JP2000114695A - Method and apparatus for manufacturing polyimide board with copper layer - Google Patents
Method and apparatus for manufacturing polyimide board with copper layerInfo
- Publication number
- JP2000114695A JP2000114695A JP10287742A JP28774298A JP2000114695A JP 2000114695 A JP2000114695 A JP 2000114695A JP 10287742 A JP10287742 A JP 10287742A JP 28774298 A JP28774298 A JP 28774298A JP 2000114695 A JP2000114695 A JP 2000114695A
- Authority
- JP
- Japan
- Prior art keywords
- copper
- window member
- quartz window
- synthetic quartz
- polyimide
- 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.)
- Granted
Links
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、銅層を有するポリ
イミド基板の製造方法および装置に係り、特にフレキシ
ブルプリント配線板に用いて好適な銅層を有するポリイ
ミド基板の製造方法および装置に関する。The present invention relates to a method and an apparatus for producing a polyimide substrate having a copper layer, and more particularly to a method and an apparatus for producing a polyimide substrate having a copper layer suitable for use in a flexible printed wiring board.
【０００２】[0002]
【従来の技術】全芳香族ポリイミドは接着が困難であ
り、またこれを溶解する有機溶剤も存在しないため、そ
の前駆体である可溶性ポリイミド酸の状態で適用し、こ
れを加熱してイミド化することが行われている。しかし
ながら、接着加工時に揮発分が発生してボイドができや
すく、またイミド化に３００℃以上の高温を必要とする
等の問題があり、大面積の接着には適していない。2. Description of the Related Art Since a wholly aromatic polyimide is difficult to adhere and there is no organic solvent for dissolving the polyimide, the polyimide is applied in the form of a soluble polyimide acid which is a precursor thereof, and is heated to be imidized. That is being done. However, it is not suitable for bonding in a large area because there are problems such as generation of volatiles during bonding processing and easy formation of voids, and high temperature of 300 ° C. or more is required for imidization.
【０００３】これに対し、熱硬化型ポリイミドは、全芳
香族ポリイミドに比べて耐熱性は低いが、２００℃とい
う低温でも形成できることから、プリント配線用基板と
して広く使われている。On the other hand, thermosetting polyimides are widely used as printed wiring boards because they have lower heat resistance than wholly aromatic polyimides, but can be formed even at a low temperature of 200 ° C.
【０００４】特に、ビスマレイミド系の樹脂は形成性が
良好で、下地を粗面化した銅箔上にモールドされた状態
で熱硬化させ、プリント配線基板を製造している。しか
し、この銅と樹脂間の接合は、あくまでアンカー効果に
よるものであって、しかも耐熱性に劣る点から、半田鏝
による配線時に注意を要していた。[0004] In particular, bismaleimide-based resins have good formability, and are thermoset in a state of being molded on a copper foil having a roughened base to produce a printed wiring board. However, the connection between the copper and the resin is due to the anchor effect, and is inferior in heat resistance.
【０００５】一方、ポリイミドの接着性向上について
は、村原は、「エキシマ光によるプラスチック表面への
官能基置換と非線形性発現の可能性」と題して、毛細管
現象を用いた表面改質法（特開平６−３３５６３１号公
報）を利用して、メチルアルコール水溶液や水の薄液層
を、ポリイミド樹脂表面と合成石英層との間に形成さ
せ、これにＡｒＦレーザー光を選択的に照射して、照射
部（露光部）においてのみＣＨ3 基やＯＨ基を置換し
て、親油性や親水性に改質し、接着性を向上させること
を教示している（Polyfile, Vol. 33 (385) ３月号，(1
996), pp 31；およびMRS Sympo., Proc., Vol. 397, pp
555 (1996)）。[0005] On the other hand, regarding the improvement of the adhesiveness of polyimide, Murahara proposed a surface modification method using a capillary phenomenon, entitled "Possibility of functional group substitution on plastic surface by excimer light and development of nonlinearity." Utilizing JP-A-6-335631), a thin liquid layer of a methyl alcohol aqueous solution or water is formed between the polyimide resin surface and the synthetic quartz layer, and this is selectively irradiated with ArF laser light. Teaches that the CH 3 group or OH group is substituted only in the irradiated part (exposed part) to improve the lipophilicity or hydrophilicity and improve the adhesion (Polyfile, Vol. 33 (385) March issue, (1
996), pp 31; and MRS Sympo., Proc., Vol. 397, pp.
555 (1996)).
【０００６】また、フッ素樹脂に銅を成長させてプリン
ト基板を作る方法として、ヒドラジンの存在下でフッ素
樹脂基板にＡｒＦレーザー光を照射し、このフッ素樹脂
基板をＳｎＣｌ2 とＨＣｌとの混液に浸して触媒を付与
し、ＰｄＣｌ2 とＨＣｌとの混液により活性処理を行っ
た後、無電解銅メッキ処理を行い、フッ素樹脂基板表面
に銅箔を成長する方法も開示されている（特開平７−５
７７６号公報）。Further, as a method of producing a printed circuit board by growing copper on a fluororesin, an ArF laser beam is applied to the fluororesin substrate in the presence of hydrazine, and the fluororesin substrate is immersed in a mixed solution of SnCl 2 and HCl. A method of growing a copper foil on the surface of a fluororesin substrate by performing an activation treatment with a mixed solution of PdCl 2 and HCl after applying a catalyst by applying a catalyst and performing electroless copper plating treatment (Japanese Patent Application Laid-Open No. 5
776).
【０００７】村原らは、フッ素樹脂表面と合成石英窓部
材との間に硫酸銅あるいは銅の無電解メッキ液などの薄
液層を毛細管現像を用いて形成させ、合成石英窓部材側
から回路パターン状にＡｒＦレーザー光を照射して、照
射露光部のみに銅の核を形成させる方法も示している
（MRS Sympo., Proc., Vol. 397, pp. 655 (1996); AP
L, Vol. 72(20), pp. 2616 (1998)）。この方法は、フ
ッ素樹脂のフッ素原子を硫酸銅水溶液から光解離された
水素原子を用いて脱フッ素化し、その未結合手に、硫酸
銅水溶液から光解離された酸素原子および銅原子が、Ｃ
−Ｏ−Ｃｕの形で結合して、Ｃｕ核を生成させるもので
あり、その後の無電解メッキ処理によって銅を成長させ
るものである。Murahara et al. Formed a thin liquid layer such as an electroless plating solution of copper sulfate or copper between the surface of a fluororesin and a synthetic quartz window member by using capillary development, and formed a circuit from the side of the synthetic quartz window member. A method of irradiating an ArF laser beam in a pattern to form a copper nucleus only at an irradiated and exposed portion is also shown (MRS Sympo., Proc., Vol. 397, pp. 655 (1996); AP).
L, Vol. 72 (20), pp. 2616 (1998)). In this method, fluorine atoms of a fluororesin are defluorinated using hydrogen atoms photodissociated from an aqueous solution of copper sulfate, and oxygen and copper atoms photodissociated from the aqueous solution of copper sulfate have C
It bonds in the form of -O-Cu to generate Cu nuclei, and grows copper by a subsequent electroless plating process.
【０００８】[0008]
【発明が解決しようとする課題】レーザーを用いた上記
方法では、ＡｒＦレーザー光を少なくとも３０００パル
ス照射しなければならなかった。In the above method using a laser, at least 3000 pulses of ArF laser light had to be irradiated.
【０００９】そこで本発明は、レーザー照射時間を非常
に短くし、すべての種類のポリイミドに対して有効に実
施でき、経済的で簡便な、フレキシブルプリント配線板
用の銅層を有するポリイミド基板の製造方法およびこれ
を製造するための装置を提供することを課題とする。Therefore, the present invention provides an economical and simple method of manufacturing a polyimide substrate having a copper layer for a flexible printed wiring board, in which the laser irradiation time is extremely short, which can be effectively applied to all kinds of polyimides. It is an object to provide a method and an apparatus for manufacturing the same.
【００１０】[0010]
【課題を解決するための手段】上記課題を解決するため
に、毛細管現像を利用してポリイミド樹脂表面と合成石
英窓部材との間に薄液層を形成する技術に基づいて鋭意
研究した結果、合成石英窓部材にＡｒＦレーザー光を照
射すると、銅化合物水溶液は、光分解して石英窓部材に
銅が析出してしまい、これら銅化合物水溶液の下に位置
するポリイミド樹脂表面に光が到達困難となることがわ
かった。銅が合成石英窓部材に析出すると、合成石英窓
部材側から入射したレーザー光が銅化合物水溶液を通っ
てポリイミド樹脂表面に到達し得ず、その表面を励起し
得ない。Means for Solving the Problems In order to solve the above problems, as a result of earnest research based on a technique of forming a thin liquid layer between a polyimide resin surface and a synthetic quartz window member using capillary development, When the synthetic quartz window member is irradiated with ArF laser light, the aqueous copper compound solution is photolyzed and copper is deposited on the quartz window member, and it is difficult for light to reach the polyimide resin surface located under these copper compound aqueous solutions. It turned out to be. When copper deposits on the synthetic quartz window member, the laser light incident from the synthetic quartz window member side cannot reach the polyimide resin surface through the copper compound aqueous solution and cannot excite the surface.
【００１１】すなわち、上記課題を解決するためには、
銅化合物水溶液は、ポリイミド樹脂表面のみで光分解
し、ポリイミド樹脂表面のみで光化学反応を起こし、そ
こに銅を析出させ、合成石英窓部材に銅を析出させない
ことが必要である。That is, in order to solve the above problems,
It is necessary that the aqueous copper compound solution be decomposed only on the surface of the polyimide resin, cause a photochemical reaction only on the surface of the polyimide resin, deposit copper there, and not deposit copper on the synthetic quartz window member.
【００１２】このための条件は、（１）銅化合物水溶液
の薄液層を極薄くして、ポリイミド樹脂表面近傍のみで
光化学反応を起こさせること；（２）ポリイミド樹脂表
面に光が到達し、かつ、光分解で銅原子が置換されるだ
けの銅原子を有する銅化合物水溶液にするため、その銅
濃度を低くすること；（３）光照射時間が長くなると合
成石英窓部材に析出する遊離銅の量が多くなるため、光
照射時間を極短くすることであることがわかった。The conditions for this are (1) to make the thin liquid layer of the copper compound aqueous solution extremely thin so that a photochemical reaction occurs only near the polyimide resin surface; (2) light reaches the polyimide resin surface; In addition, the concentration of copper should be reduced in order to obtain a copper compound aqueous solution having only copper atoms that can be replaced by photolysis. (3) Free copper that precipitates on a synthetic quartz window member when the light irradiation time is prolonged Therefore, it has been found that the light irradiation time is to be made extremely short because the amount of is increased.
【００１３】本発明者らは、この条件を満たすべく鋭意
研究した結果、銅化合物水溶液の薄液層を極めて薄くす
るため毛細管現象を利用し、銅化合物水溶液の濃度を１
％以下に設定し、照射する波長が１７０〜２００ｎｍ
で、エネルギー密度が４０ｍＪ／ｃｍ2 以下の紫外光を
５パルス以下で照射することにより所期の目的が達成し
得ることを見いだした。The present inventors have conducted intensive studies to satisfy this condition. As a result, the concentration of the copper compound aqueous solution was adjusted to 1 by utilizing the capillary phenomenon in order to make the thin liquid layer of the copper compound aqueous solution extremely thin.
% Or less, and the irradiation wavelength is 170 to 200 nm.
It was found that the intended purpose can be achieved by irradiating ultraviolet light having an energy density of 40 mJ / cm 2 or less with 5 pulses or less.
【００１４】すなわち、本発明によれば、ポリイミド基
板と合成石英窓部材との間に毛細管現象により濃度１％
以下の銅化合物水溶液の薄液層を形成させ、合成石英窓
部材側からエネルギー密度４０ｍＪ／ｃｍ2 以下で波長
１７０〜２００ｎｍの紫外光を５パルス以下照射して該
ポリイミド基板表面の紫外光照射部における置換により
該水溶液中の銅原子を析出させ、この銅が析出したポリ
イミド基板を銅メッキ処理に供することを特徴とする銅
層を有するポリイミド基板の製造方法が提供される。That is, according to the present invention, the concentration between the polyimide substrate and the synthetic quartz window member is 1% by capillary action.
A thin liquid layer of the following copper compound aqueous solution is formed, and from the side of the synthetic quartz window member, 5 pulses or less of ultraviolet light having an energy density of 40 mJ / cm 2 or less and a wavelength of 170 to 200 nm are irradiated and an ultraviolet light irradiating portion on the surface of the polyimide substrate Wherein copper atoms in the aqueous solution are precipitated by the substitution in step (a), and the copper-deposited polyimide substrate is subjected to a copper plating process, thereby providing a method for producing a polyimide substrate having a copper layer.
【００１５】本発明において、ポリイミド基板表面の全
面に銅を析出させることもできるし、所定のパターン状
（例えば、回路パターン状）に銅を析出させることもで
きる。In the present invention, copper can be deposited on the entire surface of the polyimide substrate, or copper can be deposited in a predetermined pattern (for example, a circuit pattern).
【００１６】また、本発明によれば、ポリイミド基板の
表面に平板状合成石英窓部材との間に毛細管現象により
銅化合物水溶液の薄液層を形成するための手段と、該薄
液層に対して実質的に垂直に所定のパターン状に紫外光
を照射するための手段とを備えることを特徴とする銅層
を有するポリイミド基板の製造装置が提供される。この
装置によれば、銅は、所定のパターン状に析出する。Further, according to the present invention, there is provided means for forming a thin liquid layer of an aqueous solution of a copper compound by capillary action between a surface of a polyimide substrate and a flat synthetic quartz window member. Means for irradiating ultraviolet light in a predetermined pattern substantially vertically in a predetermined pattern. The apparatus for producing a polyimide substrate having a copper layer is provided. According to this apparatus, copper is deposited in a predetermined pattern.
【００１７】さらに、本発明によれば、回転自在に設け
られたローラと、このローラと平行に回転自在に設けら
れた円柱状または円筒状の合成石英窓部材と、この合成
石英窓部材の上方に設けられ、ローラと合成石英窓部材
との間の対向部分に紫外線を線状に照射するための紫外
線照射手段と、ローラと合成石英窓部材との間にポリイ
ミドフィルムを走行させるための手段と、合成石英窓部
材をローラ方向に押圧して毛細管現象により銅化合物水
溶液の薄液を形成させるための押圧手段とを具備する銅
層を有するポリイミド基板の製造装置が提供される。こ
の装置によれば、銅は、ポリイミドフィルム表面の全面
にわたって析出し得る。Further, according to the present invention, a roller provided rotatably, a columnar or cylindrical synthetic quartz window member rotatably provided in parallel with the roller, and an upper portion of the synthetic quartz window member are provided. UV irradiation means for irradiating ultraviolet rays linearly to the opposing portion between the roller and the synthetic quartz window member, and means for running the polyimide film between the roller and the synthetic quartz window member Further, there is provided an apparatus for producing a polyimide substrate having a copper layer, comprising: pressing means for pressing a synthetic quartz window member in a roller direction to form a thin liquid of a copper compound aqueous solution by capillary action. According to this apparatus, copper can be deposited over the entire surface of the polyimide film.
【００１８】本発明において、銅化合物水溶液の濃度
は、０．５重量％以下であることが好ましく、特に濃度
０．５重量％以下の硫酸銅を用いることが好ましい。In the present invention, the concentration of the aqueous solution of the copper compound is preferably 0.5% by weight or less, particularly preferably copper sulfate having a concentration of 0.5% by weight or less.
【００１９】本発明において、紫外光は、２パルスまた
は１パルス照射で所望の銅を析出させることができる。
紫外光としては、エネルギー密度が２８ｍＪ／ｃｍ2 以
下のＡｒＦエキシマレーザ光を用いることが特に好まし
い。In the present invention, ultraviolet light can deposit desired copper by irradiation of two or one pulse.
As the ultraviolet light, it is particularly preferable to use ArF excimer laser light having an energy density of 28 mJ / cm 2 or less.
【００２０】本発明では、銅とポリイミドとの接合にア
ンカー効果や接着剤を用いないものであり、紫外光照射
により、その照射部分において銅水溶液が分解して銅、
酸素、Ｈのラジカルが生成し、照射部分においてポリイ
ミドのＣ−Ｈ結合から水素が引き抜かれ、そこに酸素が
置換されることによってＣ−Ｏ−Ｃｕ結合が生じ、ポリ
イミド表面に共有結合により結合した銅核が生成する。
このように、本発明によれば、純粋な化学結合によりポ
リイミド表面に銅を導入することができるので、ポリイ
ミド本来の性質が１００％発揮され、電子工業、機械工
業、化学工業、航空宇宙分やあるいは原子力分野におい
て有用に利用し得る銅層を有するポリイミド基板を製造
することができる。In the present invention, an anchor effect or an adhesive is not used for bonding copper and polyimide, and the copper aqueous solution is decomposed at the irradiated portion by ultraviolet light irradiation, so that copper,
Oxygen and H radicals were generated, hydrogen was extracted from the C—H bond of the polyimide in the irradiated portion, and oxygen was substituted there, thereby forming a C—O—Cu bond, which was bonded to the polyimide surface by a covalent bond. Copper nuclei are formed.
As described above, according to the present invention, copper can be introduced to the polyimide surface by a pure chemical bond, so that 100% of the original properties of the polyimide are exhibited, and the electronics, machinery, chemical, aerospace, Alternatively, a polyimide substrate having a copper layer that can be usefully used in the field of nuclear power can be manufactured.
【００２１】[0021]
【発明の実施の形態】以下、本発明の実施の形態を詳し
く説明する。Embodiments of the present invention will be described below in detail.
【００２２】本発明で使用するポリイミド基板は、当該
分野で知られているいずれのタイプのポリイミドで形成
されていてもよく、全芳香族ポリイミド、ビスマレイミ
ド系ポリイミド等その種類を問わずに使用することがで
きる。基板の形態としては、特にフィルムまたはシート
等のフレキシブルな形態が好ましい。The polyimide substrate used in the present invention may be made of any type of polyimide known in the art, such as wholly aromatic polyimide or bismaleimide-based polyimide. be able to. As a form of the substrate, a flexible form such as a film or a sheet is particularly preferable.
【００２３】合成石英窓部材は、紫外光、特にエキシマ
レーザーを透過して、それにより劣化しないものであ
る。The synthetic quartz window member transmits ultraviolet light, in particular, an excimer laser, and is not deteriorated by the light.
【００２４】銅化合物としては、ＣｕＣｌ2 、Ｃｕ（Ｃ
ｌＯ3 ）2 、Ｃｕ（ＣｌＯ4 ）2 、ＣｕＢｒ2 、ＣｕＳ
Ｏ4 、Ｃｕ2 Ｏ、Ｃｕ（ＮＯ3 ）2 、ＣｕＳｅＯ4 、Ｃ
ｕ（ＯＨ）2 、Ｃｕ（ＣＨ3 ＣＯＯ）2 、［Ｃｕ（ＮＨ
3 ）4 ］ＳＯ4 、［Ｃｕ（Ｃ 2 Ｈ8 Ｎ2 ）2 ］ＳＯ4 、
Ｋ3 ［Ｃｕ（ＣＮ）4 ］等を好ましく使用することがで
きる。特に硫酸銅が好ましい。As the copper compound, CuClTwo, Cu (C
10Three)Two, Cu (ClOFour)Two, CuBrTwo, CuS
OFour, CuTwoO, Cu (NOThree)Two, CuSeOFour, C
u (OH)Two, Cu (CHThreeCOO)Two, [Cu (NH
Three)Four] SOFour, [Cu (C TwoH8NTwo)Two] SOFour,
KThree[Cu (CN)Four] Can be preferably used.
Wear. Particularly, copper sulfate is preferable.
【００２５】本発明において水溶液中の銅化合物の濃度
は１重量％以下である。好ましい銅化合物濃度は、０．
５重量％以下である。本発明において、濃度０．５重量
％以下の硫酸銅水溶液を用いることが特に好ましい。In the present invention, the concentration of the copper compound in the aqueous solution is 1% by weight or less. A preferred copper compound concentration is 0.1.
5% by weight or less. In the present invention, it is particularly preferable to use an aqueous solution of copper sulfate having a concentration of 0.5% by weight or less.
【００２６】本発明において使用する紫外光は、波長が
１７０〜２００ｎｍで、エネルギー密度が４０ｍＪ／ｃ
ｍ2 以下のものである。本発明において、エネルギー密
度が２８ｍＪ／ｃｍ2 以下のＡｒＦエキシマレーザ光を
用いることが特に好ましい。The ultraviolet light used in the present invention has a wavelength of 170 to 200 nm and an energy density of 40 mJ / c.
m 2 or less. In the present invention, it is particularly preferable to use ArF excimer laser light having an energy density of 28 mJ / cm 2 or less.
【００２７】このように、紫外光を照射して所定の銅核
をポリイミド表面に形成した後、従来公知の銅メッキ処
理に供して銅をさらに成長させる。銅メッキ処理として
は、電解メッキ処理、無電解メッキ処理のいずれをも使
用することができ、それらを組合せて使用することもで
きる。銅核をポリイミド基板表面全面に形成し、これを
銅メッキ処理に供した場合は、従来のエッチング手法に
より回路パターンを形成することができる。As described above, after a predetermined copper nucleus is formed on the polyimide surface by irradiating ultraviolet light, copper is further grown by subjecting it to a conventionally known copper plating treatment. As the copper plating treatment, either an electrolytic plating treatment or an electroless plating treatment can be used, and a combination thereof can also be used. When copper nuclei are formed on the entire surface of the polyimide substrate and subjected to copper plating, a circuit pattern can be formed by a conventional etching method.
【００２８】図１は、所定のパターン状に銅を析出させ
るために好適な装置の一例を示す概略図である。図１に
示す装置は、ポリイミド基板（シートまたはフィルム
等）１１に銅化合物水溶液の液滴を滴下し、その上に平
板状石英窓部材１２を載せ、毛細管現象により、ポリイ
ミド基板１１と平板状石英窓部材との間に液滴を広げて
薄液層を形成させる薄液形部位１３を備える。より詳し
くは、図２に示すように、ポリイミド基板１１上に銅化
合物水溶液の液滴ＬＤを滴下し（図２（ａ））、その上
に平板状合成石英窓部材１２を載置する。すると、毛細
管現象により、液滴ＬＤは、ポリイミド基板１１と平板
上合成石英窓部材１２との間の極狭い隙間で広がり、非
常に薄い薄液層ＬＦを形成する。FIG. 1 is a schematic view showing an example of an apparatus suitable for depositing copper in a predetermined pattern. In the apparatus shown in FIG. 1, a droplet of an aqueous solution of a copper compound is dropped on a polyimide substrate (sheet or film or the like) 11, and a flat quartz window member 12 is placed thereon. A thin liquid portion 13 is formed between the window member and the opening to spread a liquid droplet to form a thin liquid layer. More specifically, as shown in FIG. 2, a droplet LD of a copper compound aqueous solution is dropped on a polyimide substrate 11 (FIG. 2A), and a flat synthetic quartz window member 12 is placed thereon. Then, due to the capillary phenomenon, the droplet LD spreads in an extremely narrow gap between the polyimide substrate 11 and the synthetic quartz window member 12 on the flat plate, and forms a very thin thin liquid layer LF.
【００２９】図１に示す装置において、紫外光源例えば
ＡｒＦエキシマレーザ源１７からのレーザ光ＬＢは、正
多面体プリズムのようなホモジナイザー１６により均一
化され、ミラー１５により、ポリイミド基板１１に対し
て垂直に入射するように指向される。ミラー１５と石英
窓部材１２との間には、所定パターン（好ましくは、所
望の回路パターン）のレチクル（ホトマスク）１４が設
けられている。In the apparatus shown in FIG. 1, a laser beam LB from an ultraviolet light source, for example, an ArF excimer laser source 17 is homogenized by a homogenizer 16 such as a regular polyhedral prism, and is perpendicular to a polyimide substrate 11 by a mirror 15. It is directed to be incident. A reticle (photomask) 14 having a predetermined pattern (preferably, a desired circuit pattern) is provided between the mirror 15 and the quartz window member 12.
【００３０】この装置によれば、ポリイミド基板１１の
表面に所定のパターン状に銅核が析出する。According to this apparatus, copper nuclei are deposited on the surface of the polyimide substrate 11 in a predetermined pattern.
【００３１】図３は、ポリイミド基板表面の全面にわた
って銅核を析出する装置の一例を示す概略図である。FIG. 3 is a schematic view showing an example of an apparatus for depositing copper nuclei over the entire surface of a polyimide substrate.
【００３２】図３の装置は、回転自在に設けられたロー
ラ例えばゴムローラ２１と、このローラ２１と平行に回
転自在に設けられた円柱状または円筒状の合成石英窓部
材２２を有する。合成石英窓部材２２の上方には、ロー
ラ２１と合成石英窓部材２２との間の対向部分に紫外線
を線状に照射するための紫外線照射手段が設けられてい
る。この紫外線照射手段は、図示しない紫外線源と、こ
の紫外線源からの帯状の紫外線（好ましくは、ＡｒＦレ
ーザ光）ＬＢを上記線状に集束させるためのシリンドリ
カルレンズ２３を備える。ローラ２１と合成石英窓部材
２２との間にポリイミドフィルム２４が矢印Ａ方向に走
行される。合成石英窓部材２２をローラ２１方向に押圧
して合成石英窓部材２２とポリイミドフィルム２４との
間に毛細管現象により銅化合物水溶液の薄液を形成させ
るために、バネ等の押圧手段２５、２５がローラ２１の
両軸部に取着されている。The apparatus shown in FIG. 3 has a roller provided rotatably, for example, a rubber roller 21, and a cylindrical or cylindrical synthetic quartz window member 22 provided rotatably in parallel with the roller 21. Above the synthetic quartz window member 22, there is provided an ultraviolet irradiation means for irradiating ultraviolet rays linearly to an opposing portion between the roller 21 and the synthetic quartz window member 22. The ultraviolet irradiation means includes an ultraviolet light source (not shown) and a cylindrical lens 23 for converging the band-like ultraviolet light (preferably ArF laser light) LB from the ultraviolet light source into the linear shape. The polyimide film 24 runs in the direction of arrow A between the roller 21 and the synthetic quartz window member 22. In order to press the synthetic quartz window member 22 in the direction of the roller 21 to form a thin liquid of the aqueous copper compound solution by capillary action between the synthetic quartz window member 22 and the polyimide film 24, pressing means 25, 25 such as springs are provided. The roller 21 is attached to both shaft portions.
【００３３】図３に示す装置において、銅化合物水溶液
を滴下手段２６により上流側においてポリイミドフィル
ム２４の表面に滴下すると、この水溶液の液滴２７は、
合成石英窓部材２２の下面に達したとき、毛細管現象に
より、ポリイミドフィルム２４との間で合成石英窓部材
２２の下面に沿って広がり薄液層となる。したがって、
その状態で紫外線照射手段（図示せず）から紫外線、好
ましくはＡｒＦエキシマレーザ光をポリイミドフィルム
２４の表面に照射することにより、ポリイミドフィルム
２４の表面に連続的に銅を析出させることができる。In the apparatus shown in FIG. 3, when an aqueous copper compound solution is dropped on the surface of the polyimide film 24 on the upstream side by the dropping means 26, the droplet 27 of this aqueous solution becomes
When it reaches the lower surface of the synthetic quartz window member 22, it spreads along the lower surface of the synthetic quartz window member 22 with the polyimide film 24 by a capillary phenomenon to form a thin liquid layer. Therefore,
In this state, by irradiating the surface of the polyimide film 24 with ultraviolet rays, preferably ArF excimer laser light, from ultraviolet irradiation means (not shown), copper can be continuously deposited on the surface of the polyimide film 24.
【００３４】実施例１ 図１に示す装置を用い、硫酸銅水溶液の濃度を１〜０．
０１重量％に変化させて、ビフェニルテトラカルボン酸
系ポリイミド基板と平板場合成石英窓部材との間に毛細
管現象により形成された硫酸銅水溶液の薄液層に３０ｍ
Ｊ／ｃｍ2 のＡｒＦレーザー光を１パルス照射したとこ
ろ、濃度０．７重量％以上では合成石英窓部材に銅が析
出する傾向にあることがわかった。さらに、濃度０．２
重量％以下ではポリイミド樹脂表面は親水性にはなる
が、無電解メッキ処理を施しても析出した銅が剥がれる
傾向にあることがわかった。濃度０．２〜０．７重量％
の間では、合成石英窓部材には銅は一切析出されず、ポ
リイミド基板表面には、銅の析出が顕微鏡下で確認でき
た。これに無電解メッキ処理を施すと、露光部のみに、
銅箔が成長した。特に濃度０．５％のとき、銅成長が顕
著で、かつ銅箔の耐剥離強度も大きかった。EXAMPLE 1 Using the apparatus shown in FIG.
01% by weight, and a thin layer of an aqueous solution of copper sulfate formed by a capillary phenomenon between the biphenyltetracarboxylic acid-based polyimide substrate and the quartz window member in the case of a flat plate was formed to have a thickness of 30 m.
When one pulse of an ArF laser beam of J / cm 2 was irradiated, it was found that when the concentration was 0.7% by weight or more, copper tended to precipitate on the synthetic quartz window member. In addition, a concentration of 0.2
It was found that the polyimide resin surface becomes hydrophilic when the content is less than the weight%, but the deposited copper tends to be peeled off even when the electroless plating treatment is performed. Concentration 0.2-0.7% by weight
During the period, no copper was deposited on the synthetic quartz window member, and the deposition of copper was confirmed on the surface of the polyimide substrate under a microscope. When electroless plating is applied to this, only the exposed part,
Copper foil grew. In particular, when the concentration was 0.5%, the copper growth was remarkable, and the peel resistance of the copper foil was also large.
【００３５】実施例２ 銅の核を効率良く成長させるためのレーザーエネルギー
密度を明らかにするために、硫酸銅水溶液の濃度を０．
５％として、ビフェニルテトラカルボン酸系ポリイミド
基板に銅核を形成し、その際の銅核密度のレーザーエネ
ルギー密度依存性を調べた。結果を図４に示す。図４に
示すように、ＡｒＦレーザエネルギー密度が２８ｍＪ／
ｃｍ2 のときが最適であった。Example 2 In order to clarify the laser energy density for growing copper nuclei efficiently, the concentration of the aqueous solution of copper sulfate was set at 0.
Copper nuclei were formed on a biphenyltetracarboxylic acid-based polyimide substrate at 5%, and the dependence of the copper nucleus density on the laser energy density at that time was examined. FIG. 4 shows the results. As shown in FIG. 4, the ArF laser energy density was 28 mJ /
cm 2 was optimal.
【００３６】そこで、ＡｒＦレーザーのエネルギー密度
を２８ｍＪ／ｃｍ2 として、レーザーパルス依存性を調
べた。結果を図５に示す。図５に示すように２パルス
（１０ナノ秒／パルス）が最も効果的であった。Therefore, the laser pulse dependence was examined by setting the energy density of the ArF laser to 28 mJ / cm 2 . FIG. 5 shows the results. As shown in FIG. 5, two pulses (10 ns / pulse) were most effective.
【００３７】実施例３ 図１の装置を用いて、硫酸銅水溶液濃度０．５％、溶液
温度２５℃の条件で、ビフェニルテトラカルボン酸系ポ
リイミドフィルム基板と平板状合成石英窓部材との間に
薄液層を形成し、これにＡｒＦレーザーのエネルギー密
度２８ｍＪ／ｃｍ2 、レーザーパルス数２で、回路パタ
ーンマスクをレンズで投影露光後、６０℃の無電解銅メ
ッキ液に６０分浸したところ、露光部分に約１ミクロン
の銅が析出し、所望の回路パターン状の銅箔がポリイミ
ドフィルム上に形成された。Example 3 Using the apparatus shown in FIG. 1, a copper sulfate aqueous solution concentration of 0.5% and a solution temperature of 25 ° C. were applied between a biphenyltetracarboxylic acid-based polyimide film substrate and a flat synthetic quartz window member. After forming a thin liquid layer and projecting and exposing the circuit pattern mask with a lens at an energy density of 28 mJ / cm 2 of an ArF laser and a laser pulse number of 2 using a lens, it was immersed in an electroless copper plating solution at 60 ° C. for 60 minutes. Approximately 1 micron of copper was deposited on the exposed portion, and a copper foil having a desired circuit pattern was formed on the polyimide film.
【００３８】実施例４ 図３に示す装置を用い、ＡｒＦレーザー光を帯状ビーム
にして、ビフェニルテトラカルボン酸系ポリイミドフィ
ルムの表面で線状に集光させ、ポリイミドフィルム表面
に０．５％の硫酸銅水溶液を１滴ずつ滴下し、ポリイミ
ドフィルムを移動させながら、連続的に、銅の核形成を
行った。その後、６０℃に温めた市販の無電解銅メッキ
液に３０分間浸し、全面に銅箔を成長させた後、電解銅
メッキを施し、金属光沢のある５ミクロン厚の長尺、幅
広のプリント基板を製作した。Example 4 Using an apparatus shown in FIG. 3, an ArF laser beam was converted into a band-like beam and condensed linearly on the surface of a biphenyltetracarboxylic acid-based polyimide film. A copper aqueous solution was added dropwise, and copper nucleation was continuously performed while moving the polyimide film. Then, dipped in a commercially available electroless copper plating solution heated to 60 ° C. for 30 minutes to grow a copper foil on the entire surface, and then subjected to electrolytic copper plating, and a long and wide printed board with a metallic luster of 5 μm thickness. Was made.
【００３９】[0039]
【発明の効果】以上述べたように、本発明によれば、簡
便な手法により、レーザパルス数を極めて少なくして
（したがって、短時間で）高い接合力をもって接着され
た銅層を有するポリイミド基板を製造することができ
る。さらにエッチング加工により回路パターンを形成す
る場合にもパターン精度を高めることができる。As described above, according to the present invention, according to the present invention, a polyimide substrate having a copper layer adhered with a high bonding force with a very small number of laser pulses (and therefore in a short time) by a simple method. Can be manufactured. Further, the pattern accuracy can be improved even when a circuit pattern is formed by etching.
【図１】本発明に係る銅核を形成するための装置の一例
を示す概略図。FIG. 1 is a schematic view showing an example of an apparatus for forming a copper nucleus according to the present invention.
【図２】図１に示す装置において、銅化合物水溶液の薄
液層を形成する手法を説明するための図。FIG. 2 is a view for explaining a method for forming a thin liquid layer of a copper compound aqueous solution in the apparatus shown in FIG. 1;
【図３】本発明に係る銅核を形成するための別の装置を
示す概略図。FIG. 3 is a schematic view showing another apparatus for forming a copper nucleus according to the present invention.
【図４】銅核密度のＡｒＦレーザエネルギー密度依存性
を示すグラフ図。FIG. 4 is a graph showing the dependence of the copper nucleus density on the ArF laser energy density.
【図５】銅核密度のＡｒＦレーザパルス依存性を示すグ
ラフ図。FIG. 5 is a graph showing the dependence of the copper nucleus density on the ArF laser pulse.
１１，２４…ポリイミド基板 １２…平板状合成石英窓部材 １３…薄液層形成部位 １４…レチクル １５…ミラー １６…ホモジナイザー １７…レーザ光源 ２１…ローラ ２２…円柱状または円筒状合成石英窓部材 ２３…シリンドリカルレンズ ２５…押圧手段 ２６…銅化合物水溶液滴下手段 ２７…銅化合物水溶液の液滴 11, 24: Polyimide substrate 12: Flat synthetic quartz window member 13: Thin liquid layer forming portion 14: Reticle 15: Mirror 16: Homogenizer 17: Laser light source 21: Roller 22: Cylindrical or cylindrical synthetic quartz window member 23: Cylindrical lens 25 ... Pressing means 26 ... Drip means of copper compound aqueous solution 27 ... Drop of copper compound aqueous solution
───────────────────────────────────────────────────── フロントページの続き Ｆターム(参考） 4F073 AA28 AA32 BA31 BB01 BB08 CA45 EA01 EA52 GA11 4K022 AA15 AA42 BA08 CA08 DA08 DB30 5E343 AA18 AA33 BB24 DD33 DD43 GG01 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 4F073 AA28 AA32 BA31 BB01 BB08 CA45 EA01 EA52 GA11 4K022 AA15 AA42 BA08 CA08 DA08 DB30 5E343 AA18 AA33 BB24 DD33 DD43 GG01
Claims (4)
に毛細管現象により濃度１％以下の銅化合物水溶液の薄
液層を形成させ、合成石英窓部材側からエネルギー密度
４０ｍＪ／ｃｍ2 以下で波長１７０〜２００ｎｍの紫外
光を５パルス以下照射して該ポリイミド基板表面の紫外
光照射部における置換により該水溶液中の銅原子を析出
させ、この銅が析出したポリイミド基板を銅メッキ処理
に供することを特徴とする銅層を有するポリイミド基板
の製造方法。1. A thin liquid layer of an aqueous solution of a copper compound having a concentration of 1% or less is formed between a polyimide substrate and a synthetic quartz window member by a capillary phenomenon, and a wavelength of energy of 40 mJ / cm 2 or less from the synthetic quartz window member side. Irradiating ultraviolet light of 170 to 200 nm for 5 pulses or less to precipitate the copper atoms in the aqueous solution by substitution in the ultraviolet light irradiating portion on the surface of the polyimide substrate, and subjecting the polyimide substrate on which the copper is deposited to copper plating treatment. A method for producing a polyimide substrate having a characteristic copper layer.
れを所定パターンのホトマスクを介して照射することを
特徴とする請求項１記載の製造方法。2. The method according to claim 1, wherein the ultraviolet light is homogenized by a homogenizer and is irradiated through a photomask having a predetermined pattern.
窓部材との間に毛細管現象により銅化合物水溶液の薄液
層を形成するための手段と、該薄液層に対して実質的に
垂直に所定のパターン状に紫外光を照射するための手段
とを備えることを特徴とする銅層を有するポリイミド基
板の製造装置。3. A means for forming a thin liquid layer of an aqueous solution of a copper compound by capillary action between a surface of a polyimide substrate and a plate-shaped synthetic quartz window member, and substantially perpendicular to the thin liquid layer. Means for irradiating a predetermined pattern with ultraviolet light, the apparatus for manufacturing a polyimide substrate having a copper layer.
ーラと平行に回転自在に設けられた円柱状または円筒状
の合成石英窓部材と、この合成石英窓部材の上方に設け
られ、ローラと合成石英窓部材との間の対向部分に紫外
線を線状に照射するための紫外線照射手段と、ローラと
合成石英窓部材との間にポリイミドフィルムを走行させ
るための手段と、合成石英窓部材をローラ方向に押圧し
て毛細管現象により銅化合物水溶液の薄液を形成させる
ための押圧手段とを具備することを特徴とする銅層を有
するポリイミド基板の製造装置。4. A roller provided rotatably, a columnar or cylindrical synthetic quartz window member rotatably provided in parallel with the roller, and a roller provided above the synthetic quartz window member. UV irradiating means for linearly irradiating ultraviolet rays to the facing portion between the synthetic quartz window member, means for running the polyimide film between the roller and the synthetic quartz window member, and a synthetic quartz window member. An apparatus for producing a polyimide substrate having a copper layer, comprising: pressing means for pressing in the direction of a roller to form a thin liquid of an aqueous copper compound solution by capillary action.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP28774298A JP4097803B2 (en) | 1998-10-09 | 1998-10-09 | Method and apparatus for producing a polyimide substrate having a copper layer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP28774298A JP4097803B2 (en) | 1998-10-09 | 1998-10-09 | Method and apparatus for producing a polyimide substrate having a copper layer |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2000114695A true JP2000114695A (en) | 2000-04-21 |
| JP4097803B2 JP4097803B2 (en) | 2008-06-11 |
Family
ID=17721178
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP28774298A Expired - Fee Related JP4097803B2 (en) | 1998-10-09 | 1998-10-09 | Method and apparatus for producing a polyimide substrate having a copper layer |
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| Country | Link |
|---|---|
| JP (1) | JP4097803B2 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004182516A (en) * | 2002-12-02 | 2004-07-02 | Tokai Univ | Method of photochemically modifying solid material surface |
| JP2010185085A (en) * | 2010-04-30 | 2010-08-26 | Masataka Murahara | Method of photochemically reforming surface of solid material |
| US9745428B2 (en) | 2013-08-09 | 2017-08-29 | Canon Components, Inc. | Method for processing resin product and resin product |
-
1998
- 1998-10-09 JP JP28774298A patent/JP4097803B2/en not_active Expired - Fee Related
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004182516A (en) * | 2002-12-02 | 2004-07-02 | Tokai Univ | Method of photochemically modifying solid material surface |
| JP2010185085A (en) * | 2010-04-30 | 2010-08-26 | Masataka Murahara | Method of photochemically reforming surface of solid material |
| US9745428B2 (en) | 2013-08-09 | 2017-08-29 | Canon Components, Inc. | Method for processing resin product and resin product |
Also Published As
| Publication number | Publication date |
|---|---|
| JP4097803B2 (en) | 2008-06-11 |
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