JPH06336533A - Polyimide film of improved adhesiveness - Google Patents
Polyimide film of improved adhesivenessInfo
- Publication number
- JPH06336533A JPH06336533A JP5151159A JP15115993A JPH06336533A JP H06336533 A JPH06336533 A JP H06336533A JP 5151159 A JP5151159 A JP 5151159A JP 15115993 A JP15115993 A JP 15115993A JP H06336533 A JPH06336533 A JP H06336533A
- Authority
- JP
- Japan
- Prior art keywords
- polyimide film
- aminosilane
- adhesiveness
- present
- silane coupling
- 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.)
- Withdrawn
Links
Landscapes
- Coating Of Shaped Articles Made Of Macromolecular Substances (AREA)
- Manufacturing Of Printed Wiring (AREA)
- Lead Frames For Integrated Circuits (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は接着剤に影響を与えず且
つ接着性の優れるポリイミドフィルムに関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polyimide film which does not affect the adhesive and has excellent adhesiveness.
【０００２】[0002]
【従来の技術】ＦＰＣ（フレキシブルプリント配線板）
のベースフィルムは高い耐熱性と、優れた機械的・電気
的特性を備えていることが望ましいことから、近年、ポ
リイミドフィルムがＦＰＣのベースフィルムとして使用
されるようになってきた。ところが、ポリイミドフィル
ムは接着性に乏しい。そこで、その接着性を改善するこ
とを目的に、コロナ放電処理やアルカリ処理などの表面
処理をポリイミドフィルムに施して使用されることが一
般的になっている。2. Description of the Related Art FPC (flexible printed wiring board)
Since it is desirable that the base film of 1) has high heat resistance and excellent mechanical and electrical characteristics, in recent years, a polyimide film has come to be used as a base film for FPC. However, the polyimide film has poor adhesiveness. Therefore, for the purpose of improving the adhesiveness, it is generally used by subjecting a polyimide film to a surface treatment such as corona discharge treatment or alkali treatment.
【０００３】[0003]
【発明が解決しようとする課題】しかしながら、コロナ
放電処理やアルカリ処理などの表面処理を施したポリイ
ミドフィルムを用いて作製したＦＰＣは、配線パターン
の精密化、細線化が進むのに伴い、接着性における信頼
性が乏しいという問題点があった。However, the FPC produced by using the polyimide film which has been subjected to surface treatment such as corona discharge treatment or alkali treatment has been found to have poor adhesiveness as the wiring pattern becomes finer and finer. However, there was a problem that the reliability was poor.
【０００４】そこで、本発明者らは上記問題点を解決す
ることを目的に鋭意研究を重ねた結果、本発明に至った
のであり、本発明は接着性に優れたポリイミドフィルム
を提供することを目的とする。Therefore, the inventors of the present invention have conducted intensive studies for the purpose of solving the above problems, and as a result, have reached the present invention. The present invention provides a polyimide film having excellent adhesiveness. To aim.
【０００５】[0005]
【課題を解決するための手段】本発明に係る接着性を改
良したポリイミドフィルムの要旨とするところは、ポリ
イミドフィルムの両面又は片面に、シラン系カップリン
グ剤を塗布したポリイミドフィルムにおいて、シラン系
カップリング剤がアミノシランであることにある。Means for Solving the Problems The subject matter of a polyimide film with improved adhesion according to the present invention is that a polyimide film obtained by applying a silane coupling agent on both or one side of a polyimide film is a silane-based cup. The ring agent is aminosilane.
【０００６】[0006]
【実施例】以下、本発明に係る接着性を改良したポリイ
ミドフィルムの実施例について説明する。EXAMPLES Examples of polyimide films having improved adhesion according to the present invention will be described below.
【０００７】本発明に適用されるポリイミドフィルム
は、４，４−ジアミノジフェニルエーテルに代表される
芳香族ジアミンと、ピロメリット酸二無水物に代表され
る芳香族テトラカルボン酸二無水物を用い、公知の方法
で得られる。より具体的に本発明に適用されるポリイミ
ドフィルムは、ジアミノジフェニルエーテル、パラフェ
ニレンジアミンビス（アミノフェノキシフェニル）プロ
パンなどを始めとする種々のジアミン成分と、ピロメリ
ット酸二無水物、ビフェニルテトラカルボン酸二無水
物、ベンゾフェノンテトラカルボン酸二無水物などを始
めとする種々の酸無水物成分との重合反応によって得ら
れるポリアミド酸を溶液状態でフィルム状に成形し、こ
れを脱水閉環すなわちイミド化することによって得られ
る。The polyimide film applied to the present invention uses an aromatic diamine typified by 4,4-diaminodiphenyl ether and an aromatic tetracarboxylic dianhydride typified by pyromellitic dianhydride. Can be obtained by More specifically, the polyimide film applied to the present invention comprises various diamine components such as diaminodiphenyl ether and paraphenylenediamine bis (aminophenoxyphenyl) propane, pyromellitic dianhydride, and biphenyltetracarboxylic acid dianhydride. Anhydrides, polyamic acid obtained by polymerization reaction with various acid anhydride components such as benzophenone tetracarboxylic acid dianhydride is formed into a film in a solution state, and by dehydration ring closure or imidization can get.
【０００８】また、本発明に用いられるポリイミドフィ
ルムは、上記ポリアミド酸をイミド化させて得られるポ
リイミドに代えて、ポリアミドイミド、ポリエーテルイ
ミドなどの準イミド材料を成形して得られたフィルムを
用いることもでき、本発明におけるポリイミドフィルム
はこれらを含む概念である。更に、本発明に用いられる
ポリイミドフィルムは各種の充填剤や補強剤などを添加
して形成されたものであっても良く、なんら限定される
ものではない。As the polyimide film used in the present invention, a film obtained by molding a quasi-imide material such as polyamideimide or polyetherimide is used instead of the polyimide obtained by imidizing the polyamic acid. The polyimide film in the present invention is a concept including these. Further, the polyimide film used in the present invention may be formed by adding various fillers, reinforcing agents, etc., and is not limited at all.
【０００９】得られたポリイミドフィルムに接着剤を付
与するのにあたり、ポリイミドフィルムとの接着性を良
くするために、そのポリイミドフィルムの片面又は両面
にはシラン系カップリング剤が塗布される。本発明にお
いては、シラン系カップリング剤として特にアミノシラ
ンが用いられる。より具体的に、本発明に用いられるア
ミノシランとして、Ｎ−フェニル−γ−アミノプロピル
トリメトキシシラン、γ−アミノプロピルトリエトキシ
シラン、Ｎ−β（アミノエチル）γ−アミノプロピルト
リメトキシシラン、Ｎ−β（アミノエチル）γ−アミノ
プロピルメチルジメトキシシランなどが挙げられる。When applying an adhesive to the obtained polyimide film, a silane coupling agent is applied to one side or both sides of the polyimide film in order to improve the adhesiveness with the polyimide film. In the present invention, aminosilane is particularly used as the silane coupling agent. More specifically, as the aminosilane used in the present invention, N-phenyl-γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N- Examples include β (aminoethyl) γ-aminopropylmethyldimethoxysilane and the like.
【００１０】シラン系カップリング剤であるアミノシラ
ンは溶剤に溶解させられて用いられる。溶剤はアミノシ
ランが溶解する溶剤であれば何でも良いが、好ましくは
メタノール、エタノールなどのアルコール類が良い。溶
剤に溶解させられたアミノシランの濃度は０．００５〜
２０重量％程度が好ましく、濃度が低い場合にはアミノ
シランによる接着性の改良がなされず、また、濃度が高
い場合にはポリイミドフィルムの表面にアミノシランの
皮膜が形成され、却って接着性が低下することになる。
なお、アミノシランの溶液に塗布時に発生する泡を消す
ための消泡剤などを添加することは一向にかまわない。Aminosilane, which is a silane coupling agent, is used after being dissolved in a solvent. Any solvent may be used as long as it can dissolve aminosilane, but alcohols such as methanol and ethanol are preferable. The concentration of aminosilane dissolved in the solvent is 0.005
About 20% by weight is preferable, and when the concentration is low, the adhesiveness is not improved by aminosilane, and when the concentration is high, a film of aminosilane is formed on the surface of the polyimide film, which rather reduces the adhesiveness. become.
It should be noted that it is all right to add an antifoaming agent or the like for eliminating bubbles generated at the time of application to the aminosilane solution.
【００１１】ポリイミドフィルムの表面にアミノシラン
を塗布する方法としては、ポリイミドフィルムをアミノ
シランの溶媒溶液中に浸漬したり、あるいはポリイミド
フィルムにアミノシランの溶媒溶液を液状又は霧状に吹
付けたり、あるいはアミノシランの溶媒溶液を含浸させ
たローラや刷毛などによって塗布するなどの方法があ
り、いずれの方法であっても良く、なんら限定されるも
のではない。ポリイミドフィルムに片面又は両面に塗布
されたアミノシランは溶媒の成分が蒸発するまで乾燥さ
せられる。As a method of applying aminosilane to the surface of the polyimide film, the polyimide film may be dipped in a solvent solution of aminosilane, or the solvent solution of aminosilane may be sprayed onto the polyimide film in a liquid or mist state, or an aminosilane solution may be used. There is a method of applying with a roller impregnated with a solvent solution or a brush, and any method may be used without any limitation. The aminosilane coated on one or both sides of the polyimide film is dried until the solvent components have evaporated.
【００１２】次いで、アミノシランが塗布されたポリイ
ミドフィルムの表面に接着剤が被着された後、銅箔が接
着されて、ＦＣＣＬ（フレキシブル銅張積層板）が作製
される。ここで、接着剤としてはアクリル系、エポキシ
系、ポリアミド系、フェノール系、ポリイミド系、ゴム
系など、各種の接着剤を用いることができ、これら各種
の接着剤を単独で、あるいは種々の割合で溶剤とともに
混合したものを用いることができる。更に、本発明に用
いられる接着剤は必要に応じて硬化剤や硬化促進剤など
の添加剤を添加したものを用いることができる。Next, an adhesive is applied to the surface of the polyimide film coated with aminosilane, and then a copper foil is adhered to produce FCCL (flexible copper clad laminate). Here, as the adhesive, various adhesives such as acrylic, epoxy, polyamide, phenol, polyimide, and rubber can be used, and these various adhesives can be used alone or in various ratios. A mixture with a solvent can be used. Further, as the adhesive used in the present invention, an adhesive to which an additive such as a curing agent or a curing accelerator is added can be used if necessary.
【００１３】接着剤はポリイミドフィルムの表面に直
接、均一に塗布されても良いが、通常は、保護フィルム
の表面に接着剤を均一に塗布して乾燥させた後、その保
護フィルムをポリイミドフィルムに加熱圧着してラミネ
ートし、その後、保護フィルムを剥離して接着剤層がポ
リイミドフィルムに転写される。次に、この接着剤層の
上に銅箔を配設して、加熱圧着し、ＦＣＣＬ（フレキシ
ブル銅張積層板）が作製されるのである。Although the adhesive may be directly and evenly applied to the surface of the polyimide film, usually, the adhesive is evenly applied and dried on the surface of the protective film, and then the protective film is applied to the polyimide film. The adhesive layer is transferred to the polyimide film by peeling off the protective film after heat-pressing and laminating. Next, a copper foil is placed on the adhesive layer and heat-pressed to produce FCCL (flexible copper clad laminate).
【００１４】なお、保護フィルムは接着剤の乾燥時やラ
ミネート時に軟化したり、変質したりしない程度の耐熱
性を有していればどのようなものであっても良いが、た
とえばポリエチレンテレフタレートなどのポリエステル
フィルム、あるいはポリプロピレンなどのポリオレフィ
ンフィルムが好ましい。また、銅箔はいかなる種類の銅
箔であっても良く、特に本発明においては、銅箔以外の
アルミニウム箔などの金属箔であっても良いのは言うま
でもない。The protective film may be of any type as long as it has heat resistance to the extent that it does not soften or deteriorate when the adhesive is dried or laminated. For example, polyethylene terephthalate or the like can be used. A polyester film or a polyolefin film such as polypropylene is preferable. Further, it goes without saying that the copper foil may be any kind of copper foil, and particularly in the present invention, it may be a metal foil such as an aluminum foil other than the copper foil.
【００１５】次に、本発明に係る接着性を改良したポリ
イミドフィルムの実施例を具体的に説明するが、本発明
はこれらの実施例に限定されるものではなく、その他、
本発明はその趣旨を逸脱しない範囲内で、当業者の知識
に基づき種々なる改良、修正、変形を加えた態様で実施
し得るものである。Next, examples of the polyimide film with improved adhesion according to the present invention will be specifically described, but the present invention is not limited to these examples, and
The present invention can be carried out in a mode in which various improvements, modifications and variations are added based on the knowledge of those skilled in the art without departing from the spirit of the present invention.
【００１６】実施例 １ まず、４，４−ジアミノジフェニルエーテルとピロメリ
ット酸二無水物から得られたポリイミドフィルム（アピ
カル２５ＡＨ、鐘淵化学工業（株）社製）を用いた。一
方、γ−アミノプロピルトリエトキシシラン（シランカ
ップリング剤ＫＢＥ９０３、信越化学工業（株）社製）
をメタノールで溶解し、濃度０．０１重量％、０．１重
量％、１重量％及び１０重量％の４種類のγ−アミノプ
ロピルトリエトキシシランのメタノール溶液を作った。
次に、この４種類のメタノール溶液をそれぞれポリイミ
ドフィルムに塗布し、８０℃で１分間乾燥させた後、そ
のポリイミドフィルムとパイララックス（アクリル系接
着剤、デュポン社製）とを１８０℃でラミネートした。
その後、さらに電解銅箔（３５μｍ厚み、三井金属鉱業
（株）社製）と１８０℃でラミネートした後、１８０℃
で６０分間、加熱処理を行ない、４種類のＦＣＣＬ（フ
レキシブル銅張積層板）を作製した。Example 1 First, a polyimide film obtained from 4,4-diaminodiphenyl ether and pyromellitic dianhydride (Apical 25AH, manufactured by Kanegafuchi Chemical Co., Ltd.) was used. On the other hand, γ-aminopropyltriethoxysilane (silane coupling agent KBE903, manufactured by Shin-Etsu Chemical Co., Ltd.)
Was dissolved in methanol to prepare a methanol solution of four kinds of γ-aminopropyltriethoxysilane having concentrations of 0.01% by weight, 0.1% by weight, 1% by weight and 10% by weight.
Next, each of these four types of methanol solutions was applied to a polyimide film and dried at 80 ° C. for 1 minute, and then the polyimide film and Piralux (acrylic adhesive, manufactured by DuPont) were laminated at 180 ° C. .
Then, after further laminating with electrolytic copper foil (thickness of 35 μm, manufactured by Mitsui Mining & Smelting Co., Ltd.) at 180 ° C., 180 ° C.
By heat treatment for 60 minutes, four types of FCCL (flexible copper clad laminate) were produced.
【００１７】このようにして作製したＦＣＣＬ（フレキ
シブル銅張積層板）の接着性を評価した。接着性の評価
として９０°剥離接着強度を用いた。接着強度測定法
は、ＦＣＣＬから３cm×８cmの試験片を切り出し、３mm
のパターンを５本形成し、ＩＮＳＴＲＯＮ ＴＥＮＳＩ
ＬＥ ＴＥＳＴＥＲにて剥離角度９０°、隔離速度５０
mm／分で剥離の強度を測定した。ｎ＝５の測定値の平均
を接着強度とした。The adhesion of the FCCL (flexible copper clad laminate) thus produced was evaluated. The 90 ° peel adhesive strength was used as the evaluation of the adhesiveness. Adhesive strength is measured by cutting a 3 cm x 8 cm test piece from FCCL and 3 mm
5 patterns are formed and INSTRON TENSI
LE TESTER, peeling angle 90 °, isolation speed 50
The peel strength was measured in mm / min. The average of the measured values of n = 5 was taken as the adhesive strength.
【００１８】その評価結果を表１に示す。The evaluation results are shown in Table 1.
【表１】 [Table 1]
【００１９】比較例 １ 実施例１で用いた厚み２５μｍのポリイミドフィルムに
コロナ処理を施した。コロナ処理の条件は、Ｗ密度が２
００Ｗmin/ m2 であった。このコロナ処理を施したポリ
イミドフィルムを用いて、実施例１と同様にしてＦＣＣ
Ｌ（フレキシブル銅張積層板）を作製した。ただし、ポ
リイミドフィルムの表面に表面処理は施していない。得
られたＦＣＣＬについて、実施例１と同様にして接着性
を評価した。Comparative Example 1 The 25 μm thick polyimide film used in Example 1 was subjected to corona treatment. The condition for corona treatment is that the W density is 2
It was 00 Wmin / m 2 . Using this corona-treated polyimide film, FCC was performed in the same manner as in Example 1.
L (flexible copper clad laminate) was produced. However, no surface treatment was applied to the surface of the polyimide film. The obtained FCCL was evaluated for adhesiveness in the same manner as in Example 1.
【００２０】その評価結果を表２に示す。The evaluation results are shown in Table 2.
【表２】 [Table 2]
【００２１】比較例 ２ 実施例１で用いた厚み２５μｍのポリイミドフィルムに
表面処理を施さないで実施例１と同様にしてＦＣＣＬを
作製した。得られたＦＣＣＬについて、実施例１と同様
にして接着性を評価した。その評価結果を表２に示す。Comparative Example 2 An FCCL was prepared in the same manner as in Example 1 except that the 25 μm thick polyimide film used in Example 1 was not surface-treated. The obtained FCCL was evaluated for adhesiveness in the same manner as in Example 1. The evaluation results are shown in Table 2.
【００２２】表１及び表２より明らかなように、本実施
例に示すシラン系カップリング剤を塗布したポリイミド
フィルムは接着性が大幅に改善されることが分かる。As is clear from Tables 1 and 2, it can be seen that the polyimide film coated with the silane coupling agent shown in this example has a significantly improved adhesiveness.
【００２３】比較例 ３ 実施例１で用いたポリイミドフィルムに、γ−グリシド
キシプロピルトリメトキシシラン（シランカップリング
剤ＫＢＭ４０３、信越化学工業（株）社製）の１重量％
メタノール溶液を塗布した後、実施例１と同様にして、
ＦＣＣＬを作製した。このようにして作製したＦＣＣＬ
の接着性を評価した。その評価結果を表３に示す。Comparative Example 3 1% by weight of γ-glycidoxypropyltrimethoxysilane (silane coupling agent KBM403, manufactured by Shin-Etsu Chemical Co., Ltd.) was added to the polyimide film used in Example 1.
After applying the methanol solution, in the same manner as in Example 1,
FCCL was prepared. FCCL produced in this way
Was evaluated for adhesiveness. The evaluation results are shown in Table 3.
【表３】 [Table 3]
【００２４】比較例 ４ 実施例１で用いたポリイミドフィルムに、γ−クロロプ
ロピルトリメトキシシラン（シランカップリング剤ＫＢ
Ｍ５７３、信越化学工業（株）社製）の１重量％メタノ
ール溶液を塗布した後、実施例１と同様にして、ＦＣＣ
Ｌを作製した。このようにして作製したＦＣＣＬの接着
性を評価した。その評価結果を表３に示す。Comparative Example 4 γ-chloropropyltrimethoxysilane (silane coupling agent KB was added to the polyimide film used in Example 1).
After applying a 1 wt% methanol solution of M573, manufactured by Shin-Etsu Chemical Co., Ltd., FCC was performed in the same manner as in Example 1.
L was produced. The FCCL thus produced was evaluated for adhesiveness. The evaluation results are shown in Table 3.
【００２５】以上の比較例３，４に示すように、実施例
１と比較すれば、シラン系カップリング剤を塗布したポ
リイミドフィルムにおいて、シラン系カップリング剤と
してアミノシランを用いることにより、ポリイミドフィ
ルムに良好な接着性を付与することができることが分か
る。As shown in Comparative Examples 3 and 4, as compared with Example 1, in the polyimide film coated with the silane coupling agent, by using aminosilane as the silane coupling agent, a polyimide film was obtained. It can be seen that good adhesiveness can be imparted.
【００２６】[0026]
【発明の効果】以上のように本発明は、シラン系カップ
リング剤を塗布したポリイミドフィルムにおいて、特に
シラン系カップリング剤にアミノシランを用いることに
よって接着剤に影響を与えず、且つ接着性の優れたポリ
イミドフィルムを実現できるものである。As described above, according to the present invention, in a polyimide film coated with a silane coupling agent, particularly by using aminosilane as the silane coupling agent, the adhesive is not affected and the adhesiveness is excellent. And a polyimide film can be realized.
Claims (1)
シラン系カップリング剤を塗布したポリイミドフィルム
において、シラン系カップリング剤がアミノシランであ
ることを特徴とする接着性を改良したポリイミドフィル
ム。1. A polyimide film on both sides or one side,
A polyimide film coated with a silane coupling agent, wherein the silane coupling agent is aminosilane.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5151159A JPH06336533A (en) | 1993-05-27 | 1993-05-27 | Polyimide film of improved adhesiveness |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5151159A JPH06336533A (en) | 1993-05-27 | 1993-05-27 | Polyimide film of improved adhesiveness |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH06336533A true JPH06336533A (en) | 1994-12-06 |
Family
ID=15512642
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP5151159A Withdrawn JPH06336533A (en) | 1993-05-27 | 1993-05-27 | Polyimide film of improved adhesiveness |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH06336533A (en) |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1614535A1 (en) | 2004-07-09 | 2006-01-11 | DuPont-Toray Company, Ltd. | Multi-layer polyimide films and flexible circuit substrates therefrom |
| US7452610B2 (en) | 2005-06-29 | 2008-11-18 | Du Pont Toray Company Limited | Multi-layer polyimide films and flexible circuit substrates therefrom |
| JP2009064872A (en) * | 2007-09-05 | 2009-03-26 | Sharp Corp | Method of forming metal thin film on front surface of polyimide resin surface |
| US8415024B2 (en) | 2005-04-07 | 2013-04-09 | Ube Industries, Ltd. | Process for producing polyimide film, and polyimide film |
| KR101451264B1 (en) * | 2006-07-04 | 2014-10-15 | 신닛테츠 수미킨 가가쿠 가부시키가이샤 | Method of modifying surface of polyimide resin layer and process for producing metal-clad laminate |
| WO2019099826A1 (en) * | 2017-11-17 | 2019-05-23 | Corning Incorporated | Direct graphene transfer and graphene-based devices |
| JP2020037265A (en) * | 2018-09-03 | 2020-03-12 | 東洋紡株式会社 | Polyimide film laminate and production method of polyimide film laminate |
| US11485673B2 (en) | 2017-08-24 | 2022-11-01 | Corning Incorporated | Glasses with improved tempering capabilities |
| US11643355B2 (en) | 2016-01-12 | 2023-05-09 | Corning Incorporated | Thin thermally and chemically strengthened glass-based articles |
| US11697617B2 (en) | 2019-08-06 | 2023-07-11 | Corning Incorporated | Glass laminate with buried stress spikes to arrest cracks and methods of making the same |
| US11891324B2 (en) | 2014-07-31 | 2024-02-06 | Corning Incorporated | Thermally strengthened consumer electronic glass and related systems and methods |
-
1993
- 1993-05-27 JP JP5151159A patent/JPH06336533A/en not_active Withdrawn
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1614535A1 (en) | 2004-07-09 | 2006-01-11 | DuPont-Toray Company, Ltd. | Multi-layer polyimide films and flexible circuit substrates therefrom |
| US8415024B2 (en) | 2005-04-07 | 2013-04-09 | Ube Industries, Ltd. | Process for producing polyimide film, and polyimide film |
| US7452610B2 (en) | 2005-06-29 | 2008-11-18 | Du Pont Toray Company Limited | Multi-layer polyimide films and flexible circuit substrates therefrom |
| KR101451264B1 (en) * | 2006-07-04 | 2014-10-15 | 신닛테츠 수미킨 가가쿠 가부시키가이샤 | Method of modifying surface of polyimide resin layer and process for producing metal-clad laminate |
| JP2009064872A (en) * | 2007-09-05 | 2009-03-26 | Sharp Corp | Method of forming metal thin film on front surface of polyimide resin surface |
| US11891324B2 (en) | 2014-07-31 | 2024-02-06 | Corning Incorporated | Thermally strengthened consumer electronic glass and related systems and methods |
| US11643355B2 (en) | 2016-01-12 | 2023-05-09 | Corning Incorporated | Thin thermally and chemically strengthened glass-based articles |
| US11485673B2 (en) | 2017-08-24 | 2022-11-01 | Corning Incorporated | Glasses with improved tempering capabilities |
| US11214491B2 (en) | 2017-11-17 | 2022-01-04 | Corning Incorporated | Direct graphene transfer and graphene-based devices |
| KR20200088869A (en) * | 2017-11-17 | 2020-07-23 | 코닝 인코포레이티드 | Direct graphene transcription and graphene-based devices |
| WO2019099826A1 (en) * | 2017-11-17 | 2019-05-23 | Corning Incorporated | Direct graphene transfer and graphene-based devices |
| US12006221B2 (en) | 2017-11-17 | 2024-06-11 | Corning Incorporated | Direct graphene transfer and graphene-based devices |
| JP2020037265A (en) * | 2018-09-03 | 2020-03-12 | 東洋紡株式会社 | Polyimide film laminate and production method of polyimide film laminate |
| US11697617B2 (en) | 2019-08-06 | 2023-07-11 | Corning Incorporated | Glass laminate with buried stress spikes to arrest cracks and methods of making the same |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A300 | Withdrawal of application because of no request for examination |
Free format text: JAPANESE INTERMEDIATE CODE: A300 Effective date: 20000801 |