JP2008088524A - Copper sulfate plating solution for printed board - Google Patents
Copper sulfate plating solution for printed board Download PDFInfo
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- JP2008088524A JP2008088524A JP2006272492A JP2006272492A JP2008088524A JP 2008088524 A JP2008088524 A JP 2008088524A JP 2006272492 A JP2006272492 A JP 2006272492A JP 2006272492 A JP2006272492 A JP 2006272492A JP 2008088524 A JP2008088524 A JP 2008088524A
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- 238000007747 plating Methods 0.000 title claims abstract description 101
- 229910000365 copper sulfate Inorganic materials 0.000 title claims abstract description 76
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 title claims abstract description 76
- 239000000203 mixture Substances 0.000 claims abstract description 33
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 24
- 229920000768 polyamine Polymers 0.000 claims abstract description 22
- 150000001875 compounds Chemical class 0.000 claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 14
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 10
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 7
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 5
- 125000005843 halogen group Chemical group 0.000 claims abstract description 5
- 150000002367 halogens Chemical class 0.000 claims abstract description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 9
- -1 3-chloro-2-hydroxypropyl group Chemical group 0.000 claims description 8
- 229910052801 chlorine Inorganic materials 0.000 claims description 8
- 239000000460 chlorine Substances 0.000 claims description 8
- 125000004432 carbon atom Chemical group C* 0.000 claims description 6
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 4
- 125000004429 atom Chemical group 0.000 claims 2
- 238000004070 electrodeposition Methods 0.000 abstract description 11
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 22
- 239000000654 additive Substances 0.000 description 17
- 238000012360 testing method Methods 0.000 description 14
- 229910052802 copper Inorganic materials 0.000 description 13
- 239000010949 copper Substances 0.000 description 13
- 230000000996 additive effect Effects 0.000 description 11
- 239000011889 copper foil Substances 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 5
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 4
- 239000002202 Polyethylene glycol Substances 0.000 description 4
- 125000001309 chloro group Chemical group Cl* 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 229920001223 polyethylene glycol Polymers 0.000 description 4
- 230000000704 physical effect Effects 0.000 description 3
- 229940057838 polyethylene glycol 4000 Drugs 0.000 description 3
- 230000035939 shock Effects 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 150000003457 sulfones Chemical class 0.000 description 3
- 239000004593 Epoxy Substances 0.000 description 2
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 2
- 229920002873 Polyethylenimine Polymers 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- PEVJCYPAFCUXEZ-UHFFFAOYSA-J dicopper;phosphonato phosphate Chemical compound [Cu+2].[Cu+2].[O-]P([O-])(=O)OP([O-])([O-])=O PEVJCYPAFCUXEZ-UHFFFAOYSA-J 0.000 description 2
- 238000009429 electrical wiring Methods 0.000 description 2
- 238000005530 etching Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 235000011187 glycerol Nutrition 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 229920001983 poloxamer Polymers 0.000 description 2
- BBEAQIROQSPTKN-UHFFFAOYSA-N pyrene Chemical compound C1=CC=C2C=CC3=CC=CC4=CC=C1C2=C43 BBEAQIROQSPTKN-UHFFFAOYSA-N 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000005282 brightening Methods 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- GVEPBJHOBDJJJI-UHFFFAOYSA-N fluoranthrene Natural products C1=CC(C2=CC=CC=C22)=C3C2=CC=CC3=C1 GVEPBJHOBDJJJI-UHFFFAOYSA-N 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
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Abstract
Description
本発明はプリント基板用硫酸銅めっき液に関し、更に詳細には、プリント基板に設けられたスルーホール内での優れた均一電着性を得ることのできるプリント基板用硫酸銅めっきに関する。 The present invention relates to a copper sulfate plating solution for a printed circuit board, and more particularly to a copper sulfate plating for a printed circuit board that can obtain excellent uniform electrodeposition within a through hole provided in the printed circuit board.
プリント基板では、上面の銅箔と下面の銅箔を導通させ、立体的な回路を形成するために、スルーホールが多用されている。このプリント基板のスルーホールは、ドリル、レーザー等で形成した後、その内面にめっき等により銅を析出させ、上面銅箔と下面銅箔の導通を可能とするのであるが、スルーホールの内面は銅箔面に比べ、電流密度が低く、スルーホール内は銅箔面に比較してめっき厚が薄くなる傾向にあるため、均一電着性の良いものが求められていた。すなわち、スルーホール内面と銅箔面でのめっき析出量の差が小さいものを選ぶことにより、より短時間でスルーホール内のめっき厚が確保され、また、配線形成時の銅箔表面めっきのエッチング時間が短くなり、高精細配線を可能とする。 In a printed circuit board, through holes are frequently used in order to make a copper foil on the upper surface and a copper foil on the lower surface conductive to form a three-dimensional circuit. The through hole of this printed circuit board is formed with a drill, a laser, etc., and then copper is deposited on the inner surface by plating or the like to enable conduction between the upper surface copper foil and the lower surface copper foil. Since the current density is lower than that of the copper foil surface and the plating thickness tends to be thinner in the through hole than that of the copper foil surface, a material having good throwing power has been demanded. In other words, by selecting the one with a small difference in the amount of plating deposition between the inner surface of the through hole and the copper foil surface, the plating thickness in the through hole can be secured in a shorter time, and the etching of the copper foil surface plating during wiring formation Time is shortened and high-definition wiring is possible.
従来、硫酸銅めっきは、装飾めっきのために広く使用されており、これをプリント基板に応用することも試みられたが、装飾めっきに利用される硫酸銅めっきは、基本的には均一電着性が悪く、その利用には困難が伴っていた。そこで、プリント基板めっきには、主にピロリン酸銅めっきが利用されていた。 Conventionally, copper sulfate plating has been widely used for decorative plating, and attempts have been made to apply it to printed circuit boards. However, copper sulfate plating used for decorative plating is basically uniform electrodeposition. It was not easy to use and it was difficult to use. Therefore, copper pyrophosphate plating has been mainly used for printed circuit board plating.
しかしながら、近年、排水処理の面から、ピロリン酸銅の使用が問題視されており、従来の装飾用の硫酸銅めっき液組成とは全く異なる、硫酸銅濃度が低く、硫酸濃度が高いハイスロー組成の硫酸銅めっき液が利用されるようになっている。しかしながら、このハイスロー組成の硫酸銅めっきで、均一電着性は改善されてはいるものの、スルーホールの小径化の著しい近年では満足の得られないケースが増加している。 However, in recent years, the use of copper pyrophosphate has been regarded as a problem from the viewpoint of wastewater treatment, and has a high-throw composition with a low copper sulfate concentration and a high sulfuric acid concentration, which is completely different from the conventional copper sulfate plating solution composition for decoration. Copper sulfate plating solution is used. However, with this high-throw composition copper sulfate plating, the throwing power has been improved, but in recent years when the through-hole diameter has been remarkably reduced, the number of cases where satisfaction cannot be obtained is increasing.
従って、硫酸銅めっき浴を基本組成としながら、優れた均一電着性を有するめっき浴を得ることのできる手段の開発が求められており、このような手段の提供が本発明の課題である。 Accordingly, development of means capable of obtaining a plating bath having excellent throwing power while using a copper sulfate plating bath as a basic composition is required, and the provision of such means is an object of the present invention.
本発明者らは、上記課題を解決すべく鋭意研究を行っていたところ、ハイスロー組成の硫酸銅めっき液に、特定のポリアミン系化合物を添加すれば、優れた均一電着性のものとすることができることを見出し、本発明を完成した。 The inventors of the present invention have been diligently researching to solve the above-mentioned problems. When a specific polyamine compound is added to a copper sulfate plating solution having a high-throw composition, the electrodeposition should have excellent throwing power. The present invention has been completed.
すなわち本発明は、４０〜１００ｇ／Ｌの硫酸銅および１５０〜２５０ｇ／Ｌの硫酸を含有する硫酸銅めっき基本組成に、下記式（Ｉ）または（II）
で表される構造単位を有するポリアミン系化合物を添加してなることを特徴とするプリント基板用硫酸銅めっき液である。
That is, the present invention provides a copper sulfate plating basic composition containing 40 to 100 g / L of copper sulfate and 150 to 250 g / L of sulfuric acid with the following formula (I) or (II):
A copper sulfate plating solution for printed circuit boards, comprising a polyamine compound having a structural unit represented by the formula:
また本発明は、スルーホールを有する銅張プリント基板を、上記硫酸銅めっき液中でめっきすることを特徴とするスルーホールを有するプリント基板のめっき方法である。 Moreover, this invention is a plating method of the printed circuit board which has a through hole characterized by plating the copper clad printed circuit board which has a through hole in the said copper sulfate plating solution.
本発明の硫酸銅めっき液は、硫酸銅めっき液でありながら高い均一電着性を有するものであり、プリント基板に設けられたスルーホール内にも均一電着性良く銅皮膜を形成することができるものである。 Although the copper sulfate plating solution of the present invention is a copper sulfate plating solution, it has high throwing power and can form a copper film with good throwing power in a through hole provided in a printed circuit board. It can be done.
本発明のプリント基板用硫酸銅めっき液において、添加剤として使用されるポリアミン系化合物は、上記式（Ｉ）または（II）で表される構造単位を有するものである。このうち、式（Ｉ）で表される構造単位を有するものは、ポリンアミンスルホンとも呼ばれる化合物である。このポリンアミンスルホン（Ｉ）において、基Ｒ１およびＲ２は、水素原子またはメチル基、エチル基、プロピル基、イソプロピル基、ｎ−ブチル基、イソブチル基、ｔｅｒｔ−ブチル基等の、炭素数１ないし４のアルキル基である。また、基Ｘは、塩素、臭素等のハロゲン原子である。 In the copper sulfate plating solution for printed circuit boards of the present invention, the polyamine compound used as an additive has a structural unit represented by the above formula (I) or (II). Among these, what has a structural unit represented by a formula (I) is a compound called a polyamine amine sulfone. In this polyamine amine sulfone (I), the groups R 1 and R 2 are each a hydrogen atom or a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a tert-butyl group, or the like. Or 4 alkyl groups. The group X is a halogen atom such as chlorine or bromine.
また、式（II）で表される構造単位を有するポリアミン系化合物において、基Ｒ１、基Ｒ２および基Ｘは、ポリアミンスルホン（Ｉ）と同様であり、基Ｒ３は、３−ハロゲノ−２−ヒドロキシプロピル基のような、水酸基およびハロゲンを有する炭素数２〜４のアルキル基である。 In the polyamine compound having the structural unit represented by the formula (II), the group R 1 , the group R 2 and the group X are the same as those of the polyamine sulfone (I), and the group R 3 is 3-halogeno- It is a C2-C4 alkyl group having a hydroxyl group and a halogen, such as a 2-hydroxypropyl group.
上記ポリアミン系化合物は、その分子量が、１,０００ないし１００,０００であるものが好ましく、特に、４,０００ないし４０,０００のものが好ましい。 The polyamine compound preferably has a molecular weight of 1,000 to 100,000, particularly preferably 4,000 to 40,000.
本発明で使用するポリアミン系化合物は、いずれも既に公知の化合物である。式（Ｉ）の構造単位のポリアミンスルホンのうち、Ｒ１およびＲ２が共にメチル基であるものとしては、ＰＡＳ−Ａ−１、ＰＡＳ−Ａ−５、ＰＡＳ−Ａ−１２０ＬおよびＰＡＳ−Ａ−１２０Ｌが、また、Ｒ１およびＲ２が共に水素原子であるものとして、ＰＡＳ−９２がそれぞれ日東紡株式会社から市販されている。更に、式（II）の構造単位のポリアミン系化合物のうち、Ｒ１およびＲ２が共にメチル基で、Ｒ３が３−クロロ−２−ヒドロキシプロピル基であるものも、ＰＡＳ−８８０として日東紡株式会社から市販されている。 All of the polyamine compounds used in the present invention are known compounds. Among the polyamine sulfones of the structural unit of the formula (I), those in which R 1 and R 2 are both methyl groups include PAS-A-1, PAS-A-5, PAS-A-120L and PAS-A-. PAS-92 is commercially available from Nittobo Co., Ltd., assuming that 120L is R 1 and R 2 are both hydrogen atoms. Furthermore, among the polyamine compounds of the structural unit of the formula (II), those in which R 1 and R 2 are both methyl groups and R 3 is a 3-chloro-2-hydroxypropyl group are also known as PAS-880. It is commercially available from the corporation.
なお、ポリアミンスルホンを硫酸銅めっき液中に添加することは、既に特許文献１に開示されているが、これは分子量１,９００程度のものが単に開示されているに過ぎず、しかも、本文献中では、これを硫酸銅めっき液に添加した場合の効果については、何一つ教示していない。 The addition of polyamine sulfone to the copper sulfate plating solution has already been disclosed in Patent Document 1, but this is merely disclosed as having a molecular weight of about 1,900. Nothing is taught about the effect of adding this to a copper sulfate plating solution.
一方、本発明のプリント基板用硫酸銅めっき液（以下、「本発明硫酸銅めっき液」という）の基本組成は、４０〜１００ｇ／Ｌの硫酸銅および１５０〜２５０ｇ／Ｌの硫酸を含有する組成である。この液組成は、一般にはハイスロー組成と呼ばれるものであり、好ましくは、硫酸銅が６０〜９０ｇ／Ｌ、硫酸が１７０〜２３０ｇ／Ｌである。また、この浴には、塩素が２０〜１００ｍｇ／Ｌ程度含有されていても良い。 On the other hand, the basic composition of the copper sulfate plating solution for printed circuit boards of the present invention (hereinafter referred to as “the copper sulfate plating solution of the present invention”) is a composition containing 40 to 100 g / L copper sulfate and 150 to 250 g / L sulfuric acid. It is. This liquid composition is generally referred to as a high-throw composition, and is preferably 60 to 90 g / L for copper sulfate and 170 to 230 g / L for sulfuric acid. Further, this bath may contain about 20 to 100 mg / L of chlorine.
本発明硫酸銅めっき液は、上記した基本組成に、前記のポリアミン系化合物を、１ないし５００ｍｇ／Ｌ程度、好ましくは、５ないし２００ｍｇ／Ｌ添加することにより調製される。 The copper sulfate plating solution of the present invention is prepared by adding about 1 to 500 mg / L, preferably 5 to 200 mg / L of the polyamine compound to the above basic composition.
また、本発明硫酸銅めっき液には、本発明の効果を妨げない範囲において、各種の公知の添加剤を加えることも可能である。この添加剤は特に制約されるものではないが、ポリエチレングリコール（ＰＥＧ）、プルロニック型界面活性剤、グリセリンＰＥＧ付加物等の湿潤成分や、ビススルホプロパンスルホン酸ナトリウム（ＳＰＳ）等の光沢化剤成分が例示される。 In addition, various known additives can be added to the copper sulfate plating solution of the present invention as long as the effects of the present invention are not hindered. This additive is not particularly limited, but is a moistening component such as polyethylene glycol (PEG), a pluronic surfactant, a glycerin PEG adduct, and a brightening agent component such as sodium bissulfopropanesulfonate (SPS). Is exemplified.
以上説明した本発明硫酸銅めっき液を用いて、スルーホールを有する銅張プリント基板（以下、単に「プリント基板」という）のスルーホール内壁に銅めっきを析出させ、所望の電気配線を有するプリント基板を得るには、次のようにすればよい。 Using the copper sulfate plating solution of the present invention described above, copper plating is deposited on the inner wall of a through hole of a copper-clad printed circuit board (hereinafter simply referred to as “printed circuit board”) having a through hole, and a printed circuit board having a desired electrical wiring. To get it, you can do the following:
すなわち、まず、常法に従って、スルーホール内や、プリント基板上を清浄化した後、例えば、ホルマリンを還元剤とする無電解銅めっき等の手段により、スルーホール内に導電化皮膜を形成する。次いで、銅電極または不溶解性電極を設置しためっき槽中に本発明硫酸銅めっき液を入れ、プリント基板上の銅皮膜を陰極とし、電気めっきを行う。所定時間めっきを行った後、周知のレジスト法およびエッチング法を使用することにより、所望の電気配線を有するプリント基板を調製することができる。 That is, first, after the inside of a through hole or a printed board is cleaned according to a conventional method, a conductive film is formed in the through hole by means such as electroless copper plating using formalin as a reducing agent. Next, the copper sulfate plating solution of the present invention is placed in a plating tank provided with a copper electrode or an insoluble electrode, and electroplating is performed using the copper film on the printed circuit board as a cathode. After plating for a predetermined time, a printed circuit board having desired electrical wiring can be prepared by using a well-known resist method and etching method.
上記方法において、硫酸銅めっきは、スルーホールの径や、深さによっても異なるが、一般には、０.５ないし５Ａ／ｄｍ２程度、好ましくは、１.５ないし３.０Ａ／ｄｍ２程度の電流密度で、３０ないし３００分間、好ましくは、５０ないし１００分間行えば良い。また、その際のめっき液の温度は、２０ないし３０℃程度とすれば良く、撹拌も、エアー攪拌、噴流攪拌等を利用することができる。 In the above method, the copper sulfate plating varies depending on the diameter and depth of the through hole, but is generally about 0.5 to 5 A / dm 2 , preferably about 1.5 to 3.0 A / dm 2 . The current density may be 30 to 300 minutes, preferably 50 to 100 minutes. Further, the temperature of the plating solution at that time may be about 20 to 30 ° C., and air stirring, jet stirring or the like can be used for stirring.
上述の本発明方法は、従来の硫酸銅めっき液を使用する方法に比べ、均一電着性が極めて良いため、プリント基板上に設けられた、孔径０.１５ないし０.３ｎｍ程度、アスペクト比（板厚／孔径）５ないし１０程度のスルーホールでも十分に膜厚分布の優れためっきが可能である。 Since the above-described method of the present invention has extremely good electrodeposition compared to the conventional method using a copper sulfate plating solution, the pore diameter provided on the printed circuit board is about 0.15 to 0.3 nm, and the aspect ratio ( (Thickness / hole diameter) Even a through hole of about 5 to 10 can be plated with a sufficiently excellent film thickness distribution.
以下、実施例および試験例を挙げ、本発明を更に詳しく説明するが、本発明はこれら実施例等に何ら制約されるものではない。 EXAMPLES Hereinafter, although an Example and a test example are given and this invention is demonstrated in more detail, this invention is not restrict | limited at all by these Examples.
実 施 例 １
プリント基板用硫酸銅めっき液（１）：
硫酸銅を７５ｇ／Ｌ、硫酸を１８０ｇ／Ｌおよび塩素を６０ｍｇ／Ｌ含有する硫酸銅めっき浴基本組成（以下、「基本組成」という）に、下記組成となるよう添加剤を加え、本発明硫酸銅めっき浴（１）を得た。
Example 1
Copper sulfate plating solution for printed circuit boards (1):
An additive is added to a copper sulfate plating bath basic composition (hereinafter referred to as “basic composition”) containing 75 g / L of copper sulfate, 180 g / L of sulfuric acid and 60 mg / L of chlorine, and the sulfuric acid of the present invention. A copper plating bath (1) was obtained.
（ 添加剤組成 ）
ポリエチレングリコール４０００ ２００ｍｇ／Ｌ
ＳＰＳ ５ｍｇ／Ｌ
ＰＡＳ−Ａ−１＊（Ｍ.Ｗ＝５,０００） ５０ｍｇ／Ｌ
*式（Ｉ）中、Ｒ１、Ｒ２ ＝メチル、Ｘ＝塩素／日東紡株式会社製
(Additive composition)
Polyethylene glycol 4000 200mg / L
SPS 5mg / L
PAS-A-1 * (M.W = 5,000) 50 mg / L
* In the formula (I), R 1 , R 2 = methyl, X = chlorine / Nittobo Co., Ltd.
実 施 例 ２
プリント基板用硫酸銅めっき液（２）：
実施例と同じ基本組成に、下記組成となるよう添加剤を加え、本発明硫酸銅めっき浴（２）を得た。
Example 2
Copper sulfate plating solution for printed circuit boards (2):
Additives were added to the same basic composition as in the examples so that the following composition was obtained, to obtain the copper sulfate plating bath (2) of the present invention.
（ 添加剤組成 ）
ポリエチレングリコール４０００ ２００ｍｇ／Ｌ
ＳＰＳ ５ｍｇ／Ｌ
ＰＡＳ−Ａ−５＊（Ｍ.Ｗ＝４,０００） １００ｍｇ／Ｌ
*式（Ｉ）中、Ｒ１、Ｒ２ ＝メチル、Ｘ＝塩素／日東紡株式会社製
(Additive composition)
Polyethylene glycol 4000 200mg / L
SPS 5mg / L
PAS-A-5 * (M.W = 4,000) 100 mg / L
* In formula (I), R 1 , R 2 = methyl, X = chlorine / Nittobo Co., Ltd.
実 施 例 ３
プリント基板用硫酸銅めっき液（３）：
実施例と同じ基本組成に、下記組成となるよう添加剤を加え、本発明硫酸銅めっき浴（３）を得た。
Example 3
Copper sulfate plating solution for printed circuit boards (3):
Additives were added to the same basic composition as in the examples so as to obtain the following composition to obtain a copper sulfate plating bath (3) of the present invention.
（ 添加剤組成 ）
ポリエチレングリコール１００００ ５００ｍｇ／Ｌ
ＳＰＳ ２ｍｇ／Ｌ
ＰＡＳ−８８０＊（Ｍ.Ｗ＝４０,０００） １００ｍｇ／Ｌ
*式（Ｉ）中、Ｒ１、Ｒ２ ＝メチル、Ｒ３＝３−クロロ−２−ヒドロキシ
プロピル基、Ｘ＝塩素／日東紡株式会社製
(Additive composition)
Polyethylene glycol 10000 500mg / L
SPS 2mg / L
PAS-880 * (MW = 40,000) 100 mg / L
* In formula (I), R 1 , R 2 = methyl, R 3 = 3-chloro-2-hydroxy
Propyl group, X = chlorine / Nittobo Co., Ltd.
実 施 例 ４
プリント基板用硫酸銅めっき液（４）：
実施例と同じ基本組成に、下記組成となるよう添加剤を加え、本発明硫酸銅めっき浴（４）を得た。
Example 4
Copper sulfate plating solution for printed circuit boards (4):
Additives were added to the same basic composition as in the examples so as to obtain the following composition to obtain the copper sulfate plating bath (4) of the present invention.
（ 添加剤組成 ）
ポリオキシエチレンポリオキシプロ ３０ｍｇ／Ｌ
ピレン縮合物 *
ＳＰＳ １５ｍｇ／Ｌ
ＰＡＳ−９２＊＊（Ｍ.Ｗ＝５,０００） １００ｍｇ／Ｌ
*プルロニック Ｌ３４／旭電化株式会社製
**式（Ｉ）中、Ｒ１、Ｒ２ ＝メチル、Ｘ＝塩素／日東紡株式会社製
(Additive composition)
Polyoxyethylene polyoxypro 30mg / L
Pyrene condensate *
SPS 15mg / L
PAS-92 ** (M.W = 5,000) 100mg / L
* Pluronic L34 / Asahi Denka Co., Ltd.
** In formula (I), R 1 , R 2 = methyl, X = chlorine / Nittobo Co., Ltd.
比 較 例 １
比較プリント基板用硫酸銅めっき液：
実施例と同じ基本組成に、下記組成となるよう添加剤を加え、比較硫酸銅めっき浴を得た。なお、ここで用いたポリエチレンイミン等は、プリント配線板めっき浴として従来から実績のある添加剤であるので、これを比較標準とした。
Comparative Example 1
Copper sulfate plating solution for comparative printed circuit boards:
Additives were added to the same basic composition as in the examples so as to obtain the following composition to obtain a comparative copper sulfate plating bath. In addition, since polyethyleneimine etc. used here are additives with a track record as a printed wiring board plating bath, this was used as a comparative standard.
（ 添加剤組成 ）
ポリエチレングリコール４０００ ２００ｍｇ／Ｌ
ＳＰＳ １ｍｇ／Ｌ
ポリエチレンイミン（Ｍ.Ｗ＝２,０００） ２ｍｇ／Ｌ
(Additive composition)
Polyethylene glycol 4000 200mg / L
SPS 1mg / L
Polyethyleneimine (MW = 2,000) 2mg / L
試 験 例 １
均一電着性試験（１）：
めっき試料としては、下記に示す孔径、深さ（素材厚さ）のスルーホールをドリルで形成したガラスエポキシプリント基板（松下ＦＲ４）を用い、標準的な無電解銅めっきプロセス（ライザトロンプロセス；荏原ユージライト株式会社製）により、スルーホールの無電解銅めっきを予め行なった。次いで、実施例１のプリント基板用硫酸銅めっき浴および比較例１の硫酸銅めっき浴を用い、陰極電流密度（Ｄｋ）２.０Ａ／ｄｍ２の条件および陰極電流密度１.０Ａ／ｄｍ２の条件にて、それぞれ２０μｍの膜厚となるまでめっきを行った。その後、以下の方法に従い均一電着性を調べた。この結果を表１に示す。
Test example 1
Uniform electrodeposition test (1):
As the plating sample, a glass epoxy printed circuit board (Matsushita FR4) in which through holes with the following hole diameter and depth (material thickness) were formed by a drill was used, and a standard electroless copper plating process (Risertron process; Sugawara) Through-hole electroless copper plating was performed in advance by Eugelite Co., Ltd. Next, using the copper sulfate plating bath for printed circuit board of Example 1 and the copper sulfate plating bath of Comparative Example 1, the conditions of cathode current density (Dk) 2.0 A / dm 2 and cathode current density 1.0 A / dm 2 were obtained. Plating was performed under the conditions until the film thickness became 20 μm. Thereafter, uniform electrodeposition was examined according to the following method. The results are shown in Table 1.
＜均一電着性の算出方法＞
めっき後のスルーホールを断面カットし、図１に示す位置（ａ〜ｆ）における膜厚を測定し、以下の式により均一電着性を算出した。
The through hole after plating was cut in cross section, the film thickness at the positions (af) shown in FIG. 1 was measured, and the uniform electrodeposition was calculated by the following equation.
上記の結果から明らかなように、本発明のプリント基板用硫酸銅めっき浴の均一電着性は、従来の比較標準のプリント基板用硫酸銅めっき浴に比べ優れていた。 As is clear from the above results, the throwing power of the copper sulfate plating bath for printed circuit boards of the present invention was superior to that of a conventional copper sulfate plating bath for printed circuit boards.
試 験 例 ２
均一電着性試験（２）：
試験例１に準じて、実施例２ないし４で調製したプリント基板用硫酸銅めっき浴についても、それらの均一電着性を調べた。この試験においては、試験するスルーホールの孔径、深さは２点とし、めっきは、陰極電流密度２.０Ａ／ｄｍ２で、２０μｍの膜厚となるまで行った。この結果を表２に示す。
Test example 2
Uniform electrodeposition test (2):
The throwing power of the copper sulfate plating baths for printed circuit boards prepared in Examples 2 to 4 according to Test Example 1 was also examined. In this test, the hole diameter and depth of the through hole to be tested were two points, and plating was performed at a cathode current density of 2.0 A / dm 2 until a film thickness of 20 μm was obtained. The results are shown in Table 2.
この結果から明らかなように、実施例２ないし４で調製したプリント基板用硫酸銅めっき浴も優れた均一電着性を有していた。 As is apparent from this result, the copper sulfate plating bath for printed circuit boards prepared in Examples 2 to 4 also had excellent uniform electrodeposition.
試 験 例 ３
基本組成濃度の影響：
硫酸銅、硫酸の基本組成濃度が均一電着性に及ぼす影響を調べた。この試験で使用した硫酸銅めっき添加剤の組成は、実施例１のものと同じであり、めっきは陰極電流密度２.０Ａ／ｄｍ２で行った。なお、均一電着性は、１.６ｍｍｔ、０.３ｍｍΦのスルーホールと、３.２ｍｍｔ、０.３ｍｍΦのスルーホールで測定した。この結果を表３に示す。
Test example 3
Effect of basic composition concentration:
The effect of the basic composition concentration of copper sulfate and sulfuric acid on the throwing power was investigated. The composition of the copper sulfate plating additive used in this test was the same as that of Example 1, and plating was performed at a cathode current density of 2.0 A / dm 2 . The throwing power was measured with a through hole of 1.6 mmt and 0.3 mmΦ and a through hole of 3.2 mmt and 0.3 mmΦ. The results are shown in Table 3.
一般的にプリント基板のスルーホール内での均一電着性は少なくとも７０％以上は要望されるが、硫酸銅濃度と硫酸濃度は重要な条件であることがわかる。いかに優れた添加剤を用いても、硫酸銅濃度が高く硫酸濃度が低い従来の装飾硫酸銅めっき用の基本組成では、性能を発揮することができないことが上記試験結果から明らかである。 Generally, it is desired that the throwing power in the through hole of the printed circuit board is at least 70%, but it is understood that the copper sulfate concentration and the sulfuric acid concentration are important conditions. It is clear from the above test results that no matter how excellent the additive is used, the conventional basic composition for decorative copper sulfate plating having a high copper sulfate concentration and a low sulfuric acid concentration cannot exhibit performance.
試 験 例 ４
サーマルショック試験：
実施例１ないし４で調製したプリント基板用硫酸銅めっき浴について、その銅皮膜の物性を調べるため、サーマルショック試験を行った。サーマルショック試験は、めっき条件２Ａ／ｄｍ２で２５μｍとなるまで硫酸銅めっきを行った各プリント基板について、２６０℃のグリセリンに１０秒浸漬後、２５℃のトリクレンに１０秒浸漬する工程を所定回数繰り返し、その後、スルホール（１.６ｍｍｔ、０.３ｍｍΦ）内を断面カットし、クラックの有無を観察することにより行った。スルホール１０穴を観察し、各コーナー計４０箇所および各穴中心部計２０箇所に計６０箇所に生じたクラックの数を数え、評価した。この結果を表４に示す。
Test example 4
Thermal shock test:
For the copper sulfate plating bath for printed circuit boards prepared in Examples 1 to 4, a thermal shock test was conducted in order to examine the physical properties of the copper film. In the thermal shock test, for each printed circuit board on which copper sulfate plating was performed until the plating condition was 2 A / dm 2 until 25 μm, the step of immersing in glycerin at 260 ° C. for 10 seconds and then immersing in trichrene at 25 ° C. for 10 seconds was performed a predetermined number of times. Repeatedly, after that, the inside of the through hole (1.6 mmt, 0.3 mmΦ) was cut in cross section, and the presence or absence of cracks was observed. Ten through holes were observed, and the number of cracks generated at a total of 60 locations at 40 locations at each corner and 20 locations at the center of each hole was counted and evaluated. The results are shown in Table 4.
以上の結果より、本発明の硫酸銅めっき浴は、皮膜物性としても従来から使用されている添加剤を用いたものと遜色ない性質であり、実用的に全く問題ないものであることが明らかとなった。 From the above results, it is clear that the copper sulfate plating bath of the present invention is a property that is inferior to that using an additive conventionally used as a film physical property, and that there is no practical problem at all. became.
本発明の硫酸銅めっき液は、他の硫酸銅めっき液に比べ、均一電着性が高く、しかも、優れた物性の銅皮膜を得ることができるものである。 The copper sulfate plating solution of the present invention has high electrodeposition properties compared to other copper sulfate plating solutions, and can obtain a copper film having excellent physical properties.
従って、本発明の硫酸銅めっき液は、特にスルーホールや、ビアを有するプリント基板用の銅めっき液として、広く使用できるものである。 Therefore, the copper sulfate plating solution of the present invention can be widely used as a copper plating solution for printed circuit boards having through holes and vias.
１ …… 絶縁部（ガラスエポキシ部分等）
２ …… 銅箔
３ …… 硫酸銅めっき
４ …… スルーホール
ａ〜ｆ …… 膜厚測定位置
以 上
1 ...... Insulation part (glass epoxy part, etc.)
2 ...
more than
Claims (10)
で表される構造単位を有するポリアミン系化合物を添加してなることを特徴とするプリント基板用硫酸銅めっき液。 A copper sulfate plating basic composition containing 40 to 100 g / L of copper sulfate and 150 to 250 g / L of sulfuric acid has the following formula (I) or (II):
A copper sulfate plating solution for printed circuit boards, comprising a polyamine compound having a structural unit represented by the formula:
で表される構造単位を有するポリアミン系化合物を含有する硫酸銅めっき液中でめっきすることを特徴とするスルーホールを有するプリント基板のめっき方法。 A copper-clad printed circuit board having a through hole is obtained by using 40 to 100 g / L copper sulfate, 150 to 250 g / L sulfuric acid, and the following formula (I) or (II)
A plating method for a printed circuit board having a through hole, wherein the plating is performed in a copper sulfate plating solution containing a polyamine compound having a structural unit represented by:
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