JPH1135768A - Ethylene-vinyl acetate-based copolymer saponified product composition and molded product therefrom - Google Patents
Ethylene-vinyl acetate-based copolymer saponified product composition and molded product therefromInfo
- Publication number
- JPH1135768A JPH1135768A JP9213974A JP21397497A JPH1135768A JP H1135768 A JPH1135768 A JP H1135768A JP 9213974 A JP9213974 A JP 9213974A JP 21397497 A JP21397497 A JP 21397497A JP H1135768 A JPH1135768 A JP H1135768A
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- JP
- Japan
- Prior art keywords
- evoh
- film
- acid
- stretching
- water
- 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.)
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- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、エチレン−酢酸ビ
ニル系共重合体ケン化物（以下、ＥＶＯＨと略記する）
を主剤とするＥＶＯＨ組成物及び該組成物からの成形
物、特にフィルム等の成形物に関する。The present invention relates to a saponified ethylene-vinyl acetate copolymer (hereinafter abbreviated as EVOH).
The present invention relates to an EVOH composition comprising, as a main component, and a molded product from the composition, particularly a molded product such as a film.
【０００２】[0002]
【従来の技術】従来より、ＥＶＯＨフィルムは、そのガ
スバリヤー性を生かして、各種包装用途に多用されてい
る。かかるＥＶＯＨフィルムの製造法としては、ＥＶＯ
Ｈ（ペレット）を溶融押出機等によりフィルム状に成形
し、更に１軸或いは２軸に延伸するのが一般的である
が、該製造法によっては、得られたＥＶＯＨフィルムに
ダイラインやフィッシュアイ等が生じたり、或いは透明
性に劣ったりすることも多く、又、製造中にゲルや目ヤ
ニ等が発生しロングラン成形が困難となり、実用に供す
るのが難しくなる。 かかる対策として、本出願人は、
ＥＶＯＨに水を含有せしめてなる樹脂組成物を用いるこ
とを提案した（特願平８−３１３０５０号）。2. Description of the Related Art Heretofore, EVOH films have been frequently used in various packaging applications, taking advantage of their gas barrier properties. As a method for producing such an EVOH film, EVO is used.
In general, H (pellet) is formed into a film by a melt extruder or the like, and further uniaxially or biaxially stretched. However, depending on the production method, a die line, a fish eye, or the like may be added to the obtained EVOH film. Often occur or the transparency is inferior. In addition, gel or tanning occurs during production, making long-run molding difficult, and making it difficult to put into practical use. As such a measure, the applicant has
It has been proposed to use a resin composition prepared by adding water to EVOH (Japanese Patent Application No. 8-313050).
【０００３】[0003]
【発明が解決しようとする課題】しかしながら、本発明
者が詳細に検討した結果、上記技術ではフィッシュアイ
の低減は認められるものの、長時間の連続運転における
ＥＶＯＨ成形物の外観外観及び品質の安定性については
改善の余地が残るものであり、技術の高度化と多様化に
伴い、更にロングラン性に優れ、スジやフィッシュアイ
のない、透明性に優れた外観の良好なＥＶＯＨ成形物
（フィルム、シート、等）が望まれている。However, as a result of a detailed study conducted by the present inventors, although the reduction of fish eyes is recognized in the above-mentioned technology, the stability of appearance and appearance and quality of EVOH molded articles during long-time continuous operation is confirmed. There is still room for improvement, and with the advancement and diversification of technology, EVOH moldings (films, sheets, etc.) having excellent long-run properties, no streaks and fish eyes, and excellent transparency and excellent appearance. , Etc.) are desired.
【０００４】[0004]
【課題を解決するための手段】そこで、本発明者はかか
る事情に鑑みて鋭意研究を重ねた結果、ＥＶＯＨ
（Ａ）、２５℃におけるｐＫａが５．０以下の酸基を有
する酸（Ｂ）及び２５℃におけるｐＫａが３．４以下の
酸基を有する多塩基酸の第１カルシウム塩又はマグネシ
ウム塩（Ｃ）、水（Ｄ）からなり、前記（Ｂ）の酸、
（Ｃ）の塩の少なくとも一方はリン酸基を含有するもの
であると共に、該ＥＶＯＨ（Ａ）において（１）アルカ
リ金属の含有量が０．００１〜０．０５重量％、（２）
リン酸基に対するアルカリ金属のモル比が１〜３０、
（３）リン酸基に対するカルシウム又はマグネシウムの
モル比が０．１〜５、（４）該ＥＶＯＨ（Ａ）１００重
量部に対して水（Ｄ）が１０〜１４０重量部となるよう
に含有させてなるＥＶＯＨ組成物が、上記の課題を解決
するものであることを見出し本発明を完成するに至っ
た。本発明において上記ＥＶＯＨ組成物を溶融押出して
成形物、特にフィルム、シートとすることが好ましい。The inventor of the present invention has conducted intensive studies in view of such circumstances, and has found that EVOH
(A) a first calcium salt or magnesium salt of an acid (B) having an acid group having a pKa at 25 ° C of 5.0 or less and a polybasic acid having an acid group having a pKa at 25 ° C of 3.4 or less (C ), Water (D), the acid of the above (B),
At least one of the salts (C) contains a phosphate group, and the EVOH (A) has (1) an alkali metal content of 0.001 to 0.05% by weight, (2)
The molar ratio of the alkali metal to the phosphate group is 1 to 30,
(3) Calcium or magnesium molar ratio to phosphate group is 0.1-5, (4) water (D) is 10-140 parts by weight with respect to 100 parts by weight of the EVOH (A). The present inventors have found that the above EVOH composition solves the above-mentioned problems, and have completed the present invention. In the present invention, it is preferable that the EVOH composition is melt-extruded to form a molded product, particularly a film or sheet.
【０００５】又、本発明では、上記ＥＶＯＨ組成物を溶
融押出して得られた成形物、特にフィルム、シートを含
水率５〜５０重量％で延伸することも好ましく、フィル
ム外観の優れた成形物が得られるのである。即ち、本発
明は、長時間の連続運転においても膜厚が均一でスジや
フィッシュアイのない外観の良好なＥＶＯＨ組成物の成
形物（フィルム、シート等）を得ることができるのであ
る。In the present invention, it is also preferable that a molded product obtained by melt-extruding the above-mentioned EVOH composition, particularly a film or sheet, is stretched at a water content of 5 to 50% by weight. You get it. That is, according to the present invention, it is possible to obtain a molded product (film, sheet, etc.) of the EVOH composition having a uniform film thickness and good appearance without streaks or fish eyes even during long-time continuous operation.
【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。本発明のＥＶＯＨ（Ａ）としては、エチレン含
量５〜６０モル％、好ましくは１０〜６０モル％、更に
好ましくは２０〜５５モル％、酢酸ビニル成分のケン化
度が９０モル％以上、好ましくは９５モル％以上のもの
が好適に用いられ、エチレン含量が５モル％未満では耐
水性が不十分となり、一方６０モル％を越えるとガスバ
リヤー性が低下して好ましくない。又、ケン化度が９０
モル％未満では耐水性が不十分となって好ましくない。BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described specifically. As the EVOH (A) of the present invention, the ethylene content is 5 to 60 mol%, preferably 10 to 60 mol%, more preferably 20 to 55 mol%, and the degree of saponification of the vinyl acetate component is 90 mol% or more, preferably When the ethylene content is less than 5 mol%, the water resistance becomes insufficient. On the other hand, when the ethylene content exceeds 60 mol%, the gas barrier property decreases, which is not preferable. The saponification degree is 90
If the amount is less than mol%, the water resistance becomes insufficient, which is not preferable.
【０００７】又、該ＥＶＯＨ（Ａ）は更に少量のプロピ
レン、イソブテン、α−オクテン、α−ドデセン、α−
オクタデセン等のα−オレフィン、不飽和カルボン酸又
はその塩・部分アルキルエステル・完全アルキルエステ
ル・ニトリル・アミド・無水物、不飽和スルホン酸又は
その塩、ビニルシラン化合物、塩化ビニル、スチレン等
のコモノマーを含んでいても差し支えない。又、本発明
の範囲で、ウレタン化、アセタール化、シアノエチル化
等「後変性」にされても差し支えない。The EVOH (A) may further contain a small amount of propylene, isobutene, α-octene, α-dodecene, α-
Includes α-olefins such as octadecene, unsaturated carboxylic acids or salts thereof, partial alkyl esters, complete alkyl esters, nitriles, amides, anhydrides, unsaturated sulfonic acids or salts thereof, vinyl silane compounds, vinyl chloride, and comonomers such as styrene. You can go out. Also, within the scope of the present invention, "post-modified" such as urethanization, acetalization, cyanoethylation, etc. may be used.
【０００８】本発明において用いる酸（Ｂ）は２５℃に
おけるｐＫａが５．０以下の酸基を有する酸及び、塩
（Ｃ）は２５℃におけるｐＫａが３．４以下の酸基を有
する多塩基酸の第１カルシウム塩又はマグネシウム塩で
あり、（Ｂ）、（Ｃ）の少なくとも一つはリン酸基をも
つことが必要である。（Ｂ）、（Ｃ）それぞれを単独使
用しても、ロングラン性の向上及びフィッシュアイの減
少という両者の効果を同時に得ることはできない。The acid (B) used in the present invention is an acid having an acid group having a pKa at 25 ° C. of 5.0 or less, and the salt (C) is a polybasic having an acid group having a pKa at 25 ° C. of 3.4 or less. It is a primary calcium salt or magnesium salt of an acid, and at least one of (B) and (C) needs to have a phosphate group. Even if each of (B) and (C) is used alone, it is not possible to simultaneously obtain the effects of improving the long run property and reducing the fish eye.
【０００９】（Ｂ）、（Ｃ）におけるｐＫａとは、酸の
解離定数をＫａとするとき、ｐＫａ＝−ｌｏｇＫａで定
義したものである。かかる酸が多塩基酸の時はｐＫａが
５．０以下の酸基を含むものであれば、いずれも使用可
能である。（Ｂ）に属する酸としては、酢酸、リン酸、
第１リン酸ナトリウムが好適に使用される。ｐＫａが
５．０を越える酸基を含む酸を用いたのではロングラン
成形時の熱着色抑制効果が劣ることとなる。（Ｂ）に含
まれる酸はいずれか１種又は２種以上用いられるが、特
に好ましいのは酢酸／オルトリン酸あるいは酢酸／第１
リン酸ナトリウムによる処理である。The pKa in (B) and (C) is defined as pKa = -logKa when the dissociation constant of the acid is Ka. When the acid is a polybasic acid, any acid can be used as long as it contains an acid group having a pKa of 5.0 or less. As the acid belonging to (B), acetic acid, phosphoric acid,
Monobasic sodium phosphate is preferably used. If an acid containing an acid group having a pKa of more than 5.0 is used, the effect of suppressing thermal coloring during long run molding will be poor. The acid contained in (B) may be used alone or in combination of two or more. Particularly preferred is acetic acid / orthophosphoric acid or acetic acid / first acid.
Treatment with sodium phosphate.
【００１０】又、（Ｃ）に属する塩としては、第１リン
酸カルシウム、第１リン酸マグネシウム、第１クエン酸
カルシウム、第１酒石酸カルシウム、第１マロン酸カル
シウム、第１マレイン酸カルシウムが例示され、第１リ
ン酸カルシウム及び第１リン酸マグネシウムが有利に用
いられる。ｐＫａが３．４未満の酸基を有しない多塩基
酸の第１塩を用いてもロングラン成形時の熱着色抑制効
果が劣ることとなり、工業的な実施には不適である。The salts belonging to (C) include, for example, monobasic calcium phosphate, monobasic magnesium phosphate, calcium citrate 1, calcium tartrate, calcium malonate 1 and calcium maleate 1 Monocalcium phosphate and magnesium phosphate are advantageously used. Even if a polybasic acid first salt having a pKa of less than 3.4 and having no acid group is used, the effect of suppressing thermal coloring during long-run molding is inferior, which is not suitable for industrial practice.
【００１１】本発明においては、上記のＥＶＯＨ
（Ａ）、酸（Ｂ）、塩（Ｃ）、及び水（Ｄ）からＥＶＯ
Ｈ組成物を製造するが、最終的に（１）アルカリ金属の
含有量が０．００１〜０．０５重量％、好ましくは０．
００２〜０．０３重量％、（２）リン酸基に対するアル
カリ金属のモル比が１〜３０、好ましくは２〜２０、
（３）リン酸基に対するカルシウム又はマグネシウムの
モル比が０．１〜５、好ましくは０．２〜４、（４）該
ＥＶＯＨ（Ａ）１００重量部に対して水（Ｄ）が１０〜
１４０重量部、好ましくは１５〜１２０重量部、更に好
ましくは２０〜１００重量部となるように含有させなけ
ればならない。In the present invention, the above EVOH
EVO from (A), acid (B), salt (C) and water (D)
The H composition is produced, and finally (1) the content of the alkali metal is 0.001 to 0.05% by weight, preferably 0.1 to 0.05% by weight.
002 to 0.03% by weight, (2) the molar ratio of alkali metal to phosphate groups is 1 to 30, preferably 2 to 20,
(3) The molar ratio of calcium or magnesium to phosphate groups is 0.1 to 5, preferably 0.2 to 4, and (4) water (D) is 10 to 100 parts by weight of the EVOH (A).
It must be contained in an amount of 140 parts by weight, preferably 15 to 120 parts by weight, more preferably 20 to 100 parts by weight.
【００１２】アルカリ金属の含有量が０．００１重量％
未満では、本発明の効果を得ることができず、０．０５
重量％を越えると着色性が増大してしまい品質が低下す
る。リン酸基に対するアルカリ金属のモル比が１未満で
は本発明の効果を得ることができず、一方３０を越える
と熱安定性が低下する点で不利となる。更に、リン酸基
に対するカルシウム又はマグネシウムのモル比が０．１
未満では本発明の効果を得ることができず、逆に５を越
えると微小なフィッシュアイの増加が顕著になり、実用
性がなくなる。An alkali metal content of 0.001% by weight
If less than 0.05, the effect of the present invention cannot be obtained, and
If the content is more than 10% by weight, the coloring property increases and the quality deteriorates. If the molar ratio of the alkali metal to the phosphate group is less than 1, the effect of the present invention cannot be obtained, while if it exceeds 30, the heat stability is disadvantageously reduced. Furthermore, the molar ratio of calcium or magnesium to phosphate groups is 0.1
If it is less than 5, the effect of the present invention cannot be obtained. Conversely, if it exceeds 5, the increase of minute fish eyes becomes remarkable, and the practicality is lost.
【００１３】水の含有量はＥＶＯＨ（Ａ）１００重量部
に対して１０〜１４０重量部、好ましくは１５〜１２０
重量部、更に好ましくは２０〜１００重量部である。水
の含有量が１０重量部未満ではロングラン（成形）性が
低下するばかりでなく均一な延伸が困難となり、本発明
の効果を得ることができず、逆に１４０重量部を越える
と押出機中で樹脂と水分の一部分離が起こり押出が不安
定になる。The content of water is from 10 to 140 parts by weight, preferably from 15 to 120 parts by weight, per 100 parts by weight of EVOH (A).
Parts by weight, more preferably 20 to 100 parts by weight. If the water content is less than 10 parts by weight, not only does the long-run (molding) property deteriorate, but also it becomes difficult to perform uniform stretching, and the effect of the present invention cannot be obtained. In this case, the resin and water are partially separated, and the extrusion becomes unstable.
【００１４】かかるＥＶＯＨ組成物の製造方法について
は特に制限はなく、要はＥＶＯＨ（Ａ）、酸（Ｂ）、塩
（Ｃ）及び水（Ｄ）を上記範囲に含有されるようにすれ
ばよく、例えば、ＥＶＯＨ（Ａ）の粉末、ペレット、
粒状物に酸（Ｂ）や塩（Ｃ）を粉末状、溶液状、分散液
状の任意の形態にして混合し、水（Ｄ）を混合する方
法、ＥＶＯＨ（Ａ）製造時の任意の段階、即ち重合
時、ケン化時、後処理時、乾燥時の任意の段階で酸
（Ｂ）や塩（Ｃ）を所定量含有させ、ＥＶＯＨの製造後
に水（Ｄ）を混合する方法、ＥＶＯＨ（Ａ）と水
（Ｄ）を混合撹拌してあるいは蒸気を吹き込んで吸水さ
せた後酸（Ｂ）や塩（Ｃ）を混合する方法、ＥＶＯＨ
（Ａ）の水／メタノール混合液を凝固液槽中に押出して
多孔性の含水ＥＶＯＨ成形物を得た後、水中で酸（Ｂ）
や塩（Ｃ）を含浸させて、上記範囲の含水量まで乾燥す
る方法、等の方法が挙げられる。但し、これらに限定さ
れることはなく、本発明では各成分の含有量が上記範囲
のものとなりうるのであれば任意の方法が採用され得
る。The method for producing such an EVOH composition is not particularly limited, and the point is that the EVOH (A), the acid (B), the salt (C) and the water (D) may be contained in the above range. , For example, EVOH (A) powder, pellets,
A method in which an acid (B) or a salt (C) is mixed with granules in any form of powder, solution, or dispersion, and water (D) is mixed; EVOH (A) is prepared at any stage; That is, a method in which a predetermined amount of an acid (B) or a salt (C) is contained at any stage during polymerization, saponification, post-treatment, and drying, and water (D) is mixed after production of EVOH; ) And water (D) by mixing and stirring or by blowing steam to absorb water and then mixing acid (B) or salt (C), EVOH
The water / methanol mixture of (A) is extruded into a coagulation bath to obtain a porous water-containing EVOH molded product, and then the acid (B) in water is obtained.
Or a method of impregnating with a salt (C) and drying to a water content within the above range. However, the present invention is not limited to these, and any method can be adopted in the present invention as long as the content of each component can be in the above range.
【００１５】又、ＥＶＯＨ（Ａ）の製造時に若干のメタ
ノール、イソプロピルアルコール等のアルコールと共に
含水させておいたり、乾燥条件等をコントロールしたり
して調整することも可能である。この際、少量のエチレ
ングリコール、プロピレングリコール、グリセリンなど
の可塑剤を含んでいても差し支えない。エチレングリコ
ール、プロピレングリコール、グリセリン等の可塑剤の
含有量は０．２〜１０重量％程度が適当である。It is also possible to adjust the pH of the EVOH (A) by manufacturing the EVOH (A) with a slight amount of alcohol such as methanol or isopropyl alcohol, or by controlling the drying conditions. At this time, a small amount of a plasticizer such as ethylene glycol, propylene glycol, or glycerin may be contained. The content of the plasticizer such as ethylene glycol, propylene glycol, and glycerin is suitably about 0.2 to 10% by weight.
【００１６】又、酸化防止剤、滑剤、ハイドロタルサイ
ト類、帯電防止剤、着色剤、紫外線吸収剤、無機・有機
充填材、抗菌剤等を本発明の効果を阻害しない範囲で添
加することができる。Further, antioxidants, lubricants, hydrotalcites, antistatic agents, coloring agents, ultraviolet absorbers, inorganic and organic fillers, antibacterial agents and the like may be added within a range not to impair the effects of the present invention. it can.
【００１７】かくして本発明のＥＶＯＨ組成物が得られ
る。該ＥＶＯＨ組成物は次いで溶融押出機に供されて成
形物に溶融成形される。フィルムの場合、かかる成形時
の条件としては、特に限定されないが、通常はノンベン
ト、スクリュータイプ押出機を用い溶融温度４０〜１５
０℃で押出製膜される。製膜されたフィルム中に均一な
分布で水を残留させる為に、圧縮比２．０〜４．０のス
クリューを用いることが好ましい。Thus, the EVOH composition of the present invention is obtained. The EVOH composition is then provided to a melt extruder and melt-molded into a molded product. In the case of a film, the conditions at the time of such molding are not particularly limited, but usually a non-vented, screw-type extruder is used and a melting temperature of 40 to 15 is used.
Extruded at 0 ° C. It is preferable to use a screw having a compression ratio of 2.0 to 4.0 in order to leave water in a uniform distribution in the formed film.
【００１８】上記の方法で得られたフィルム状のＥＶＯ
Ｈ組成物の成形物は、必要に応じて次いで延伸に供され
るのであるが、かかる延伸時（延伸直前）のＥＶＯＨ組
成物の成形物の含水率を５〜５０重量％、好ましくは７
〜４５重量％、更に好ましくは１０〜４０重量％に調整
することも重要で、かかる含水率が５重量％未満では延
伸斑を生じやすく、破断の原因ともなり、逆に５０重量
％を越えると充分な延伸配向によるガスバリヤー性と強
度の改善効果が得られず、好ましくない。かかる含水率
の調整方法としては、特に限定されず、製膜直後に調湿
操作を加えることもできる。The film-like EVO obtained by the above method
The molded product of the H composition is then subjected to stretching if necessary. The water content of the molded product of the EVOH composition at the time of such stretching (immediately before stretching) is 5 to 50% by weight, preferably 7% by weight.
It is also important to adjust the water content to 45 to 45% by weight, more preferably 10 to 40% by weight. If the water content is less than 5% by weight, unevenness in stretching is liable to occur, causing breakage. The effect of improving the gas barrier property and the strength by sufficient stretching orientation cannot be obtained, which is not preferable. The method for adjusting the water content is not particularly limited, and a humidity control operation can be performed immediately after film formation.
【００１９】延伸については、１軸延伸法、２軸延伸法
（同時、逐次）等があり、特に限定されないが、本発明
は、特に逐次２軸延伸法における第１次（ＭＤ方向）延
伸に効果的であり、かかる延伸方法について詳細に説明
する。The stretching includes a uniaxial stretching method and a biaxial stretching method (simultaneous and sequential), and is not particularly limited. However, the present invention is particularly applicable to the primary (MD direction) stretching in the sequential biaxial stretching method. The stretching method is effective and will be described in detail.
【００２０】上記の含水率が調整されたフィルム状のＥ
ＶＯＨ組成物の成形物は、第１次（ＭＤ方向）延伸工程
に供される。かかる第１次（ＭＤ方向）延伸は、公知の
方法を利用することができ、上記の成形物を４０〜１０
０℃の条件下で縦方向に１．５〜８倍に延伸するのであ
る。かかる第１次（ＭＤ方向）延伸の処理後の含水率は
０．５〜４５重量％、好ましくは１〜４０重量％にする
ことが望ましく、０．５重量％未満では第２次（ＴＤ方
向）延伸での延伸斑が生じ、同時の延伸倍率まで延伸す
ることが困難となり、逆に４５重量％を越えると第１次
の延伸配向効果が期待できず、ガスバリヤー性、強度の
改善効果が少なくなって好ましくない。かかる含水率の
調整方法としては予熱ロールの温度と時間、第１次（Ｍ
Ｄ方向）延伸の温度と延伸速度等により行うことができ
る。The above-mentioned film-form E whose water content is adjusted
The molded product of the VOH composition is subjected to a first (MD direction) stretching step. For the primary (MD direction) stretching, a known method can be used.
The film is stretched 1.5 to 8 times in the machine direction at 0 ° C. The water content after the primary (MD direction) stretching treatment is desirably 0.5 to 45% by weight, preferably 1 to 40% by weight, and if it is less than 0.5% by weight, the secondary (TD direction). ) Unevenness in stretching occurs, making it difficult to stretch to the same stretching ratio. Conversely, if it exceeds 45% by weight, the primary stretching orientation effect cannot be expected, and the effect of improving gas barrier properties and strength will be reduced. It is not preferable because it decreases. As a method for adjusting the water content, the temperature and time of the preheating roll, the first (M
D direction) The stretching can be carried out according to the stretching temperature and the stretching speed.
【００２１】上記の第１次（ＭＤ方向）延伸されたＥＶ
ＯＨ組成物フィルムは、続いて第２次（ＴＤ方向）延伸
工程で横方向の延伸に供されるのであるが、かかる工程
においては、公知の方法を利用することができ、上記の
ＥＶＯＨ組成物フィルムを６０〜１４０℃の条件下で横
方向に１．５〜８倍に延伸するのである。通常は、フィ
ルム両耳部をクリップではさむテンター方式で行われ
る。本条件以外ではクリップ部、クリップ−クリップ間
及びフイルム巾方向の中間部でのいずれかの破断が生
じ、目標の延伸フィルムを得ることは極めて困難であ
る。又、通常は更に熱固定を行う。熱固定とは緊張下に
温度１２０〜２００℃で数秒ないし数分間フィルムを加
熱することで、更に熱固定後のフィルムに柔軟性と寸法
安定性を付与するために、含水率が０．３〜３重量％、
好ましくは０．５〜２重量％程度になるまでフィルムを
調湿してもよい。The above-mentioned primary (MD direction) stretched EV
The OH composition film is subsequently subjected to stretching in the transverse direction in a second (TD direction) stretching step. In this step, a known method can be used, and the above-described EVOH composition is used. The film is stretched 1.5 to 8 times in the transverse direction under the condition of 60 to 140 ° C. Usually, it is performed by a tenter method in which both ears of a film are clipped. Except for these conditions, any breakage occurs at the clip portion, between the clips, and at the intermediate portion in the film width direction, and it is extremely difficult to obtain a target stretched film. Usually, heat setting is further performed. Heat setting is to heat the film at a temperature of 120 to 200 ° C. for several seconds to several minutes under tension, and in order to further impart flexibility and dimensional stability to the film after heat setting, the water content is 0.3 to 3% by weight,
Preferably, the humidity of the film may be adjusted to about 0.5 to 2% by weight.
【００２２】かくして上記の如くＥＶＯＨ（Ａ）、酸
（Ｂ）、塩（Ｃ）、水（Ｄ）からなり各成分の含有量を
特定の範囲にコントロールして調製されたＥＶＯＨ組成
物を用いることにより、ロングラン性に優れ、溶融押出
により、スジやフィッシュアイのない、透明性に優れた
外観の良好な成形物を得ることができるのである。本発
明で得られたＥＶＯＨ組成物の成形物（フィルム、シー
ト等）は、単層のみならず、かかるフィルムを少なくと
も一層とする積層体として実用に供せられることが多
い。該積層体の製造に当たっては、本発明の製造法によ
り得られたフィルム、シート等の成形物の層の片面又は
両面に他の基材をラミネートするのであるが、ラミネー
ト方法としては、例えば、該成形物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、ポリエチレンイミン系化合物、ポリエステル系化合
物、ポリウレタン系化合物等の公知の接着剤を用いてラ
ミネートする方法等が挙げられる。Thus, the use of an EVOH composition comprising EVOH (A), acid (B), salt (C) and water (D) and controlling the content of each component within a specific range as described above. As a result, a molded article having excellent long-run properties and excellent appearance with excellent transparency without streaks or fish eyes can be obtained by melt extrusion. The molded product (film, sheet, etc.) of the EVOH composition obtained in the present invention is often used not only as a single layer but also as a laminate having at least one such film. In the production of the laminate, a film obtained by the production method of the present invention, another substrate is laminated on one or both sides of a layer of a molded product such as a sheet. A method of laminating a molded product and a film or sheet of another base material with a known adhesive such as an organic titanium compound, an isocyanate compound, a polyethyleneimine compound, a polyester compound, or a polyurethane compound is used.
【００２３】かかる他の基材フィルムとしては、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等の広義のポリオ
レフィン系樹脂、ポリスチレン系樹脂、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、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、Ｅ
ＶＯＨ等が挙げられ、更には、紙、金属箔、１軸又は２
軸延伸プラスチックフイルム又はシート、織布、不織
布、金属綿条、木質面なども使用可能である。Such other base films include linear low density polyethylene, low density polyethylene, medium density polyethylene, high density polyethylene, ethylene-vinyl acetate copolymer, ionomer, ethylene-propylene copolymer, ethylene- Acrylic ester copolymer, polypropylene, propylene-α-olefin (C 4-20
Α-olefins) copolymers, polyolefins such as polybutene and polypentene, and polyolefins in a broad sense, such as homo- or copolymers of these olefins, or homo- or copolymers of these olefins graft-modified with unsaturated carboxylic acids or esters thereof Resin, polystyrene resin, polyester,
Polyamide, copolymerized polyamide, polyvinyl chloride, polyvinylidene chloride, acrylic resin, vinyl ester resin, polyester elastomer, polyurethane elastomer, chlorinated polyethylene, chlorinated polypropylene, E
VOH and the like, and further, paper, metal foil, uniaxial or
An axially stretched plastic film or sheet, a woven fabric, a nonwoven fabric, a metal cotton strip, a wooden surface, or the like can also be used.
【００２４】積層体の層構成としては、ＥＶＯＨ組成物
フィルムの層をI（I1，I2，・・・）、他の基材、例え
ば熱可塑性樹脂層をII（II1，II2，・・・）とすると
き、フィルム、シート状であれば、I／IIの二層構造の
みならず、II／I／II、I／II／I、I1／I2／II、I／II1
／II2、II2／II1／I／II1／II2など任意の組合せが可能
である。As for the layer structure of the laminate, the layer of the EVOH composition film is I (I1, I2,...), And the other base material, for example, the thermoplastic resin layer is II (II1, II2,...). In the case of a film or sheet, not only a two-layer structure of I / II, but also II / I / II, I / II / I, I1 / I2 / II, I / II1
Any combination such as / II2, II2 / II1 / I / II1 / II2 is possible.
【００２５】かくして、本発明のＥＶＯＨ組成物の成形
物（フィルム、シート等）やその積層体は、その特性、
即ち外観特性、ガスバリヤー性等に優れるため、食品や
医薬品、農薬品、工業薬品包装用のフィルム、シート、
チューブ、袋、容器等の用途に非常に有用である。Thus, a molded article (film, sheet, etc.) of the EVOH composition of the present invention and a laminate thereof have properties,
That is, because of excellent appearance properties, gas barrier properties, etc., food and pharmaceutical products, agricultural chemicals, films and sheets for packaging industrial chemicals,
Very useful for applications such as tubes, bags, containers and the like.
【００２６】[0026]
【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、例中、「部」、「％」とあるのは、特に断り
のない限り重量基準を意味する。尚、以下の実施例及び
比較例において、リン酸基の定量は次の方法で行った。
即ち、温希硫酸を用いて試料より酸及び塩類を抽出し、
該抽出液について、リン酸基ＰＯ4はＪＩＳ−Ｋ−０１
０２に準じて吸光光度法（モリブデン青による）で定量
した。又、ナトリウム、カルシウム、マグネシウムは試
料をルツボに入れ、硫酸を加えて灰化し、灰分を希塩酸
に溶解し、原子吸光法で測定した。The present invention will be specifically described below with reference to examples. In the examples, “parts” and “%” mean on a weight basis unless otherwise specified. In the following Examples and Comparative Examples, the phosphate groups were quantified by the following method.
That is, acid and salts are extracted from the sample using warm dilute sulfuric acid,
Regarding the extract, the phosphate group PO 4 was determined according to JIS-K-01.
Quantitation was performed by an absorption spectrophotometric method (with molybdenum blue) according to the method described in No. 02. Further, sodium, calcium and magnesium were measured by placing a sample in a crucible, adding sulfuric acid to incinerate, dissolving the ash in dilute hydrochloric acid, and measuring by an atomic absorption method.
【００２７】実施例１ エチレン含量３０モル％のエチレン−酢酸ビニル共重合
体の４０％メタノール溶液１００部に水酸化ナトリウム
の１０％メタノール溶液１０部を加え、温度４０℃にて
３時間混練した。この際、反応の途中でペーストは白濁
し、系はスラリー状となった。この一次ケン化反応終了
後、酢酸を加え中和を行い、酢酸メチル６０部を加えて
析出を完了させてからろ別して乾燥し、１０メッシュよ
り大きい粒子（全粒子の６％）をふるい分けにより除去
した。Example 1 10 parts of a 10% methanol solution of sodium hydroxide was added to 100 parts of a 40% methanol solution of an ethylene-vinyl acetate copolymer having an ethylene content of 30 mol%, and kneaded at a temperature of 40 ° C for 3 hours. At this time, the paste became cloudy during the reaction, and the system became a slurry. After the completion of the primary saponification reaction, acetic acid is added for neutralization, 60 parts of methyl acetate is added to complete the precipitation, and the mixture is filtered and dried, and particles larger than 10 mesh (6% of all particles) are removed by sieving. did.
【００２８】かくして得られた部分ケン化物１００部を
水酸化ナトリウム１％水溶液５００部中に投入し、温度
６５℃にてスラリー状で３時間撹拌して二次ケン化を行
い、次いで酢酸で中和した後粒子をろ別し、更に１００
０部の水を加えて３０℃で１時間撹拌してからろ別する
操作を３度繰り返した。該粒子中の酢酸ナトリウムの含
有量は０．２２％であった。得られたＥＶＯＨ（Ａ）の
ケン化度９９．０％であった。次に乾燥該粒子（ＥＶＯ
Ｈ（Ａ））１００部を５００部の水と混合して再度スラ
リー化し、５％酢酸水溶液１０部、１％第１リン酸カル
シウム水溶液１８部を加えて３０℃、４時間撹拌後、ろ
別し、ＥＶＯＨ（Ａ）１００部に対して水７０部となる
ように乾燥してＥＶＯＨ組成物を得た。該ＥＶＯＨ組成
物中のナトリウム含有量は０．０１１％、リン酸基に対
するナトリウムのモル比は２．５、リン酸基に対するカ
ルシウムのモル比は０．５であった。100 parts of the partially saponified product thus obtained is put into 500 parts of a 1% aqueous solution of sodium hydroxide, stirred at a temperature of 65 ° C. in the form of a slurry for 3 hours to perform secondary saponification, and then acetic acid is added. After the addition, the particles are separated by filtration and further 100
The operation of adding 0 parts of water, stirring at 30 ° C. for 1 hour, and filtering off was repeated three times. The content of sodium acetate in the particles was 0.22%. The degree of saponification of the obtained EVOH (A) was 99.0%. Next, dry the particles (EVO
H (A)) was mixed again with 500 parts of water and slurried again, 10 parts of a 5% acetic acid aqueous solution and 18 parts of a 1% aqueous solution of monobasic calcium phosphate were added, stirred at 30 ° C. for 4 hours, and filtered off. The EVOH (A) was dried such that the amount of water became 70 parts with respect to 100 parts of EVOH (A) to obtain an EVOH composition. The sodium content in the EVOH composition was 0.011%, the molar ratio of sodium to phosphate groups was 2.5, and the molar ratio of calcium to phosphate groups was 0.5.
【００２９】そして、該ＥＶＯＨ組成物をＴダイを備え
た単軸押出機に供給し、厚さ１２０μｍのＥＶＯＨ組成
物フィルムの成形を行った。単軸押出機による製膜条件
は下記の通りとした。 スクリュー内径 ４０ｍｍ Ｌ／Ｄ ２８ スクリュー圧縮比 ３．２ Ｔダイ コートハンガータイプ ダイ巾 ４５０ｍｍ 押出温度 Ｃ1：１１０℃、 Ｈ：１１０℃ Ｃ2：１２０℃、 Ｄ：１１０℃ Ｃ3：１００℃、 Ｃ4：１００℃Then, the EVOH composition was supplied to a single screw extruder equipped with a T-die to form a 120 μm-thick EVOH composition film. The film forming conditions using a single screw extruder were as follows. Screw inner diameter 40 mm L / D 28 Screw compression ratio 3.2 T die Coat hanger type Die width 450 mm Extrusion temperature C1: 110 ° C, H: 110 ° C C2: 120 ° C, D: 110 ° C C3: 100 ° C, C4: 100 ° C
【００３０】長時間（４日間及び１０日間）連続運転時
のＥＶＯＨ組成物フィルムの外観について下記の項目を
評価した。 （フィルム外観） スジ スジの有無を下記の基準で評価した。 ○・・・スジは認められなかった。 △・・・スジが僅かに認められるが、実用上問題なし。 ×・・・スジが多発し、実用上使用困難であった。The following items were evaluated for the appearance of the EVOH composition film during continuous operation for a long time (4 days and 10 days). (Film appearance) Streaks The presence or absence of streaks was evaluated according to the following criteria.・ ・ ・: No streak was observed. Δ: Streaks are slightly observed, but there is no practical problem. X: Streaks occurred frequently and it was practically difficult to use.
【００３１】フィッシュアイ フィッシュアイの有無を下記の基準で評価した。 ○・・・０〜３個／１００ｃｍ2（フィルムサイズ；１
０ｃｍ×１０ｃｍ） △・・・４〜２０個／１００ｃｍ2 ×・・・２１個以上／１００ｃｍ2 Fish Eye The presence or absence of fish eyes was evaluated according to the following criteria.・ ・ ・: 0 to 3 pieces / 100 cm 2 (film size: 1
0cm × 10cm) △ ・ ・ ・ 4-20 / 100cm 2 × ・ ・ ・ 21 or more / 100cm 2
【００３２】着色 着色の有無を下記の基準で評価した。 ○・・・着色は認められなかった。 △・・・黄着色が僅かに認められた。 ×・・・黄着色が大で実用上使用困難であった。Coloring The presence or absence of coloring was evaluated according to the following criteria.・ ・ ・: No coloring was observed. Δ: Yellow coloring was slightly observed. ×: Yellow coloring was large and practically difficult to use.
【００３３】次いで、上記の成形で得られたＥＶＯＨ組
成物フィルム（含水率３５％）を原反として、連続的に
下記の条件で逐次２軸延伸、熱固定及び調湿を行って、
ＥＶＯＨ組成物延伸フィルムを得た。Next, using the EVOH composition film (water content 35%) obtained by the above molding as a raw material, biaxial stretching, heat setting and humidity control were successively performed under the following conditions continuously.
An EVOH composition stretched film was obtained.
【００３４】［第１次延伸（縦延伸）条件］ 延伸機 ロール式１次延伸機 延伸ロール温度 ７０℃ 縦方向延伸倍率 ２．０倍 延伸後の膜厚 ６０μｍ 延伸後の含水率 ３０％ ［第２次延伸（横延伸）条件］ 延伸機 テンター式２軸延伸機 延伸温度 １１０℃ 横方向延伸倍率 ３．０倍 延伸後の膜厚 ２０μｍ 延伸後の含水率 ２％[Primary stretching (longitudinal stretching) conditions] Stretching machine Roll-type primary stretching machine Stretching roll temperature 70 ° C Longitudinal stretching ratio 2.0 times Film thickness after stretching 60 μm Moisture content after stretching 30% Secondary Stretching (Lateral Stretching) Conditions] Stretcher Tenter type biaxial stretching machine Stretching temperature 110 ° C. Stretching ratio in the transverse direction 3.0 times Film thickness after stretching 20 μm Moisture content after stretching 2%
【００３５】［熱固定条件］ 温度 １６０℃ 時間 ３秒 ［調湿条件］ ２０℃、６５％ＲＨ下に７日放置 調湿後の含水率 ２．７％ 得られたＥＶＯＨ組成物（２軸）延伸フィルムについ
て、上記と同様の評価を行った。[Heat setting conditions] Temperature 160 ° C. Time 3 seconds [Humidity control condition] Leave at 20 ° C. and 65% RH for 7 days Water content after humidity control 2.7% The obtained EVOH composition (biaxial) The same evaluation as described above was performed for the stretched film.
【００３６】実施例２ 実施例１において、エチレン含有量が３５モル％、ケン
化度が９９．８モル％のＥＶＯＨ（Ａ）を用い、酢酸、
リン酸及び第１リン酸カルシウム水溶液で処理し、ＥＶ
ＯＨ（Ａ）１００部に対して水を３４部含有せしめ、Ｅ
ＶＯＨ（Ａ）に対してナトリウム含有量を０．０１４
％、リン酸基に対するナトリウムのモル比を７．５、リ
ン酸基に対するカルシウムのモル比を１．１とした以外
は同様に行いＥＶＯＨ組成物を得、該ＥＶＯＨ組成物よ
りＥＶＯＨ組成物フィルム及びＥＶＯＨ組成物延伸フィ
ルムを得て、同様に評価を行った。この時のＥＶＯＨ組
成物フィルムの含水率は２２％、第１次延伸後の水分率
は２０％、第２次延伸後の水分率は０．６％、調湿後の
含水率は２．５％であった。Example 2 In Example 1, EVOH (A) having an ethylene content of 35 mol% and a saponification degree of 99.8 mol% was used, and acetic acid,
Treatment with phosphoric acid and aqueous solution of monobasic calcium phosphate, EV
34 parts of water was added to 100 parts of OH (A),
0.014 sodium content with respect to VOH (A)
%, The molar ratio of sodium to phosphate groups was 7.5, and the molar ratio of calcium to phosphate groups was 1.1, to obtain an EVOH composition. From the EVOH composition, an EVOH composition film and An EVOH composition stretched film was obtained and evaluated similarly. At this time, the moisture content of the EVOH composition film was 22%, the moisture content after the first stretching was 20%, the moisture content after the second stretching was 0.6%, and the moisture content after the moisture conditioning was 2.5%. %Met.
【００３７】実施例３ 実施例１において、エチレン含有量が３５モル％、ケン
化度が９９．８モル％のＥＶＯＨ（Ａ）を用い、酢酸、
リン酸及び第１リン酸マグネシウム水溶液で処理し、Ｅ
ＶＯＨ（Ａ）１００部に対して水を５５部含有せしめ、
ＥＶＯＨ（Ａ）に対してナトリウム含有量を０．００９
％、リン酸基に対するナトリウムのモル比を４．５、リ
ン酸基に対するマグネシウムのモル比を０．７とした以
外は同様に行いＥＶＯＨ組成物を得、該ＥＶＯＨ組成物
よりＥＶＯＨ組成物フィルム及びＥＶＯＨ組成物延伸フ
ィルムを得て、同様に評価を行った。この時のＥＶＯＨ
組成物フィルムの含水率は３３％、第１次延伸後の水分
率は２８％、第２次延伸後の水分率は１．５％、調湿後
の含水率は２．５％であった。Example 3 In Example 1, EVOH (A) having an ethylene content of 35 mol% and a saponification degree of 99.8 mol% was used, and acetic acid,
Treated with phosphoric acid and an aqueous solution of monobasic magnesium phosphate,
55 parts of water is added to 100 parts of VOH (A),
0.009 sodium content with respect to EVOH (A)
%, The molar ratio of sodium to phosphate groups was 4.5, and the molar ratio of magnesium to phosphate groups was 0.7, an EVOH composition was obtained, and an EVOH composition film and an EVOH composition film were obtained from the EVOH composition. An EVOH composition stretched film was obtained and evaluated similarly. EVOH at this time
The moisture content of the composition film was 33%, the moisture content after the first stretching was 28%, the moisture content after the second stretching was 1.5%, and the moisture content after moisture conditioning was 2.5%. .
【００３８】実施例４ 実施例１において、エチレン含有量が２８モル％、ケン
化度が９８．６モル％のＥＶＯＨ（Ａ）を用い、酢酸、
リン酸及び第１リン酸マグネシウム水溶液で処理し、Ｅ
ＶＯＨ（Ａ）１００部に対して水を５５部含有せしめ、
ＥＶＯＨ（Ａ）に対してナトリウム含有量を０．０２５
％、リン酸基に対するナトリウムのモル比を１０．５、
リン酸基に対するマグネシウムのモル比を０．９とした
以外は同様に行いＥＶＯＨ組成物を得、該ＥＶＯＨ組成
物よりＥＶＯＨ組成物フィルム及びＥＶＯＨ組成物延伸
フィルムを得て、同様に評価を行った。この時のＥＶＯ
Ｈ組成物フィルムの含水率は３３％、第１次延伸後の水
分率は２８％、第２次延伸後の水分率は１．５％、調湿
後の含水率は２．８％であった。Example 4 In Example 1, EVOH (A) having an ethylene content of 28 mol% and a saponification degree of 98.6 mol% was used, and acetic acid,
Treated with phosphoric acid and an aqueous solution of monobasic magnesium phosphate,
55 parts of water is added to 100 parts of VOH (A),
Sodium content of 0.025 with respect to EVOH (A)
%, The molar ratio of sodium to phosphate groups is 10.5,
An EVOH composition was obtained in the same manner except that the molar ratio of magnesium to the phosphate group was set to 0.9. An EVOH composition film and an EVOH composition stretched film were obtained from the EVOH composition, and evaluation was similarly performed. . EVO at this time
The moisture content of the H composition film was 33%, the moisture content after the first stretching was 28%, the moisture content after the second stretching was 1.5%, and the moisture content after humidity control was 2.8%. Was.
【００３９】比較例１ 実施例１において、ＥＶＯＨ（Ａ）を酸及び塩で処理す
ることなく、ＥＶＯＨ（Ａ）１００部に対して７０部と
なるように含有せしめた以外は同様に行い、ＥＶＯＨ組
成物フィルム及びＥＶＯＨ組成物延伸フィルムを得て、
同様に評価を行った。この時のＥＶＯＨ組成物フィルム
の含水率は３５％、第１次延伸後の水分率は３０％、第
２次延伸後の水分率は２％、調湿後の含水率は２．７％
であった。Comparative Example 1 The procedure of Example 1 was repeated, except that the EVOH (A) was not treated with an acid and a salt, but was contained in an amount of 70 parts with respect to 100 parts of the EVOH (A). Obtaining a composition film and an EVOH composition stretched film,
Evaluation was performed similarly. At this time, the moisture content of the EVOH composition film was 35%, the moisture content after the first stretching was 30%, the moisture content after the second stretching was 2%, and the moisture content after moisture conditioning was 2.7%.
Met.
【００４０】比較例２ 実施例１において、酢酸及び第１リン酸カルシウム水溶
液で処理し、ナトリウム含有量を０．０００８％、リン
酸基に対するナトリウムのモル比を２．５、リン酸基に
対するマグネシウムのモル比を０．５とした以外は同様
に行いＥＶＯＨ組成物を得、該ＥＶＯＨ組成物よりＥＶ
ＯＨ組成物フィルム及びＥＶＯＨ組成物延伸フィルムを
得て、同様に評価を行った。この時のＥＶＯＨ組成物フ
ィルムの含水率は３５％、第１次延伸後の水分率は３
０、第２次延伸後の水分率は２％、調湿後の含水率は
２．７％であった。COMPARATIVE EXAMPLE 2 The procedure of Example 1 was repeated except that the mixture was treated with acetic acid and an aqueous solution of monobasic calcium phosphate, the sodium content was 0.0008%, the molar ratio of sodium to phosphate groups was 2.5, and the molar ratio of magnesium to phosphate groups was 2.5. An EVOH composition was obtained in the same manner except that the ratio was set to 0.5.
An OH composition film and an EVOH composition stretched film were obtained and similarly evaluated. At this time, the moisture content of the EVOH composition film was 35%, and the moisture content after the first stretching was 3%.
0, the moisture content after the second stretching was 2%, and the moisture content after humidity control was 2.7%.
【００４１】比較例３ 実施例１において、酢酸及び第１リン酸カルシウム水溶
液で処理し、ナトリウム含有量を０．０８％、リン酸基
に対するナトリウムのモル比を２．５、リン酸基に対す
るカルシウムのモル比を０．５とした以外は同様に行い
ＥＶＯＨ組成物を得、該ＥＶＯＨ組成物よりＥＶＯＨ組
成物フィルム及びＥＶＯＨ組成物延伸フィルムを得て、
同様に評価を行った。この時のＥＶＯＨ組成物フィルム
の含水率は３５％、第１次延伸後の水分率は３０％、第
２次延伸後の水分率は２％、調湿後の含水率は２．７％
であった。COMPARATIVE EXAMPLE 3 The procedure of Example 1 was repeated except that the mixture was treated with acetic acid and an aqueous solution of monobasic calcium phosphate. The sodium content was 0.08%, the molar ratio of sodium to phosphate groups was 2.5, and the molar ratio of calcium to phosphate groups was 2.5. An EVOH composition was obtained in the same manner except that the ratio was set to 0.5, and an EVOH composition film and an EVOH composition stretched film were obtained from the EVOH composition.
Evaluation was performed similarly. At this time, the moisture content of the EVOH composition film was 35%, the moisture content after the first stretching was 30%, the moisture content after the second stretching was 2%, and the moisture content after moisture conditioning was 2.7%.
Met.
【００４２】比較例４ 実施例１において、酢酸、リン酸及び第１リン酸カルシ
ウム水溶液で処理し、ナトリウム含有量を０．０１１
％、リン酸基に対するナトリウムのモル比を０．１、リ
ン酸基に対するカルシウムのモル比を０．３とした以外
は同様に行いＥＶＯＨ組成物を得、該ＥＶＯＨ組成物よ
りＥＶＯＨ組成物フィルム及びＥＶＯＨ組成物延伸フィ
ルムを得て、同様に評価を行った。この時のＥＶＯＨ組
成物フィルムの含水率は３５％、第１次延伸後の水分率
は３０％、第２次延伸後の水分率は２％、調湿後の含水
率は２．７％であった。COMPARATIVE EXAMPLE 4 The procedure of Example 1 was repeated, except that the mixture was treated with an aqueous solution of acetic acid, phosphoric acid and monobasic calcium phosphate to reduce the sodium content to 0.011.
%, The molar ratio of sodium to phosphate groups was set to 0.1, and the molar ratio of calcium to phosphate groups was set to 0.3, to obtain an EVOH composition. From the EVOH composition, an EVOH composition film and An EVOH composition stretched film was obtained and evaluated similarly. At this time, the moisture content of the EVOH composition film was 35%, the moisture content after the first stretching was 30%, the moisture content after the second stretching was 2%, and the moisture content after moisture conditioning was 2.7%. there were.
【００４３】比較例５ 実施例１において、酢酸及び第１リン酸カルシウム水溶
液で処理し、ナトリウム含有量を０．０１１％、リン酸
基に対するナトリウムのモル比を４５、リン酸基に対す
るカルシウムのモル比を０．５とした以外は同様に行い
ＥＶＯＨ組成物を得、該ＥＶＯＨ組成物よりＥＶＯＨ組
成物フィルム及びＥＶＯＨ組成物延伸フィルムを得て、
同様に評価を行った。この時のＥＶＯＨ組成物フィルム
の含水率は３５％、第１次延伸後の水分率は３０％、第
２次延伸後の水分率は２％、調湿後の含水率は２．７％
であった。COMPARATIVE EXAMPLE 5 In Example 1, treatment was performed with acetic acid and an aqueous solution of monobasic calcium phosphate. The sodium content was 0.011%, the molar ratio of sodium to phosphate groups was 45, and the molar ratio of calcium to phosphate groups was An EVOH composition was obtained in the same manner except that it was set to 0.5, and an EVOH composition film and an EVOH composition stretched film were obtained from the EVOH composition.
Evaluation was performed similarly. At this time, the moisture content of the EVOH composition film was 35%, the moisture content after the first stretching was 30%, the moisture content after the second stretching was 2%, and the moisture content after moisture conditioning was 2.7%.
Met.
【００４４】比較例６ 実施例１において、酢酸、リン酸及び第１リン酸カルシ
ウム水溶液で処理し、ナトリウム含有量を０．０１１
％、リン酸基に対するナトリウムのモル比を２．５、リ
ン酸基に対するカルシウムのモル比を０．０５とした以
外は同様に行いＥＶＯＨ組成物を得、該ＥＶＯＨ組成物
よりＥＶＯＨ組成物フィルム及びＥＶＯＨ組成物延伸フ
ィルムを得て、同様に評価を行った。この時のＥＶＯＨ
組成物フィルムの含水率は３５％、第１次延伸後の水分
率は３０％、第２次延伸後の水分率は２％、調湿後の含
水率は２．７％であった。Comparative Example 6 The procedure of Example 1 was repeated, except that the solution was treated with an aqueous solution of acetic acid, phosphoric acid and monobasic calcium phosphate to reduce the sodium content to 0.011.
%, The molar ratio of sodium to phosphate groups was 2.5, and the molar ratio of calcium to phosphate groups was 0.05, an EVOH composition was obtained in the same manner, and an EVOH composition film and An EVOH composition stretched film was obtained and evaluated similarly. EVOH at this time
The moisture content of the composition film was 35%, the moisture content after the first stretching was 30%, the moisture content after the second stretching was 2%, and the moisture content after humidity control was 2.7%.
【００４５】比較例７ 実施例１において、酢酸、リン酸及びクエン酸モノカル
シウム水溶液で処理し、ナトリウム含有量を０．０１１
％、リン酸基に対するナトリウムのモル比を２．５、リ
ン酸基に対するカルシウムのモル比を８とした以外は同
様に行いＥＶＯＨ組成物を得、該ＥＶＯＨ組成物よりＥ
ＶＯＨ組成物フィルム及びＥＶＯＨ組成物延伸フィルム
を得て、同様に評価を行った。この時のＥＶＯＨ組成物
フィルムの含水率は３５％、第１次延伸後の水分率は３
０％、第２次延伸後の水分率は２％、調湿後の含水率は
２．７％であった。COMPARATIVE EXAMPLE 7 The procedure of Example 1 was repeated, except that the mixture was treated with an aqueous solution of acetic acid, phosphoric acid and monocalcium citrate to reduce the sodium content to 0.011.
%, The molar ratio of sodium to phosphate groups was set to 2.5, and the molar ratio of calcium to phosphate groups was set to 8, to obtain an EVOH composition.
A VOH composition film and an EVOH composition stretched film were obtained and similarly evaluated. At this time, the moisture content of the EVOH composition film was 35%, and the moisture content after the first stretching was 3%.
0%, the moisture content after the second stretching was 2%, and the moisture content after the humidity control was 2.7%.
【００４６】 比較例８実施例１において、水を５部とした以外は同様
に行った。但し、１２０℃では樹脂が溶融せずに押出不
可であるので、１９０℃で成形した。又、延伸処理にお
いて、第２次延伸時にフィルムの破断が生じ、安定した
延伸が不可能で、延伸フィルムを得ることができなかっ
た。Comparative Example 8 The procedure of Example 1 was repeated, except that the water content was changed to 5 parts. However, since the resin was not melted at 120 ° C. and could not be extruded, it was molded at 190 ° C. In the stretching treatment, the film was broken at the time of the second stretching, and stable stretching was impossible, and a stretched film could not be obtained.
【００４７】比較例９ 実施例１において、水を２００部とした以外は同様に行
った。ＥＶＯＨ組成物フィルム（原反フィルム）の成形
時において、バレルのフィールド部に水が析出し、吐出
不安定となり、膜厚が不均一な延伸用原反フィルムしか
得られなかったが、実施例１と同様に連続的に延伸処理
を行った。Comparative Example 9 The same procedure as in Example 1 was carried out except that the water content was changed to 200 parts. At the time of forming the EVOH composition film (raw film), water was precipitated in the field portion of the barrel, the discharge became unstable, and only a raw film for stretching having a non-uniform film thickness was obtained. The stretching treatment was continuously performed in the same manner as described above.
【００４８】比較例１０ 実施例１において、水を加えなかった以外は同様に行っ
た。但し、１２０℃では樹脂が溶融せずに押出不可であ
るので、２１０℃で成形した。又、延伸処理において、
第２次延伸時にフィルムの破断が生じ、安定した延伸が
不可能で、延伸フィルムを得ることができなかった。実
施例及び比較例の評価結果を表１、２に示す。Comparative Example 10 The procedure of Example 1 was repeated except that no water was added. However, since the resin could not be extruded at 120 ° C. without melting, it was molded at 210 ° C. In the stretching process,
During the second stretching, the film was broken, stable stretching was not possible, and a stretched film could not be obtained. Tables 1 and 2 show the evaluation results of Examples and Comparative Examples.
【００４９】[0049]
【表１】 （ＥＶＯＨ組成物フィルム（原反フィルム）） ４日間連続運転時 １０日間連続運転時 フィルム外観 フィルム外観 スジ フィッシュアイ 着色 スジ フィッシュアイ 着色 実施例１ ○ ○ ○ ○ ○ ○ 〃 ２ ○ ○ ○ ○ ○ ○ 〃 ３ ○ ○ ○ ○ ○ ○ 〃 ４ ○ ○ ○ ○ ○ ○ 比較例１ ○ ○ ○ △ × ○ 〃 ２ ○ ○ ○ △ × ○ 〃 ３ △ ○ × △ △ × 〃 ４ ○ ○ ○ △ × ○ 〃 ５ △ △ ○ × × ○ 〃 ６ ○ ○ ○ × × ○ 〃 ７ ○ × △ △ × × 〃 ８ × ○ ○ × × △ 〃 ９ × ○ ○ × ○ ○ 〃 10 × × ○ × × △ [Table 1] (EVOH composition film (raw film)) During continuous operation for 4 days During continuous operation for 10 days Film appearance Film appearance Striped fish eye Colored striped fish eye Colored Example 1 ○ ○ ○ ○ ○ ○ 〃 2 ○ ○ ○ ○ ○ ○ 〃 3 ○ ○ ○ ○ ○ ○ ○ 4 ○ ○ ○ ○ ○ ○ Comparative Example 1 ○ ○ ○ △ × ○ 〃 2 ○ ○ ○ △ × ○ ３ 3 △ ○ × △ △ × 〃 4 ○ ○ ○ △ × ○ ５ 5 △ △ ○ × × ○ 〃 6 ○ ○ ○ × × ○ 〃 7 ○ × △ △ × × 〃 8 × ○ ○ × × △ 〃 9 × ○ ○ × ○ ○ 〃 10 × × ○ × × △
【００５０】[0050]
【表２】 （ＥＶＯＨ組成物延伸フィルム） ４日間連続運転時 １０日間連続運転時 フィルム外観 フィルム外観 スジ フィッシュアイ 着色 スジ フィッシュアイ 着色 実施例１ ○ ○ ○ ○ ○ ○ 〃 ２ ○ ○ ○ ○ ○ ○ 〃 ３ ○ ○ ○ ○ ○ ○ 〃 ４ ○ ○ ○ ○ ○ ○ 比較例１ ○ ○ ○ △ × ○ 〃 ２ ○ ○ ○ △ × ○ 〃 ３ △ ○ × △ △ × 〃 ４ ○ ○ ○ △ × ○ 〃 ５ ○ △ ○ × × ○ 〃 ６ ○ ○ ○ × × ○ 〃 ７ ○ × △ △ × × 〃 ８ 延伸フィルムは得られなかった 〃 ９ × ○ ○ × ○ ○ 〃 10 延伸フィルムは得られなかった [Table 2] (Stretched film of EVOH composition) During continuous operation for 4 days During continuous operation for 10 days Film appearance Film appearance Stripe fish eye Coloring Stripe fish eye Coloring Example 1 ○ ○ ○ ○ ○ ○ ○ 2 ○ ○ ○ ○ ○ ○ ○ ３ 3 ○ ○ ○ ○ ○ 〃 ４ 4 ○ ○ ○ ○ ○ 比較 Comparative example 1 ○ ○ △ × ○ 2 ○ ○ △ × × ○ 3 ○ × △ △ 3 ○ × △ △ × 4 ○ 4 ○ ○ △ × ○ ○ 5 ○ △ ○ × × ○ ６ 6 ○ ○ ○ × × ○ 〃 7 ○ × △ △ × × ８ 8 Stretched film not obtained ９ 9 × ○ ○ × ○ ○ 〃 10 Stretched film not obtained
【００５１】[0051]
【発明の効果】本発明は、ＥＶＯＨ（Ａ）、特定の酸
（Ｂ）及び特定の塩（Ｃ）、水（Ｄ）からなり、各成分
を特定範囲で含有させてなるため、溶融成形時のロング
ラン性に非常に優れ、更にガスバリヤー性はもとより、
長時間の連続運転においてもスジ、フィッシュアイのな
いフィルム外観や透明性に優れた成形物を得ることがで
き、又、本発明の成形物（フィルム、延伸フィルム等）
を少なくとも１層とした多層積層体は、食品や医薬品、
農薬品、工業薬品等の包装用材料として非常に有用であ
る。The present invention comprises EVOH (A), a specific acid (B), a specific salt (C), and water (D), and contains each component in a specific range. Is extremely excellent in long-running properties, and, in addition to gas barrier properties,
A molded product excellent in film appearance and transparency without streaks and fish eyes can be obtained even during long-time continuous operation, and the molded product of the present invention (film, stretched film, etc.)
Is a multilayer laminate having at least one layer,
It is very useful as a packaging material for agricultural and industrial chemicals.
─────────────────────────────────────────────────────
────────────────────────────────────────────────── ───
【手続補正書】[Procedure amendment]
【提出日】平成１０年７月１５日[Submission date] July 15, 1998
【手続補正１】[Procedure amendment 1]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】０００３[Correction target item name] 0003
【補正方法】変更[Correction method] Change
【補正内容】[Correction contents]
【０００３】[0003]
【発明が解決しようとする課題】しかしながら、本発明
者が詳細に検討した結果、上記技術ではフィッシュアイ
の低減は認められるものの、長時間の連続運転における
ＥＶＯＨ成形物の外観及び品質の安定性については改善
の余地が残るものであり、技術の高度化と多様化に伴
い、更にロングラン性に優れ、スジやフィッシュアイの
ない、透明性に優れた外観の良好なＥＶＯＨ成形物（フ
ィルム、シート、等）が望まれている。However, as a result of a detailed study conducted by the present inventors, although the reduction of fish eyes is recognized in the above-mentioned technique, the appearance and quality stability of the EVOH molded product during long-time continuous operation are not considered. There is room for improvement, and with the advancement and diversification of technology, EVOH molded products (films, sheets, Etc.) are desired.
【手続補正２】[Procedure amendment 2]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】００１０[Correction target item name] 0010
【補正方法】変更[Correction method] Change
【補正内容】[Correction contents]
【００１０】又、（Ｃ）に属する塩としては、第１リン
酸カルシウム、第１リン酸マグネシウム、第１クエン酸
カルシウム、第１酒石酸カルシウム、第１マロン酸カル
シウム、第１マレイン酸カルシウムが例示され、第１リ
ン酸カルシウム及び第１リン酸マグネシウムが有利に用
いられる。ｐＫａが３．４以下の酸基を有しない多塩基
酸の第１塩を用いてもロングラン成形時の熱着色抑制効
果が劣ることとなり、工業的な実施には不適である。The salts belonging to (C) include, for example, monobasic calcium phosphate, monobasic magnesium phosphate, calcium citrate 1, calcium tartrate, calcium malonate 1 and calcium maleate 1 Monocalcium phosphate and magnesium phosphate are advantageously used. Even if the first salt of a polybasic acid having no pKa of 3.4 or less is used, the effect of suppressing thermal coloring during long-run molding is inferior, which is not suitable for industrial practice.
【手続補正３】[Procedure amendment 3]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】００２８[Correction target item name] 0028
【補正方法】変更[Correction method] Change
【補正内容】[Correction contents]
【００２８】かくして得られた部分ケン化物１００部を
水酸化ナトリウム１％水溶液５００，部中に投入し、温
度６５℃にてスラリー状で３時間撹拌して二次ケン化を
行い、次いで酢酸で中和した後粒子をろ別し、更に１０
００部の水を加えて３０℃で１時間撹拌してからろ別す
る操作を３度繰り返した。該粒子中の酢酸ナトリウムの
含有量は０．２２％であった。得られたＥＶＯＨ（Ａ）
のケン化度９９．０％であった。次に乾燥該粒子（ＥＶ
ＯＨ（Ａ））１００部を５００部の水と混合して再度ス
ラリー化し、５％酢酸水溶液１０部、１％第１リン酸カ
ルシウム水溶液１８部を加えて３０℃、４時間撹拌後、
ろ別し、ＥＶＯＨ（Ａ）１００部に対して水７０部とな
るように乾燥してＥＶＯＨ組成物を得た。該ＥＶＯＨ組
成物中のナトリウム含有量はＥＶＯＨ（Ａ）に対して
０．０１１％、リン酸基に対するナトリウムのモル比は
２．５、リン酸基に対するカルシウムのモル比は０．５
であった。100 parts of the partially saponified compound thus obtained is
Pour into 500 parts of 1% aqueous solution of sodium hydroxide
The slurry is stirred at 65 ° C for 3 hours for secondary saponification.
After neutralizing with acetic acid, the particles are filtered off and further
Add 00 parts of water, stir at 30 ° C for 1 hour, and filter
Was repeated three times. Of sodium acetate in the particles
The content was 0.22%. EVOH (A) obtained
Was 99.0%. Next, dry the particles (EV
OH (A)) was mixed with 500 parts of water and mixed again.
Rally, 10 parts of 5% acetic acid aqueous solution, 1% primary phosphoric acid
After adding 18 parts of an aqueous solution of lithium and stirring at 30 ° C. for 4 hours,
It is filtered and 70 parts of water is added to 100 parts of EVOH (A).
And dried to obtain an EVOH composition. The EVOH group
Sodium content in the productFor EVOH (A)
0.011%, molar ratio of sodium to phosphate groups is
2.5, the molar ratio of calcium to phosphate groups is 0.5
Met.
Claims (3)
物（Ａ）、２５℃におけるｐＫａが５．０以下の酸基を
有する酸（Ｂ）及び２５℃におけるｐＫａが３．４以下
の酸基を有する多塩基酸の第１カルシウム塩又はマグネ
シウム塩（Ｃ）、水（Ｄ）からなり、前記（Ｂ）の酸、
（Ｃ）の塩の少なくとも一方はリン酸基を含有するもの
であると共に、該共重合体ケン化物（Ａ）において
（１）アルカリ金属の含有量が０．００１〜０．０５重
量％、（２）リン酸基に対するアルカリ金属のモル比が
１〜３０、（３）リン酸基に対するカルシウム又はマグ
ネシウムのモル比が０．１〜５、（４）該共重合体ケン
化物（Ａ）１００重量部に対して水（Ｄ）が１０〜１４
０重量部となるように含有させてなることを特徴とする
エチレン−酢酸ビニル系共重合体ケン化物組成物。1. An saponified ethylene-vinyl acetate copolymer (A), an acid (B) having an acid group having a pKa of not more than 5.0 at 25 ° C., and an acid group having a pKa of not more than 3.4 at 25 ° C. A first calcium salt or a magnesium salt of a polybasic acid having the formula (C) and water (D);
At least one of the salts of (C) contains a phosphate group, and the saponified copolymer (A) has a content of (1) an alkali metal of 0.001 to 0.05% by weight, 2) The molar ratio of the alkali metal to the phosphate group is from 1 to 30, (3) the molar ratio of calcium or magnesium to the phosphate group is from 0.1 to 5, (4) 100 parts by weight of the saponified copolymer (A) 10-14 water (D) per part
A saponified ethylene-vinyl acetate copolymer composition, which is contained so as to be 0 parts by weight.
共重合体ケン化物組成物を溶融押出してなることを特徴
とする成形物。2. A molded product obtained by melt-extruding the saponified ethylene-vinyl acetate copolymer composition according to claim 1.
重量％で延伸してなることを特徴とする成形物。3. The molded product according to claim 2, wherein the water content is 5 to 50.
A molded article characterized by being stretched by weight%.
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9213974A JPH1135768A (en) | 1997-07-23 | 1997-07-23 | Ethylene-vinyl acetate-based copolymer saponified product composition and molded product therefrom |
| EP98113243A EP0892006B1 (en) | 1997-07-18 | 1998-07-16 | Hydrous pellets of ethylene-vinyl acetate copolymer hydrolyzate, production thereof and moldings from such hydrous pellets |
| DE69831703T DE69831703T2 (en) | 1997-07-18 | 1998-07-16 | Hydrous granules of hydrolysates of an ethylene-vinyl acetate polymer, their preparation and articles made therewith |
| US09/118,018 US6184288B1 (en) | 1997-07-18 | 1998-07-17 | Hydrous pellets of ethylene-vinyl acetate copolymer hydrolyzate, production thereof and moldings from such hydrous pellets |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9213974A JPH1135768A (en) | 1997-07-23 | 1997-07-23 | Ethylene-vinyl acetate-based copolymer saponified product composition and molded product therefrom |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH1135768A true JPH1135768A (en) | 1999-02-09 |
Family
ID=16648158
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP9213974A Pending JPH1135768A (en) | 1997-07-18 | 1997-07-23 | Ethylene-vinyl acetate-based copolymer saponified product composition and molded product therefrom |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH1135768A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPWO2011118648A1 (en) * | 2010-03-25 | 2013-07-04 | 株式会社クラレ | Resin composition, method for producing the same, and multilayer structure |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62143954A (en) * | 1985-11-22 | 1987-06-27 | Nippon Synthetic Chem Ind Co Ltd:The | Method for treating saponified ethylene-vinyl acetate copolymer |
| JPH0687969A (en) * | 1992-09-07 | 1994-03-29 | Nippon Synthetic Chem Ind Co Ltd:The | Biodegradable foamed resin article |
| JPH08259802A (en) * | 1995-03-22 | 1996-10-08 | Kuraray Co Ltd | Gas-barrier resin composition |
| JPH08311276A (en) * | 1995-05-19 | 1996-11-26 | Nippon Synthetic Chem Ind Co Ltd:The | Composition of saponified ethylene/vinyl acetate copolymer resin and multilayer structure using the same |
| JPH0940825A (en) * | 1995-07-28 | 1997-02-10 | Nippon Synthetic Chem Ind Co Ltd:The | Resin composition and its use |
-
1997
- 1997-07-23 JP JP9213974A patent/JPH1135768A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62143954A (en) * | 1985-11-22 | 1987-06-27 | Nippon Synthetic Chem Ind Co Ltd:The | Method for treating saponified ethylene-vinyl acetate copolymer |
| JPH0687969A (en) * | 1992-09-07 | 1994-03-29 | Nippon Synthetic Chem Ind Co Ltd:The | Biodegradable foamed resin article |
| JPH08259802A (en) * | 1995-03-22 | 1996-10-08 | Kuraray Co Ltd | Gas-barrier resin composition |
| JPH08311276A (en) * | 1995-05-19 | 1996-11-26 | Nippon Synthetic Chem Ind Co Ltd:The | Composition of saponified ethylene/vinyl acetate copolymer resin and multilayer structure using the same |
| JPH0940825A (en) * | 1995-07-28 | 1997-02-10 | Nippon Synthetic Chem Ind Co Ltd:The | Resin composition and its use |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPWO2011118648A1 (en) * | 2010-03-25 | 2013-07-04 | 株式会社クラレ | Resin composition, method for producing the same, and multilayer structure |
| JP2014111793A (en) * | 2010-03-25 | 2014-06-19 | Kuraray Co Ltd | Resin composition, method for preparing the same, and multilayer structure |
| JP2014177644A (en) * | 2010-03-25 | 2014-09-25 | Kuraray Co Ltd | Resin composition, method for producing the same and multilayer structure |
| JP5619874B2 (en) * | 2010-03-25 | 2014-11-05 | 株式会社クラレ | Resin composition, method for producing the same, and multilayer structure |
| US9073293B2 (en) | 2010-03-25 | 2015-07-07 | Kuraray Co., Ltd. | Resin composition, method for production thereof and multilayered structure |
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