JP2002361667A - Method for manufacturing laminate rubber plug - Google Patents
Method for manufacturing laminate rubber plugInfo
- Publication number
- JP2002361667A JP2002361667A JP2001171194A JP2001171194A JP2002361667A JP 2002361667 A JP2002361667 A JP 2002361667A JP 2001171194 A JP2001171194 A JP 2001171194A JP 2001171194 A JP2001171194 A JP 2001171194A JP 2002361667 A JP2002361667 A JP 2002361667A
- Authority
- JP
- Japan
- Prior art keywords
- film
- treatment
- plasma
- plug
- ethylene
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Landscapes
- Treatments Of Macromolecular Shaped Articles (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Closures For Containers (AREA)
- Casting Or Compression Moulding Of Plastics Or The Like (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、薬剤容器の口部を
密封するためのラミネートゴム栓に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a laminated rubber stopper for sealing the mouth of a medicine container.
【０００２】[0002]
【従来の技術】フッ素樹脂は、一般に、極めて不活性で
あると共に、非常に優れた耐薬品性を有していることか
ら、従来、薬剤容器の口部を密封するゴム栓として、こ
れをラミネートしたゴム栓が多用されている。しかしな
がら、フッ素樹脂は、極めて不活性であるため、ゴムと
の接着性および相溶性が悪く、フッ素樹脂ラミネートゴ
ム栓を製造するために、従来、フッ素樹脂フィルムを予
め接着処理してからゴム栓と接着している（特公昭５２
−１３５５号公報、特公昭５７−５３１８４号公報、特
開昭５９−５０４６号公報など）。2. Description of the Related Art Fluororesins are generally very inert and have very good chemical resistance. Therefore, conventionally, a fluororesin is used as a rubber stopper for sealing the mouth of a drug container. Rubber stoppers are frequently used. However, since fluororesin is extremely inert, it has poor adhesion and compatibility with rubber.To produce a fluororesin laminate rubber stopper, conventionally, a fluororesin film was previously subjected to an adhesive treatment and then a rubber stopper. Adhered (Japanese Patent Publication Sho 52
JP-A-1355, JP-B-57-53184, JP-A-59-5046 and the like.
【０００３】特公昭５２−１３５５号公報には、フィル
ムの片面をナトリウムナフタレンで接着処理して栓形状
に成形し、これを未加硫ゴムと相対させ、金型内で加圧
加熱して栓の形状に成形する方法が記載されており、特
公昭５７−５３１８４号公報には、フィルムシートと未
加硫ゴムシートを金型内で積相し、加圧加熱して栓の形
状に成形する方法が記載されている。また、特開昭５９
−５０４６号公報には、フィルムの表面を予めコロナ放
電、グロー放電、アーク放電等により処理して、表面に
架橋被膜を形成し、これを処理面が未加硫ゴムシートと
相対するように積相し、金型内で加圧加熱して栓の形状
に成形する方法が記載されている。[0003] Japanese Patent Publication No. 52-1355 discloses that one side of a film is treated with sodium naphthalene to form a plug, which is made to face unvulcanized rubber, and heated under pressure in a mold to form a plug. And Japanese Patent Publication No. 57-53184 discloses a method in which a film sheet and an unvulcanized rubber sheet are stacked in a mold, heated under pressure and formed into a plug shape. A method is described. Also, Japanese Unexamined Patent Publication No.
In Japanese Patent No. -5046, the surface of a film is previously treated by corona discharge, glow discharge, arc discharge, etc. to form a crosslinked film on the surface, and the film is laminated so that the treated surface faces the unvulcanized rubber sheet. In addition, there is described a method of forming a stopper by pressurizing and heating in a mold.
【０００４】しかしながら、上記特公昭５２−１３５５
号公報の方法は、金属ナトリウムを使用することから、
製造が煩雑である。また、特公昭５７−５３１８４号公
報の方法も特開昭５９−５０４６号公報の方法も、積層
シートをゴム栓の形状に成形する際に、フッ素樹脂フィ
ルムが延伸されるので、フィルムとゴムとの接着性が良
くない。そこで、上記のような欠点を解決するものとし
て、特公平５−２７５３６号公報の方法が提案されてい
る。この方法は、フィルムの片面に放電処理量0.1〜20
Ｗ・秒／cm2の条件下でスパッタエッチング処理を施
し、処理面を未加硫ゴムシートと積層して金型内で加圧
加熱し、栓の形状に成形することを特徴とするものであ
る。[0004] However, the above-mentioned Japanese Patent Publication No. 52-1355.
The method disclosed in Japanese Patent Publication No.
The production is complicated. Also, in both the method of JP-B-57-53184 and the method of JP-A-59-5046, the fluororesin film is stretched when the laminated sheet is formed into the shape of a rubber stopper. Has poor adhesion. In order to solve the above-mentioned disadvantages, a method disclosed in Japanese Patent Publication No. Hei 5-27536 has been proposed. This method uses a discharge treatment amount of 0.1 to 20 on one side of the film.
The sputter etching process is performed under the condition of W · sec / cm 2 , the treated surface is laminated with an unvulcanized rubber sheet, and heated under pressure in a mold to form a plug. is there.
【０００５】しかしながら、この特公平５−２７５３６
号公報の方法は、スパッタエッチング処理が、耐圧容器
内で、常温域で１０−３〜１０−１Ｔｏｒｒという減圧
雰囲気下において行われるため、処理作業が煩雑であ
る。また、短時間で処理を行う場合に何らかの理由で放
電処理量が上限を超える虞があるが、この場合フィルム
が変形する虞がある。[0005] However, Japanese Patent Publication No.
In the method disclosed in Japanese Patent Application Laid - Open No. H11-284, the sputter etching process is performed in a pressure-resistant container in a normal temperature range under a reduced pressure atmosphere of 10 −3 to 10 −1 Torr, so that the processing operation is complicated. In addition, when processing is performed in a short time, the discharge processing amount may exceed the upper limit for some reason. In this case, the film may be deformed.
【０００６】[0006]
【発明が解決しようとする課題】本発明は、如上の事情
に鑑みてなされたもので、接着処理によりフィルムが変
形する虞が無く、処理作業が容易なラミネートゴム栓の
製造方法を提供することを目的とする。SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and provides a method of manufacturing a laminated rubber plug which does not have a risk of deformation of a film due to an adhesion process and which can be easily processed. With the goal.
【０００７】[0007]
【課題を解決するための手段】本発明者は上記課題を解
決するために、鋭意検討の結果、大気圧で大気中の空気
をプラズマヘッド内で放電させて、そのプラズマを対象
物に照射する（以下、空気プラズマ処理という）こと
で、対象物の表面の濡れ性を高めることが出来ることに
着目するに至り、本発明を完成した。すなわち本発明
は、変性タイプのエチレン−テトラフルオロエチレン共
重合体で形成されたフィルムの片面を、１ＫＷ・秒／ｃ
ｍ２以上の放電処理量で空気プラズマ処理した後、該フ
ィルムを処理面が未加硫ゴムシートと相対するように積
層し、金型内で加圧加熱して栓の形状に成形することを
特徴とするラミネートゴム栓の製造方法に関する。ここ
で、変性タイプのエチレン−テトラフルオロエチレン共
重合体は、エチレンとテトラフルオロエチレンとこれら
と共重合可能な含フッ素ビニルモノマーとを三元共重合
させてなるものが好ましい。Means for Solving the Problems In order to solve the above problems, the present inventors have made intensive studies and as a result, discharge air in the atmosphere at atmospheric pressure in a plasma head and irradiate the object with the plasma. (Hereinafter, referred to as air plasma treatment), it has been noted that the wettability of the surface of the object can be enhanced, and the present invention has been completed. That is, the present invention relates to a method in which one side of a film formed of a modified type ethylene-tetrafluoroethylene copolymer is treated at 1 KW · sec / c.
After air plasma treated with m 2 or more discharge processing amount, that the process surface the film is laminated so as to face the unvulcanized rubber sheet, by heating in the mold pressurized and molded into the shape of the plug The present invention relates to a method for producing a laminated rubber stopper. Here, the modified type ethylene-tetrafluoroethylene copolymer is preferably one obtained by terpolymerizing ethylene, tetrafluoroethylene and a fluorine-containing vinyl monomer copolymerizable therewith.
【０００８】本発明においては、変性タイプのエチレン
−テトラフルオロエチレン共重合体製のフィルムに接着
性を付与するために、その表面に空気プラズマ処理を施
している。空気プラズマ処理は、大気圧で大気中の空気
をプラズマヘッド内で放電させて、そのプラズマを対象
物に照射する表面処理方法であり、表面の濡れ性をたか
めることができる。この方法は、アルゴンやヘリウムな
どのガスを使わずに空気から安定してプラズマを発生さ
せることができるので、低ランニングコスト化が実現で
きるという利点を有している。空気プラズマ処理では、
対象物が樹脂の場合、対象物表面に付着している汚れ
（有機物）にプラズマ粒子が結合して、表面を洗浄する
という効果（洗浄効果）と、プラズマ粒子により対象物
表面の分子結合に変化が生じ、液体となじみやすい親水
基ができて接着性が良くなるという効果（活性効果）が
起こる。In the present invention, the surface of the modified type ethylene-tetrafluoroethylene copolymer film is subjected to air plasma treatment in order to impart adhesiveness. The air plasma treatment is a surface treatment method in which air in the atmosphere is discharged at atmospheric pressure in a plasma head and the object is irradiated with the plasma, and the wettability of the surface can be enhanced. This method has an advantage that a low running cost can be realized because plasma can be stably generated from air without using a gas such as argon or helium. In air plasma treatment,
When the object is a resin, the plasma particles combine with the dirt (organic matter) attached to the surface of the object and clean the surface (cleaning effect), and the plasma particles change into molecular bonds on the surface of the object. Is generated, and an effect (active effect) that a hydrophilic group that is easily compatible with the liquid is formed and the adhesiveness is improved occurs.
【０００９】本発明における空気プラズマ処理は、放電
処理量１ＫＷ・秒／ｃｍ２以上で行われる。放電処理量
が１ＫＷ・秒／ｃｍ２より小さいと十分な接着性が得ら
れない。空気プラズマ処理では対処物の表面活性が高く
なるが、表面を変形するものではない。従って、放電処
理量は１ＫＷ・秒／ｃｍ２以上であればいくらであって
もよいが、通常、プラズマ放射器の放電処理量は、コス
トおよび効率を考慮して１〜１．１１ＫＷ・秒／ｃｍ２
に制御される。空気プラズマ処理は、大気圧で大気中の
空気をプラズマヘッド内で放電させる処理方法なので、
スパッタエッチング処理における減圧室のような特別の
照射室を必要としない。従って、空気プラズマ処理で
は、連続的な処理が可能であり、また、減圧室が不要な
分、装置の大型化も可能である。The air plasma treatment in the present invention is performed at a discharge treatment amount of 1 kW · sec / cm 2 or more. If the discharge treatment amount is less than 1 kW · sec / cm 2 , sufficient adhesiveness cannot be obtained. The air plasma treatment increases the surface activity of the object, but does not deform the surface. Therefore, the discharge treatment amount may be any value as long as it is 1 KW · sec / cm 2 or more, but usually, the discharge treatment amount of the plasma radiator is 1 to 1.11 KW · sec / cm in consideration of cost and efficiency. cm 2
Is controlled. Air plasma processing is a processing method that discharges air in the atmosphere at atmospheric pressure in a plasma head.
There is no need for a special irradiation chamber such as a reduced pressure chamber in the sputter etching process. Therefore, in the air plasma processing, continuous processing is possible, and the size of the apparatus can be increased because the decompression chamber is unnecessary.
【００１０】[0010]
【発明の実施の形態】〔実施例１、比較例１〜３〕 表
１に示すようなフッ素樹脂製フィルムについて、プラズ
マ照射器（キーエンス社製、型式ＳＴ−7000、大気プラ
ズマ式）を用いて、その片面を表２に示すような時間プ
ラズマ処理した後、このフィルムをその処理面が未加硫
のブチルゴムシートと相対するように重ね合わせ、凍結
乾燥用試作９個取り金型（キャビティの深さ１０．８４
ｍｍ）で、フィルムがゴム栓の足側に接触する状態にし
て真空プレスで加硫成形し、得られたゴム栓（各２個）
について、目視で足先端部破れとバリ部での剥離性（接
着性）を確認したところそれぞれ表３および表４のよう
な結果が得られた。但し、プラズマ処理は、電圧１０Ｋ
Ｖ、電流２００ｍＡ、照射幅３８ｍｍ、照射長さ２０ｍ
ｍで行った。また、成形時の金型温度は１７０±３℃、
加硫時間は４２０秒、フィルムの予備加熱時間は３０秒
であった。表３および表４から空気プラズマ処理適性
（接着性と耐破れ性の両方を満足）を有しているのは変
性ＥＴＦＥのみであるがことが分かる。DESCRIPTION OF THE PREFERRED EMBODIMENTS [Example 1, Comparative Examples 1 to 3] For a fluororesin film as shown in Table 1, a plasma irradiator (manufactured by KEYENCE CORPORATION, model ST-7000, atmospheric plasma type) was used. After plasma treatment on one side for the time shown in Table 2, this film was overlaid so that the treated side was opposed to the unvulcanized butyl rubber sheet, and a 9-piece trial mold for freeze-drying (cavity depth) was used. 10.84
mm), the film is in contact with the foot side of the rubber stopper, and vulcanization molding is performed by a vacuum press, and the obtained rubber stoppers (two each)
As to the results, when the tip of the foot was torn and the releasability (adhesion) at the burr was confirmed visually, the results shown in Tables 3 and 4 were obtained. However, the plasma processing is performed at a voltage of 10K.
V, current 200mA, irradiation width 38mm, irradiation length 20m
m. The mold temperature during molding is 170 ± 3 ° C,
The vulcanization time was 420 seconds, and the preheating time of the film was 30 seconds. From Tables 3 and 4, it can be seen that only modified ETFE has air plasma treatment suitability (satisfies both adhesion and tear resistance).
【００１１】[0011]
【表１】 ＊１：エチレンとテトラフルオロエチレンと含フッ素樹
脂ビニルモノマーとの三元共重合体 ＊２：エチレン−テトラフルオロエチレン共重合体 ＊３：テトラフルオロエチレン−パーフルオロアルキル
ビニルエーテル共重合体 ＊４：ポリテトラフルオロエチレン[Table 1] * 1: Terpolymer of ethylene, tetrafluoroethylene, and fluorine-containing resin vinyl monomer * 2: Ethylene-tetrafluoroethylene copolymer * 3: Tetrafluoroethylene-perfluoroalkylvinyl ether copolymer * 4: Poly Tetrafluoroethylene
【００１２】[0012]
【表２】 ○：プラズマ処理を実施[Table 2] ○: Plasma treatment
【００１３】[0013]
【表３】 ○：剥離しない ×：剥離する[Table 3] ：: No peeling ×: Peeling
【００１４】[0014]
【表４】 ○：破れナシ −：未接着のため評価不可[Table 4] ：: No tear-: Not evaluated due to non-adhesion
【００１５】〔試験例１〜４〕 実施例および比較例に
おいてプラズマ処理されたフイルムについて、引っ張り
試験機（島津製作所製オートグラフ、ＡＧ−５００Ｄ）
を用いて、試料幅２ｍｍ、試料長約８ｍｍ、昇温速度１
０℃／min．、静的荷重０．０５Ｎで、窒素雰囲気下で
その伸び率を測定したところ、表５のような結果が得ら
れた。表５では、変性ＥＴＦＥは伸び変化率（％）がも
っとも大きく、また、変性ＥＴＦＥのみがプラズマ処理
によって伸び変化率が向上している。表５からプレス成
形ではフィルムが延伸されるため、伸び率が重要な決め
手になっていることがわかる。[Test Examples 1 to 4] Tensile test machines (Autograph, AG-500D, manufactured by Shimadzu Corporation) for the plasma-treated films in Examples and Comparative Examples.
, A sample width of 2 mm, a sample length of about 8 mm, and a heating rate of 1
0 ° C / min. When the elongation was measured under a nitrogen atmosphere with a static load of 0.05 N, the results shown in Table 5 were obtained. In Table 5, the modified ETFE has the largest elongation change rate (%), and only the modified ETFE has the elongation change rate improved by the plasma treatment. From Table 5, it can be seen that the elongation is an important decisive factor because the film is stretched by press molding.
【００１６】[0016]
【表５】 [Table 5]
【００１７】[0017]
【発明の効果】以上述べたことから明らかなように、本
発明によれば、以下のような効果が期待できる。すなわ
ち、空気プラズマ処理は、スパッタエッチング処理にお
ける減圧室のような特別の照射室を必要としないので、
連続的な処理が可能であり、また、装置の大型化も可能
である。また、接着処理によりフィルムが変形する虞が
無く、処理作業が容易である。従って、生産性が良く、
また、大幅なコストダウンが可能である。As is apparent from the above description, according to the present invention, the following effects can be expected. That is, air plasma processing does not require a special irradiation chamber such as a reduced pressure chamber in sputter etching processing,
Continuous processing is possible, and the size of the apparatus can be increased. In addition, there is no possibility that the film is deformed by the bonding process, and the processing operation is easy. Therefore, the productivity is good,
In addition, significant cost reduction is possible.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.7 識別記号 ＦＩ テーマコート゛(参考） Ｂ２９Ｋ 27:12 Ｂ２９Ｋ 27:12 27:18 27:18 Ｂ２９Ｌ 9:00 Ｂ２９Ｌ 9:00 31:56 31:56 Ｆターム(参考） 3E084 AB05 BA01 CC03 CC08 CC10 DC03 DC08 DC10 EC03 EC09 EC10 FA09 4F073 AA01 BA07 BA15 BA16 BB01 CA01 4F204 AA16E AA17 AD04 AD32 AG03 AH57 FA01 FB01 FB11 FF01 FF05 ──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. 7 Identification symbol FI Theme coat ゛ (Reference) B29K 27:12 B29K 27:12 27:18 27:18 B29L 9:00 B29L 9:00 31:56 31: 56 F term (reference) 3E084 AB05 BA01 CC03 CC08 CC10 DC03 DC08 DC10 EC03 EC09 EC10 FA09 4F073 AA01 BA07 BA15 BA16 BB01 CA01 4F204 AA16E AA17 AD04 AD32 AG03 AH57 FA01 FB01 FB11 FF01 FF05
Claims (2)
エチレン共重合体で形成されたフィルムの片面を、１Ｋ
Ｗ・秒／ｃｍ２以上の放電処理量で空気プラズマ処理し
た後、該フィルムを処理面が未加硫ゴムシートと相対す
るように積層し、金型内で加圧加熱して栓の形状に成形
することを特徴とするラミネートゴム栓の製造方法。1. One side of a film formed of a modified type ethylene-tetrafluoroethylene copolymer is 1K
After air plasma treatment at a discharge treatment amount of W · sec / cm 2 or more, the film is laminated so that the treated surface faces the unvulcanized rubber sheet, and heated and pressed in a mold to form a plug. A method for producing a laminated rubber stopper, comprising molding.
エチレン共重合体が、エチレンとテトラフルオロエチレ
ンとこれらと共重合可能な含フッ素ビニルモノマーとを
三元共重合させてなる請求項１に記載の製造方法。2. The process according to claim 1, wherein the modified ethylene-tetrafluoroethylene copolymer is obtained by terpolymerizing ethylene, tetrafluoroethylene and a fluorine-containing vinyl monomer copolymerizable therewith. Method.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2001171194A JP2002361667A (en) | 2001-06-06 | 2001-06-06 | Method for manufacturing laminate rubber plug |
| CN 02122272 CN1253295C (en) | 2001-06-06 | 2002-06-04 | Method for producing laminated rubber plug |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2001171194A JP2002361667A (en) | 2001-06-06 | 2001-06-06 | Method for manufacturing laminate rubber plug |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2002361667A true JP2002361667A (en) | 2002-12-18 |
Family
ID=19013001
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2001171194A Pending JP2002361667A (en) | 2001-06-06 | 2001-06-06 | Method for manufacturing laminate rubber plug |
Country Status (2)
| Country | Link |
|---|---|
| JP (1) | JP2002361667A (en) |
| CN (1) | CN1253295C (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009173713A (en) * | 2008-01-22 | 2009-08-06 | Uinzu:Kk | Method for bonding |
| WO2016035894A1 (en) * | 2014-09-05 | 2016-03-10 | 国立大学法人大阪大学 | Method for manufacturing surface-modified molded article, and method for manufacturing composite using surface-modified molded article |
| WO2017082315A1 (en) * | 2015-11-13 | 2017-05-18 | 旭硝子株式会社 | Resin film and production process therefor |
| WO2022102180A1 (en) * | 2020-11-10 | 2022-05-19 | 日東電工株式会社 | Fluororesin film, molded rubber object, and method for producing molded rubber object |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102408579A (en) * | 2010-09-25 | 2012-04-11 | 中国科学院化学研究所 | Antimony-free polyester film rubber composite material and preparation method and application thereof |
| CN116479392A (en) * | 2023-03-24 | 2023-07-25 | 江苏博生医用新材料股份有限公司 | Medicinal rubber stopper coating film device |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62139668A (en) * | 1985-12-16 | 1987-06-23 | 株式会社大協精工 | Laminated plug for syringe |
| JPH01138242A (en) * | 1987-11-24 | 1989-05-31 | Toray Ind Inc | Surface modification of polymer resin |
| JPH0527536B2 (en) * | 1985-06-04 | 1993-04-21 | Daikyo Gomu Seiko Kk | |
| JPH08198984A (en) * | 1995-01-26 | 1996-08-06 | Nippon Paint Co Ltd | Method for modifying surface of fluororesin film |
-
2001
- 2001-06-06 JP JP2001171194A patent/JP2002361667A/en active Pending
-
2002
- 2002-06-04 CN CN 02122272 patent/CN1253295C/en not_active Expired - Lifetime
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0527536B2 (en) * | 1985-06-04 | 1993-04-21 | Daikyo Gomu Seiko Kk | |
| JPS62139668A (en) * | 1985-12-16 | 1987-06-23 | 株式会社大協精工 | Laminated plug for syringe |
| JPH01138242A (en) * | 1987-11-24 | 1989-05-31 | Toray Ind Inc | Surface modification of polymer resin |
| JPH08198984A (en) * | 1995-01-26 | 1996-08-06 | Nippon Paint Co Ltd | Method for modifying surface of fluororesin film |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009173713A (en) * | 2008-01-22 | 2009-08-06 | Uinzu:Kk | Method for bonding |
| WO2016035894A1 (en) * | 2014-09-05 | 2016-03-10 | 国立大学法人大阪大学 | Method for manufacturing surface-modified molded article, and method for manufacturing composite using surface-modified molded article |
| US10730253B2 (en) | 2014-09-05 | 2020-08-04 | Osaka University | Process for producing surface-modified molded article, and process for producing composite using surface-modified molded article |
| WO2017082315A1 (en) * | 2015-11-13 | 2017-05-18 | 旭硝子株式会社 | Resin film and production process therefor |
| KR20180082421A (en) * | 2015-11-13 | 2018-07-18 | 아사히 가라스 가부시키가이샤 | Resin film and manufacturing method thereof |
| US10807776B2 (en) | 2015-11-13 | 2020-10-20 | AGC Inc. | Resin film and process for its production |
| KR102678421B1 (en) | 2015-11-13 | 2024-06-25 | 에이지씨 가부시키가이샤 | Resin film and its manufacturing method |
| WO2022102180A1 (en) * | 2020-11-10 | 2022-05-19 | 日東電工株式会社 | Fluororesin film, molded rubber object, and method for producing molded rubber object |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1253295C (en) | 2006-04-26 |
| CN1389334A (en) | 2003-01-08 |
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