JPH0225325B2 - - Google Patents
Info
- Publication number
- JPH0225325B2 JPH0225325B2 JP57041855A JP4185582A JPH0225325B2 JP H0225325 B2 JPH0225325 B2 JP H0225325B2 JP 57041855 A JP57041855 A JP 57041855A JP 4185582 A JP4185582 A JP 4185582A JP H0225325 B2 JPH0225325 B2 JP H0225325B2
- Authority
- JP
- Japan
- Prior art keywords
- nylon
- film
- polyamide
- biaxially stretched
- dimensional stability
- 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 - Lifetime
Links
- 229920002647 polyamide Polymers 0.000 claims description 20
- 239000004952 Polyamide Substances 0.000 claims description 19
- 229920002302 Nylon 6,6 Polymers 0.000 claims description 16
- 229920002292 Nylon 6 Polymers 0.000 claims description 15
- 238000010438 heat treatment Methods 0.000 claims description 13
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 3
- 238000000034 method Methods 0.000 description 10
- 238000002844 melting Methods 0.000 description 8
- 230000008018 melting Effects 0.000 description 8
- 239000002994 raw material Substances 0.000 description 4
- 230000001954 sterilising effect Effects 0.000 description 4
- 238000004659 sterilization and disinfection Methods 0.000 description 4
- 239000002131 composite material Substances 0.000 description 3
- 239000005003 food packaging material Substances 0.000 description 3
- 239000005022 packaging material Substances 0.000 description 3
- 239000003963 antioxidant agent Substances 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 238000004806 packaging method and process Methods 0.000 description 2
- 229920006122 polyamide resin Polymers 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 239000004677 Nylon Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229920006280 packaging film Polymers 0.000 description 1
- 239000012785 packaging film Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000012748 slip agent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/001—Combinations of extrusion moulding with other shaping operations
- B29C48/0018—Combinations of extrusion moulding with other shaping operations combined with shaping by orienting, stretching or shrinking, e.g. film blowing
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/001—Combinations of extrusion moulding with other shaping operations
- B29C48/0019—Combinations of extrusion moulding with other shaping operations combined with shaping by flattening, folding or bending
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
- B29C48/09—Articles with cross-sections having partially or fully enclosed cavities, e.g. pipes or channels
- B29C48/10—Articles with cross-sections having partially or fully enclosed cavities, e.g. pipes or channels flexible, e.g. blown foils
Landscapes
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Shaping By String And By Release Of Stress In Plastics And The Like (AREA)
Description
本発明は、機械的性質と寸法安定性の優れたポ
リアミド２軸延伸フイルムの製造方法に関するも
のである。
ポリアミド２軸延伸フイルムは優れた機械的、
化学的および光学的性質を備え、包装材料として
要求される多くの性能を満足するものであるた
め、特に食品包装分野において広く使用されてい
る。これはポリアミドの分子構造等に基づく本来
の素性の良さが２軸延伸という操作によつてさら
に開発されたという相乗効果に由来するものであ
ると考えられる。
しかしながら、ポリアミド２軸延伸フイルムの
諸性能のうち、寸法安定性、特に熱水中の寸法安
定性はその親水基を有する分子構造が逆に障害と
なるためか、改良が困難であつた。
すなわち、ポリアミド２軸延伸フイルムは高温
雰囲気中、特に高温の水中又は蒸気中において収
縮する傾向を示し、これはボイル殺菌、レトルト
殺菌用包装材料としては欠点となる。
寸法安定性を改良するための最も一般的な方法
は、２軸延伸後のフイルムを熱風あるいは熱ロー
ル等の加熱手段により高温熱処理することであ
り、この場合、寸法安定性を改良するためにはで
きるだけ高い温度が必要となる。しかしながら、
熱処理温度がポリアミドの融点に近づくとフイル
ムが溶断したり、またテンシヨン等の応力がフイ
ルムに作用している場合は、その僅かな力によつ
てフイルムが切断したりする。
したがつて、ポリアミドとしてはできるだけ融
点の高いものほど熱処理温度を高くすることが一
般的には可能であり、その結果、高温下の寸法安
定性を改良することができることになる。
ボイル殺菌、レトルト殺菌用食品包装材はその
目的とするところから、寸法安定性以外に破袋、
ピンホール等に対する抵抗力の優れたものである
必要がある。
本発明者等はこの目的に対して、ナイロン66が
最も優れた素材であることを知つた。ナイロン66
は脂肪性ポリアミドの中では大量生産型のポリマ
ーであるため、食品包装材料として最初に要求さ
れる経済性を備え、融点が高いため耐熱性に優
れ、その分子構造的性格から特にその２軸延伸フ
イルムは食品包装材料に要求される各種の実用強
度、抵抗力を本来的に有するからである。
しかしながら、ナイロン66はナイロン６にくら
べて結晶性が強いため２軸延伸が難しい。特に一
般的な逐次２段延伸法では最初の一方向延伸時に
結晶化度が高くなり、次の他方向延伸が難しくな
るという問題がある。また、ナイロン66は高温下
では酸化されやすく、２軸延伸後のフイルムを高
温度で熱処理すると酸化がすすみ強度が低下す
る。特開昭56−4632号公報にはナイロン66、２軸
延伸フイルムの熱処理時の劣化を防止し、寸法安
定性と強度の優れたフイルムを製造するために、
不活性ガス中で熱処理する方法が記載されてい
る。しかしながら、この方法では高価な不活性ガ
スを熱処理機中に閉じ込め、しかもその濃度をコ
ントロールするための設備と運転条件の管理が複
雑となり、必ずしも工業的に有利な方法とはいえ
ない。
本発明者等は、寸法安定性と包装材として要求
される機械的性質の優れたポリアミド２軸延伸フ
イルムを製造する方法について鋭意研究した結
果、本発明に到達した。
すなわち、本発明者等はポリアミド樹脂の中で
は繊維、成形品等の用途範囲が広くて生産量が多
く、したがつて安価なポリマーであるナイロン66
とナイロン６の混合物を原料とし、その混合比を
６：４〜９：１の範囲とし、しかもこの混合比率
では未だ結晶性の高いフイルムに適した同時２軸
延伸法を採用して２軸延伸し、２軸延伸後のフイ
ルムをナイロン66の融点（250〜260℃）以下で、
かつナイロン６の融点（210〜225℃）以上の温度
範囲から選ばれた230〜245℃の温度で短時間熱処
理をすることを特徴とする製造方法である。
本発明によりポリアミド２軸延伸フイルムの寸
法安定性が改良されるメカニズムは定かではない
が想像すれば次のようになる。すなわち、２軸延
伸により混合ポリアミド中の各成分ポリアミドは
同じように２軸配向されるが、熱処理工程で融点
以上の熱履歴を受けるポリアミド成分には再溶融
もしくはそれに近い変化が生じ、最初の配向状態
は消失もしくは緩和し、その結果、熱処理後のフ
イルムは配向状態が熱固定された高融点ポリアミ
ド組織中に無配向のポリアミドが、マトリツクス
を形成した複合構造物となる。無配向のポリアミ
ド組織は熱収縮挙動または吸湿による収縮挙動を
示さないから、上記複合構造物中では寸法変化に
対する抵抗体または緩衝体となり、その結果、複
合構造物全体としての寸法安定性が改良される。
第１表はナイロン66とナイロン６の混合物よりな
る２軸延伸フイルムの引張強伸度と130℃（2.8
Kg／mm2）飽和水蒸気中に30分放置したときの収縮
率を示したものである。なお、延伸は縦横それぞ
れ３倍に同時２軸延伸し、熱処理はRUN11以外
は235℃、RUN11は210℃で行つた。また、強伸
度および収縮率は縦および横方向の平均値で示し
た。
The present invention relates to a method for producing a biaxially stretched polyamide film having excellent mechanical properties and dimensional stability. Polyamide biaxially oriented film has excellent mechanical properties,
It is widely used, especially in the food packaging field, because it has chemical and optical properties and satisfies many of the performances required of packaging materials. This is thought to be due to the synergistic effect that the inherent good properties of polyamide based on its molecular structure etc. were further developed by the operation of biaxial stretching. However, among the various properties of polyamide biaxially stretched films, it has been difficult to improve the dimensional stability, especially the dimensional stability in hot water, probably because the molecular structure having hydrophilic groups becomes an obstacle. That is, polyamide biaxially stretched films tend to shrink in high-temperature atmospheres, particularly in high-temperature water or steam, which is a drawback when used as packaging materials for boil sterilization and retort sterilization. The most common method for improving dimensional stability is to subject the biaxially stretched film to high-temperature heat treatment using heating means such as hot air or hot rolls. A temperature as high as possible is required. however,
When the heat treatment temperature approaches the melting point of polyamide, the film may melt or break, and when stress such as tension is acting on the film, the slight force may cause the film to break. Therefore, it is generally possible to increase the heat treatment temperature for a polyamide having a melting point as high as possible, and as a result, the dimensional stability at high temperatures can be improved. Due to the purpose of food packaging materials for boil sterilization and retort sterilization, in addition to dimensional stability, bag breakage and
It must have excellent resistance to pinholes, etc. The inventors have found that nylon 66 is the best material for this purpose. nylon 66
Since it is a mass-produced polymer among fatty polyamides, it has the economic efficiency required first as a food packaging material, has excellent heat resistance due to its high melting point, and is especially suitable for biaxial stretching due to its molecular structure. This is because films inherently have various practical strengths and resistances required for food packaging materials. However, since nylon 66 has stronger crystallinity than nylon 6, biaxial stretching is difficult. In particular, the common two-step sequential stretching method has a problem in that the degree of crystallinity increases during the first stretching in one direction, making subsequent stretching in the other direction difficult. Furthermore, nylon 66 is easily oxidized at high temperatures, and when a biaxially stretched film is heat treated at high temperatures, oxidation progresses and the strength decreases. JP-A No. 56-4632 discloses that in order to prevent deterioration during heat treatment of nylon 66, biaxially stretched film, and to produce a film with excellent dimensional stability and strength,
A method of heat treatment in an inert gas is described. However, in this method, expensive inert gas is confined in the heat treatment machine, and the management of equipment and operating conditions for controlling its concentration is complicated, so it is not necessarily an industrially advantageous method. The present inventors have arrived at the present invention as a result of intensive research into a method for manufacturing a polyamide biaxially stretched film that has excellent dimensional stability and mechanical properties required as a packaging material. In other words, the present inventors selected nylon 66, which is a polyamide resin that has a wide range of uses such as fibers and molded products, is produced in large quantities, and is therefore inexpensive.
A mixture of Nylon 6 and Nylon 6 is used as a raw material, and the mixing ratio is in the range of 6:4 to 9:1.Moreover, at this mixing ratio, a simultaneous biaxial stretching method is used, which is suitable for films that are still highly crystalline. Then, the film after biaxial stretching is heated below the melting point of nylon 66 (250-260℃),
This manufacturing method is characterized by carrying out heat treatment for a short time at a temperature of 230 to 245°C, which is selected from a temperature range equal to or higher than the melting point of nylon 6 (210 to 225°C). The mechanism by which the dimensional stability of polyamide biaxially stretched films is improved by the present invention is not clear, but it can be imagined as follows. That is, by biaxial stretching, each polyamide component in the mixed polyamide is biaxially oriented in the same way, but the polyamide components that undergo a heat history above the melting point in the heat treatment process undergo remelting or a change close to it, and the initial orientation The state disappears or relaxes, and as a result, the film after heat treatment becomes a composite structure in which non-oriented polyamide forms a matrix in a high-melting-point polyamide structure whose oriented state is heat-fixed. Since the non-oriented polyamide structure does not show thermal shrinkage behavior or shrinkage behavior due to moisture absorption, it becomes a resistor or buffer against dimensional changes in the composite structure, and as a result, the dimensional stability of the composite structure as a whole is improved. Ru.
Table 1 shows the tensile strength and elongation of a biaxially stretched film made of a mixture of nylon 66 and nylon 6 at 130°C (2.8
Kg/mm 2 ) This shows the shrinkage rate when left in saturated steam for 30 minutes. Note that the stretching was simultaneous biaxial stretching 3 times in the length and width, and the heat treatment was performed at 235°C for all but RUN11, and at 210°C for RUN11. In addition, the strength and elongation and shrinkage percentage were shown as average values in the longitudinal and transverse directions.
【表】
ナイロン66とナイロン６の混合比が６：４〜
９：１の範囲で強度、伸度、収縮率のバランスの
優れたフイルムが得られる。
本発明の基本的効果はナイロン66とナイロン６
を混合して２軸延伸フイルムとなし、ナイロン66
の融点以下、ナイロン６の融点以上の温度で加工
することにより生じる。また、ナイロン66、ナイ
ロン６ともポリアミド樹脂のなかでは品質バラン
ス、加工性ともに優れた大量生産型の汎用樹脂で
あるため、本発明方法により価値の高い包装用フ
イルムが経済的に生産される。ただし、ナイロン
66とナイロン６以外に少量の添加剤、たとえば滑
剤、帯電防止剤、酸化防止剤等を加えてフイルム
の品質をさらに改良することも可能である。
混合原料は原料チツプをドライブレンドした
後、成形用の単軸押出機に供給する方法が簡単で
あり、ナイロン66とナイロン６は相溶性が良いた
め特に複雑な混練工程は不要である。
本発明はポリアミド２軸延伸フイルムの寸法安
定性を改良するために従来においてしばしば採用
されていた極限的な熱処理を不要のものとする。
その結果、ポリアミド２軸延伸フイルムの本来有
する優れた機械的性質、すなわち引張強度、屈曲
強度、ピンホール強度を低下させることなく、寸
法安定性にも優れたフイルムを製造することが可
能となり、その工業的価値は大きい。
以下、実施例を挙げてさらに詳細に説明する。
実施例
相対粘度3.8のナイロン66 100重量部と相対粘
度3.0のナイロン６ 25重量部よりなる混合ポリ
アミドに酸化防止剤およびスリツプ剤を少量添加
したものを原料として90mm押出機と400mm巾のＴ
ダイとにより、厚み150μの未延伸フイルムを製
膜した。次にこのフイルムをテンター式同時２軸
延伸装置に繰込み、縦横それぞれ３倍に同時２軸
延伸した後、温度235℃で５秒間熱処理した。得
られた２軸延伸フイルムの性能を評価したところ
第２表の結果が得られた。[Table] Mixing ratio of nylon 66 and nylon 6 is 6:4 ~
A film with an excellent balance of strength, elongation, and shrinkage ratio can be obtained in the range of 9:1. The basic effect of the present invention is that nylon 66 and nylon 6
Mixed with biaxially stretched film, nylon 66
It is produced by processing at a temperature below the melting point of nylon 6 and above the melting point of nylon 6. Furthermore, since both nylon 66 and nylon 6 are mass-produced general-purpose resins that are excellent in both quality balance and processability among polyamide resins, high-value packaging films can be economically produced by the method of the present invention. However, nylon
In addition to 66 and nylon 6, it is also possible to add small amounts of additives such as lubricants, antistatic agents, antioxidants, etc. to further improve the quality of the film. The mixed raw material can be simply supplied to a single-screw extruder for molding after dry blending the raw material chips, and since nylon 66 and nylon 6 have good compatibility, a particularly complicated kneading process is not necessary. The present invention obviates the need for the extreme heat treatments often employed in the past to improve the dimensional stability of polyamide biaxially oriented films.
As a result, it has become possible to produce a film with excellent dimensional stability without reducing the inherently excellent mechanical properties of polyamide biaxially stretched film, namely tensile strength, bending strength, and pinhole strength. It has great industrial value. Hereinafter, the present invention will be explained in more detail by giving Examples. Example A mixed polyamide consisting of 100 parts by weight of nylon 66 with a relative viscosity of 3.8 and 25 parts by weight of nylon 6 with a relative viscosity of 3.0, to which a small amount of an antioxidant and a slip agent were added, was used as a raw material, and a 90 mm extruder and a T of 400 mm width were used.
An unstretched film with a thickness of 150 μm was formed using a die. Next, this film was loaded into a tenter-type simultaneous biaxial stretching device, and after being simultaneously biaxially stretched three times in the length and width directions, it was heat-treated at a temperature of 235° C. for 5 seconds. When the performance of the obtained biaxially stretched film was evaluated, the results shown in Table 2 were obtained.
【表】
このフイルムは強度と寸法安定性に優れ、レト
ルト食品包装用基材フイルムとして適したもので
あつた。[Table] This film had excellent strength and dimensional stability, and was suitable as a base film for retort food packaging.
Claims (1)
りなる２軸延伸フイルムを製造する方法におい
て、ナイロン66とナイロン６の混合比を６：４〜
９：１の範囲として未延伸フイルムを製膜した
後、該フイルムを同時２軸延伸し、その後230〜
245℃の温度で短時間熱処理することを特徴とす
るポリアミド２軸延伸フイルムの製造方法。1. In a method for producing a biaxially stretched film consisting essentially of a mixture of nylon 66 and nylon 6, the mixing ratio of nylon 66 and nylon 6 is 6:4 to 6:4.
After forming an unstretched film in the range of 9:1, the film is simultaneously biaxially stretched, and then
A method for producing a biaxially stretched polyamide film, characterized by heat treatment at a temperature of 245°C for a short time.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP57041855A JPS58158224A (en) | 1982-03-16 | 1982-03-16 | Manufacture of biaxially oriented polyamide film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP57041855A JPS58158224A (en) | 1982-03-16 | 1982-03-16 | Manufacture of biaxially oriented polyamide film |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS58158224A JPS58158224A (en) | 1983-09-20 |
| JPH0225325B2 true JPH0225325B2 (en) | 1990-06-01 |
Family
ID=12619861
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP57041855A Granted JPS58158224A (en) | 1982-03-16 | 1982-03-16 | Manufacture of biaxially oriented polyamide film |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS58158224A (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0613641B2 (en) * | 1985-02-15 | 1994-02-23 | 旭化成工業株式会社 | Glass fiber reinforced polyamide resin composition |
| JPH0712649B2 (en) * | 1988-04-19 | 1995-02-15 | 三菱化学株式会社 | Transparent plastic film with excellent gas barrier properties |
| DE69231163T2 (en) * | 1991-10-28 | 2000-11-16 | Idemitsu Petrochemical Co | Oriented separable film and process for its manufacture |
| BE1010777A4 (en) * | 1996-12-02 | 1999-01-05 | Dsm Nv | Process for the production of polyamide shape bodies with improved crystallization behavior. |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5168660A (en) * | 1974-12-12 | 1976-06-14 | Toray Industries | Horiamido fuirumu |
-
1982
- 1982-03-16 JP JP57041855A patent/JPS58158224A/en active Granted
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5168660A (en) * | 1974-12-12 | 1976-06-14 | Toray Industries | Horiamido fuirumu |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS58158224A (en) | 1983-09-20 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JPS6147234A (en) | Manufacturing method of heat shrinkable polypropylene film | |
| US4167620A (en) | Method for heat treating shaped articles of amide-imide or amic acid polymers | |
| US5143983A (en) | Heat resistant polyamide film | |
| JPH0225325B2 (en) | ||
| JPS61295036A (en) | Heat-shrinkable laminated film | |
| EP0158807B1 (en) | Polyamide film and process for its production | |
| JPS6161967B2 (en) | ||
| JPS6445439A (en) | Polyarylenethioetherketone based stretched film and production thereof | |
| JPH0222032A (en) | Biaxially oriented polyamide film | |
| JPS59184620A (en) | Thermocontracting molded article | |
| JPH10175255A (en) | Manufacture of biaxially oriented polyamide film | |
| JPH10329211A (en) | Manufacture of biaxially oriented polyamide film | |
| DE2160118A1 (en) | Process for the production of biaxially oriented polyamide film | |
| JPS6166617A (en) | Manufacture of polyamide molded shape | |
| EP0315238B1 (en) | Bi-oriented films of ethylene/alfa -olephin copolymers | |
| JPS5852821B2 (en) | Nylon stretched film and its manufacturing method | |
| JPS6237051B2 (en) | ||
| JP4252419B2 (en) | Gas barrier shrink film and method for producing the same | |
| JPH02297421A (en) | Biaxially-oriented polyester film | |
| KR0134560B1 (en) | Preparation process of polyamide film | |
| JPH02189338A (en) | Oriented nylon 66 film and its production | |
| KR100962078B1 (en) | Biaxial polyamid film for retort foodstuffs packing and the manufacturing method | |
| JP4434433B2 (en) | Barrier shrink film | |
| KR19990042595A (en) | Polyamide Resin Composition for Film | |
| JPH02106319A (en) | Biaxially oriented polyamide film |