JP3193355B2 - Desmear treatment solution - Google Patents
Desmear treatment solutionInfo
- Publication number
- JP3193355B2 JP3193355B2 JP10108299A JP10108299A JP3193355B2 JP 3193355 B2 JP3193355 B2 JP 3193355B2 JP 10108299 A JP10108299 A JP 10108299A JP 10108299 A JP10108299 A JP 10108299A JP 3193355 B2 JP3193355 B2 JP 3193355B2
- Authority
- JP
- Japan
- Prior art keywords
- desmear treatment
- desmear
- solution
- treatment liquid
- halogen
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Landscapes
- Printing Elements For Providing Electric Connections Between Printed Circuits (AREA)
- Manufacturing Of Printed Wiring (AREA)
- Detergent Compositions (AREA)
Description
【０００１】[0001]
【発明の属する技術分野】本発明はプリント回路基板、
特にハロゲンフリーのプリント回路基板の製造における
デスミア処理プロセスにおいて好ましく用いることので
きるデスミア処理液に関する。The present invention relates to a printed circuit board,
In particular, the present invention relates to a desmear treatment liquid that can be preferably used in a desmear treatment process in manufacturing a halogen-free printed circuit board.
【０００２】[0002]
【従来の技術】プリント回路基板の製造工程において、
穿孔によってスルーホールを形成した際には、孔内の導
体の露出表面に絶縁基板樹脂が付着するため、これを取
り除く作業が必要である。付着した絶縁基板樹脂（スミ
ア）を除去する作業はデスミア処理と称され、薬液によ
るウェット法とプラズマ等によるドライ法とに大別され
る。このうち、薬液によるウェット法において用いられ
るデスミア処理液としては、古くは濃硫酸やクロム酸が
用いられていたが、近年では、アルカリ性過マンガン酸
塩溶液が主流となっている。2. Description of the Related Art In a manufacturing process of a printed circuit board,
When a through hole is formed by perforation, the insulating substrate resin adheres to the exposed surface of the conductor in the hole, and it is necessary to remove the insulating substrate resin. The operation of removing the adhered insulating substrate resin (smear) is called desmear treatment, and is roughly classified into a wet method using a chemical solution and a dry method using plasma or the like. Of these, concentrated sulfuric acid and chromic acid have long been used as desmear treatment solutions used in the wet method using a chemical solution, but in recent years, alkaline permanganate solutions have become the mainstream.
【０００３】一方、絶縁基板材料としては、現在、難燃
性成分としてハロゲンを加えた樹脂が広く用いられてい
るが、廃棄の際に焼却するとダイオキシン等の有害な有
機ハロゲン化合物などが発生する等の問題があり、ハロ
ゲンを含まない所謂ハロゲンフリーの樹脂基材が求めら
れている。例えばドイツ等においては、法規制によりハ
ロゲンを含有する基板樹脂材料の使用が制限される方向
にあり、我が国においても環境保護の見地から法規制が
強化されていくと思われ、ハロゲンフリーの基板樹脂材
料に対する需要が更に高まっていくものと考えられる。On the other hand, as an insulating substrate material, a resin to which halogen is added as a flame-retardant component is widely used at present, but when incinerated at the time of disposal, harmful organic halogen compounds such as dioxin are generated. Therefore, there is a demand for a so-called halogen-free resin base material containing no halogen. For example, the use of halogen-containing substrate resin materials is being restricted by laws and regulations in Germany and other countries, and in Japan it is expected that laws and regulations will be tightened from the viewpoint of environmental protection, and halogen-free substrate resins will be used. It is thought that the demand for materials will further increase.
【０００４】[0004]
【発明が解決しようとする課題】しかしながら、ハロゲ
ンフリーの基板樹脂材料に対して、アルカリ性過マンガ
ン酸塩溶液などの薬液によるデスミア処理を行うと、デ
スミア処理液を繰り返し使用するに連れてエッチング量
が大きく低下してしまうという問題があることが分かっ
た。デスミア処理液は、浴負荷として１リットルあたり
５０〜６０ｍ2まで基板を処理するのが通常であり、使
用によってそのデスミア性（エッチング量）が大きく低
下するという傾向を有すると、新液の状態でデスミア処
理条件を定めると処理液を使い込んだときにはエッチン
グ量が低下しデスミア性が悪くなってしまい、逆にエッ
チング量の低下を予め見越してデスミア処理条件を定め
ると新液の状態では相当に過剰なデスミア処理条件とな
ってしまうという問題がある。このため、ハロゲンフリ
ーの基板樹脂材料に対するアルカリ性過マンガン酸塩溶
液によるデスミア処理においては、デスミア性を管理す
ることが極めて困難である。However, when a desmear treatment is performed on a halogen-free substrate resin material with a chemical such as an alkaline permanganate solution, the etching amount decreases as the desmear treatment liquid is used repeatedly. It turned out that there is a problem that it is greatly reduced. The desmear treatment liquid is usually used to treat a substrate up to 50 to 60 m 2 per liter as a bath load. If the desmear property (etching amount) tends to be greatly reduced by use, the desmear treatment liquid may be used as a new liquid. When the desmear processing conditions are determined, when the processing liquid is used, the etching amount is reduced and the desmear property is deteriorated. There is a problem that desmear processing conditions are set. For this reason, it is extremely difficult to control the desmear property in the desmear treatment of the halogen-free substrate resin material with an alkaline permanganate solution.
【０００５】本発明者らは、かかる問題点の解決方法を
探るべく鋭意研究を重ねた結果、ハロゲンフリー基板樹
脂材料をアルカリ性過マンガン酸塩デスミア処理液によ
ってデスミア処理すると、基板樹脂材料の骨格構造成分
がデスミア液によって溶出して、デスミア処理液中にベ
ンゼンカルボン酸系化合物が蓄積することを見出し、使
用によるデスミア処理液のデスミア性の低下は、このベ
ンゼンカルボン酸系化合物の蓄積に起因するものである
と考えた。この問題は、従来のハロゲンを含む基板樹脂
材料においてはあまり問題にはならなかったが、樹脂材
料をハロゲンフリーとすることによってアルカリ性過マ
ンガン酸塩溶液による骨格構造成分の溶出の度合いが大
きくなり、問題が顕在化したものと考えられる。The inventors of the present invention have conducted intensive studies to find a solution to the above problem. As a result, when the halogen-free substrate resin material is desmeared with an alkaline permanganate desmearing solution, the skeleton structure of the substrate resin material is reduced. The components were eluted by the desmear solution, and the benzene carboxylic acid compound was found to accumulate in the desmear treatment solution.The decrease in desmear property of the desmear treatment solution due to use was caused by the accumulation of the benzene carboxylic compound. I thought it was. This problem did not cause much problem in the conventional substrate resin material containing halogen, but by making the resin material halogen-free, the degree of elution of the skeletal structure component by the alkaline permanganate solution increases, It is considered that the problem became apparent.
【０００６】[0006]
【課題を解決するための手段】本発明者らは、上記の知
見に基づき、アルカリ性過マンガン酸塩デスミア処理液
中に予めベンゼンカルボン酸系化合物を添加しておくこ
とにより、繰り返しデスミア処理に使用するとデスミア
処理液のデスミア性が大きく低下するという問題を解消
し、処理ｍ2数に拘わらず一定のデスミア性を保つこと
ができることを見出し、本発明を完成するに至った。Means for Solving the Problems Based on the above findings, the present inventors have added a benzenecarboxylic acid-based compound to an alkaline permanganate desmear treatment solution in advance so that it can be repeatedly used for desmear treatment. then to solve the problem of desmearing of desmear treatment liquid is greatly reduced, it found that it is possible to maintain a constant desmear property regardless of the processing m the number 2, to complete the present invention.
【０００７】即ち、本発明は、デスミア処理有効成分を
含む液中にベンゼンカルボン酸系化合物が添加されてい
ることを特徴とするデスミア処理液に関する。本発明に
おいては、上記のように、デスミア処理液中に予めベン
ゼンカルボン酸系化合物を添加して十分量蓄積させた状
態をつくることによって、基板樹脂材料の骨格成分がデ
スミア処理液中に溶出することを抑制し、これにより、
使用に連れてデスミア処理液のデスミア性が低下するこ
とを防止して、一定のデスミア性を保持することに成功
した。理論に縛られることは意図しないが、この基板樹
脂材料の骨格成分の溶出の抑制は、予めベンゼンカルボ
ン酸系化合物をデスミア処理液中に十分に蓄積させて、
平衡状態を形成させることによって達成されるものと推
測される。したがって、本発明にかかるデスミア処理液
は、特に、ハロゲンフリーのプリント回路基板のデスミ
ア処理に用いるのに好適である。That is, the present invention relates to a desmear treatment solution characterized in that a benzenecarboxylic acid compound is added to a solution containing a desmear treatment active ingredient. In the present invention, as described above, the skeleton component of the substrate resin material is eluted into the desmear treatment liquid by adding a benzenecarboxylic acid-based compound to the desmear treatment liquid in advance and creating a state in which a sufficient amount is accumulated. That is,
It was possible to prevent the desmear property of the desmear treatment liquid from decreasing with use, and to maintain a certain desmear property. Although not intending to be bound by theory, the suppression of the elution of the skeleton component of the substrate resin material is achieved by sufficiently accumulating a benzenecarboxylic acid-based compound in the desmear treatment solution in advance,
It is presumed that this is achieved by forming an equilibrium state. Therefore, the desmear treatment liquid according to the present invention is particularly suitable for use in desmear treatment of a halogen-free printed circuit board.
【０００８】本発明において用いることのできるデスミ
ア処理液としては、現在最も多く用いられているアルカ
リ性過マンガン酸塩溶液を挙げることができる。アルカ
リ性過マンガン酸塩溶液としては、例えば過マンガン酸
カリウムを、水酸化ナトリウムなどのアルカリ溶液と共
に水中に溶解したものが好適に用いられる。また、過マ
ンガン酸ナトリウムなどの他の過マンガン酸塩を用いる
こともできる。デスミア処理液中に添加するベンゼンカ
ルボン酸系化合物としては、安息香酸、トリメリット酸
などが好適に用いられる。デスミア処理液中に添加する
ベンゼンカルボン酸系化合物の濃度は、処理する基板樹
脂材料の種類、求められるエッチング量、デスミア処理
条件、デスミア処理液の組成及び濃度などの種々の条件
によって変動し、当業者が経験的に決定することができ
るが、一般的には、０．０００１〜１ｍｏｌ／ｌ、好ま
しくは０．００１〜０．０５ｍｏｌ／ｌの範囲が好適で
ある。As the desmear treatment solution that can be used in the present invention, an alkaline permanganate solution that is currently most frequently used can be mentioned. As the alkaline permanganate solution, for example, a solution in which potassium permanganate is dissolved in water together with an alkaline solution such as sodium hydroxide is preferably used. Also, other permanganates such as sodium permanganate can be used. Benzoic acid, trimellitic acid, and the like are preferably used as the benzenecarboxylic acid-based compound added to the desmear treatment solution. The concentration of the benzene carboxylic acid compound to be added to the desmear treatment liquid varies depending on various conditions such as the type of substrate resin material to be treated, the required etching amount, the desmear treatment conditions, the composition and concentration of the desmear treatment liquid, and the like. Although it can be determined empirically by a trader, it is generally in the range of 0.0001 to 1 mol / l, preferably 0.001 to 0.05 mol / l.
【０００９】本発明のデスミア処理液は、特にハロゲン
フリーのプリント回路基板のデスミア処理において、使
用によるデスミア性の低下がなく、繰り返しの使用にお
いても一定のデスミア性を保持することができるので、
好適に用いることができる。The desmear treatment liquid of the present invention does not cause a decrease in desmear property due to use in a desmear treatment of a halogen-free printed circuit board, and can maintain a constant desmear property even in repeated use.
It can be suitably used.
【００１０】[0010]
【実施例】以下の実施例によって本発明を更に詳細に説
明するが、これらは、本発明を限定するものではない。 実施例１ 実験用基板としては、東芝ケミカル社製のＦＲ−４相当
ハロゲンフリー基板（ＵＬ認定品）を、銅箔エッチアウ
トして両面の銅箔層を除去し、デスミア処理による骨格
成分の溶出度合を加速するものを試験片として用いた。
この基板を１０ｃｍ×１０ｃｍにカットし、２４０番の
耐水ペーパーで端面を加工した。次に、１００℃で６０
分間ベイキングして、デシケーター内で１５分放冷した
後、重量を測定し、以下に説明するデスミア処理プロセ
スにかけた。１セットのデスミア処理プロセスにおい
て、３枚の試験片を処理した。The present invention will be described in more detail with reference to the following examples, which do not limit the present invention. Example 1 As an experimental substrate, a FR-4 equivalent halogen-free substrate (UL certified product) manufactured by Toshiba Chemical Co., Ltd. was etched out of copper foil to remove copper foil layers on both sides, and skeleton components were eluted by desmear treatment. The one that accelerated the degree was used as a test piece.
This substrate was cut into a size of 10 cm × 10 cm, and the end face was processed with a 240-degree waterproof paper. Next, at 100 ° C. for 60
After baking for 15 minutes and allowing to cool in a desiccator for 15 minutes, the weight was measured and subjected to the desmearing process described below. In one set of desmear treatment processes, three test pieces were processed.
【００１１】デスミア処理プロセスにおいては、まず、
試験片を、荏原電産製のプリント回路用膨潤剤：ＤＩ−
４６４（濃度５０容量％）中に、７５℃で７分間浸漬す
ることによって膨潤させた。次に、試験片を水で洗浄し
た後、荏原電産製のデスミア処理剤：ＰＭ−４６５を用
いてデスミア処理を行った。ＰＭ−４６５のＡ剤（過マ
ンガン酸カリウム）を５０ｇ／Ｌ、Ｂ剤（アルカリ剤）
を１３容量％の濃度となるように水中に溶解し、更に、
ベンゼンカルボン酸系化合物として安息香酸を０．００
８ｍｏｌ／Ｌの濃度で溶解することによって、本発明に
係るデスミア処理液を調製した。デスミア処理は、処理
液中に試験片を７５℃で１５分間浸漬することによって
行った。デスミア処理後の試験片を水洗した後、荏原電
産製のデスミア中和液：ＮＬ−４６６ＬＳ（濃度１５容
量％）中に、室温で５分間浸漬することによって中和し
た。中和処理後の試験片を水洗した後、ハンディードラ
イヤーで乾燥した。なお、膨潤処理、デスミア処理及び
中和処理は、いずれも、ビーカー内において、揺動させ
ながら行った。In the desmear treatment process, first,
The test piece was used as a swelling agent for printed circuit manufactured by Ebara Densan: DI-
It was swelled by immersion in 464 (concentration 50% by volume) at 75 ° C. for 7 minutes. Next, the test piece was washed with water, and then subjected to desmear treatment using a desmear treatment agent PM-465 manufactured by Ebara Densan. PM-465 A agent (potassium permanganate) 50 g / L, B agent (alkali agent)
Is dissolved in water to a concentration of 13% by volume.
Benzoic acid as a benzenecarboxylic acid-based compound is 0.00
By dissolving at a concentration of 8 mol / L, a desmear treatment liquid according to the present invention was prepared. The desmear treatment was performed by immersing the test piece in a treatment liquid at 75 ° C. for 15 minutes. After the test piece after the desmear treatment was washed with water, it was neutralized by immersing it in a desmear neutralizing solution: NL-466LS (concentration: 15% by volume) manufactured by Ebara Densan at room temperature for 5 minutes. After the test piece after the neutralization treatment was washed with water, it was dried with a handy drier. The swelling, desmearing, and neutralization treatments were all performed while rocking in a beaker.
【００１２】上記のデスミア処理プロセスを行った試験
片を１００℃で６０分間ベイキングし、デシケーター内
で１５分間放冷した後、重量を測定し、エッチング量を
算出した。The test piece subjected to the above desmearing process was baked at 100 ° C. for 60 minutes, allowed to cool in a desiccator for 15 minutes, weighed, and the etching amount was calculated.
【００１３】使用したデスミア処理液をそのまま繰り返
して用いて基板試験片のデスミア処理を全部で５セット
行い、５セット目の処理のエッチング量を同様に測定し
た。結果を表１に示す。 比較例１ デスミア処理液中に安息香酸を添加しなかった他は実施
例１と同様に、基板試験片のデスミア処理を合計で５セ
ット行い、１セット目と５セット目の処理のエッチング
量を測定した。結果を表１に示す。The desmear treatment solution used was repeatedly used as it was, and a total of five sets of desmear treatment of the substrate test piece were performed. The etching amount of the fifth set of treatments was measured in the same manner. Table 1 shows the results. Comparative Example 1 In the same manner as in Example 1, except that benzoic acid was not added to the desmear treatment solution, a total of five sets of desmear treatments of the substrate test piece were performed, and the etching amounts of the first set and the fifth set were determined. It was measured. Table 1 shows the results.
【００１４】[0014]
【表１】 [Table 1]
【００１５】上記の結果から、従来のデスミア処理液に
よるデスミアプロセスにおいては、デスミア処理液の使
用によってそのエッチング量が大きく低下するのに対し
て、ベンゼンカルボン酸系化合物を予めデスミア処理液
中に添加した本発明にかかるデスミア処理液によるデス
ミアプロセスにおいては、新液（１セット目）と使い込
んだ状態（５セット目）の液で、エッチング量に差がな
いことが分かった。From the above results, in the conventional desmear process using a desmear treatment solution, the use of the desmear treatment solution greatly reduces the etching amount, whereas a benzenecarboxylic acid compound is previously added to the desmear treatment solution. In the desmear process using the desmear treatment liquid according to the present invention, it was found that there was no difference in the etching amount between the new liquid (first set) and the used liquid (fifth set).
【００１６】[0016]
【発明の効果】本発明にかかるデスミア処理液によれ
ば、デスミア処理に繰り返し使用した後もそのデスミア
性（エッチング量）が一定に保たれるので、デスミア条
件を最適状態に定めることが容易である。よって、本発
明にかかるデスミア処理液を用いれば、特にハロゲンフ
リーのプリント基板に対してコントロールされたデスミ
ア処理を行うことができる。According to the desmear treatment liquid of the present invention, the desmear property (etching amount) is kept constant even after repeated use in the desmear treatment, so that it is easy to set the desmear condition to an optimum state. is there. Therefore, when the desmear treatment liquid according to the present invention is used, a controlled desmear treatment can be particularly performed on a halogen-free printed circuit board.
───────────────────────────────────────────────────── フロントページの続き (58)調査した分野(Int.Cl.7，ＤＢ名) H05K 3/00 - 3/46 C11D 7/00 - 7/60 ──────────────────────────────────────────────────続 き Continued on the front page (58) Field surveyed (Int. Cl. 7 , DB name) H05K 3/00-3/46 C11D 7 /00-7/60
Claims (3)
ア処理有効成分を含む液中にベンゼンカルボン酸系化合
物が添加されていることを特徴とするデスミア処理液。1. A desmear treatment liquid characterized in that a benzenecarboxylic acid compound is added to a liquid containing a desmear treatment active ingredient containing an alkaline permanganate.
処理液中に０．０００１〜１ｍｏｌ／ｌの範囲の濃度で
添加されている請求項１に記載のデスミア処理液。2. The desmear treatment liquid according to claim 1, wherein the benzenecarboxylic acid compound is added to the desmear treatment liquid at a concentration in the range of 0.0001 to 1 mol / l.
である請求項１又は２に記載のデスミア処理液。3. The desmear treatment liquid according to claim 1, wherein the benzenecarboxylic acid compound is benzoic acid.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10108299A JP3193355B2 (en) | 1999-04-08 | 1999-04-08 | Desmear treatment solution |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10108299A JP3193355B2 (en) | 1999-04-08 | 1999-04-08 | Desmear treatment solution |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2000294907A JP2000294907A (en) | 2000-10-20 |
| JP3193355B2 true JP3193355B2 (en) | 2001-07-30 |
Family
ID=14291189
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP10108299A Expired - Fee Related JP3193355B2 (en) | 1999-04-08 | 1999-04-08 | Desmear treatment solution |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3193355B2 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP6406841B2 (en) * | 2014-03-24 | 2018-10-17 | アトテック・ドイチュラント・ゲーエムベーハーＡｔｏｔｅｃｈ Ｄｅｕｔｓｃｈｌａｎｄ Ｇｍｂｈ | Metal layer forming method and printed circuit board manufacturing method |
| JP2016203403A (en) * | 2015-04-16 | 2016-12-08 | セイコーエプソン株式会社 | Circuit board, printing material container and printer |
-
1999
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