JPS63317681A - Metallized film - Google Patents
Metallized filmInfo
- Publication number
- JPS63317681A JPS63317681A JP15009487A JP15009487A JPS63317681A JP S63317681 A JPS63317681 A JP S63317681A JP 15009487 A JP15009487 A JP 15009487A JP 15009487 A JP15009487 A JP 15009487A JP S63317681 A JPS63317681 A JP S63317681A
- Authority
- JP
- Japan
- Prior art keywords
- film
- stretching
- metallized film
- treatment
- metallized
- 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
- 239000011104 metalized film Substances 0.000 title claims abstract description 19
- 239000010408 film Substances 0.000 claims abstract description 71
- 239000011248 coating agent Substances 0.000 claims abstract description 20
- 238000000034 method Methods 0.000 claims abstract description 20
- 239000003990 capacitor Substances 0.000 claims abstract description 18
- XWUCFAJNVTZRLE-UHFFFAOYSA-N 7-thiabicyclo[2.2.1]hepta-1,3,5-triene Chemical compound C1=C(S2)C=CC2=C1 XWUCFAJNVTZRLE-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000000839 emulsion Substances 0.000 claims abstract description 5
- 238000010030 laminating Methods 0.000 claims abstract description 5
- 229920005989 resin Polymers 0.000 claims abstract description 4
- 239000011347 resin Substances 0.000 claims abstract description 4
- 229910052751 metal Inorganic materials 0.000 claims description 20
- 239000002184 metal Substances 0.000 claims description 20
- 208000028659 discharge Diseases 0.000 claims description 18
- 238000003851 corona treatment Methods 0.000 claims description 10
- 239000010409 thin film Substances 0.000 claims description 6
- 238000009832 plasma treatment Methods 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 238000000576 coating method Methods 0.000 abstract description 12
- 238000007740 vapor deposition Methods 0.000 abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 4
- 229920000642 polymer Polymers 0.000 description 14
- 238000010438 heat treatment Methods 0.000 description 11
- 239000011247 coating layer Substances 0.000 description 7
- 229910052782 aluminium Inorganic materials 0.000 description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 6
- 239000002585 base Substances 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 238000006116 polymerization reaction Methods 0.000 description 6
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 5
- 239000010410 layer Substances 0.000 description 5
- -1 poly-p-phenylene sulfite Chemical compound 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- 239000012298 atmosphere Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 229920001577 copolymer Polymers 0.000 description 4
- 238000004544 sputter deposition Methods 0.000 description 4
- 239000010419 fine particle Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 229920000298 Cellophane Polymers 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 239000004734 Polyphenylene sulfide Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 230000000903 blocking effect Effects 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000010894 electron beam technology Methods 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000009998 heat setting Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000002798 polar solvent Substances 0.000 description 2
- 229920000069 polyphenylene sulfide Polymers 0.000 description 2
- 229920005749 polyurethane resin Polymers 0.000 description 2
- 229910000679 solder Inorganic materials 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 description 1
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 241000218202 Coptis Species 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- 244000062175 Fittonia argyroneura Species 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- 229920006269 PPS film Polymers 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 229920002433 Vinyl chloride-vinyl acetate copolymer Polymers 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 238000012661 block copolymerization Methods 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000003518 caustics Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 239000003989 dielectric material Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 229920005570 flexible polymer Polymers 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- 229920002681 hypalon Polymers 0.000 description 1
- 150000003949 imides Chemical class 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000005240 physical vapour deposition Methods 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- 239000011134 resol-type phenolic resin Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229920005573 silicon-containing polymer Polymers 0.000 description 1
- 229910052979 sodium sulfide Inorganic materials 0.000 description 1
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 229920006230 thermoplastic polyester resin Polymers 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 238000001771 vacuum deposition Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Landscapes
- Laminated Bodies (AREA)
- Chemically Coating (AREA)
- Physical Vapour Deposition (AREA)
- Other Surface Treatments For Metallic Materials (AREA)
- Fixed Capacitors And Capacitor Manufacturing Machines (AREA)
Abstract
Description
【発明の詳細な説明】
〔発明の技術分野〕
本発明は、ポリ−ｐ−フェニレンスルフィト（以下Ｉ’
１８と略称する）系フィルムを基体とし、金属薄膜を積
層してなる、主としてコンデンサー用フィルムとして用
いられる金属薄膜とＰＰ８フイルムとの接着性に優れた
金属化フィルムに関する。Detailed Description of the Invention [Technical Field of the Invention] The present invention relates to poly-p-phenylene sulfite (hereinafter referred to as I'
The present invention relates to a metallized film which has excellent adhesion between a metal thin film and a PP8 film, which is mainly used as a film for capacitors, and which is formed by laminating a metal thin film on a base film (abbreviated as 18).
従来％２軸配向ポリフェニレンスルフィドの金属化フィ
ルムを、例えばコンデンサーの誘電体として用い、周波
数特性、温度特性、耐ノ・ンダ性に優れたコンデンサー
を得ることが出来る事が特開昭５ｙ−１ａｙｓ２７号公
報、特開昭６’０−２５７５１０号公報等において知ら
れている。It was disclosed in Japanese Patent Application Laid-open No. 5Y-1AYS 27 that a metallized film of biaxially oriented polyphenylene sulfide can be used as a dielectric material in a capacitor, for example, to obtain a capacitor with excellent frequency characteristics, temperature characteristics, and resistance to cracking and undulation. This method is known in Japanese Patent Application Laid-Open No. 6'0-257510.
しかるに、フィルムコンデンサー用途のうちでも金属特
にアルミを蒸着してコンデンサーとする蒸着コンデンサ
ー用途その他金属化フィルムを用いる用途において、そ
のＰＰ８化学構造から推測がつくようにＰＰ、系フィル
ムは金属との接着性に劣るため、密着性が不足して容易
に剥離してしまうという重大な欠点を有しているので、
ＰＰＳ系フィルムを蒸着コンデンサー等金属化フィルム
に適用することが不可能であった。However, among film capacitor applications, in vapor-deposited capacitor applications in which capacitors are made by vapor-depositing metal, particularly aluminum, and other applications using metallized films, PP-based films have poor adhesion to metals, as can be inferred from their PP8 chemical structure. It has the serious disadvantage of poor adhesion and easy peeling.
It has not been possible to apply PPS-based films to metallized films such as vapor-deposited capacitors.
上記欠点を解消する方法として、ＰＰ８フイルムに二軸
延伸・熱固定後コロナ放電処理又はプラズマ処理を施す
ことが試みられている（特開昭５７−１８７５２７号公
報）。しかしながら、単々る上記の処理だけではＩ’Ｐ
Ｓフィルムと金属との接着性は充分とは言えないもので
あった。As a method to eliminate the above-mentioned drawbacks, an attempt has been made to subject a PP8 film to a corona discharge treatment or a plasma treatment after biaxial stretching and heat setting (Japanese Unexamined Patent Publication No. 187527/1987). However, with the above processing alone, I'P
The adhesion between the S film and the metal was not sufficient.
上記のごとき問題点を解決すべく鋭意検討の結果、ポリ
−ルーフユニレンスルフイドを主成分とする未延伸フィ
ルムを縦延伸・横延伸する過程において、少く共片面に
必要に応じて放電処理し更に該処理面に、塗布剤を塗布
後横延伸・熱固定したフィルムに対して金属薄膜を積層
することによυ、解決出来る事を見い出し本発明をなす
Ｋいたったものである。As a result of intensive studies to solve the above-mentioned problems, in the process of vertically and horizontally stretching an unstretched film containing poly-roof unilene sulfide as a main component, we applied electrical discharge treatment to a small number of both sides as necessary. Furthermore, we have discovered that this problem can be solved by laminating a thin metal film on a film that has been laterally stretched and heat-set after applying a coating agent on the treated surface, which has led to the present invention.
即チ、本発明はポリ−ルーフユニレンスルフイド系未延
伸フィルムを、縦延伸したのち横延伸して二軸配向フィ
ルムを製造するに際し、未延伸フィルム作成後横延伸工
程前のいずれかの時点において少くとも片面に放電処理
を行ない、該処理面に、水溶性樹脂を含む水溶液又はエ
マルジョンからなる塗布剤を塗布した後、横延伸・熱固
定したフィルムに金属薄膜を積層してなる金属化フィル
ムである。That is, the present invention provides for producing a biaxially oriented film by longitudinally stretching and laterally stretching a poly-roof unilene sulfide-based unstretched film, at any point after producing the unstretched film and before the transversely stretching step. A metallized film obtained by performing electrical discharge treatment on at least one side of the film, applying a coating agent consisting of an aqueous solution or emulsion containing a water-soluble resin to the treated surface, and then laterally stretching and heat-setting the film with a metal thin film laminated thereon. It is.
本発明にいうポリ−ｐ−フェニレンスルフィドとは、ポ
リマー構造の繰り返し単位にΣＳ）を主たる構成単位と
するものであり、好ましくは、本構成単位が８０モルチ
以上であることが本発明の効果を大きくするために重要
である。The poly-p-phenylene sulfide referred to in the present invention has ΣS as a repeating unit in the polymer structure as a main constituent unit, and preferably, the content of this constituent unit is 80 molti or more to obtain the effects of the present invention. It is important to make it big.
好ましくは８５モルチ以上更に好ましくは９０モルチ以
上である。It is preferably 85 molti or more, more preferably 90 molti or more.
該ポリマーの繰シ返し単位の残りの２０モルチ未溝につ
いては本発明の効果を阻害しない範囲において、次の結
合構造を有するものを含有チル結合−ｅＱ−−６、スル
ホン結合
Ｒ）づＯ２令、ナフチル結合べ））８チ、Ｒａアルギル
、ニトロ、フェニル、アルコキシ基を示す）、三官能フ
ェニルスルフィド結合又上記構造のものを含有せしめる
方法としては、全体のポリマーの融点（Ｔｍ ）が２６
０℃以上、二次転移点（’ｌ’ｆ）が７０℃以上である
限りにおいて、ランダム共重合、ブロック共重合、又は
ブレンドのいずれであってもさしつかえない。The remaining 20 moles of the repeating unit of the polymer contains those having the following bond structure, within a range that does not impede the effects of the present invention.Chill bond -eQ--6, sulfone bond R) , naphthyl bond)), Ra argyl, nitro, phenyl, alkoxy group), trifunctional phenyl sulfide bond, or a method for incorporating the above structure, the melting point (Tm) of the entire polymer is 26
Random copolymerization, block copolymerization, or blending may be used as long as the temperature is 0°C or higher and the second-order transition point ('l'f) is 70°C or higher.
融点が２６０℃未満又は二次転移点が７０℃未満となる
ものでは、本発明のＰＰＳ系フィルムとしての耐熱性の
特徴が失われるため不適当である。Those having a melting point of less than 260°C or a secondary transition point of less than 70°C are unsuitable because the heat resistance characteristics of the PPS film of the present invention are lost.
また、フィルムの表面性をコントロールしたり、機械特
性を改良する目的で本フィルムに無機のフィラーを入れ
たり、異種ポリマーを一部ブレンドすることは本発明の
範囲を逸脱するものではない。Furthermore, it is not outside the scope of the present invention to incorporate inorganic fillers into the film or to partially blend different polymers for the purpose of controlling the surface properties of the film or improving its mechanical properties.
本発明のポリ−ｐ−フェニレンスルフィト系フィルムは
、二軸延伸・熱固定したフィルムでなければならない。The poly-p-phenylene sulfite film of the present invention must be a biaxially stretched and heat-set film.
二輪延伸Ｑ熱固定したフィルムにおいても、まず縦方向
にロールで延伸され、その後横方向にテンターで横延伸
したのち、熱固定したり同時にテンターで２軸延伸した
りする事が好ましい。いずれにせよテンターで延伸する
ことが必須である。それ故、横延伸後書縦延伸したシ再
横延伸したり、縦延伸を多段で延伸したりという公知の
種々の延伸処理を組み合せる事は任意である。Even in the case of a two-wheel stretched Q heat-set film, it is preferable to first stretch it in the longitudinal direction with a roll, then laterally stretch it in the transverse direction with a tenter, and then heat-set it or simultaneously biaxially stretch it with a tenter. In any case, stretching with a tenter is essential. Therefore, it is optional to combine various known stretching processes, such as transverse stretching followed by longitudinal stretching, re-transverse stretching, or longitudinal stretching in multiple stages.
本発明において、放電処理とはコロナ放電処理、ＴＪｖ
照射処理、低温プラズマ処理、電子線照射処理、放射線
照射処理、グロー放電処理等を含むものであるが、好ま
しくはコロナ放電処理、低温プラズマ処理が推賞される
。放電処理に必要なエネルギーはその目的によシ決めら
れるものであるが、一般には５ワツト・分／惰３以上２
００ワット・分／ｆ１％３以下が好ましい。In the present invention, discharge treatment refers to corona discharge treatment, TJv
These include irradiation treatment, low-temperature plasma treatment, electron beam irradiation treatment, radiation irradiation treatment, glow discharge treatment, etc., with corona discharge treatment and low-temperature plasma treatment being preferred. The energy required for discharge treatment is determined depending on the purpose, but generally it is 5 watts/minute/inertia 3 or more.
00 watts/min/f1%3 or less is preferable.
本発明において、コロナ放電処理とは、一般に高電圧発
生機に接続した電極と、ハイパロンなどでカバーした金
属ロールの間に１５〜１１６−程度の間隔を設は高電圧
をかけると間隙に高圧コロナを発生するので、その間隙
にフィルムを一定の速度で走らせる処理法であり、公知
の手段を用いることができる。In the present invention, corona discharge treatment generally means that a gap of about 15 to 116 mm is set between an electrode connected to a high voltage generator and a metal roll covered with Hypalon, etc., and when a high voltage is applied, a high voltage corona appears in the gap. This is a processing method in which a film is run at a constant speed through the gap, and known means can be used.
一方本発明は、コロナ放電処理゛に限らず減圧下におい
て施されるグロー放電処理、特にアルゴンや酸素、窒素
、二酸化炭素およびそれらの混合物を主成分とした放電
ガス中でのグロー放電処理は好ましい手段である。On the other hand, the present invention is not limited to corona discharge treatment, but preferably glow discharge treatment performed under reduced pressure, particularly glow discharge treatment in a discharge gas containing argon, oxygen, nitrogen, carbon dioxide, or a mixture thereof as a main component. It is a means.
該放電処理は、ポリ−ｐ−フェニレンスルフィド系フィ
ルムを未延伸フィルムの作成工程後、テンターでの延伸
前の工程でかつ後述する塗布処理工程以前に少く共片面
に放電処理されているのが好ましい。It is preferable that the discharge treatment is performed on both sides of the poly-p-phenylene sulfide film after the step of creating an unstretched film, before stretching it in a tenter, and before the coating treatment step described below. .
本発明でいう塗布処理層とはベースフィルムあるいはそ
の放電処理面と金属蒸着面との間に水系の塗布剤をコー
ティングによって設けられたフレキシブルな高分子塗布
層を言う。The coating layer used in the present invention refers to a flexible polymer coating layer provided by coating a water-based coating agent between the base film or its discharge-treated surface and metal vapor deposition surface.
塗布層の厚さは、ドライでα０１以上１．０μ以下であ
る。塗布厚さが１０１μ未満では、接着性の効果を示さ
なかったり、塗布が不均一であったりして不適当である
。一方１．０μを超えるとブロッキングし易く好ましく
ない。The thickness of the coating layer is in the range of α01 or more and 1.0μ or less when dry. If the coating thickness is less than 101 μm, it is inappropriate because no adhesive effect is exhibited or the coating is uneven. On the other hand, if it exceeds 1.0μ, blocking tends to occur, which is not preferable.
又該塗布層は、特に限定されないが、水系の塗布剤のコ
ーティングによってベースフィルムに塗布し得るものな
ら特にその組成を問わない。Further, the coating layer is not particularly limited, but may have any composition as long as it can be coated on the base film by coating with a water-based coating agent.
具体的にはウレタン系重合体、塩化ビニリデン系重合体
、アクリル系重合体、アミド系重合体、エポキシ系重合
体、イミド系重合体、シリコーン系重合体、フッ素系重
合体、スチレン系重合体、尿素系重合体、ポリエステル
系重合体、およびそれらの共重合体が望ましい。Specifically, urethane polymers, vinylidene chloride polymers, acrylic polymers, amide polymers, epoxy polymers, imide polymers, silicone polymers, fluorine polymers, styrene polymers, Preferably, urea-based polymers, polyester-based polymers, and copolymers thereof.
塗布層として特に望ましい組成物の例としては、ポリウ
レタン樹脂、塩化ビニル−酢酸ビニル共重合体、エポキ
シ樹脂、熱可塑性ポリエステル樹脂、塩化ビニリデン−
アクリロニトリル共重合体、アクリフニトリル−ブタジ
ェン共重合体、スチレン−ブタジェンエラストマー、レ
ゾール型フェノール樹脂等の水溶液又は水溶性エマルジ
ョン、水溶性サスペンションｌ［したものでなければな
らない。溶媒が水系以外のものでは、通常、延伸用テン
ターでは乾燥出来ないため不適当である。Examples of particularly desirable compositions for the coating layer include polyurethane resins, vinyl chloride-vinyl acetate copolymers, epoxy resins, thermoplastic polyester resins, and vinylidene chloride-vinyl acetate copolymers.
It must be an aqueous solution, water-soluble emulsion, or water-soluble suspension of acrylonitrile copolymer, acrylonitrile-butadiene copolymer, styrene-butadiene elastomer, resol type phenolic resin, etc. If the solvent is other than aqueous, it is usually not suitable because it cannot be dried using a stretching tenter.
塗布層に表面平滑度の調整、遮光、塗膜乾燥速度の調節
等の目的で、シリカ、アルミナ、酸化チタン、炭酸カル
シウム、カーボンブラック、酸化鉄などの微粒子を添加
してもよい。Fine particles of silica, alumina, titanium oxide, calcium carbonate, carbon black, iron oxide, etc. may be added to the coating layer for the purpose of adjusting surface smoothness, blocking light, controlling coating film drying speed, etc.
これらの微粒子の平均粒径は５μ駕以下より好ましくは
５μ偽以下である。The average particle size of these fine particles is less than 5 microns, preferably less than 5 microns.
又該塗布層に、硬化剤、安定剤、酸化防止剤等の添加物
も通常添加される程度の量なら添加して支障はない。Furthermore, additives such as curing agents, stabilizers, and antioxidants may be added to the coating layer in amounts that are normally added without any problem.
かくして得られたフィルムは例えばコンデンサーとする
ために金属薄膜を積層する。本発明における金属薄膜と
フィルムの積層は、前述の放電処理し、塗布処理された
二軸延伸のボＩＪ 、＋ｐ−フエニレンスルフイドフイ
ルムヲ支持体トして、その表面に蒸着、メッキ等の方法
で形成された非自己支持体の金属膜であり、その厚さは
ｒＬ０１〜ａｓμ惟が好ましい。The film thus obtained is laminated with a metal thin film, for example to form a capacitor. In the present invention, the metal thin film and the film are laminated by using the above-mentioned discharge-treated and coating-treated biaxially stretched IJ, +p-phenylene sulfide film as a support, and depositing, plating, etc. on the surface thereof. It is a non-self-supporting metal film formed by the method described above, and its thickness is preferably rL01 to asμ.
これら金属膜の材質は特に限定されないが、アルミニウ
ム、亜鉛、ニッケル、クロム、銅もしくは、これらの合
金が好ましい。The material of these metal films is not particularly limited, but aluminum, zinc, nickel, chromium, copper, or an alloy thereof is preferable.
一方蒸着の方法としては、真空蒸着法、スパッタリング
法等公知の物理蒸着法が通常用いられる。On the other hand, as a vapor deposition method, a known physical vapor deposition method such as a vacuum vapor deposition method or a sputtering method is usually used.
真空蒸着法の場合、蒸発源の加熱はエレクトロンビーム
加熱によるのが好゛ましく、ｊ〔突変はＳ Ｘ １０−
’ 〜Ｉ Ｘ １０−’Ｔｏｒｒの範囲内の真空度、蒸
発源偏度は１４００〜１８００℃の範囲内の温度が適宜
採用される。In the case of the vacuum evaporation method, the heating of the evaporation source is preferably by electron beam heating;
A degree of vacuum within a range of 10 to 10 Torr and a temperature within a range of 1400 to 1800° C. are appropriately adopted as the evaporation source polarity.
スパッタリング法の場合、通常５Ｘ１０−”〜１×１０
″″” Ｔｏｒｒ程度のアルゴンガス雰囲気が採用され
る。In the case of sputtering method, usually 5×10-” to 1×10
An argon gas atmosphere of approximately ``'''' Torr is employed.
かくして得られた金属化フィルムは、その熱収縮率が２
５０℃、３０分間加熱した場合０〜８チ（より好ましく
は０〜６チ）であることが好ましい。The metallized film thus obtained has a heat shrinkage rate of 2
When heated at 50°C for 30 minutes, it is preferably 0 to 8 inches (more preferably 0 to 6 inches).
本発明の複合化フィルムを用いてコンデンサーを作った
場合のコンデンサーの形状としては、通常のリード線を
有するタイプ、もしくはリード線を有さす基板にハンダ
を用いて直付けするタイプ（いわゆるチップコンデンサ
ー）のいずれでもよい。When a capacitor is made using the composite film of the present invention, the shape of the capacitor is a type that has normal lead wires, or a type that is directly attached to a board with lead wires using solder (so-called chip capacitor). Either of these is fine.
又二軸配向ＰＰＥＩそのものは、大気中の湿気の影響を
全く受けないが電極がアルミニウムの薄膜で形成される
場合のように大気中の湿気の影響を受ける時はコンデン
サーの周囲に外被を設けることが好ましい。Biaxially oriented PPEI itself is completely unaffected by moisture in the atmosphere, but when it is affected by moisture in the atmosphere, such as when the electrodes are formed from thin aluminum films, an outer jacket is provided around the capacitor. It is preferable.
かかる外被の材質としては、アルミニウム々どの金属、
ガラスなどの無機物、プラスチック等が挙げられるが、
チップコンデンサーの場合には、軟化点が２００℃以上
（より好ましくは２４０℃以上）の樹脂組成物よシなる
外被を設けるのが好ましい。The material of the outer sheath includes metals such as aluminum,
Examples include inorganic materials such as glass, plastics, etc.
In the case of a chip capacitor, it is preferable to provide an outer covering made of a resin composition having a softening point of 200° C. or higher (more preferably 240° C. or higher).
又本発明の金属化フィルムは、コンデンサー以外にも金
銀糸系、鏡、ネーマー磁気テープ等にも好適に使用され
るが、コストパフォーマンスの点で蒸着コンデンサーに
適用するのが最も好ましい。In addition to capacitors, the metallized film of the present invention can also be suitably used for gold and silver thread systems, mirrors, Nehmer magnetic tape, etc., but it is most preferably applied to vapor-deposited capacitors in terms of cost performance.
以下に本発明の金属化フィルムの製造方法について説明
するが、その要旨を超えない限り、これに限定されるも
のではない。The method for producing a metallized film of the present invention will be described below, but the method is not limited thereto unless it exceeds the gist thereof.
まず、本発明に使用するＦＰ日の重合方法としては、硫
化アルカリとＰ−ジハロベンゼンを極性溶媒中で高温高
圧下に反応させる方法を用いる。特に硫化ナトリウムと
ｐ−ジクロルベンゼンをＮ−メチル−ピロリドン等のア
ミド系高沸点極性溶媒中で反応させるのが好ましい。First, as the polymerization method for the FP day used in the present invention, a method is used in which alkali sulfide and P-dihalobenzene are reacted in a polar solvent at high temperature and high pressure. In particular, it is preferable to react sodium sulfide and p-dichlorobenzene in an amide-based high-boiling polar solvent such as N-methyl-pyrrolidone.
この場合、重合度を調整するために、か性アルカリ、カ
ルボン酸アルカリ金属塩などのいわゆる重合助剤°を添
加して、２５０℃〜２８０℃で反応させるのが最も好ま
しい。In this case, in order to adjust the degree of polymerization, it is most preferable to add a so-called polymerization aid such as a caustic alkali or an alkali metal carboxylic acid salt, and to carry out the reaction at 250°C to 280°C.
重合系内の圧力及び重合時間は、使用する助剤の種類や
量及び所望する重合度などによって適宜決定される。The pressure within the polymerization system and the polymerization time are appropriately determined depending on the type and amount of the auxiliary agent used, the desired degree of polymerization, and the like.
斯くして得られたＰＰＥＩは、エクストルーダーに代表
される周知の溶融押出装置に供給され、溶融される。The PPEI thus obtained is supplied to a well-known melt extrusion device such as an extruder and melted.
係る溶融押出工程以前の任意の段階で、フィルムの表面
あらさを整える目的で、ポリマ中に、平均−欠粒径が５
〜５００ｎｍ（より好ましくは、６〜１０１００ｎの微
粒子を均一に分散させておくことが好ましい。At any stage before the melt extrusion process, in order to improve the surface roughness of the film, an average particle diameter of 5.
It is preferable to uniformly disperse fine particles of ~500 nm (more preferably 6 ~ 10100 nm).
溶融された樹脂を、いわゆるＴダイから連続的に押出し
、冷却された金属ドラム上にキャストして、急冷固化し
、未配向非晶状態のシートとする。The molten resin is continuously extruded from a so-called T-die, cast onto a cooled metal drum, and rapidly solidified to form an unoriented amorphous sheet.
また、金属ドラム上の溶融フィルムに対して、正又は負
の静電荷を印加し、フィルムをドラムに密着せしめるの
が好ましい。Further, it is preferable to apply a positive or negative electrostatic charge to the molten film on the metal drum to bring the film into close contact with the drum.
次に、このようＫして得られたシートを２軸延伸する。Next, the sheet thus obtained is biaxially stretched.
従来プラスチックフィルムの延伸法として、逐次２軸延
伸法、同時２軸延伸法等種々の方法が知られているが、
本発明品のベースフィルムとして用いるＰ１’Ｓフィル
ムを安定して得るためには、ロール群によってシート長
手方向に急速延伸した後に、テンターによって幅方向に
延伸する、いわゆる縦横逐次２軸延伸法を用いることが
好ましい。Conventionally, various methods such as sequential biaxial stretching method and simultaneous biaxial stretching method are known as stretching methods for plastic films.
In order to stably obtain the P1'S film used as the base film of the product of the present invention, a so-called vertical and horizontal sequential biaxial stretching method is used, in which the sheet is rapidly stretched in the longitudinal direction by a group of rolls, and then stretched in the width direction by a tenter. It is preferable.
長手方向の延伸（縦延伸）は、周速の異なるロール間で
急速延伸することによるが、このときの延伸直前のフィ
ルム温度は９５〜１０５℃の範囲で、かつ巾方向の温度
差（後に有効に横延伸される部分の、最高温度と最低温
度の差）が５℃以下となるようにする。Stretching in the longitudinal direction (longitudinal stretching) is performed by rapid stretching between rolls with different circumferential speeds, but the film temperature immediately before stretching is in the range of 95 to 105°C, and the temperature difference in the width direction (later effective The difference between the highest temperature and the lowest temperature of the part that is laterally stretched is 5°C or less.
また延伸速度は、ｓｏ、ｏｏｏチ／ ｍｉｎ以上になる
ようにする。巾方向の温度差が大きかったり、延伸速度
が遅いと、得られる２軸延伸フイルムの厚み均一性に欠
けるだけでなく、熱膨張係数の面内等方法も得られない
。延伸倍率は次のようにして決める。すなわち、横延伸
直前の光学的配向度がα１４５〜ＣＬ１６５の範囲にな
るように倍率を選ぶのである。延伸倍率はｚＯ〜５．０
倍の範囲である。In addition, the stretching speed is set to be at least so, ooo chi/min. If the temperature difference in the width direction is large or the stretching speed is slow, not only will the obtained biaxially stretched film lack uniformity in thickness, but also it will not be possible to obtain an in-plane coefficient of thermal expansion. The stretching ratio is determined as follows. That is, the magnification is selected so that the degree of optical orientation immediately before lateral stretching is in the range of α145 to CL165. Stretching ratio is zO~5.0
This is twice the range.
かくして得られた縦−軸延伸フィルムを、放電処理を行
ないかつ、該放電処理機と、次に示すテンターとの間に
備えつけた塗布装置により塗布を行なう。The longitudinally-axially stretched film thus obtained is subjected to an electric discharge treatment and coated using a coating device installed between the electric discharge treatment machine and a tenter as described below.
かくして得られたフィルムをテンターによって、横延伸
する。延伸温度は９５〜１１０℃、延伸速度Ｖは、延伸
温度を７℃とするとき、少なくともＶ＝ＪＯＴ−５２０
０（単位： ｌ／ｍ１ｎ）以上にする必要がある。延伸
温度は低すぎても高すぎても延伸中にフィルムが流れて
しまう。The film thus obtained is laterally stretched using a tenter. The stretching temperature is 95 to 110°C, and the stretching speed V is at least V=JOT-520 when the stretching temperature is 7°C.
It is necessary to make it 0 (unit: l/m1n) or more. If the stretching temperature is too low or too high, the film will flow during stretching.
延伸速度が遅い場合も同様である。延伸倍率は２．５〜
４．５倍の範囲に選ぶ。The same applies when the stretching speed is slow. Stretching ratio is 2.5~
Select a range of 4.5 times.
次にこうして得られた延伸フィルムを定長熱処理する。Next, the stretched film thus obtained is subjected to fixed length heat treatment.
かかる熱処理は、通常、延伸と同じテンター内に延伸室
のあとに熱処理室を設けて行うが、別のテンターや、加
熱ロールによってもよい。いずれの場合も熱処理は長手
方向、幅方向ともに定長で行う必要がある。Such heat treatment is usually carried out by providing a heat treatment chamber after the stretching chamber in the same tenter used for stretching, but it may also be carried out using a separate tenter or heating rolls. In either case, the heat treatment must be performed with a constant length in both the longitudinal and width directions.
とζに言う定長とは、熱処理中の幅及び長さの変化が１
−以下にカるようにすることを意味する。熱処理温度は
２００〜２５０℃（より好ましくは２１０〜２４０℃）
の範囲に選び、５〜５０秒間行う。The constant length referred to as ζ means that the change in width and length during heat treatment is 1
−It means to do the following. Heat treatment temperature is 200 to 250°C (more preferably 210 to 240°C)
Choose a range and do it for 5 to 50 seconds.
定長熱処理の後に、熱処理温度以下の温度で、長手方向
又は／及び幅方向に数多以下のリラックスを行うことは
差しつかえない。After the fixed-length heat treatment, it is acceptable to perform a number of relaxations in the longitudinal direction and/or width direction at a temperature below the heat treatment temperature.
このようにして得られたＰＰＢフィルムを、ベースフィ
ルムとして用いる。The PPB film thus obtained is used as a base film.
該フィルムをベースにして蒸着やスパッタリングなどに
より、金属層を積層し、本発明の金属化フィルムを得る
ことができる。The metallized film of the present invention can be obtained by laminating a metal layer using the film as a base by vapor deposition, sputtering, or the like.
以下実施例によって本発明の詳細な説明する。The present invention will be described in detail below with reference to Examples.
実施例ｔ
５００℃における溶融粘度が約５０００ボイズのポリ−
ｐ−７二二レンスルフイドを押出機からキャスト急冷し
て厚さ５０μのシートを作った後、９０℃で縦方向に五
６倍延伸し５０ワツト・分／慣鵞の処理強度で空気中で
コロナ放電を行なった。Example t Polymer with a melt viscosity of about 5000 voids at 500°C
P-7 22lene sulfide was cast from an extruder and quenched to form a sheet with a thickness of 50 μm, then stretched 56 times in the longitudinal direction at 90°C and corona-treated in air at a processing intensity of 50 W min/t. Discharge was performed.
該コロナ処理面をテンター人口前にもうけた塗布装置を
用いて次に示す組成の水系エマルジョンをウェット厚み
Ｓμで塗布した。該塗布フィルムを次工程のテンターに
導き、横方向に９５℃で五８倍延伸した。これを緊張下
で２７０℃で５秒間処理することＫより、寸法安定性、
平面性の良好な厚さ約４μの２軸延伸ポリ−ｐ−フユニ
レンスルフイドフイルムを？ｌ。The corona-treated surface was coated with an aqueous emulsion having the following composition to a wet thickness Sμ using a coating device installed before the tenter was installed. The coated film was introduced into a tenter for the next step and stretched 58 times in the transverse direction at 95°C. By treating this under tension at 270°C for 5 seconds, the dimensional stability,
A biaxially stretched poly-p-fuynylene sulfide film with a thickness of about 4μ and good flatness? l.
（塗布剤組成）
ポリウレタン樹脂 ３部
ポリエステル樹脂 １部
水 ９６部
得られたフィルム上にアルミを蒸着して金属化フィルム
を作成した。該フィルムの蒸着層は、セロテープテスト
で全く剥離しない極めて満足できる付着強度で基材フィ
ルムに密着しており、コンデンサーとして用いた時電気
的特性、特に誘電損失は１００℃を越えるまでＩ ＫＢ
Ｌで（１０８チ以下であった。なお、ここで得られた金
属化フィルムは２５０℃で熱収縮が２．０チと小さく、
２４０℃のハンダ浴に浸漬しても、蒸着層のはがれや変
形は見られなかった。(Coating agent composition) Polyurethane resin 3 parts Polyester resin 1 part Water 96 parts Aluminum was vapor-deposited on the obtained film to create a metallized film. The vapor-deposited layer of this film adheres to the base film with an extremely satisfactory adhesion strength that does not peel off at all in the sellotape test, and when used as a capacitor, the electrical properties, especially the dielectric loss, remain stable until the temperature exceeds 100°C.
L (108 inches or less.The metallized film obtained here had a small heat shrinkage of 2.0 inches at 250°C.
Even when immersed in a 240°C solder bath, no peeling or deformation of the vapor deposited layer was observed.
比較例１゜
実施例１において、コロナ処理も、塗布処理も行なわな
い場合、蒸着層はセロテープテストにより簡単に剥離し
てしまった。Comparative Example 1 In Example 1, when neither the corona treatment nor the coating treatment was performed, the vapor deposited layer was easily peeled off by the cellophane tape test.
比較例２
実施例１において塗布延伸を行なわず、コロナ処理のみ
行なった場合も、蒸着層はセロテープテストにより′簡
単に剥離してしまった。Comparative Example 2 Even when only the corona treatment was performed without coating and stretching in Example 1, the vapor-deposited layer was easily peeled off by the cellophane tape test.
比較例＆
実施例１のフィルムを熱固定後コロナ処理を行ないその
上に蒸着を行なったところ、比較例２よりは良好であっ
たが、実施例１に比べると不充分なものであった。Comparative Example & When the film of Example 1 was heat-set and then subjected to corona treatment and vapor deposition was performed thereon, the film was better than Comparative Example 2, but was unsatisfactory compared to Example 1.
実施例λ
実施例１におけるコロナ処理の代りに３５ワツト・分／
惰３という比較的低いエネルギーで１ Ｔｏｒｒ炭酸ガ
ス雰囲気中でグロー放電処理を行なった。使用したグロ
ー放電処理設備は金属製のドラムをアースとし、その上
にフィルムを巻きつけ、電極はドラムから１備離れた棒
状電極を使用した。電源は１五５６ ＭＨｚを用いた。Example λ 35 watts/min instead of corona treatment in Example 1
Glow discharge treatment was performed in a 1 Torr carbon dioxide atmosphere using a relatively low energy of Ina 3. In the glow discharge treatment equipment used, a metal drum was grounded, a film was wrapped around it, and a rod-shaped electrode was used that was one space apart from the drum. A power source of 1556 MHz was used.
該フィルムにアルミをスパッタリングしたフィルムは金
属とフィルムの接着性は極めて強固なものであった。The film obtained by sputtering aluminum onto the film had extremely strong adhesion between the metal and the film.
Claims (1)
を縦延伸したのち横延伸して、二軸配向フィルムを製造
するに際し、未延伸フィルム作成後横延伸工程前のいず
れかの時点で、少くとも片面に必要に応じて放電処理を
行ない、該処理面に水溶性樹脂を含む水溶液又は水性エ
マルジョンからなる塗布剤を塗布した後、横延伸・熱固
定したフィルムに金属薄膜を積層してなる金属化フィル
ム。 ２、放電処理が、コロナ処理又は低温プラズマ処理であ
る特許請求の範囲第１項記載の金属化フィルム。 ３、金属化フィルムがコンデンサー用金属化フィルムで
ある特許請求の範囲第１項又は第２項記載の金属化フィ
ルム。[Scope of Claims] 1. When producing a biaxially oriented film by longitudinally stretching an unstretched poly-p-phenylene sulfide film and then laterally stretching it, the following steps are taken before the transverse stretching process: At some point, at least one side is subjected to electrical discharge treatment as necessary, and after applying a coating agent consisting of an aqueous solution or aqueous emulsion containing a water-soluble resin to the treated side, metal is applied to the transversely stretched and heat-set film. A metallized film made by laminating thin films. 2. The metallized film according to claim 1, wherein the discharge treatment is a corona treatment or a low-temperature plasma treatment. 3. The metallized film according to claim 1 or 2, wherein the metallized film is a metallized film for a capacitor.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP15009487A JPS63317681A (en) | 1987-06-18 | 1987-06-18 | Metallized film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP15009487A JPS63317681A (en) | 1987-06-18 | 1987-06-18 | Metallized film |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS63317681A true JPS63317681A (en) | 1988-12-26 |
Family
ID=15489380
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP15009487A Pending JPS63317681A (en) | 1987-06-18 | 1987-06-18 | Metallized film |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS63317681A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0661601A (en) * | 1992-06-04 | 1994-03-04 | Internatl Business Mach Corp <Ibm> | Metallized layer and its formation method |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS57187327A (en) * | 1981-05-13 | 1982-11-18 | Toray Ind Inc | Poly-p-phenylene sulfide film |
| JPS5951424A (en) * | 1982-08-20 | 1984-03-24 | イ−トン・コ−ポレイシヨン | Illuminator toggle switch |
| JPS6031918A (en) * | 1983-07-29 | 1985-02-18 | 関西日本電気株式会社 | Adhesive sheet for dicing semiconductor wafer |
-
1987
- 1987-06-18 JP JP15009487A patent/JPS63317681A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS57187327A (en) * | 1981-05-13 | 1982-11-18 | Toray Ind Inc | Poly-p-phenylene sulfide film |
| JPS5951424A (en) * | 1982-08-20 | 1984-03-24 | イ−トン・コ−ポレイシヨン | Illuminator toggle switch |
| JPS6031918A (en) * | 1983-07-29 | 1985-02-18 | 関西日本電気株式会社 | Adhesive sheet for dicing semiconductor wafer |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0661601A (en) * | 1992-06-04 | 1994-03-04 | Internatl Business Mach Corp <Ibm> | Metallized layer and its formation method |
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