JPH0550375B2 - - Google Patents
Info
- Publication number
- JPH0550375B2 JPH0550375B2 JP12656885A JP12656885A JPH0550375B2 JP H0550375 B2 JPH0550375 B2 JP H0550375B2 JP 12656885 A JP12656885 A JP 12656885A JP 12656885 A JP12656885 A JP 12656885A JP H0550375 B2 JPH0550375 B2 JP H0550375B2
- Authority
- JP
- Japan
- Prior art keywords
- evoh
- layer
- weight
- stretching
- amide
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 229920000219 Ethylene vinyl alcohol Polymers 0.000 claims description 107
- 238000000034 method Methods 0.000 claims description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- 238000010438 heat treatment Methods 0.000 claims description 14
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 9
- 239000005977 Ethylene Substances 0.000 claims description 9
- 150000008430 aromatic amides Chemical class 0.000 claims description 9
- 238000007127 saponification reaction Methods 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 150000008431 aliphatic amides Chemical class 0.000 claims description 4
- 125000001931 aliphatic group Chemical group 0.000 claims description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 3
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 3
- 125000003118 aryl group Chemical group 0.000 claims description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims 1
- 150000002763 monocarboxylic acids Chemical class 0.000 claims 1
- UFRKOOWSQGXVKV-UHFFFAOYSA-N ethene;ethenol Chemical compound C=C.OC=C UFRKOOWSQGXVKV-UHFFFAOYSA-N 0.000 description 102
- 239000004715 ethylene vinyl alcohol Substances 0.000 description 102
- 239000010410 layer Substances 0.000 description 67
- 230000004888 barrier function Effects 0.000 description 34
- 239000007789 gas Substances 0.000 description 24
- -1 polypropylene Polymers 0.000 description 17
- 238000000465 moulding Methods 0.000 description 16
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 15
- 229910052760 oxygen Inorganic materials 0.000 description 15
- 239000001301 oxygen Substances 0.000 description 15
- 229920005992 thermoplastic resin Polymers 0.000 description 15
- 239000000203 mixture Substances 0.000 description 14
- 229920005989 resin Polymers 0.000 description 11
- 239000011347 resin Substances 0.000 description 11
- 239000008188 pellet Substances 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 8
- FGTVYMTUTYLLQR-UHFFFAOYSA-N n-ethyl-1-phenylmethanesulfonamide Chemical compound CCNS(=O)(=O)CC1=CC=CC=C1 FGTVYMTUTYLLQR-UHFFFAOYSA-N 0.000 description 8
- 239000004840 adhesive resin Substances 0.000 description 7
- 229920006223 adhesive resin Polymers 0.000 description 7
- 239000004014 plasticizer Substances 0.000 description 7
- 238000003856 thermoforming Methods 0.000 description 7
- 230000001070 adhesive effect Effects 0.000 description 6
- 229920006122 polyamide resin Polymers 0.000 description 6
- 239000004743 Polypropylene Substances 0.000 description 5
- 239000000853 adhesive Substances 0.000 description 5
- LYRFLYHAGKPMFH-UHFFFAOYSA-N octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(N)=O LYRFLYHAGKPMFH-UHFFFAOYSA-N 0.000 description 5
- 229920001155 polypropylene Polymers 0.000 description 5
- 239000000654 additive Substances 0.000 description 4
- 239000012790 adhesive layer Substances 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- 235000013305 food Nutrition 0.000 description 4
- 238000003475 lamination Methods 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 238000004806 packaging method and process Methods 0.000 description 4
- YCMLQMDWSXFTIF-UHFFFAOYSA-N 2-methylbenzenesulfonimidic acid Chemical compound CC1=CC=CC=C1S(N)(=O)=O YCMLQMDWSXFTIF-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000005038 ethylene vinyl acetate Substances 0.000 description 3
- 238000001125 extrusion Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 3
- 229920000728 polyester Polymers 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 229940124530 sulfonamide Drugs 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- 239000004677 Nylon Substances 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 125000003368 amide group Chemical group 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 238000000071 blow moulding Methods 0.000 description 2
- DQXBYHZEEUGOBF-UHFFFAOYSA-N but-3-enoic acid;ethene Chemical class C=C.OC(=O)CC=C DQXBYHZEEUGOBF-UHFFFAOYSA-N 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 238000009820 dry lamination Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 150000004668 long chain fatty acids Chemical class 0.000 description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 2
- 229920001778 nylon Polymers 0.000 description 2
- FATBGEAMYMYZAF-KTKRTIGZSA-N oleamide Chemical compound CCCCCCCC\C=C/CCCCCCCC(N)=O FATBGEAMYMYZAF-KTKRTIGZSA-N 0.000 description 2
- 230000035699 permeability Effects 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 239000004800 polyvinyl chloride Substances 0.000 description 2
- 229920000915 polyvinyl chloride Polymers 0.000 description 2
- IPEHBUMCGVEMRF-UHFFFAOYSA-N pyrazinecarboxamide Chemical compound NC(=O)C1=CN=CC=N1 IPEHBUMCGVEMRF-UHFFFAOYSA-N 0.000 description 2
- 239000002356 single layer Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- XXUNIGZDNWWYED-UHFFFAOYSA-N 2-methylbenzamide Chemical compound CC1=CC=CC=C1C(N)=O XXUNIGZDNWWYED-UHFFFAOYSA-N 0.000 description 1
- 241000251468 Actinopterygii Species 0.000 description 1
- KXDAEFPNCMNJSK-UHFFFAOYSA-N Benzamide Chemical compound NC(=O)C1=CC=CC=C1 KXDAEFPNCMNJSK-UHFFFAOYSA-N 0.000 description 1
- 239000004230 Fast Yellow AB Substances 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- 150000007933 aliphatic carboxylic acids Chemical class 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- DPYKEYXMUFFQAI-UHFFFAOYSA-N diphenylmethanesulfonamide Chemical compound C=1C=CC=CC=1C(S(=O)(=O)N)C1=CC=CC=C1 DPYKEYXMUFFQAI-UHFFFAOYSA-N 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- HSEMFIZWXHQJAE-UHFFFAOYSA-N hexadecanamide Chemical compound CCCCCCCCCCCCCCCC(N)=O HSEMFIZWXHQJAE-UHFFFAOYSA-N 0.000 description 1
- 125000001165 hydrophobic group Chemical group 0.000 description 1
- 229960001545 hydrotalcite Drugs 0.000 description 1
- 229910001701 hydrotalcite Inorganic materials 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 229920000554 ionomer Polymers 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 235000013372 meat Nutrition 0.000 description 1
- 150000002762 monocarboxylic acid derivatives Chemical class 0.000 description 1
- AUNYWGYRPIHMLM-UHFFFAOYSA-N n,1-diphenylmethanesulfonamide Chemical compound C=1C=CC=CC=1NS(=O)(=O)CC1=CC=CC=C1 AUNYWGYRPIHMLM-UHFFFAOYSA-N 0.000 description 1
- VLYFHHYLZLDEIU-UHFFFAOYSA-N n-ethyloctadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(=O)NCC VLYFHHYLZLDEIU-UHFFFAOYSA-N 0.000 description 1
- PAYCIKRBIVVVGK-UHFFFAOYSA-N n-octadecylbenzenesulfonamide Chemical compound CCCCCCCCCCCCCCCCCCNS(=O)(=O)C1=CC=CC=C1 PAYCIKRBIVVVGK-UHFFFAOYSA-N 0.000 description 1
- 229920006280 packaging film Polymers 0.000 description 1
- 239000012785 packaging film Substances 0.000 description 1
- 238000005453 pelletization Methods 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920005990 polystyrene resin Polymers 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- 238000003303 reheating Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000000565 sealant Substances 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 229940037312 stearamide Drugs 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- LMYRWZFENFIFIT-UHFFFAOYSA-N toluene-4-sulfonamide Chemical compound CC1=CC=C(S(N)(=O)=O)C=C1 LMYRWZFENFIFIT-UHFFFAOYSA-N 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
Landscapes
- Laminated Bodies (AREA)
- Shaping By String And By Release Of Stress In Plastics And The Like (AREA)
Description
【発明の詳細な説明】
Ａ 産業上の利用分野
本発明はビンホール、クラツク、局所的偏肉な
どのない、しかもガスバリアー性の優れた、エチ
レン−ビニルアルコール共重合体（以下EVOH
と記す。）成形物の製法に関する。DETAILED DESCRIPTION OF THE INVENTION A. Field of Industrial Application The present invention is an ethylene-vinyl alcohol copolymer (hereinafter referred to as EVOH
It is written as ) Regarding the manufacturing method of molded products.
Ｂ 従来の技術
EVOHは今日、食品包装用フイルム特に酸素
に対する保護が必要な食品及び他の製品に対する
使用を目的とするフイルムにおいてかなりの価値
を持つている事が認められている。しかしなが
ら、EVOHで作つた単層フイルムはタフネスに
欠け、脆く、また、このフイルムは水又は水蒸気
によつてガスバリアー性が低下するなどの欠点が
ある。B. PRIOR ART EVOH is now recognized to be of considerable value in food packaging films, particularly those intended for use with food and other products requiring protection against oxygen. However, a single layer film made of EVOH lacks toughness and is brittle, and this film also has drawbacks such as a decrease in gas barrier properties when exposed to water or water vapor.
これらの欠点を改善する為、EVOH樹脂は通
常、ナイロン、ポリエステル、ポリプロピレン、
ポリエチレン、ポリ塩化ビニルなどの熱可塑性樹
脂を１種類又はそれ以上含む構造層と、アイオノ
マー、エチレン、酢酸ビニル共重合体などに代表
される各種、熱ミーラント層とを積層してなる多
層フイルムの形で用いられている。 To improve these drawbacks, EVOH resins are usually made of nylon, polyester, polypropylene,
A multilayer film formed by laminating a structural layer containing one or more types of thermoplastic resin such as polyethylene or polyvinyl chloride, and a thermal sealant layer of various types such as ionomer, ethylene, or vinyl acetate copolymer. It is used in
ところで、共押出、押出ラミ、ドライラミ、溶
液コーテイング法等で製造した多層のフイルム又
はシート又はバリソン等を包装用容器として二次
加工する場合、特にEVOHの融点以下で延伸成
形を行なう場合、EVOH層に小さなボイド、ク
ラツク、局所的偏肉等が発生する。その為、高い
酸素バリアー性を特長とするこれら成形物の酸素
バリアー性が大巾に低下するとともに、外見上透
明性等の悪化をもたらし、包装容器としての使用
が困難な場合が多い状況であつた。 By the way, when secondary processing a multilayer film, sheet, balisong, etc. manufactured by coextrusion, extrusion lamination, dry lamination, solution coating, etc. as a packaging container, especially when performing stretch molding at a temperature below the melting point of EVOH, the EVOH layer Small voids, cracks, local uneven thickness, etc. occur. As a result, the oxygen barrier properties of these molded products, which are characterized by their high oxygen barrier properties, are significantly reduced, and their appearance becomes less transparent, making it difficult to use them as packaging containers. Ta.
そこで従来から容器成形加工時に発生する
EVOH層のピンホール、クラツク、居所的偏肉
等を防止する対策としてEVOHにポリアミド系
樹脂のブレンド、芳香族スルホンアミド系可塑剤
の場合（特開昭59−20345）さらにはグリセリン、
各種グリコール、ポリヒドリツク化合物に代表さ
れるヒドロキシル基含有可塑剤等の混合（特開昭
53−88067）等が検討されてはいるが、いずれの
場合も下記の点で十分満足すへきものではない事
が判明した。すなわち、ポリアミド系樹脂を
EVOHにポリマーブレンドし、多層構造物を得
る場合、ポリアミド系樹脂とEVOHとが反応し、
成形物に多数のゲル状物（フイツシユアイ）が発
生するとともに着色がはげしく使用にたえない。
また多層構造物を二次成形により容器にした場合
EVOH層のクラツク、ピンホール等の発生を防
止する為に添加するポリアミド系樹脂の含有量は
EVOH100重量部に対し、10〜30重量部と多大に
添加する必要がある。その結果、ガスバリアー性
が大巾に低下し、成形容器は良好であつても、高
いガスバリアー性を特長とする食品包装分野での
使用は不可能である。 Therefore, conventionally, it occurs during container molding process.
As a measure to prevent pinholes, cracks, uneven thickness, etc. in the EVOH layer, polyamide resin is blended with EVOH, and in the case of aromatic sulfonamide plasticizer (JP-A-59-20345), glycerin,
Mixing of hydroxyl group-containing plasticizers such as various glycols and polyhydric compounds (Unexamined Japanese Patent Publication No.
53-88067), etc., but it has been found that none of them are fully satisfactory in terms of the following points. In other words, polyamide resin
When blending EVOH with a polymer to obtain a multilayer structure, the polyamide resin and EVOH react,
A large number of gel-like substances (fish eyes) are generated in the molded product, and the product is too colored to be usable.
Also, when a multilayer structure is made into a container by secondary molding,
The content of polyamide resin added to prevent the occurrence of cracks, pinholes, etc. in the EVOH layer is
It is necessary to add a large amount of 10 to 30 parts by weight per 100 parts by weight of EVOH. As a result, the gas barrier properties are greatly reduced, and even if the molded containers are good, they cannot be used in the food packaging field, which is characterized by high gas barrier properties.
またヒドロキシル基含有可塑剤系においても添
加量がEVOH100重量部に対してポリアミド系樹
脂と同様に10〜20重量部必要であり、ガスバリア
ー性が大巾に低下する。さらに悪い事には
EVOHとの相容性が十分でない為か、可塑剤が
ブリードし多層積層容器におけるEVOH層と他
の樹脂層との接着強度が経時的に大巾に低下し、
容器の型態をそこねる。すなわち、上記添加剤は
使用に耐えがたいものである。 Further, in the case of a hydroxyl group-containing plasticizer system, the addition amount is required to be 10 to 20 parts by weight per 100 parts by weight of EVOH, similar to the polyamide resin, and the gas barrier properties are greatly reduced. Even worse
Perhaps because the compatibility with EVOH is not sufficient, the plasticizer bleeds and the adhesive strength between the EVOH layer and other resin layers in the multilayer laminated container decreases significantly over time.
Damage to the shape of the container. In other words, the above additives are unacceptable to use.
それ故、ガスバリアー性の大巾な低下がなく、
かつ多層構造物における容器成形において
EVOH層のピンホール、クラツク、微少偏肉等
が生じない成形加工良好なEVOHの開発が重要
な課題の一つである。 Therefore, there is no significant decrease in gas barrier properties,
and in container forming in multilayer structures.
One of the important issues is the development of EVOH that can be easily molded without causing pinholes, cracks, or minute thickness deviations in the EVOH layer.
Ｃ 発明が解決しようとする問題点
EVOHは前記した様に優れた諸特性を持つて
いる反面、熱可塑性樹脂との積層体を容器等に二
次加工する場合、EVOH層にクラツク、ピンホ
ール、局所的偏肉等が発現し高いガスバリアー性
を特長とするEVOH多層容器のバリアー性が大
巾に悪化する結果となつている。C. Problems to be Solved by the Invention Although EVOH has various excellent properties as described above, when the laminate with thermoplastic resin is secondary processed into containers etc., cracks, pinholes, etc. may occur in the EVOH layer. The barrier properties of EVOH multilayer containers, which are characterized by high gas barrier properties, are significantly deteriorated due to localized thickness unevenness.
そこで本発明者らは、EVOHの優れたガスバ
リアー性をそこなうことなく、かつ積層体を容器
等に二次加工する場合に生じるEVOH層のクラ
ツク、ピンホール、局所的偏肉等を防止し、高い
ガスバリアー性を有するEVOH多層容器用
EVOHを開発すべく鋭意検討を行なつた結果、
本発明を完成するに至つた。 Therefore, the present inventors have developed a method to prevent cracks, pinholes, local thickness unevenness, etc. of the EVOH layer that occur when secondary processing a laminate into containers etc. without impairing the excellent gas barrier properties of EVOH. For EVOH multilayer containers with high gas barrier properties
As a result of intensive study to develop EVOH,
The present invention has now been completed.
Ｄ 問題点を解決するための手段
本発明はエチレン含量20〜60モル％、けん化度
90％以上のEVOH100重量部に長鎖脂肪族または
芳香族アミド0.5〜５重量部を配合したEVOH成
形物を加熱延伸するに際し、該成形物中の水分含
有率を0.1〜５重量％（EVOHに対する重量％）
に調節することを特徴とするEVOH成形物の製
法であり、とくに前記EVOH組成物層の少なく
とも片面に熱可塑性樹脂層を有する積層体を加熱
延伸して多層構造体を得る際に有用な方法であ
る。D Means for solving the problem The present invention has an ethylene content of 20 to 60 mol%, a degree of saponification
When heating and stretching an EVOH molded product containing 100 parts by weight of EVOH of 90% or more and 0.5 to 5 parts by weight of a long-chain aliphatic or aromatic amide, the moisture content in the molded product is adjusted to 0.1 to 5% by weight (relative to EVOH). weight%)
It is a method for producing an EVOH molded product, which is characterized by adjusting the EVOH composition layer, and is particularly useful when obtaining a multilayer structure by heating and stretching a laminate having a thermoplastic resin layer on at least one side of the EVOH composition layer. be.
Ｅ 発明の作用効果
EVOH層の片面又は両面に接着性樹脂を介し
て熱可塑性樹脂層を有する各種シート及びバリソ
ンを作成し再加熱、延伸操作によつてカツプ及び
ボルトに二次加工成形し、得られた容器の外見及
びガスバリアー性の測定よりEVOH層の成形加
工性及びガスバリアー性の優劣を判断する事が出
来る。そこで本発明者らは種々の可塑剤、ポリマ
ー等をEVOHにブレンドしてEVOHの成形加工
性及びガスバリアー性の測定を行なつた。その結
果長鎖樹脂族または芳香族系アミド化合物、とり
わけスルホンアミド系化合物を配合したEVOH
は単体EVOH及び他の可塑剤、ポリマー等をブ
レンドしたEVOH組成物と比較して良好な特性
をするか、EVOH層のピンホール、クラツク、
微少偏肉の発生を完全に防ぐことはできず、また
ガスバリアー性もかならずしも充分でなく、さら
にまた再現性の点でも不十分であつた。E Effects of the Invention Various sheets and balisons having a thermoplastic resin layer on one or both sides of the EVOH layer via an adhesive resin are prepared, and are then secondary processed into cups and bolts by reheating and stretching operations. The moldability and gas barrier properties of the EVOH layer can be determined by measuring the appearance and gas barrier properties of the container. Therefore, the present inventors blended various plasticizers, polymers, etc. with EVOH and measured the moldability and gas barrier properties of EVOH. As a result, EVOH containing long-chain resinous or aromatic amide compounds, especially sulfonamide compounds,
Does it have better properties compared to single EVOH and EVOH compositions blended with other plasticizers, polymers, etc.?
It was not possible to completely prevent the occurrence of minute thickness deviations, gas barrier properties were not necessarily sufficient, and reproducibility was also insufficient.
しかし、おどろくべきことにEVOHに該アミ
ド系化合物を配合したEVOH成形物を加熱延伸
するに際し水分を所定の値に調節することによ
り、再現性良く容器成形時のEVOH層のピンホ
ール、クラツク、微少偏肉がほとんど無い非常に
良好な成形物が得られるだけでなく、成形物のガ
スバリアー性が無添加EVOHとほとんど大差な
い非常に良好なバリアー性容器が得られる事がわ
かり本発明にいたつた。 However, surprisingly, by adjusting the moisture content to a predetermined value when heat-stretching an EVOH molded product containing the amide compound in EVOH, pinholes, cracks, and minute defects in the EVOH layer during container molding were achieved with good reproducibility. It was found that not only a very good molded product with almost no uneven thickness could be obtained, but also a container with very good gas barrier properties that was almost the same as additive-free EVOH could be obtained, leading to the present invention. .
ところでEVOHは結晶化度が高いほどガスバ
リアー性が良好となる反面、容器成形加工時、
EVOH層にクラツク、ピンホール、微少偏肉等
が生じやすくなるものと考えられる。原因はさだ
かではないが、長鎖脂肪族又は芳香族アミド化合
物含有EVHは水分と該アミド系化合物の相乗効
果により高温下で軟化剤として作用し、EVOH
層のクラツク等の発生を防止する反面、常温にお
いては大きな疏水基を持つ長鎖脂肪酸アミド又は
芳香族アミドが水分とEVOHとの相互作用を低
減し、EVOHの結晶化度の増加をもたらし、そ
の結果、バリアー性が無添加EVOHと大差が無
く良好となるのではないかと思われる。 By the way, the higher the crystallinity of EVOH, the better the gas barrier properties, but on the other hand, when forming containers,
It is thought that cracks, pinholes, minute thickness deviations, etc. are likely to occur in the EVOH layer. Although the cause is not obvious, EVH containing long-chain aliphatic or aromatic amide compounds acts as a softener at high temperatures due to the synergistic effect of moisture and the amide compound, and EVOH
While preventing the occurrence of layer cracks, at room temperature, long-chain fatty acid amides or aromatic amides with large hydrophobic groups reduce the interaction between moisture and EVOH, leading to an increase in the crystallinity of EVOH. As a result, it seems that the barrier properties will be good, with no significant difference from additive-free EVOH.
Ｆ 発明のより詳細な説明 以下本発明を更に詳しく説明する。F. More detailed description of the invention The present invention will be explained in more detail below.
本発明に使用されるEVOHは、エチレン含有
量20〜60モル％、好適には25〜55モル％、酢酸ビ
ニル成分のけん化度は90％以上、好適には95％以
上のエチレン酢酸ビニル共重合体けん化物であ
る。エチレン含量20モル％以下になると成形温度
が分解温度に近くなり成形が困難となる。一方、
エチレン含量が60モル％以上になるとガスバリア
ー性が低下し、該多層構成容器のガスバリアー性
が不満足なものとなり好ましくない。 The EVOH used in the present invention is an ethylene-vinyl acetate copolymer having an ethylene content of 20 to 60 mol%, preferably 25 to 55 mol%, and a saponification degree of the vinyl acetate component of 90% or more, preferably 95% or more. It is a combined saponified product. When the ethylene content is less than 20 mol%, the molding temperature approaches the decomposition temperature, making molding difficult. on the other hand,
If the ethylene content exceeds 60 mol %, the gas barrier properties will decrease and the gas barrier properties of the multilayered container will be unsatisfactory, which is not preferable.
また、酢酸ビニル成分のけん化度が95％未満、
とくに90％未満のEVOHは容器成形時のクラツ
ク、ピンホール等が少ない又は無いものが得られ
るが、バリアー性が悪い為好ましくない。さらに
このEVOHはASTM−D1238−65Tにより190℃
で測定されたメルトインデツクス（MI）が0.1〜
25ｇ／10min好ましくは0.3〜20ｇ／10minであ
る。 In addition, the degree of saponification of vinyl acetate component is less than 95%,
In particular, if the EVOH is less than 90%, a product with few or no cracks or pinholes during container molding can be obtained, but it is not preferable because of poor barrier properties. Furthermore, this EVOH is 190℃ according to ASTM-D1238-65T.
Melt index (MI) measured at 0.1~
25g/10min, preferably 0.3 to 20g/10min.
本発明で使用される長鎖脂肪族アミドとしては
長鎖脂肪族カルボン酸アミド、長鎖脂肪族スルホ
ン酸アミドが代表的なものとしてあげられる。こ
れらのアミド化合物は炭素数10〜20を有するもの
がよい。またアミド基にはＮ−置換アルキル基
（アルキル基の炭素数１〜５）を１または２個有
していてもよい。またカルボン酸アミドとしては
モノカルボン酸アミド、多価（ジ、トリなど）カ
ルボン酸アミドがあげられる。これらの具体例と
してはオレイン酸アミド、ステアリン酸アミド、
パルミチン酸アミド、Ｎ−エチルステアリン酸ア
ミド、Ｎ，Ｎ−ジステアリルエチレンジアミドが
あげられるが、このうちとくにステアリン酸アミ
ド、オレイン酸アミドが好適である。 Typical long-chain aliphatic amides used in the present invention include long-chain aliphatic carboxylic acid amides and long-chain aliphatic sulfonic acid amides. These amide compounds preferably have 10 to 20 carbon atoms. Further, the amide group may have one or two N-substituted alkyl groups (the alkyl group has 1 to 5 carbon atoms). Further, examples of the carboxylic acid amide include monocarboxylic acid amide and polyvalent (di, tri, etc.) carboxylic acid amide. Specific examples of these include oleic acid amide, stearic acid amide,
Examples include palmitic acid amide, N-ethylstearic acid amide, and N,N-distearylethylenediamide, among which stearic acid amide and oleic acid amide are particularly preferred.
また本発明で使用される芳香族アミドとしては
芳香族カルボン酸アミド、芳香族スルホンアミド
が代表的なものとしてあげられる。またこのアミ
ド基にはＮ−置換アルキル基（アルキル基の炭素
数１〜５）を１または２個有していてもよい。芳
香族カルボン酸アミドの具体例としてはメチル安
息香酸アミド、フエニルカルボン酸アミドなどの
フエニル基を基本骨格に持つカルボン酸アミドが
あげられ、また芳香族スルホン酸アミドの具体例
としてはフエニル基を基本骨格にスルホン酸アミ
ド基を持つものであれば、特に限定されないが、
ｐ−トルエンスルホン酸アミド、ｏ−トルエンス
ルホン酸アミド、Ｎ−エチルトルエンスルホン酸
アミド、フエニルトルエンスルホン酸アミド、Ｎ
−ステアリルフエニルスルホン酸アミド、Ｎ−フ
エニルトルエンスルホン酸アミド等があげられる
が、特にＮ−エチルトルエンスルホン酸アミドが
有効である。 Furthermore, typical aromatic amides used in the present invention include aromatic carboxylic acid amides and aromatic sulfonamides. Further, this amide group may have one or two N-substituted alkyl groups (the alkyl group has 1 to 5 carbon atoms). Specific examples of aromatic carboxylic acid amides include carboxylic acid amides having a phenyl group in the basic skeleton, such as methylbenzoic acid amide and phenylcarboxylic acid amide, and specific examples of aromatic sulfonic acid amides include those having a phenyl group in the basic skeleton. It is not particularly limited as long as it has a sulfonic acid amide group in its basic skeleton, but
p-toluenesulfonamide, o-toluenesulfonamide, N-ethyltoluenesulfonamide, phenyltoluenesulfonamide, N
-stearylphenylsulfonic acid amide, N-phenyltoluenesulfonic acid amide, etc., and N-ethyltoluenesulfonic acid amide is particularly effective.
添加量に関してはEVOH100重量部に対して長
鎖脂肪族アミド又は芳香族アミドの添加量が0.5
重量部以下の場合、容器成形時、クラツク、ピン
ホール、微少偏肉等が発生し、バリアー性が大巾
に悪化する為使用に耐えない。 Regarding the amount added, the amount of long chain aliphatic amide or aromatic amide added is 0.5 per 100 parts by weight of EVOH.
If the amount is less than 1 part by weight, cracks, pinholes, minute thickness deviations, etc. will occur during container molding, and the barrier properties will deteriorate significantly, making it unusable.
一方、長鎖脂肪酸アミド又は芳香族アミドの添
加量が５重量部以上の場合、成形品のクラツク、
ピンホール等の発生はおさえられるが、バリアー
性が十分でなく、かつ接着力も十分なものが得が
たい。好適な長鎖脂肪族アミドまたは芳香族アミ
ドの好適な配合量は0.6〜4.9重量部である。また
加熱延伸時の水分含有量が0.1重量％以下の場合、
再現性が悪くなるばかりでなく、容器成形時クラ
ツク、ピンホール等が発現しガスバリアー性悪化
により使用に耐えない。一方、水分添加量が５重
量％以上ある場合には加熱延伸時にEVOH層内
の水分が発泡し、クラツク、のびムラ等の発生が
顕著となり、ガスバリアー性も充分なものが得ら
れない。好適な水分の含有率は0.2〜３重量％で
ある。 On the other hand, if the amount of long-chain fatty acid amide or aromatic amide added is 5 parts by weight or more, cracks in the molded product,
Although the occurrence of pinholes etc. can be suppressed, it is difficult to obtain a material with sufficient barrier properties and sufficient adhesive strength. The preferred amount of long chain aliphatic amide or aromatic amide is 0.6 to 4.9 parts by weight. In addition, if the moisture content during heating stretching is 0.1% by weight or less,
Not only does reproducibility deteriorate, but cracks, pinholes, etc. appear during container molding, and the gas barrier properties deteriorate, making it unusable. On the other hand, if the amount of water added is 5% by weight or more, the water in the EVOH layer will foam during heating and stretching, causing noticeable cracks, uneven spread, etc., and insufficient gas barrier properties. A suitable water content is 0.2 to 3% by weight.
アミド系化合物のEVOHへのブレンド方法に
ついては、特に限定されるものではなく、そのま
まEVOHにドライブレンドし、バンバリーミキ
サー、単軸又は二軸ベント式押出機などを用いて
ペレツト化、乾燥を行なう事が好ましい。その際
押出機ホツパー、乾燥機内をN2にてシールする
事は着色、ゲル発生防止に効果的である。一方、
各成分を直接成形機に供給して成形機で混練しな
がら成形加工しても良い。またこれらを混練する
際、他の添加剤（各種樹脂酸化防止剤、可塑剤、
着色剤など）を本発明の作用効果が阻害されない
範囲内で使用する事は自由である。特に樹脂の熱
安定性、ゲル発生防止対策としてハイドロタルサ
イト系化合物、ヒンダードフエノール系酸化防止
剤を0.01〜１重量部添加する事は好適である。 The method of blending the amide compound with EVOH is not particularly limited, and may be dry blended with EVOH as it is, pelletized using a Banbury mixer, single-screw or twin-screw vent extruder, etc., and dried. is preferred. At this time, sealing the inside of the extruder hopper and dryer with N 2 is effective in preventing coloring and gel formation. on the other hand,
Each component may be directly fed to a molding machine and molded while being kneaded by the molding machine. In addition, when kneading these, other additives (various resin antioxidants, plasticizers,
Coloring agents, etc.) may be used freely within the range that does not impede the effects of the present invention. In particular, it is suitable to add 0.01 to 1 part by weight of a hydrotalcite compound or a hindered phenol antioxidant to improve the thermal stability of the resin and to prevent gel formation.
また水分の含有率のコントロールに関しては、
特に限定されるものではないが、たとえば、成形
時水分含有ペレツトを使用する方法、または加熱
延伸前の成形物を温度、湿度をコントロールした
室に放置するか、または温水、加熱水、スチーム
等に短時間接触させるなどの方法がある。 Regarding the control of moisture content,
Examples include, but are not limited to, a method of using moisture-containing pellets during molding, or leaving the molded product in a temperature and humidity controlled room before heating and stretching, or exposing it to hot water, heated water, steam, etc. There are methods such as short-term contact.
ここで加熱延伸とは
Ｘ−10℃≧Ｙ≧Ｘ−110℃
（ただしＸはEVOHの融点℃を、Ｙは加熱延伸
温度℃を示す。）
を満足する条件で、一軸延伸、二軸延伸（同時ま
たは遂次）する操作を意味する。延伸倍率は目的
に応じて適宜選択することができるが、フイルム
状物を得る場合の延伸倍率は一軸延伸の場合は、
縦方向に2.0〜5.0倍、二軸延伸する場合は縦方向
に２〜４倍、横方向に２〜４倍、面積倍率で４〜
16倍が好ましい。 Here, heating stretching means uniaxial stretching, biaxial stretching ( (simultaneous or sequential) operations. The stretching ratio can be selected as appropriate depending on the purpose, but in the case of uniaxial stretching, the stretching ratio when obtaining a film-like product is
2.0 to 5.0 times in the vertical direction, 2 to 4 times in the vertical direction when biaxially stretched, 2 to 4 times in the horizontal direction, 4 to 4 times in area magnification
16 times is preferable.
本発明のEVOH組成物は周知の溶融成形法、
圧縮成形法によりフイルム、シート、チユーブ、
ボルトなどの任意の成形品に成型することができ
るが、前述したとおり該組成物を多層構造体の一
層として使用するときに顕著な特長が発揮される
ので、以下この点についての説明を加える。 The EVOH composition of the present invention can be prepared by the well-known melt molding method.
Films, sheets, tubes,
Although it can be molded into any molded product such as a bolt, as mentioned above, remarkable features are exhibited when the composition is used as one layer of a multilayer structure, so a description of this point will be added below.
まず多層構造体を得る方法としては、該
EVOH組成物と熱可塑性樹脂とを接着剤を介し
て押出ラミ法、ドライラミ法、共押出ラミ法、共
押出シート作成法（フイードブロツク、マルチマ
ニホーハド法）、共押出パイプ作成法、共インジ
エクシヨン法、各種溶液コート法により積層体を
得、次いでこれを真空圧空深絞り成形機、二軸延
伸プロ−機等によりEVOHの融点以下の範囲内
で再加熱し延伸操作を行なう方法あるいは前記積
層体（シートまたはフイルム）を二軸延伸押機に
共し、加熱延伸する方法、さらにはEVOH組成
物と熱可塑性樹脂とを共射出二軸延伸する方法な
どがあるげられる。なおここで使用する接着性樹
脂に関してはEVOHの融点以下で延伸、成形可
能な樹脂であれば特に限定されるものではない。 First, as a method to obtain a multilayer structure,
An EVOH composition and a thermoplastic resin are bonded via an adhesive using an extrusion lamination method, a dry lamination method, a coextrusion lamination method, a coextrusion sheet making method (feedblock, multi-manifold method), a coextrusion pipe making method, a coextrusion lamination method, A method in which a laminate is obtained by an in-die extension method or various solution coating methods, and then reheated to a temperature below the melting point of EVOH using a vacuum-pressure deep drawing machine, a biaxial stretching machine, etc., and a stretching operation is performed, or the above-mentioned laminate method is used. Examples include a method in which a body (sheet or film) is heated and stretched using a biaxial stretching press, and a method in which an EVOH composition and a thermoplastic resin are co-injected and biaxially stretched. The adhesive resin used here is not particularly limited as long as it can be stretched and molded at a temperature below the melting point of EVOH.
ここで使用される熱可塑性樹脂としては、下記
式で示されるが熱延伸温度の範囲内で延伸可能な
ものであればいづれも使用できる。 The thermoplastic resin used here is represented by the following formula, but any resin that can be stretched within the hot stretching temperature range can be used.
Ｘ−10℃≧Ｙ≧Ｘ−110℃
（ただし、Ｘはエチレン−ビニルアルコール共重
合体の融点℃を、Ｙは加熱延伸温度℃を示す。）
このような熱可塑性樹脂として、ポリプロピレ
ン系樹脂、ポリスチレン系樹脂、ポリアミド系樹
脂、飽和ポリエステル系樹脂、ポリ塩化ビニル系
樹脂が好適なものとしてあげられる。これらの熱
可塑性樹脂はEVOHの諸欠点（タフネスに欠け、
脆くまた水または水蒸気の接触によつてガスバリ
アー性が低下することなど）を改善するために用
いられるものである。 X-10℃≧Y≧X-110℃ (However, X indicates the melting point of the ethylene-vinyl alcohol copolymer in degrees Celsius, and Y indicates the heating stretching temperature in degrees Celsius.) Such thermoplastic resins include polypropylene resins, Preferred examples include polystyrene resins, polyamide resins, saturated polyester resins, and polyvinyl chloride resins. These thermoplastic resins have the disadvantages of EVOH (lack of toughness,
It is used to improve problems such as brittleness and deterioration of gas barrier properties due to contact with water or steam.
またここで使用される接着性樹脂としてはとく
に限定されるものではなく、上記式で示される加
熱延伸温度の範囲内で延伸可能で、しかも
EVOHおよび熱可塑性樹脂に対して接着性を有
するものであればいづれも使用できる。 Furthermore, the adhesive resin used here is not particularly limited, and can be stretched within the heating stretching temperature range shown by the above formula.
Any material that has adhesive properties to EVOH and thermoplastic resins can be used.
さらに多層構造体の厚み構成に関しても特に限
定されるものではないが、成形性、コスト等を考
慮した場合、全厚みに対するEVOH層厚み比は
２〜20％程度が好適である。 Further, the thickness of the multilayer structure is not particularly limited, but when considering moldability, cost, etc., the EVOH layer thickness ratio to the total thickness is preferably about 2 to 20%.
本発明において加熱延伸多層構造体とは前記し
たとおり、加熱延伸することにより得られるカツ
ト、ボルトなどの容器、あるいはシートまたはフ
イルム状物であり、また加熱延伸とは上記式で示
される加熱延伸温度の範囲内で行なわれることを
意味する。加熱延伸温度(Y)がＸ−110℃以下の場
合、熱可塑性樹脂のガラス転移温度（Tg）が室
温以下となるため、成形物の室温下での形状安定
性が悪く、目的とする多層構造体が得られない。
またＹがＸ−10℃より高い場合、EVOHが部分
融解または完全融解するので、配向効果が減少す
る。また加熱とは多層積層体を加熱延伸に必要な
温度に所定の時間放置し、該多層積層体が熱的に
均一によるように操作することを意味し操業性を
考慮して種々のヒーターで加熱均一化する操作が
もつとも好適である。加熱操作は延伸と同時に行
なつてもよいし、また延伸前に行なつてもよい。
また延伸とは熱的に均一に加熱された多層積層体
をチヤツク、プラグ、真空、圧空、ブローなどに
より容器またはシートまたはフイルム状に均一に
成形する操作を意味し、一軸延伸、二軸延伸（同
時または逐次）のいづれも使用できる。また延伸
倍率は目的に応じて適宜選択することができる。 In the present invention, the heat-stretched multilayer structure is, as described above, a container such as a cut or bolt, or a sheet or film-like material obtained by heat-stretching, and heat-stretching is a heat-stretching temperature expressed by the above formula. means that it is carried out within the scope of If the heating stretching temperature (Y) is below X-110°C, the glass transition temperature (Tg) of the thermoplastic resin will be below room temperature, resulting in poor shape stability of the molded product at room temperature and the desired multilayer structure. I can't get a body.
Moreover, when Y is higher than X-10°C, EVOH is partially or completely melted, so that the orientation effect is reduced. In addition, heating means to leave the multilayer laminate at the temperature required for heating and stretching for a predetermined period of time, and to operate the multilayer laminate so that it is thermally uniform. A uniformizing operation is also preferred. The heating operation may be performed simultaneously with the stretching, or may be performed before the stretching.
Stretching refers to the operation of uniformly shaping a thermally uniformly heated multilayer laminate into a container, sheet, or film by chuck, plug, vacuum, pressure, blow, etc., and includes uniaxial stretching, biaxial stretching ( (simultaneous or sequential) can be used. Further, the stretching ratio can be appropriately selected depending on the purpose.
また多層構造体の層構成としては、EVOH組
成物層／接着性樹脂層／熱可塑性樹脂層、熱可塑
性樹脂層／接着性樹脂／EVOH組成物層／接着
性樹脂層／熱可塑性樹脂層が代表的なものとして
あげられる。両外層に熱可塑性樹脂層を設ける場
合は該樹脂は異なるものでもよいし、また同じも
のでもよい。 Typical layer configurations of multilayer structures include EVOH composition layer/adhesive resin layer/thermoplastic resin layer, thermoplastic resin layer/adhesive resin/EVOH composition layer/adhesive resin layer/thermoplastic resin layer. It can be cited as something. When thermoplastic resin layers are provided on both outer layers, the resins may be different or may be the same.
このようにして得られた本発明の加熱延伸多層
構造体はEVOH組成物層にピンホール、クラツ
ク、偏肉がみられないので、ガスバリヤー性は極
めて良好であり、食品包装用容器、あるいはガス
バリアー性を要求される容器として有用である。 The thus obtained heat-stretched multilayer structure of the present invention has no pinholes, cracks, or uneven thickness in the EVOH composition layer, so it has extremely good gas barrier properties and can be used as food packaging containers or gas It is useful as a container that requires barrier properties.
以下実施例により本発明をさらに説明するが、
本発明はこれによつてなんら限定を受けるもので
はない。 The present invention will be further explained below with reference to Examples.
The present invention is not limited in any way by this.
〈EVOH層の水分の測定法〉
加熱延伸加工直前の多層構造体にあるEVOH
層をはくりし、120℃24時間熱風乾燥機に放置し、
重量減少よりEVOH層の水分を求める。この値
をパーセント表示し揮発分と称する事にする。<Method for measuring moisture in EVOH layer> EVOH in a multilayer structure just before heating and stretching
Peel off the layers and leave in a hot air dryer at 120℃ for 24 hours.
Determine the moisture content of the EVOH layer from the weight loss. This value is expressed as a percentage and is referred to as volatile content.
実施例 １
エチレン含有量31モル％、けん化度99.4％、メ
ルトインデツクス（MI190℃）1.3ｇ／10分の
EVOH（クラレ製EVAL
−EP−F101）100重量
部に対してＮ−エチルトルエンスルホン酸アミド
３重量部及び水１重量部を配合し、二軸スクリユ
ータイプベント式40φ押出機にて220℃で押出し
ペレツト化を行なつた。表面付着水を除くため得
られたペレツトを95℃−16時間乾燥した。このペ
レツトを用いてフイードブロツク型３種５層共押
出装置にかけシートを作成した。シートの構成は
両最外層ポリプロピレン（三菱油化製ノーブレン
MA−６）が各400μ、また接着材層｛三菱油化モ
デイツク300F（無水マレイン酸グラフト変性エチ
レン−酢酸ビニル共重合体）｝が各50μ、さらに
最内厚（中央）は50μの上記EVOH層である。得
られたシートを真空圧空成形機にかけ155℃で熱
成形（SPPF成形）を行なつた成形前のEVOH層
の揮発分（水分）は0.25％であつた。その結果、
透明性良好、かつクラツク微少偏肉のない良好な
成形物が得られた。なお成形物の絞り比は1.5で
あつた。この成形容器を20℃で100％RH、及び
65％RHでそれぞれ十分調湿し（約３ケ月）、モ
コン酸素分析器｛モコン（Mocon）社製｝にて
酸素透過量の測定を行なつた結果、EVOH層の
酸素透過量は0.5c.c.・20μ／m2・24hr・atm（20℃、
65％RH）、24c.c.・20μ／m2・24hr・atm（20℃、
100％RH）であり、非常に良好なガスバリアー
性を示した。Example 1 Ethylene content 31 mol%, saponification degree 99.4%, melt index (MI 190°C) 1.3 g/10 minutes
3 parts by weight of N-ethyltoluenesulfonic acid amide and 1 part by weight of water were mixed with 100 parts by weight of EVOH (EVAL-EP-F101 manufactured by Kuraray), and the mixture was heated at 220°C using a twin-screw type vent type 40φ extruder. Extrusion pelletization was carried out. The pellets obtained were dried at 95° C. for 16 hours to remove water adhering to the surface. Using this pellet, a sheet was prepared by applying it to a feedblock type 3 type 5 layer coextrusion device. The sheet is composed of both outermost layers of polypropylene (Mitsubishi Yuka Noblen).
MA-6) is 400μ each, and the adhesive layer {Mitsubishi Yuka Model 300F (maleic anhydride graft modified ethylene-vinyl acetate copolymer)} is 50μ each, and the innermost thickness (center) is 50μ. It is. The obtained sheet was subjected to thermoforming (SPPF molding) at 155° C. in a vacuum-pressure forming machine, and the volatile content (moisture) of the EVOH layer before molding was 0.25%. the result,
A good molded product with good transparency and no cracks or slight unevenness in thickness was obtained. Note that the drawing ratio of the molded product was 1.5. This molded container was heated to 20℃, 100% RH, and
As a result of thoroughly controlling the humidity at 65% RH (about 3 months) and measuring the amount of oxygen permeation using a Mocon oxygen analyzer (manufactured by Mocon), the amount of oxygen permeation through the EVOH layer was 0.5cc. 20μ/ m2・24hr・atm (20℃,
65%RH), 24c.c.・20μ/ m2・24hr・atm (20℃,
100% RH) and showed very good gas barrier properties.
比較例 １
実施例１において中間層にＮ−エチルトルエン
スルホン酸アミドと水無添加のEVOH（EVAL
−EP−F101）を用いた以外は実施例１と同様に
行なつた。その結果シートを真空圧空深絞り成形
した場合、成形容器の側面に多数の微少クラツ
ク、ピンホールが肉眼でもはつきる観察されるほ
ど発生し、この容器の酸素透過量は5000c.c.・
20μ／m2・24hr・atm（20℃、100％RH）と、多
大となりEVOH層が切断されている事がわかつ
た。参考の為、深絞り成形前のシートでEVOH
層の酸素透過量を測定した所、0.6c.c.・20μ／m2・
24hr・atm（20℃、65％RH）、24c.c.・20μ／m2・
24hr・atm（20℃、100％RH）であつた。Comparative Example 1 In Example 1, N-ethyltoluenesulfonic acid amide and water-free EVOH (EVAL
-EP-F101) was used in the same manner as in Example 1. As a result, when the sheet is vacuum-pressure deep-drawn, a large number of minute cracks and pinholes appear on the side of the molded container, visible to the naked eye, and the oxygen permeation rate of this container is 5000c.c.
It was found that the EVOH layer was severed at 20 μ/m 2 24 hr atm (20℃, 100%RH). For reference, EVOH is a sheet before deep drawing.
When the oxygen permeation rate of the layer was measured, it was 0.6cc・20μ/m 2・
24hr・atm (20℃, 65%RH), 24c.c.・20μ/ m2・
The temperature was 24 hours atm (20℃, 100%RH).
比較例 ２
実施例１において中間層にEVOH（EVAL
−
EP−F101）100重量部に対して、Ｎ−エチルト
ルエンスルホン酸アミド15重量部配合ペレツト化
した樹脂を用いた以外は実施例１と同様に行なつ
た。その結果、絞り成形容器の外観はクラツク等
のない良好な成形物であつたが、２〜３日後より
成形容器の端部よりEVOH層と接着層のはくり
が生じはじめる事、またEVOH層の酸素透過量
が５c.c.・20μ／m2・24hr・atm（20℃、65％RH）、
90c.c.・20μ／m2・24hr・atm（20℃、65％RH）と
バリアー性が悪い等の欠点が見られた。Comparative Example 2 In Example 1, EVOH (EVAL −
The same procedure as in Example 1 was conducted except that a pelletized resin containing 15 parts by weight of N-ethyltoluenesulfonic acid amide and 100 parts by weight of EP-F101) was used. As a result, the appearance of the drawn container was a good molded product with no cracks, etc. However, after 2 to 3 days, the EVOH layer and adhesive layer began to peel off from the edges of the molded container, and the EVOH layer started to peel off from the edges of the molded container. Oxygen permeation rate is 5c.c.・20μ/ m2・24hr・atm (20℃, 65%RH),
90c.c., 20μ/m 2 , 24hr, atm (20℃, 65%RH), and had drawbacks such as poor barrier properties.
比較例 ３
実施例１において中間層にEVOH（EVAL
−
EP−F101）100重量部に対して、Ｎ−エチルト
ルエンスルホン酸アミドを4.5重量部配合し、ペ
レツト化した樹脂を120℃４日間真空乾燥を行な
い十分水分を除去したものを用いた以外は実施例
１と同様に行なつた。その結果、絞り成形容器の
EVOH層にはクラツク及び微少偏肉が認められ
た。さらにEVOH層の酸素透過量を測定した所、
200c.c.・20μ／m2・24hr・atm（20℃、65％RH）
と非常に悪く使用に耐えなかつた。また熱成形直
前のEVOH層の揮発分は004％であつた。Comparative Example 3 In Example 1, EVOH (EVAL −
EP-F101) 100 parts by weight was mixed with 4.5 parts by weight of N-ethyltoluenesulfonic acid amide, and the pelletized resin was vacuum-dried at 120°C for 4 days to remove sufficient moisture. The procedure was as in Example 1. As a result, the drawn container
Cracks and slight uneven thickness were observed in the EVOH layer. Furthermore, when we measured the amount of oxygen permeation through the EVOH layer,
200c.c.・20μ/m 2・24hr・atm (20℃, 65%RH)
It was so bad that it could not be used. Further, the volatile content of the EVOH layer immediately before thermoforming was 0.04%.
比較例 ４
実施例１において中間層にEVOH（EVAL
EP
−F101）100重量部に対して水１重量部配合し、
ペレツト化した樹脂を用いた以外は実施例１と同
様に行なつた。その結果、絞り成形容器の
EVOH層にはクラツク等が認められ、ガスバリ
アー性も非常に悪かつた。この時の熱成形前
EVOH層の揮発分は0.41％であつた。Comparative Example 4 In Example 1, EVOH (EVAL EP) was used in the intermediate layer.
-F101) 1 part by weight of water is mixed with 100 parts by weight,
The same procedure as in Example 1 was carried out except that pelletized resin was used. As a result, the drawn container
Cracks were observed in the EVOH layer, and the gas barrier properties were also very poor. Before thermoforming at this time
The volatile content of the EVOH layer was 0.41%.
実施例 ２
エチレン含有量31モル％、けん化度99.4％、メ
ルトインデツクス（MI190℃）1.3ｇ／10分の
EVOH（EVAL
−EP−F101）100重量部に対し
てｏ−トルエンスルホン酸アミド４重量部、水
0.5重量部を配合し、実施例１と同様にペレツト
化、乾燥、さらにシートの作成を行なつた。その
後、80℃10分間シートを水中浸漬した後、容器成
形を実施した所、クラツクのない透明性良好な成
形物が得られた。またEVOH層の酸素透過量は、
0.5c.c.・20μ／m2・24hr・atm（20℃、65％RH）、
29c.c.・20μ／m2・24hr・atm（20℃、100％RH）
であり、非常に良好なガスバリアー性を示した。Example 2 Ethylene content 31 mol%, saponification degree 99.4%, melt index (MI 190°C) 1.3 g/10 minutes
4 parts by weight of o-toluenesulfonic acid amide, water per 100 parts by weight of EVOH (EVAL-EP-F101)
0.5 part by weight was blended, pelletized, dried, and formed into a sheet in the same manner as in Example 1. Thereafter, the sheet was immersed in water at 80°C for 10 minutes, and then molded into a container. A molded product with good transparency and no cracks was obtained. In addition, the amount of oxygen permeation through the EVOH layer is
0.5cc・20μ/m 2・24hr・atm (20℃, 65%RH),
29c.c.・20μ/m 2・24hr・atm (20℃, 100%RH)
It showed very good gas barrier properties.
比較例 ５
実施例２において製膜前のペレツトを120℃−
４日間減圧乾燥し、揮発分が0.01％以下のペレツ
トを使用した以外は実施例２と同様に行なつた。
その結果、絞り成形容器のEVOH層にクラツク
偏肉が認められ、またEVOH層の酸素透過性も
180c.c.・20μ／m2・24hr・atm（20℃、65％RH）
と悪い結果を示した。この容器の熱成形直前の
EVOH層の揮発分は0.07％（ドライベース）であ
り、またNMR法による定量の結果、ｏ−トルエ
ンスルホン酸アミドは3.6％（ドライベース）で
ある事が判明した。Comparative Example 5 In Example 2, the pellets before film formation were heated to 120℃-
The same procedure as in Example 2 was carried out except that the pellets were dried under reduced pressure for 4 days and the volatile content was 0.01% or less.
As a result, cracks and uneven thickness were observed in the EVOH layer of the drawn container, and the oxygen permeability of the EVOH layer also decreased.
180c.c.・20μ/m 2・24hr・atm (20℃, 65%RH)
showed poor results. Immediately before thermoforming of this container
The volatile content of the EVOH layer was 0.07% (dry basis), and as a result of quantitative analysis by NMR method, it was found that o-toluenesulfonic acid amide was 3.6% (dry basis).
実施例 ３
実施例１において最外層のポリプロピレンをポ
リスチレン（出光興産製スチロールET−61）に
また接着材層を東洋曹達製（メルセンM5420）
（無水マレイン酸グラフト変性エチレン−酢酸ビ
ニル共重合体）に変更し、真空圧空成形温度120
℃で実施した以外は実施例１と同様に行なつた。
その結果、クラツク等のない良好な成形物が得ら
れ、またEVOH層の酸素バリアー性も非常に良
い結果を示した。その酸素透過度はそれぞれ0.6
c.c.・20μ／m2・24hr・atm（20℃、65％RH）、
c.c.・20μ／m2・24hr・atm（20℃、100％RH）で
あつた。Example 3 In Example 1, the outermost polypropylene layer was made of polystyrene (Styrene ET-61 manufactured by Idemitsu Kosan), and the adhesive layer was made of Toyo Soda (Mersen M5420).
(Maleic anhydride graft modified ethylene-vinyl acetate copolymer), vacuum pressure molding temperature 120
The same procedure as in Example 1 was conducted except that the temperature was 0.degree.
As a result, a good molded product with no cracks etc. was obtained, and the oxygen barrier properties of the EVOH layer also showed very good results. Its oxygen permeability is 0.6 respectively
cc・20μ/ m2・24hr・atm (20℃, 65%RH),
It was cc・20μ/m 2・24hr・atm (20℃, 100%RH).
実施例 ４
エチレン含有量38モル％、けん化度99.4％、メ
ルトインデツクス1.4ｇ／10分のEVOH（EVAL
−EP−H101）100重量部に対してＮ−エチルト
ルエンスルホンアミド３重量部及び水１重量部を
配合し、二軸スクリユー40φ押出機にて押出しペ
レツト化を実施した。得られたペレツトを105℃
−６時間熱風乾燥した後、スパイラルフロータイ
プ３種５層共押出パイプ成形機にて共押出パイプ
を作成した。パイプの構成は、最外層及び最内層
はポリエステル（PET−G9921イーストマンケミ
カル製）2000μ及びEVOH中間層200μとの間に接
着性樹脂（東洋曹達製メルセン−M5420）各
200μを介したものである。得られたパイプは両
端を二軸延伸ブロー成形用パリソンに成形した
後、二軸延伸ブロー成形機にかけ、105℃で予熱
後二軸延伸ブローを行ない、クラツク、微少偏肉
の無い良好なボトルが得られた。熱成形直前の
EVOH層の揮発分は0.25％であつた。この容器の
EVOH層の酸素透過量は1.1c.c.・20μ／m2・24hr・
atm（20℃、65％RH）、21c.c.・20μ／m2・24hr・
atm（20℃、100％RH）であり、良好なバリアー
性を示した。Example 4 EVOH (EVAL) with ethylene content 38 mol%, saponification degree 99.4%, melt index 1.4 g/10
-EP-H101) 3 parts by weight of N-ethyltoluenesulfonamide and 1 part by weight of water were blended with 100 parts by weight of the mixture, and the mixture was extruded into pellets using a twin-screw extruder of 40φ. The obtained pellets were heated to 105℃.
- After drying with hot air for 6 hours, a coextrusion pipe was created using a spiral flow type 3 type 5 layer coextrusion pipe forming machine. The structure of the pipe is that the outermost layer and the innermost layer are polyester (PET-G9921 made by Eastman Chemical) 2000μ, and the EVOH middle layer is 200μ and adhesive resin (Mersen-M5420 made by Toyo Soda) is used.
It is through 200μ. The obtained pipe was formed into a parison for biaxial stretch blow molding at both ends, then put into a biaxial stretch blow molding machine, preheated at 105℃, and then biaxially stretched and blown to produce a good bottle with no cracks or slight thickness deviation. Obtained. Just before thermoforming
The volatile content of the EVOH layer was 0.25%. of this container
The oxygen permeation rate of the EVOH layer is 1.1cc・20μ/m 2・24hr・
atm (20℃, 65%RH), 21c.c.・20μ/m 2・24hr・
atm (20°C, 100% RH) and showed good barrier properties.
比較例 ６
実施例４において中間層にＮ−エチルトルエン
スルホン酸アミドおよび水無添加のEVOH
（EVAL
EP−H101）を用いた以外は実施例４
と同様に行なつた。その結果二軸延伸ブロー容器
は底部及び口金付近（肩部）に微少偏肉を生じ外
観が不良であつた。Comparative Example 6 In Example 4, N-ethyltoluenesulfonic acid amide and water-free EVOH were used in the intermediate layer.
Example 4 except that (EVAL EP-H101) was used
I did the same thing. As a result, the biaxially stretched blow container had a poor appearance due to slight unevenness in thickness at the bottom and near the mouthpiece (shoulder).
実施例 ５
実施例１において最外層のポリプロピレン及び
接着材層をナイロン６、66共重合体｛三菱化成
（ノバミド）Novamid2030｝各500μに変更して得
られたシートを80℃−20分間温水中に浸漬した後
二軸延伸試験機（東洋精機製）にて110℃３×３
倍同時二軸延伸を行なつた所、均質な多層二軸延
伸フイルムが得られた。この時熱成形直前の
EVOH層の揮発分は2.3％であつた。Example 5 In Example 1, the outermost polypropylene layer and the adhesive layer were changed to nylon 6,66 copolymer {Mitsubishi Kasei (Novamid) Novamid 2030} each with a thickness of 500μ, and the resulting sheet was placed in hot water at 80°C for 20 minutes. After immersion, 110℃ 3×3 with a biaxial stretching tester (manufactured by Toyo Seiki)
When simultaneous biaxial stretching was carried out, a homogeneous multilayer biaxially stretched film was obtained. At this time, just before thermoforming
The volatile content of the EVOH layer was 2.3%.
比較例 ７
実施例５において中間層に無添加EVOH
（EVAL
EP−F101）を用いた以外は実施例４
と同様に行なつた。その結果得られたフイルムは
局所的のびムラが発生し、外見上不良であつた。Comparative Example 7 No additive EVOH in the intermediate layer in Example 5
Example 4 except that (EVAL EP-F101) was used
I did the same thing. The resulting film had localized unevenness and had a poor appearance.
実施例 ６
エチレン含有量44モル％、けん化度99.4％、メ
ルトインデツクス5.6ｇ／10分のEVOH（EVAL
−EP−E105）100重量部に対してステアリン酸
アミド３重量部を配合してなる混合物を二軸スク
リユーベント式40φ押出機にて220℃で押出ペレ
ツト化を実施した。得られたペレツトを105℃−
16時間熱風乾燥後、Ｔダイ付40φ押出機にて100μ
の単層フイルムを得た。このフイルムを二軸延伸
試験機（東洋精機製）にて逐次二軸延伸を行なつ
た所、良好な延伸フイルムが得られた。延伸温度
は80℃、延伸直前のフイルムの揮発分は0.25％で
あつた。Example 6 EVOH (EVAL
-EP-E105) A mixture prepared by blending 3 parts by weight of stearic acid amide with 100 parts by weight was extruded into pellets at 220°C using a twin-screw vent type 40φ extruder. The obtained pellets were heated to 105℃−
After drying with hot air for 16 hours, use a 40φ extruder with a T-die to reduce the size to 100μ.
A single layer film was obtained. When this film was sequentially biaxially stretched using a biaxial stretching tester (manufactured by Toyo Seiki), a good stretched film was obtained. The stretching temperature was 80°C, and the volatile content of the film immediately before stretching was 0.25%.
比較例 ８
実施例６において添加剤を含まないEVOH
（EVAL
−EP−E105）を用いた以外実施例６
と同様に行なつた。その結果逐次二軸延伸時フイ
ルムが破れ、正常なものは得られなかつた。延伸
温度は80℃、延伸直前のフイルム揮発分は0.32％
であつた。Comparative Example 8 EVOH without additive in Example 6
Example 6 except for using (EVAL-EP-E105)
I did the same thing. As a result, the film was torn during sequential biaxial stretching, and a normal film could not be obtained. The stretching temperature is 80℃, and the volatile content of the film just before stretching is 0.32%.
It was hot.
実施例 ７
実施例６のステアリン酸アミド含有EVOHペ
レツトを用いて得た200μフイルムを塩化ビニー
ル1000μミートにドライラミネートした。接着剤
は東洋モートン製AT−335A（ポリエステル系接
着剤）を用いた。次に該シートを120℃で真空圧
空深絞り成形機により熱成形し、絞り比１の容器
を作つた所、クラツクの無い良好な成形物が得ら
れた。熱成形直前のEVOH層の揮発分は0.5％で
あつた。Example 7 A 200μ film obtained using the stearamide-containing EVOH pellets of Example 6 was dry laminated onto 1000μ vinyl chloride meat. The adhesive used was AT-335A (polyester adhesive) manufactured by Toyo Morton. Next, the sheet was thermoformed at 120° C. using a vacuum-pressure deep drawing machine to produce a container with a drawing ratio of 1, and a good molded product without cracks was obtained. The volatile content of the EVOH layer immediately before thermoforming was 0.5%.
Claims (1)
以上のエチレン−ビニルアルコール共重合体100
重量部に長鎖脂肪族または芳香族アミド0.5〜５
重量部を配合したエチレン−ビニルアルコール共
重合体成形物を加熱延伸するに際し、該成形物中
の水分含有率を0.1〜５重量％に調節することを
特徴とするエチレン−ビニルアルコール共重合体
成形物の製法。 ２ 長鎖脂肪族アミドが炭素数10〜20のモノまた
はジカルボン酸アミドである特許請求の範囲第１
項記載の成形物の製法。 ３ 芳香族系アミドが芳香族カルボン酸アミドで
ある特許請求の範囲第１項記載の成形物の製法。 ４ 芳香族系アミドが芳香族スルホン酸アミドで
ある特許請求の範囲第１項記載の成形物の製法。[Claims] 1. Ethylene content 20 to 60 mol%, saponification degree 90%
More than 100 ethylene-vinyl alcohol copolymers
0.5-5 parts by weight of long-chain aliphatic or aromatic amide
A molded ethylene-vinyl alcohol copolymer, characterized in that when heating and stretching an ethylene-vinyl alcohol copolymer molded product containing parts by weight, the water content in the molded product is adjusted to 0.1 to 5% by weight. How things are made. 2. Claim 1, wherein the long-chain aliphatic amide is a mono- or dicarboxylic acid amide having 10 to 20 carbon atoms.
Method for manufacturing the molded product described in Section 1. 3. The method for producing a molded article according to claim 1, wherein the aromatic amide is an aromatic carboxylic acid amide. 4. The method for producing a molded article according to claim 1, wherein the aromatic amide is an aromatic sulfonic acid amide.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12656885A JPS625832A (en) | 1985-06-10 | 1985-06-10 | Manufacture of molded product of ethylene-vinyl alcohol and multi-layer structure |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12656885A JPS625832A (en) | 1985-06-10 | 1985-06-10 | Manufacture of molded product of ethylene-vinyl alcohol and multi-layer structure |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS625832A JPS625832A (en) | 1987-01-12 |
| JPH0550375B2 true JPH0550375B2 (en) | 1993-07-28 |
Family
ID=14938382
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP12656885A Granted JPS625832A (en) | 1985-06-10 | 1985-06-10 | Manufacture of molded product of ethylene-vinyl alcohol and multi-layer structure |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS625832A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP7121165B1 (en) * | 2021-06-11 | 2022-08-17 | 住友化学株式会社 | Positive electrode active material for lithium secondary battery, positive electrode for lithium secondary battery and lithium secondary battery |
-
1985
- 1985-06-10 JP JP12656885A patent/JPS625832A/en active Granted
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP7121165B1 (en) * | 2021-06-11 | 2022-08-17 | 住友化学株式会社 | Positive electrode active material for lithium secondary battery, positive electrode for lithium secondary battery and lithium secondary battery |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS625832A (en) | 1987-01-12 |
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