary salt, N-vinylpyrrolidone, N-vinylformamide, N-vinylacetamide, etc. N-vinyl amides, 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, fluorine Vinyl halides such as vinylidene chloride and vinyl bromide, vinyl silanes such as trimethoxyvinyl silane, allyl acetate, allyl chloride, allyl alcohol, dimethylallyl alcohol, trimer Le - (3-acrylamido-3-dimethylpropyl) - ammonium chloride, and the like acrylamido-2-methylpropanesulfonic acid. Further, it may be post-modified such as urethanization, acetalization, cyanoethylation, etc. within the range not impairing the gist of the present invention. Furthermore, it is also possible to use EVOH containing silicon as described in JP-A-60-144304.

本発明で用いるＥＶＯＨペレットは、通常、エチレンと酢酸ビニルとをアルコール溶媒中で共重合させて、アルカリ等でケン化され、メタノール／水の凝固浴にストランド状に析出させた後切断されて得られる。   The EVOH pellets used in the present invention are usually obtained by copolymerizing ethylene and vinyl acetate in an alcohol solvent, saponifying with an alkali or the like, and depositing in a strand form in a methanol / water coagulation bath and then cutting. It is done.

そして、該ＥＶＯＨペレットは、次に水洗されるのであるが、該水洗は、１０〜６０℃の水槽中で実施される。かかる水洗によりオリゴマーや不純物が除去され、また、後述する酸性物質（Ａ）とアルカリ金属（Ｂ）の含有量もこの水洗で調整することが可能である。通常かかる水洗は、ＥＶＯＨペレット１００重量部に対して２００〜１０００重量部（好ましくは３００〜６００重量部）の水で、２０〜５０℃（２５〜３５℃）で、０．５〜５時間、１〜５回（好ましくは１回）実施される。   The EVOH pellets are then washed with water, which is carried out in a 10-60 ° C. water bath. Oligomer and impurities are removed by such water washing, and the content of the acidic substance (A) and alkali metal (B) described later can be adjusted by this water washing. Usually, the water washing is 200 to 1000 parts by weight (preferably 300 to 600 parts by weight) of water with respect to 100 parts by weight of EVOH pellets at 20 to 50 ° C. (25 to 35 ° C.) for 0.5 to 5 hours. It is carried out 1 to 5 times (preferably once).

その後、公知の流動乾燥及び／又は静置乾燥等の方法により乾燥されてＥＶＯＨペレットとして実用に供されるのであるが、本発明においては、上述のようにかかるＥＶＯＨペレットを３２メッシュ（目開き５００μ）篩を通過させて、通過する微紛の割合が全体の０．１重量％以下（さらには０．０５重量％以下、特には０．０３重量％以下）とすることを最大の特徴とするもので、かかる微紛の割合が０．１重量％を越えるときは本発明の目的を達成することが困難となる。なお、かかる微紛の割合の下限は特に限定されないが、成形時のペレット同士の滑り性等を考慮すれば、０．０００５重量％（さらには０．００１重量％）とすることが好ましい。   Thereafter, it is dried by a known method such as fluid drying and / or stationary drying, and is practically used as EVOH pellets. In the present invention, the EVOH pellets as described above are provided with 32 mesh (aperture 500 μm). ) Passing through a sieve, the maximum feature is that the ratio of fine powder passing through is 0.1% by weight or less (more 0.05% by weight or less, especially 0.03% by weight or less) of the whole. However, when the proportion of such fine powder exceeds 0.1% by weight, it is difficult to achieve the object of the present invention. The lower limit of the proportion of the fine powder is not particularly limited, but it is preferably 0.0005% by weight (further 0.001% by weight) in consideration of the sliding property between the pellets during molding.

上記のように３２メッシュ（目開き５００μ）篩を通過する微紛を０．１重量％以下にするにあたっては、通常の方法で得られたＥＶＯＨペレットを篩にかけてかかる微紛を除去する方法、サイクロン等による風力分級する方法、溶剤で洗浄・乾燥して微分を除去する方法、水を吹き付けた後に高温乾燥して微分を融着させる方法等が挙げられる。   In order to reduce the fine powder passing through the 32 mesh (aperture 500 μ) sieve to 0.1% by weight or less as described above, a method of removing the fine powder by applying EVOH pellets obtained by a usual method to a sieve, a cyclone For example, a method of classifying the wind with air, a method of removing the differential by washing and drying with a solvent, a method of fusing the differential by drying at high temperature after spraying water, and the like.

かくして、本発明のＥＶＯＨペレット群が得られるのであるが、本発明では上記のＥＶＯＨペレット中に、ホウ素化合物を含有していること、あるいは融点２００℃以下（さらには０〜１３０℃、特には０〜６５℃）の酸性物質（Ａ）及びアルカリ金属（Ｂ）を含有していることが本発明の作用効果をさらに顕著に得られる点で好ましく、これらを含有させる方法について説明する。   Thus, the EVOH pellet group of the present invention can be obtained. In the present invention, the above-mentioned EVOH pellet contains a boron compound or has a melting point of 200 ° C. or lower (more preferably 0 to 130 ° C., particularly 0). It is preferable that the acidic substance (A) and the alkali metal (B) at ˜65 ° C. are contained from the viewpoint that the effects of the present invention can be obtained more remarkably, and a method for containing them will be described.

かかるホウ素化合物としては、ホウ酸、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。   Such boron compounds include boric acid, calcium borate, cobalt borate, zinc borate (zinc tetraborate, zinc metaborate, etc.), aluminum borate / potassium 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 (silver metaborate, silver tetraborate, etc.), copper borate (cupric borate, copper metaborate, copper tetraborate, etc.), sodium borate (metaborate) Sodium, sodium diborate, sodium tetraborate, sodium pentaborate, sodium hexaborate, sodium octaborate ), Lead borate (lead metaborate, lead hexaborate, etc.), nickel borate (nickel orthoborate, nickel diborate, nickel tetraborate, nickel octaborate, etc.), barium borate (orthoboric acid) Barium, barium metaborate, barium diborate, barium tetraborate, etc.), bismuth borate, magnesium borate (magnesium orthoborate, magnesium diborate, magnesium metaborate, trimagnesium tetraborate, pentamagnesium tetraborate) ), Manganese borate (manganese borate, manganese metaborate, manganese tetraborate, etc.), lithium borate (lithium metaborate, lithium tetraborate, lithium pentaborate, etc.), borax, Borate minerals such as carnite, inyoite, agate stone, suian stone, zyberite, etc. Borax in suitable, boric acid, sodium borate (sodium metaborate, sodium diborate, sodium tetraborate, sodium pentaborate, sodium hexaborate acid, eight sodium borate) may be used.

かかるホウ素化合物の含有量は特に限定されないが、ＥＶＯＨに対してホウ素換算で０．００１〜１重量％（さらには０.００１〜０.２重量％、特には０．０２〜０．１重量％）になるように含有させることが好ましく、かかる含有量が０．００１重量％未満では添加効果に乏しく、逆に１重量％を超えると成形物中にゲルやスジが発生する傾向にあり好ましくない。   The content of the boron compound is not particularly limited, but is 0.001 to 1% by weight (more preferably 0.001 to 0.2% by weight, particularly 0.02 to 0.1% by weight) in terms of boron with respect to EVOH. It is preferable that the content is less than 0.001% by weight, and the addition effect is poor. On the other hand, if it exceeds 1% by weight, gel and streaks tend to occur in the molded product, which is not preferable. .

ＥＶＯＨにホウ素化合物を含有させるにあたっては、上記で得られたＥＶＯＨペレットをホウ素化合物の水溶液に接触させることで含有させることができ、通常は該水溶液に上記のＥＶＯＨペレットを投入して撹拌しながら、ホウ素化合物を含有させることが好ましい。   In containing the boron compound in EVOH, the EVOH pellets obtained above can be contained by contacting with an aqueous solution of the boron compound. Usually, the EVOH pellets are charged into the aqueous solution and stirred, It is preferable to contain a boron compound.

また、融点が２００℃以下の酸性物質（Ａ）としては、酢酸（融点１７℃）、アジピン酸（融点２８℃）、リン酸（融点４２℃）、安息香酸（融点１２２℃）、クエン酸（融点１５３℃）、コハク酸（融点１８５℃）等を挙げることができ、中でも酢酸やリン酸が好適である。   The acidic substance (A) having a melting point of 200 ° C. or lower includes acetic acid (melting point 17 ° C.), adipic acid (melting point 28 ° C.), phosphoric acid (melting point 42 ° C.), benzoic acid (melting point 122 ° C.), citric acid ( Melting point 153 ° C.), succinic acid (melting point 185 ° C.) and the like. Among them, acetic acid and phosphoric acid are preferable.

さらに、アルカリ金属（Ｂ）としては、ナトリウム、カリウム等のアルカリ金属やマグネシウム、カルシウム等のアルカリ土類金属を挙げることができ、ＥＶＯＨに含有させるにあたっては、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、ベヘニン酸等の有機酸や硫酸、亜硫酸、炭酸、リン酸等の無機酸の金属塩として含有させればよい。   Furthermore, examples of the alkali metal (B) include alkali metals such as sodium and potassium, and alkaline earth metals such as magnesium and calcium. When contained in EVOH, acetic acid, propionic acid, butyric acid, lauric acid, What is necessary is just to make it contain as organic acid salts, such as a stearic acid, an oleic acid, and behenic acid, and metal salts of inorganic acids, such as a sulfuric acid, a sulfurous acid, carbonic acid, and phosphoric acid.

かかる酸性物質（Ａ）の含有量は、ＥＶＯＨに対して０．００１〜０．０５重量％（さらには０．００１〜０．０３重量％、特には０．００２〜０．０１重量％）とすることが好ましく、かかる含有量が０．００１重量％未満では添加効果に乏しく、逆に０．０５重量％を超えると成形物中にゲルやスジが発生する傾向にあり好ましくない。   The content of the acidic substance (A) is 0.001 to 0.05% by weight (more 0.001 to 0.03% by weight, particularly 0.002 to 0.01% by weight) with respect to EVOH. If the content is less than 0.001% by weight, the effect of addition is poor. Conversely, if the content exceeds 0.05% by weight, gel or streaks tend to be generated in the molded product, which is not preferable.

また、アルカリ金属（Ｂ）の含有量は、ＥＶＯＨに対して０．００１〜０．５重量％（さらには０．００１〜０．０５重量％）とすることが好ましく、かかる含有量が０．００１重量％未満では添加効果に乏しく、逆に０．５重量％を超えると着色の恐れがあり好ましくない。   The content of the alkali metal (B) is preferably 0.001 to 0.5% by weight (more preferably 0.001 to 0.05% by weight) with respect to EVOH. If the amount is less than 001% by weight, the effect of addition is poor.

さらに、上記の酸性物質（Ａ）とアルカリ金属（Ｂ）との含有重量比（Ａ／Ｂ）を１〜５０（さらには１〜２０、特には１〜１０）とすることが好ましく、かかる重量比が１未満では成形時に熱分解による異臭が発生する恐れがあり、逆に５０を越えると成形機内のスクリューやダイ内での腐食発生の恐れがあり好ましくない。   Furthermore, it is preferable that the content weight ratio (A / B) of the acidic substance (A) and the alkali metal (B) is 1 to 50 (more preferably 1 to 20, particularly 1 to 10), and the weight. If the ratio is less than 1, there is a possibility that a strange odor due to thermal decomposition may occur during molding. Conversely, if it exceeds 50, corrosion in the screw or die in the molding machine may occur, which is not preferable.

ＥＶＯＨ中に上記の酸性物質（Ａ）やアルカリ金属（Ｂ）を含有させる方法については、特に限定されず、ア）含水率２０〜８０重量％のＥＶＯＨの多孔性析出物を、酸性物質（Ａ）やアルカリ金属（Ｂ）を含有する水溶液と接触させて、酸性物質（Ａ）やアルカリ金属（Ｂ）を含有させてから乾燥する方法、イ）ＥＶＯＨの均一溶液（水／アルコール溶液等）に酸性物質（Ａ）やアルカリ金属（Ｂ）を含有させた後、凝固液中にストランド状に押し出し、次いで得られたストランドを切断してペレットとして、さらに乾燥処理をする方法、ウ）ＥＶＯＨと酸性物質（Ａ）やアルカリ金属（Ｂ）を一括して混合してから押出機等で溶融混練する方法、エ）ＥＶＯＨの製造時において、ケン化工程で使用したアルカリ（水酸化ナトリウム、水酸化カリウム等）を酢酸等の酸性物質（Ａ）で中和して、残存する酢酸等の酸性物質（Ａ）や副生成する酢酸ナトリウム、酢酸カリウム等のアルカリ金属（Ｂ）塩の量を水洗処理により調整したりする方法等を挙げることができる。本発明の効果をより顕著に得るためには、酸類やその金属塩の分散性に優れるア）、イ）またはエ）の方法が好ましい。   There is no particular limitation on the method of containing the acidic substance (A) or alkali metal (B) in EVOH. A) A porous precipitate of EVOH having a water content of 20 to 80% by weight is converted into an acidic substance (A ) Or an alkali metal (B) in contact with an aqueous solution to contain the acidic substance (A) or alkali metal (B) and then drying, and a) EVOH homogeneous solution (water / alcohol solution, etc.) A method in which an acidic substance (A) or an alkali metal (B) is contained, and then extruded into a coagulating solution in the form of a strand, and then the resulting strand is cut into pellets and further dried, c) EVOH and acidic A method in which the substance (A) and the alkali metal (B) are mixed together and then melt-kneaded with an extruder or the like; d) the alkali (sodium hydroxide, hydroxide) used in the saponification step during the production of EVOH; Potassium etc.) is neutralized with acetic acid or other acidic substance (A), and the remaining amount of acidic substance (A) such as acetic acid or alkali metal (B) salt such as sodium acetate or potassium acetate formed as a by-product is washed with water. And the like. In order to obtain the effects of the present invention more remarkably, the methods a), b) and d), which are excellent in dispersibility of acids and metal salts thereof, are preferred.

かくして得られた本発明のＥＶＯＨペレット群は、かかるペレットを用いて溶融成形する際に、得られる成形物にゲルが発生しないという作用効果を有するもので、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。
また、該ＥＶＯＨペレットは、積層体用途に多用され、特にＥＶＯＨ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られる。 The EVOH pellet group of the present invention thus obtained has the effect that no gel is generated in the resulting molded product when melt-molded using such pellets. As a melt-molding method, an extrusion molding method ( T-die extrusion, inflation extrusion, blow molding, melt spinning, profile extrusion, etc.) and injection molding methods are mainly employed. The melt molding temperature is often selected from the range of 150 to 300 ° C.
The EVOH pellets are frequently used for laminates, and are used as laminates in which a thermoplastic resin layer is laminated on at least one side of a layer made of EVOH.

該積層体を製造するに当たっては、ＥＶＯＨ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ＥＶＯＨ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ＥＶＯＨを溶融押出する方法、該ＥＶＯＨ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ドライラミネートする方法等が挙げられる。   In the production of the laminate, another substrate is laminated on one or both sides of the EVOH layer. As a lamination method, for example, a method of melt-extruding a thermoplastic resin on the EVOH film or sheet, Conversely, a method of melt-extruding the EVOH on a substrate such as a thermoplastic resin, a method of co-extruding the EVOH and another thermoplastic resin, and further, an EVOH film, sheet and other group obtained by the present invention. Examples thereof include a method of dry laminating a film or sheet of a material using a known adhesive such as an organic titanium compound, an isocyanate compound, a polyester compound, or a polyurethane compound.

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、ＰＥＴ、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。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。   The other resin in the case of coextrusion is linear low density polyethylene, low density polyethylene, medium density polyethylene, high density polyethylene, ethylene-vinyl acetate copolymer, ionomer, ethylene-propylene copolymer, ethylene-acrylic acid. Ester copolymer, polypropylene, propylene-α-olefin (α-olefin having 4 to 20 carbon atoms) copolymer, polybutene, polypentene and other olefins alone or copolymers, or these olefins alone or copolymers In a broad sense such as those graft-modified with unsaturated carboxylic acid or its ester, polyester, polyamide, copolymerized polyamide, polyvinyl chloride, polyvinylidene chloride, acrylic resin, polystyrene, PET, vinyl ester resin, Polyester elastomer -Polyurethane elastomer, chlorinated polyethylene, chlorinated polypropylene and the like. 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).

さらに、本発明のＥＶＯＨペレット群から一旦フィルム、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、ＥＶＯＨの層をｘ（ｘ1、ｘ2、・・・）、他の基材、例えば熱可塑性樹脂層をｙ（ｙ1、ｙ2、・・・）とするとき、フィルム、シート、ボトル状であれば、ｘ／ｙの二層構造のみならず、ｙ／ｘ／ｙ、ｘ／ｙ／ｘ、ｘ1／ｘ2／ｙ、ｘ／ｙ1／ｙ2、ｙ2／ｙ1／ｘ／ｙ1／ｙ2等任意の組み合わせが可能であり、フィラメント状ではｘ、ｙがバイメタル型、芯（ｘ）−鞘（ｙ）型、芯（ｙ）−鞘（ｘ）型、或いは偏心芯鞘型等任意の組み合わせが可能である。 Furthermore, when a molded product such as a film or a sheet is once obtained from the EVOH pellet group of the present invention and another substrate is extrusion coated thereon, or a film or sheet of another substrate is laminated using an adhesive In addition to the thermoplastic resin, any substrate (paper, metal foil, uniaxial or biaxially stretched plastic film or sheet, woven fabric, non-woven fabric, metallic cotton, wood, etc.) can be used.
The layer structure of the laminate is such that the EVOH layer is x (x 1 , x 2 ,...), And another substrate, for example, a thermoplastic resin layer is y (y 1 , y 2 ,...). In the case of a film, sheet, or bottle, not only x / y two-layer structure, but also y / x / y, x / y / x, x 1 / x 2 / y, x / y 1 / y 2 , Any combination such as y 2 / y 1 / x / y 1 / y 2 is possible, and in the filament form, x and y are bimetal type, core (x) -sheath (y) type, core (y) -sheath ( Any combination such as x) type or eccentric core-sheath type is possible.

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。   The laminate is used in 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, and the stretching may be either uniaxial stretching or biaxial stretching. It is possible to obtain a stretched film or stretched sheet that has better physical properties when stretched at as high a magnification as possible and does not cause pinholes, cracks, stretch unevenness, delamination, or the like during stretching.

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８０〜１７０℃、好ましくは１００〜１６０℃程度の範囲から選ばれる。   As the stretching method, in addition to a roll stretching method, a tenter stretching method, a tubular stretching method, a stretching blow method, and the like, a deep drawing method, a vacuum forming method, or the like having a high stretching ratio can be employed. In the case of biaxial stretching, both a simultaneous biaxial stretching method and a sequential biaxial stretching method can be employed. The stretching temperature is selected from the range of about 80 to 170 ° C, preferably about 100 to 160 ° C.

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。
また、生肉、加工肉、チーズ等を熱収縮包装する用途に用いる場合は、延伸後の熱固定は行わず製品フィルムとし、上記生肉、加工肉、チーズ等を該フィルムに収納して、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する。 Thus, after stretching is completed, heat setting is then performed. The heat setting can be carried out by a known means, and the 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 tension state.
Moreover, when using it for the application which heat shrink-wraps raw meat, processed meat, cheese, etc., it does not heat-set after extending | stretching, it is set as a product film, the said raw meat, processed meat, cheese, etc. are accommodated in this film, 50 ~ The film is heat-shrinked at 130 ° C., preferably 70 to 120 ° C. for about 2 to 300 seconds, and the film is heat-shrinked and tightly packaged.

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。
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 laminate thus obtained may be any shape, and examples thereof include films, sheets, tapes, bottles, pipes, filaments, profile cross-section extrudates, and the like. In addition, the obtained laminate can be subjected to heat treatment, cooling treatment, rolling treatment, printing treatment, dry lamination treatment, solution or melt coating treatment, bag making processing, deep drawing processing, box processing, tube processing, split processing, etc. It can be carried out.
The film, sheet or container obtained as described above is useful as various packaging materials such as foods, pharmaceuticals, industrial chemicals and agricultural chemicals.

以下、実施例を挙げて本発明を具体的に説明する。
尚、例中、「部」とあるのは、「重量部」を意味し、「％」とあるのは、特に断りのない限り「重量％」を意味する。 Hereinafter, the present invention will be specifically described with reference to examples.
In the examples, “parts” means “parts by weight”, and “%” means “% by weight” unless otherwise specified.

実施例１
エチレン含有量３２モル％、ケン化度９９．６モル％、ＭＦＲ３ｇ／１０分（２１０℃、荷重２１６０ｇでの測定）のＥＶＯＨを水／メタノール（１／１重量比）混合溶媒に均一に溶解させた後に、１０℃水の凝固液中にストランド状に押出し析出させ、カッティングしてＥＶＯＨペレット得て、該ペレットを酢酸０．０３％と酢酸ナトリウム０．０４％含有させた水溶液に浸漬させ、さらにホウ酸の０．０１３％溶液に浸漬させて、ＥＶＯＨに対してホウ酸をホウ素換算で０．０３％、酢酸を０．０４５％、酢酸ナトリウムをナトリウム換算で０．０１５％（酢酸／ナトリウム＝１３／１）それぞれ含有するＥＶＯＨペレットを得た。
ついで、得られたＥＶＯＨペレットを３２メッシュ（目開き５００μ）の篩を通して分別し、３２メッシュオンのＥＶＯＨペレット１００部と３２メッシュ通過ＥＶＯＨペレット０．０３部（０．０３％）を混合して本発明のＥＶＯＨペレット群を得た。 Example 1
EVOH having an ethylene content of 32 mol%, a saponification degree of 99.6 mol%, and an MFR of 3 g / 10 min (measured at 210 ° C. under a load of 2160 g) is uniformly dissolved in a water / methanol (1/1 weight ratio) mixed solvent. After that, it is extruded and precipitated in a strand form in a coagulating liquid of 10 ° C., and is cut to obtain EVOH pellets. The pellets are immersed in an aqueous solution containing 0.03% acetic acid and 0.04% sodium acetate, It is immersed in a 0.013% boric acid solution, 0.03% boric acid in terms of boron, 0.045% acetic acid, and 0.015% sodium acetate in sodium equivalent to EVOH (acetic acid / sodium = 13/1) EVOH pellets contained respectively were obtained.
Next, the obtained EVOH pellets were separated through a sieve of 32 mesh (aperture 500 μm), and 100 parts of 32 mesh-on EVOH pellets and 0.03 part (0.03%) of 32 mesh-passed EVOH pellets were mixed and mixed. An EVOH pellet group of the invention was obtained.

得られたＥＶＯＨペレット群を用いて、以下の要領で多層フィルムを作製して、以下の成形性の評価を行った。
〔多層フィルムの作製〕
上記のＥＶＯＨペレット（Ｉ）、ナイロン−６〔三菱エンジニアリングプラスチックス社製「ＮＯＶＡＭＩＤ １０２２−１」〕（II）、ポリプロピレン〔日本ポリケム社製「ＦＬ６ＣＫ」〕（III）及び接着性樹脂〔三井化学社製「ＡＤＭＥＲ ＱＦ５００」、無水マレイン酸変性ポリプロピレン〕（IV）を、フィードブロック式共押出多層フィルム成形機（グンゼ産業社製）に供給して、（II）／（Ｉ）／（IV）／（III）＝１０／１０／１０／１２０（μｍ；厚み）の層構成を有する多層フィルムを得た。 Using the obtained EVOH pellet group, a multilayer film was produced in the following manner, and the following moldability was evaluated.
[Production of multilayer film]
EVOH pellets (I), nylon-6 ["NOVAMID 1022-1" manufactured by Mitsubishi Engineering Plastics] (II), polypropylene ["FL6CK" manufactured by Nippon Polychem Co., Ltd.] (III), and adhesive resin [Mitsui Chemicals, Inc. “ADMER QF500”, maleic anhydride-modified polypropylene] (IV) manufactured by feed block type coextrusion multilayer film molding machine (manufactured by Gunze Sangyo Co., Ltd.), and (II) / (I) / (IV) / ( III) A multilayer film having a layer structure of 10/10/10/120 (μm; thickness) was obtained.

（成形性）
上記の製造で４８時間後に得られた多層フィルムから１０ｃｍ×１０ｃｍの大きさのフィルムを採取して、ＥＶＯＨ層の乱れによるゲルの発生状態を目視観察して以下のように評価した。
◎・・・ゲルの発生が４個以下
○・・・ 〃 ５〜１０個
×・・・ 〃 １１個以上 (Formability)
A film having a size of 10 cm × 10 cm was collected from the multilayer film obtained after 48 hours in the above production, and the gel generation state due to the disturbance of the EVOH layer was visually observed and evaluated as follows.
◎ ・ ・ ・ Generation of 4 or less gels ○ ・ ・ ・ ５〜 5-10 pieces × ・ ・ ・ 〃 11 or more pieces

実施例２
ＥＶＯＨとして、エチレン含有量４０モル％、ケン化度９９．４モル％、ＭＦＲ１５ｇ／１０分（２１０℃、荷重２１６０ｇでの測定）を用いて、実施例１に準じてＥＶＯＨペレットを得た後、該ペレットを酢酸０．０５％と酢酸ナトリウム０．０３％含有させた水溶液に浸漬させて、ＥＶＯＨに対して酢酸を０．０６％、酢酸ナトリウムをナトリウム換算で０．０１３％（酢酸／ナトリウム＝２０／１）それぞれ含有するＥＶＯＨペレットを用いた以外は同様に行って本発明のＥＶＯＨペレット群を得て、同様に評価を行った。 Example 2
After EVOH pellets were obtained according to Example 1, using EVOH as the ethylene content 40 mol%, saponification degree 99.4 mol%, MFR 15 g / 10 min (measured at 210 ° C., load 2160 g), The pellet was immersed in an aqueous solution containing 0.05% acetic acid and 0.03% sodium acetate, and 0.06% acetic acid and 0.013% sodium acetate in terms of sodium with respect to EVOH (acetic acid / sodium = 20/1) It carried out similarly except having used each EVOH pellet, obtained the EVOH pellet group of this invention, and evaluated similarly.

実施例３
実施例１において、ＥＶＯＨペレットを３２メッシュ（目開き５００μ）の篩を通して分別し、３２メッシュオンのＥＶＯＨペレット１００部と３２メッシュ通過ＥＶＯＨペレット０．０８部（０．０８％）を混合して本発明のＥＶＯＨペレット群を得て、同様に評価を行った。 Example 3
In Example 1, the EVOH pellets were fractionated through a 32 mesh (aperture 500 μ) sieve, and 100 parts of 32 mesh-on EVOH pellets and 0.08 part (0.08%) of 32 mesh-passed EVOH pellets were mixed together. The EVOH pellet group of the invention was obtained and evaluated in the same manner.

実施例４
実施例１において、ＥＶＯＨの水／メタノール溶液をアンダーウェーターカットして球状のＥＶＯＨペレットを得た以外は同様に行って、３２メッシュ（目開き５００μ）の篩を通過する微紛の割合が０．０２％の本発明のＥＶＯＨペレット群を得て、実施例１と同様に評価を行った。 Example 4
In Example 1, the same procedure was followed except that the EVOH water / methanol solution was underwater cut to obtain spherical EVOH pellets, and the proportion of fine particles passing through a 32 mesh (aperture 500 μm) sieve was 0.00. 02% EVOH pellet group of the present invention was obtained and evaluated in the same manner as in Example 1.

比較例１
実施例１において、３２メッシュの篩で分別せずにＥＶＯＨペレット群の評価を行った。なお、かかるＥＶＯＨペレット群の３２メッシュ（目開き５００μ）篩を通過する微紛の割合は０．２％であった。 Comparative Example 1
In Example 1, the EVOH pellet group was evaluated without separation with a 32 mesh sieve. In addition, the ratio of the fine powder which passes the 32 mesh (mesh 500 micrometers) sieve of this EVOH pellet group was 0.2%.

実施例及び比較例の評価結果を表１に示す。   The evaluation results of Examples and Comparative Examples are shown in Table 1.

〔表１〕
成形性
実施例１ ◎
〃 ２ ◎
〃 ３ ○
〃 ４ ◎
比較例１ × [Table 1]
Formability
Example 1
〃 2 ◎
３ 3 ○
４ 4 ◎
Comparative Example 1 ×

本発明の、ＥＶＯＨペレット群は特定の微紛を特定量以下に押さえているため、成形物に溶融成形したときにゲルや焼けの発生がなく、良好な成形物が得られ、多層フィルム用途に有用で、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、容器等の用途をはじめとして、各種成形用途に非常に有用である。   Since the EVOH pellet group of the present invention keeps specific fine powder below a specific amount, it does not generate gel or burn when melt-formed into a molded product, and a good molded product can be obtained and used for multilayer films. It is useful and is very useful for various molding applications including foods, pharmaceuticals, agricultural chemicals, films for industrial packaging, sheets, tubes, bags, containers and the like.

Claims (3)

３２メッシュ（目開き５００μ）篩を通過する微紛の含有量が０．１重量％以下であることを特徴とするエチレン−酢酸ビニル共重合体ケン化物ペレット群。   The ethylene-vinyl acetate copolymer saponified pellet group, wherein the content of fine powder passing through a 32 mesh (aperture 500 μm) sieve is 0.1% by weight or less. エチレン−酢酸ビニル共重合体ケン化物が、エチレン‐酢酸ビニル共重合体ケン化物に対してホウ素換算で０．００１〜１重量％のホウ素化合物を含有していることを特徴とする請求項１記載のエチレン−酢酸ビニル共重合体ケン化物ペレット群。 The saponified ethylene-vinyl acetate copolymer contains 0.001 to 1% by weight of a boron compound in terms of boron based on the saponified ethylene-vinyl acetate copolymer. Of ethylene-vinyl acetate copolymer saponified pellets. 請求項１または２記載のエチレン−酢酸ビニル共重合体ケン化物ペレット群を成形してなる層を少なくとも一層含有することを特徴とする積層体。 A laminate comprising at least one layer formed by molding the ethylene-vinyl acetate copolymer saponified pellet group according to claim 1 or 2 .
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JPH1143571A (en) * 1997-07-25 1999-02-16 Nippon Synthetic Chem Ind Co Ltd:The Resin composition and its laminate
JP2001011191A (en) * 1999-07-01 2001-01-16 Nippon Synthetic Chem Ind Co Ltd:The Treatment of pellet of saponified substance of ethylene- vinyl acetate copolymer
JP2001164070A (en) * 1999-09-29 2001-06-19 Kuraray Co Ltd Resin composition composed of ethylene-vinyl alcohol copolymer having low odor
JP2001247679A (en) * 2000-03-06 2001-09-11 Nippon Synthetic Chem Ind Co Ltd:The Method for cutting vinyl alcohol-type polymer block

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JPH1143571A (en) * 1997-07-25 1999-02-16 Nippon Synthetic Chem Ind Co Ltd:The Resin composition and its laminate
JP2001011191A (en) * 1999-07-01 2001-01-16 Nippon Synthetic Chem Ind Co Ltd:The Treatment of pellet of saponified substance of ethylene- vinyl acetate copolymer
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