JP2008266722A - Additive for pulse copper-plating bath, and pulse copper-plating bath using the same - Google Patents
Additive for pulse copper-plating bath, and pulse copper-plating bath using the same Download PDFInfo
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- JP2008266722A JP2008266722A JP2007111104A JP2007111104A JP2008266722A JP 2008266722 A JP2008266722 A JP 2008266722A JP 2007111104 A JP2007111104 A JP 2007111104A JP 2007111104 A JP2007111104 A JP 2007111104A JP 2008266722 A JP2008266722 A JP 2008266722A
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- 238000007747 plating Methods 0.000 title claims abstract description 101
- 239000000654 additive Substances 0.000 title claims abstract description 45
- 230000000996 additive effect Effects 0.000 title claims abstract description 44
- 229910052802 copper Inorganic materials 0.000 claims abstract description 57
- 239000010949 copper Substances 0.000 claims abstract description 57
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 53
- 229920005862 polyol Polymers 0.000 claims abstract description 28
- 150000003077 polyols Chemical class 0.000 claims abstract description 28
- -1 tertiary amine compound Chemical class 0.000 claims abstract description 21
- 229920001515 polyalkylene glycol Polymers 0.000 claims abstract description 11
- 150000003856 quaternary ammonium compounds Chemical class 0.000 claims abstract description 10
- 239000004480 active ingredient Substances 0.000 claims abstract description 9
- 150000001412 amines Chemical class 0.000 claims abstract description 5
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 29
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 29
- 238000004519 manufacturing process Methods 0.000 claims description 19
- 150000005846 sugar alcohols Polymers 0.000 claims description 17
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 14
- 125000002947 alkylene group Chemical group 0.000 claims description 12
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- 229910052799 carbon Inorganic materials 0.000 claims description 9
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 9
- 125000004432 carbon atom Chemical group C* 0.000 claims description 7
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims description 4
- 229910001431 copper ion Inorganic materials 0.000 claims description 4
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 3
- 239000000460 chlorine Substances 0.000 claims description 3
- 229910052801 chlorine Inorganic materials 0.000 claims description 3
- 238000006735 epoxidation reaction Methods 0.000 claims description 3
- 238000000034 method Methods 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 abstract description 20
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- 239000002932 luster Substances 0.000 abstract 1
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- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 6
- OSDWBNJEKMUWAV-UHFFFAOYSA-N Allyl chloride Chemical compound ClCC=C OSDWBNJEKMUWAV-UHFFFAOYSA-N 0.000 description 5
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- 230000015572 biosynthetic process Effects 0.000 description 5
- NJZLKINMWXQCHI-UHFFFAOYSA-N sodium;3-(3-sulfopropyldisulfanyl)propane-1-sulfonic acid Chemical compound [Na].[Na].OS(=O)(=O)CCCSSCCCS(O)(=O)=O NJZLKINMWXQCHI-UHFFFAOYSA-N 0.000 description 5
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- 238000007796 conventional method Methods 0.000 description 4
- 150000001879 copper Chemical class 0.000 description 4
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- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
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- 229910015900 BF3 Inorganic materials 0.000 description 1
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- 239000005715 Fructose Substances 0.000 description 1
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- GUBGYTABKSRVRQ-QUYVBRFLSA-N beta-maltose Chemical compound OC[C@H]1O[C@H](O[C@H]2[C@H](O)[C@@H](O)[C@H](O)O[C@@H]2CO)[C@H](O)[C@@H](O)[C@@H]1O GUBGYTABKSRVRQ-QUYVBRFLSA-N 0.000 description 1
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- Electroplating And Plating Baths Therefor (AREA)
Abstract
Description
本発明は、パルス銅めっき浴用の添加剤およびこれを用いるパルス銅めっき浴に関する。 The present invention relates to an additive for a pulse copper plating bath and a pulse copper plating bath using the same.
一定の時間、めっきを行った後、めっきとは逆の電琉を短時間流すパルスめっきは、均一電着性の良いめっき方法として知られている。例えば、プリント基板のスルーホール内にまで付き回りよく銅を析出させるために、硫酸銅めっき浴を用い、パルスめっきを行う試みがなされている。 Pulse plating in which, after plating for a certain period of time, a negative electrode opposite to plating is allowed to flow for a short time is known as a plating method with good uniform electrodeposition. For example, an attempt has been made to perform pulse plating using a copper sulfate plating bath in order to deposit copper well in a through hole of a printed board.
しかしながら、硫酸銅めっき浴を用いるパルスめっき浴は、均一電着性が良いにもかかわらず、普及されていないのが実情であった。この理由は、パルスめっきでは、めっきと逆電流をかけ、一旦析出させためっき皮膜を剥離する時間を作るために専用の電源装置が必要であるという、設備的なコストの問題もあるが、主には、パルス銅めっきで得られる皮膜は、無光沢の外観であり、光沢のある銅めっき皮膜が得られないということが原因であった。 However, in reality, pulse plating baths using copper sulfate plating baths are not widely used even though they have good throwing power. The reason for this is that, in pulse plating, there is an equipment cost problem that a dedicated power supply is required to create a time for applying a reverse current to the plating and peeling the plating film once deposited. This is because the film obtained by pulse copper plating has a dull appearance and a glossy copper plating film cannot be obtained.
すなわち、プリント基板では、めっきされた銅皮膜に、20ないし30μm程度のファインパターンをエッチングにより作成するが、無光沢外観を有する銅皮膜は、表面の凹凸が大きいため、エッチング特性が問題となる可能性があった。また、無光沢の銅皮膜のように表面粗さが大きい金属皮膜は、高周波特性が劣るという問題もあった。 In other words, on printed boards, a fine pattern of about 20 to 30 μm is formed on a plated copper film by etching. However, a copper film having a dull appearance has a large surface irregularity, which may cause a problem in etching characteristics. There was sex. In addition, a metal film having a large surface roughness such as a matte copper film has a problem in that high-frequency characteristics are inferior.
このため、パルス硫酸銅めっき等のパルス銅めっきにおいて、光沢のある銅皮膜を得るための試みもおこなわれているが、満足のいく手段がまだ見出されていないというのが実情であった。 For this reason, in pulsed copper plating such as pulsed copper sulfate plating, attempts have been made to obtain a glossy copper film, but the actual situation is that no satisfactory means have yet been found.
従って本発明の課題は、パルス銅めっきでありながら、光沢のある銅皮膜を得ることのできる技術を開発することである。 Therefore, the subject of this invention is developing the technique which can obtain a glossy copper film, although it is pulse copper plating.
本発明者らは、上記課題を解決すべく、パルス銅めっきにおいて、光沢を付与する添加剤として使用可能な化合物について鋭意検索を行っていたところ、ポリアルキレングリコールまたはポリエーテルポリオールを出発物質とし、これをアミン化、更には4級アンモニウム化して得た化合物は、パルス銅めっき浴においても有効な添加剤として作用することを見出し、本発明を完成した。 In order to solve the above problems, the present inventors have been diligently searching for compounds that can be used as additives for imparting gloss in pulse copper plating.The starting material is polyalkylene glycol or polyether polyol. The compound obtained by amination and further quaternary ammonium conversion was found to act as an effective additive even in a pulse copper plating bath, and the present invention was completed.
すなわち本発明は、隣接炭素原子に水酸基を有する多価アルコールにアルキレンオキサイドを付加したポリエーテルポリオールもしくはポリアルキレングリコールから選ばれるポリオールに、エピハロヒドリンを反応させてエポキシ化し、次いで下記式(I)、
また本発明は、上記工程で得られた第3級アミン化合物に、更に下記式(II)で示される化合物、
更に本発明は、銅イオンを10〜75g/L、硫酸を40〜250g/Lおよび塩素を10〜250mg/L含有する硫酸銅めっき浴に、1mg/L〜10g/Lの上記いずれかに記載のパルス銅めっき用添加剤を含有してなるパルス銅めっき浴である。 Further, the present invention provides a copper sulfate plating bath containing 10 to 75 g / L of copper ions, 40 to 250 g / L of sulfuric acid and 10 to 250 mg / L of sulfuric acid, and 1 mg / L to 10 g / L of any of the above. This is a pulse copper plating bath containing the additive for pulse copper plating.
本発明のパルス銅めっき浴用添加剤を使用することにより、硫酸銅めっき浴中でパルスめっきを行っても、優れた光沢を有する銅皮膜を得ることができる。 By using the additive for pulse copper plating bath of the present invention, a copper film having excellent gloss can be obtained even when pulse plating is performed in a copper sulfate plating bath.
本発明のパルス銅めっき浴用添加剤の有効成分として利用しうる第3級アミン化合物は、隣接炭素原子に水酸基を有する多価アルコールにアルキレンオキサイドを付加したポリエーテルポリオール(以下、単に「ポリエーテルポリオール」という)または後記式(III)で示されるポリアルキレングリコール(以下、単に「ポリアルキレングリコール」という)から選ばれるポリオールを出発物質として合成されるものである。 The tertiary amine compound that can be used as an active ingredient of the additive for the pulse copper plating bath of the present invention is a polyether polyol obtained by adding an alkylene oxide to a polyhydric alcohol having a hydroxyl group at an adjacent carbon atom (hereinafter simply referred to as “polyether polyol”). Or a polyalkylene glycol represented by the following formula (III) (hereinafter simply referred to as “polyalkylene glycol”).
このうち、ポリエーテルポリオールを形成させるために使用される、隣接炭素原子に水酸基を有する多価アルコール(以下、「多価アルコール」という)としては、例えば、グルコース、マンノース、ガラクトース、フルクトース等の6単糖類、アラビノース、キシロース等の5単糖類、ソルビトール、マンニトール等の糖アルコール、ショ糖、麦芽糖、乳糖、トレハロース等の2糖類、グリセリン、エリスリトール、キシリトール等が挙げられる。これらの多価アルコールの中でも、ソルビトール、マンニトール等の糖アルコールが好ましい。 Among these, examples of the polyhydric alcohol having a hydroxyl group on an adjacent carbon atom (hereinafter referred to as “polyhydric alcohol”) used for forming a polyether polyol include 6 such as glucose, mannose, galactose, and fructose. Examples thereof include monosaccharides, 5 monosaccharides such as arabinose and xylose, sugar alcohols such as sorbitol and mannitol, disaccharides such as sucrose, maltose, lactose and trehalose, glycerin, erythritol and xylitol. Among these polyhydric alcohols, sugar alcohols such as sorbitol and mannitol are preferable.
これらの多価アルコールから、ポリエーテルポリオールを製造するには、これにアルキレンオキサイドを付加させることが必要である。多価アルコールへのアルキレンオキサイドの付加は、常法に従って行うことができ、例えば、オートクレーブによる加温、加圧等により行うことができる。また、多価アルコールに付加させるアルキレンオキサイドの炭素数は特に制限されないが、炭素数2〜3のアルキレンオキサイドを付加させることが好ましい。また、多価アルコールに付加させるアルキレンオキサイドのモル数も、特に制限されないが、水酸基の数に対し0.5〜3倍のアルキレンオキサイドを付加させることが好ましい。 In order to produce a polyether polyol from these polyhydric alcohols, it is necessary to add an alkylene oxide thereto. Addition of alkylene oxide to the polyhydric alcohol can be performed according to a conventional method, for example, heating by autoclave, pressurization, or the like. Further, the number of carbon atoms of the alkylene oxide added to the polyhydric alcohol is not particularly limited, but it is preferable to add an alkylene oxide having 2 to 3 carbon atoms. The number of moles of alkylene oxide added to the polyhydric alcohol is not particularly limited, but it is preferable to add 0.5 to 3 times as much alkylene oxide as the number of hydroxyl groups.
一方、ポリアルキレングリコールとしては、下記式(III)、
上記、ポリアルキレングリコールまたはポリエーテルポリオール等のポリオール(以下、単に「ポリオール」ということがある)は、次に、エピハロヒドリンと反応させてエポキシ化させる。このエピハロヒドリンとしてはエピブロモヒドリン、エピクロロヒドリン等が挙げられ、これらの中でもエピクロロヒドリンが好ましい。このエピハロヒドリンを用いたポリオールのエポキシ化は、常法に従って行うことができ、例えば、エピハロヒドリンとポリオールを触媒の存在下で加熱させることにより行うことができる。前記エポキシ化に用いられる触媒としては、フッ化水素(HF)、三フッ化ホウ素(BF3)、塩化スズ(IV)(SnCl4)等が挙げられ、特に塩化スズ(IV)が好ましい。また、これらのエポキシ化させたポリオールのエポキシ当量は100〜500が好ましく、150〜300がより好ましく、特に150〜200が好ましい。なお、エポキシ当量はJIS
K 7236に基づき測定することができる。更に、エポキシ化させたポリオールの炭素数は10〜50が好ましく、特に20〜30が好ましい。上記のようにしてエポキシ化させたポリオールとしては、例えば、ジエチレングリコールジグリシジルエーテル等のポリエチレングリコールジグリシジルエーテル等が挙げられ、これらは上記のようにして調製されたものの他に市販品を利用することができる。
The above-mentioned polyol such as polyalkylene glycol or polyether polyol (hereinafter sometimes simply referred to as “polyol”) is then epoxidized by reaction with epihalohydrin. Examples of the epihalohydrin include epibromohydrin and epichlorohydrin. Among these, epichlorohydrin is preferable. The epoxidation of the polyol using the epihalohydrin can be performed according to a conventional method, for example, by heating the epihalohydrin and the polyol in the presence of a catalyst. Examples of the catalyst used for the epoxidation include hydrogen fluoride (HF), boron trifluoride (BF 3 ), tin chloride (IV) (SnCl 4 ), and tin (IV) chloride is particularly preferable. Moreover, 100-500 are preferable, as for the epoxy equivalent of these epoxidized polyol, 150-300 are more preferable, and 150-200 are especially preferable. The epoxy equivalent is JIS
It can be measured based on K7236. Furthermore, the carbon number of the epoxidized polyol is preferably 10 to 50, and particularly preferably 20 to 30. Examples of the polyol epoxidized as described above include, for example, polyethylene glycol diglycidyl ether such as diethylene glycol diglycidyl ether, etc., and these use commercially available products in addition to those prepared as described above. Can do.
上記のようにしてエポキシ化させたポリオールは、更に下記式(I)で示される化合物を反応させて第3級アミン化合物を得ることができる。 The polyol epoxidized as described above can be further reacted with a compound represented by the following formula (I) to obtain a tertiary amine compound.
上記式(I)で示される化合物の例としては、ジエタノールアミン、ジプロパノールアミン等が挙げられる。これらの化合物の中でもジエタノールアミンが好ましい。 Examples of the compound represented by the above formula (I) include diethanolamine, dipropanolamine and the like. Of these compounds, diethanolamine is preferred.
これらの化合物(I)を用いたエポキシ化させたポリオールの第3級アミン化は、常法に従って行うことができ、例えば、エポキシ化させたポリオールと下記式(I)で示される化合物とを混合し、これを室温下で1日程度攪拌することにより行うことができる。 The tertiary amination of the epoxidized polyol using these compounds (I) can be carried out according to a conventional method. For example, the epoxidized polyol and a compound represented by the following formula (I) are mixed. This can be carried out by stirring for about one day at room temperature.
上記第3級アミン化合物は、そのまま本発明のパルス銅めっき浴用添加剤の有効成分として使用することもできるが、更に、これを第4級化して第4級アンモニウム化合物とし、これを本発明のパルス銅めっき浴用添加剤の有効成分として使用することもできる。 The tertiary amine compound can be used as it is as an active ingredient of the additive for the pulse copper plating bath of the present invention, but is further quaternized to obtain a quaternary ammonium compound. It can also be used as an active ingredient of an additive for pulse copper plating baths.
上記第3級アミン化合物を第4級化するために用いる化合物としては、下記式(II)で表される化合物を挙げることができる。 Examples of the compound used for quaternizing the tertiary amine compound include compounds represented by the following formula (II).
この化合物(II)としては、例えば、塩化アリル、臭化メチル、臭化アリル等が挙げられ、これらの中でも塩化アリルが好ましい。 Examples of this compound (II) include allyl chloride, methyl bromide, allyl bromide and the like, and among these, allyl chloride is preferred.
この化合物(II)を用いた第3級アミン化合物の第4級アンモニウム化は、常法に従って行うことができ、例えば、化合物(II)および第3級アミン化合物と、例えば、アセトン等の溶媒とを混合し、これを数時間程度加熱還流することによって行うことができる。 The quaternary ammonium conversion of the tertiary amine compound using this compound (II) can be carried out according to a conventional method. For example, the compound (II) and the tertiary amine compound, and a solvent such as acetone, for example, Can be mixed and heated under reflux for several hours.
パルス銅めっき浴用添加剤は、上記のようにして得られる第3級アミン化合物または第4級アンモニウム化合物を有効成分として配合することにより、製造することができる。すなわち、これら化合物を適当な液体あるいは固体担体と混合することにより調製することができる。 The additive for pulse copper plating bath can be produced by blending a tertiary amine compound or a quaternary ammonium compound obtained as described above as an active ingredient. That is, it can be prepared by mixing these compounds with an appropriate liquid or solid carrier.
また、本発明のパルス銅めっき浴用添加剤の調製に当たっては、従来公知の硫酸銅めっき用添加剤成分を配合することも可能である。すなわち、本発明化合物はレベラー成分として作用するので、それ以外のビス−(3−スルホプロピル)ジスルフィドジナトリウム(SPS)等の光沢化剤成分や、ポリエチレングリコール等の成分の湿潤剤成分を混合して使用することもできる。 Moreover, in preparing the additive for pulse copper plating bath of the present invention, a conventionally known additive component for copper sulfate plating can be blended. That is, since the compound of the present invention acts as a leveler component, a brightener component such as bis- (3-sulfopropyl) disulfide disodium (SPS) and a wetting agent component such as polyethylene glycol are mixed. Can also be used.
以上のようにして調製されたパルス銅めっき浴用添加剤は、標準的な硫酸銅めっき浴中に添加され、パルス銅めっき浴が調製される。 The additive for pulse copper plating bath prepared as described above is added to a standard copper sulfate plating bath to prepare a pulse copper plating bath.
すなわち、適切な濃度の硫酸銅および硫酸を含有する硫酸銅めっき浴中に、前記本発明化合物として1mg/L〜10g/L、好ましくは1mg/L〜2g/Lとなる量の添加剤を加え、パルスめっきを行なうことができる。 That is, an additive in an amount of 1 mg / L to 10 g / L, preferably 1 mg / L to 2 g / L is added as the compound of the present invention to a copper sulfate plating bath containing copper sulfate and sulfuric acid at appropriate concentrations. Pulse plating can be performed.
上記硫酸銅めっき浴中の各成分の量は、特に制約はないが、銅イオンは10〜75g/L程度、硫酸は40〜250g/L程度、塩素は10〜250mg/L程度である。 The amount of each component in the copper sulfate plating bath is not particularly limited, but is about 10 to 75 g / L for copper ions, about 40 to 250 g / L for sulfuric acid, and about 10 to 250 mg / L for chlorine.
また、上記パルス銅めっき浴を用いて行うパルスめっきの条件は、特に制約があるわけではないが、一般には、銅めっき皮膜析出のためのフォワード電流は、0.2〜20A/dm2程度、好ましくは、1〜10A/dm2程度であり、析出した銅めっき皮膜を溶解するためのリバース電流は、0.4〜40A/dm2程度、好ましくは、2〜30A/dm2程度である。 In addition, the conditions of pulse plating performed using the pulse copper plating bath are not particularly limited, but in general, the forward current for copper plating film deposition is about 0.2 to 20 A / dm 2 , preferably is about 1 to 10 a / dm 2, a reverse current to dissolve the precipitated copper plating film, 0.4~40A / dm 2 mm, preferably, 2~30A / dm 2 about.
また、その継続時間は、フォワード電流が2〜300msec程度、好ましくは、10〜30msec程度、リバース電流が0.1〜6msec程度、好ましくは0.5〜2msec程度とすれば良い。 The duration time may be about 2 to 300 msec for the forward current, preferably about 10 to 30 msec, and about 0.1 to 6 msec for the reverse current, preferably about 0.5 to 2 msec.
以上の本発明パルス銅めっき浴を用い、パルスめっきを行うことにより得られた銅皮膜は、従来の銅パルスめっきにより得られた銅皮膜に比べ、優れた光沢を有するものである。すなわち、従来の銅パルスめっきでは、無光沢の外観しか得られないが、本発明のパルス銅めっき浴を使用した場合は、通常のパルスなしの硫酸銅めっきに近い光沢外観を得ることができる。 The copper film obtained by performing pulse plating using the above-described pulse copper plating bath of the present invention has an excellent gloss as compared with a copper film obtained by conventional copper pulse plating. That is, with the conventional copper pulse plating, only a dull appearance can be obtained, but when the pulse copper plating bath of the present invention is used, a gloss appearance close to that of a normal copper sulfate plating without a pulse can be obtained.
また、パルス銅めっきの利点である均一電着性も優れたものであり、更に、銅皮膜の物性も優れたものであった。 Moreover, the uniform electrodeposition property which is the advantage of pulse copper plating was also excellent, and the physical properties of the copper film were also excellent.
以下、製造例、実施例を挙げ、本発明を更に詳しく説明するが、本発明はこれら実施例に何ら制約されるものではない。 EXAMPLES Hereinafter, although a manufacture example and an Example are given and this invention is demonstrated in more detail, this invention is not restrict | limited at all by these Examples.
製 造 例 1
レベリング剤の合成(1):
ケミカルアブストラクト(vol.73,57454n,(1970))に準じてポリエチレングリコール(9重合物)に、エピクロロヒドリンを反応させ、ポリエチレングリコールジグリシジルエーテルを得た(エポキシ当量285)。このポリエチレングリコールジグリシジルエーテル29.1gに、水300mlを加え、更にジエタノールアミン13mlを加えて室温で24時間攪拌し、第3級アミン化合物(レベリング剤1)を得た。この化合物のNMR測定を行ったところ、エポキシ基のσ(D2O)2.7、2.9ppm付近のシグナルが消えてσ2.6、3.6ppm付近にジエタノールアミンのシグナルが観測され、アミノ化を確認した。
Manufacturing example 1
Synthesis of leveling agent (1):
According to a chemical abstract (vol. 73, 57454n, (1970)), polyethylene glycol (9 polymer) was reacted with epichlorohydrin to obtain polyethylene glycol diglycidyl ether (epoxy equivalent 285). 300 ml of water was added to 29.1 g of this polyethylene glycol diglycidyl ether, 13 ml of diethanolamine was further added, and the mixture was stirred at room temperature for 24 hours to obtain a tertiary amine compound (leveling agent 1). As a result of NMR measurement of this compound, the signal of σ (D 2 O) 2.7 of the epoxy group near 2.9 and 2.9 ppm disappeared, and the signal of diethanolamine was observed at around σ 2.6 and 3.6 ppm. It was confirmed.
製 造 例 2
レベリング剤の合成(2):
上記製造例1で得たレベリング剤1を含む水溶液に、更に、アセトン300mlおよび塩化アリル20mlを加え、4時間加熱還流した後、減圧濃縮して46gの第4級アンモニウム化合物(レベリング剤2)を油状物として得た。この化合物のNMR測定を行ったところ、σ5.9、5.7、5.4ppm付近にビニルプロトンのシグナルが観測され、アリル基の導入を確認した。
Manufacturing example 2
Synthesis of leveling agent (2):
To the aqueous solution containing the leveling agent 1 obtained in Production Example 1 above, 300 ml of acetone and 20 ml of allyl chloride were further added and heated under reflux for 4 hours. Obtained as an oil. When NMR measurement was performed on this compound, a vinyl proton signal was observed in the vicinity of σ5.9, 5.7, and 5.4 ppm, confirming the introduction of an allyl group.
製 造 例 3
レベリング剤の合成(3):
市販のジエチレングリコールに、製造例1と同様にしてエピクロロヒドリンを反応させ、ジエチレングリコールジグリシジルエーテル(エポキシ当量150)を得た。これに、製造例1と同様にしてジエタノールアミンを反応させて第3級アミン化合物を得、更に、製造例2と同様にして塩化アリルを反応させて4級アンモニウム化合物(レベリング剤3)を得た。
Manufacturing example 3
Synthesis of leveling agent (3):
Epichlorohydrin was reacted with commercially available diethylene glycol in the same manner as in Production Example 1 to obtain diethylene glycol diglycidyl ether (epoxy equivalent 150). This was reacted with diethanolamine in the same manner as in Production Example 1 to obtain a tertiary amine compound, and further allyl chloride was reacted in the same manner as in Production Example 2 to obtain a quaternary ammonium compound (leveling agent 3). .
製 造 例 4
レベリング剤の合成(4):
特開昭52−61187号公報の実施例1(1)に記載されているポリオキシエチレン(6重合物)ソルビトールに、製造例1と同様にしてエピクロロヒドリンを反応させ、ポリエチレングリコールジグリシジルエーテルとし(エポキシ当量170)、更に、これにジエタノールアミンを反応させて第3級アミン化合物(レベリング剤4)を得た。
Manufacturing example 4
Synthesis of leveling agent (4):
Polyoxyethylene (hexapolymer) sorbitol described in Example 1 (1) of JP-A No. 52-61187 is reacted with epichlorohydrin in the same manner as in Production Example 1 to produce polyethylene glycol diglycidyl. Ether (epoxy equivalent 170) was further reacted with diethanolamine to obtain a tertiary amine compound (leveling agent 4).
製 造 例 5
レベリング剤の合成(5):
上記製造例4で得たレベリング剤4に、製造例2と同様にして塩化アリルを反応させて第4級アンモニウム化合物(レベリング剤5)を得た。
Manufacturing example 5
Synthesis of leveling agent (5):
The leveling agent 4 obtained in Production Example 4 was reacted with allyl chloride in the same manner as in Production Example 2 to obtain a quaternary ammonium compound (leveling agent 5).
実 施 例 1
外観および均一電着性試験(1):
下記基本浴組成の硫酸銅めっき液に、添加剤組成に示す添加剤を加え、パルスめっき浴を調製した(本発明浴(1))。この銅めっき浴を用い、スルーホール(孔径0.3mmφ、深さ1.6mm)を有するプリント基板に、フォワード電流が5A/dm2で30msec、リバース電流が15A/dm2で1msec、平均電流が4.4A/dm2のパルス条件で膜厚25μmとなるまで硫酸銅めっきを行い、めっき後の外観および均一電着性を調べた。なお、比較としては、基本組成に他社添加剤A(標準濃度で添加)を加え、上記パルス条件でめっきを行ったもの(他社添加剤A浴)および基本組成に市販硫酸銅めっき添加剤(CU−BRITE21;5ml/L)を加え、非パルス条件(DC電源にて2A/dm2)でめっきを行ったもの(CU−BRITE21浴)を用いた。この結果を表1に示す。なお、めっき外観は目視で、均一電着性は断面観察で調べた。
Example 1
Appearance and throwing power test (1):
An additive shown in the additive composition was added to a copper sulfate plating solution having the following basic bath composition to prepare a pulse plating bath (invention bath (1)). Using this copper plating bath, a printed circuit board having a through hole (hole diameter: 0.3 mmφ, depth: 1.6 mm) has a forward current of 5 A / dm 2 at 30 msec, a reverse current of 15 A / dm 2 at 1 msec, and an average current of Copper sulfate plating was performed under a pulse condition of 4.4 A / dm 2 until the film thickness reached 25 μm, and the appearance after plating and uniform electrodeposition were examined. For comparison, the additive A of the other company (added at the standard concentration) was added to the basic composition, and plating was performed under the above pulse conditions (the additive A bath of the other company) and the basic composition was a commercially available copper sulfate plating additive (CU). -BRITE 21; 5 ml / L) was added, and a non-pulse condition (2 A / dm 2 with a DC power source) was plated (CU-BRITE 21 bath). The results are shown in Table 1. The plating appearance was visually observed, and the uniform electrodeposition was examined by cross-sectional observation.
基本組成:
硫酸銅 75 g/L(銅イオンとして約19g/L)
硫 酸 180 g/L
塩 素 120mg/L*
* 添加剤としてCU−BRITE 21を用いる場合には60mg/Lとした
Basic composition:
Copper sulfate 75 g / L (about 19 g / L as copper ion)
Sulfuric acid 180 g / L
Chlorine 120mg / L *
* When CU-BRITE 21 is used as an additive, it is 60 mg / L
添加剤組成:
製造例2で得たレベリング剤2 200mg/L
SPS* 8mg/L
PEG4000 1000mg/L
* ビス−(3−スルホプロピル)ジスルフィドジナトリウム
Additive composition:
Leveling agent 2 obtained in Production Example 2 200 mg / L
SPS * 8mg / L
PEG4000 1000mg / L
* Bis- (3-sulfopropyl) disulfide disodium
結 果:
この結果から明らかなように、第4級アンモニウム化合物であるレベリング剤2を使用した場合には、優れた外観および均一電着性が得られた。これに対し、他社添加剤Aを用いた場合は、均一電着性は良いが、外観は無光沢のものとなってしまった。一方、通常の硫酸銅めっきでは、良好な光沢が得られはするものの、均一電着性がパルスめっきには及ばなかった。 As is clear from this result, when the leveling agent 2 which is a quaternary ammonium compound was used, an excellent appearance and uniform electrodeposition were obtained. On the other hand, when the additive A of other company was used, the uniform electrodeposition was good, but the appearance was matte. On the other hand, with normal copper sulfate plating, good gloss was obtained, but the throwing power did not reach that of pulse plating.
実 施 例 2
ホットオイル試験(1):
実施例1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5秒浸漬後、25℃のトリクレンに15秒浸漬する工程を所定回数繰り返した。その後、スルホール内を断面カットし、クラックの有無を観察した。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2に示す。
Example 2
Hot oil test (1):
For each printed circuit board plated with copper sulfate in Example 1, the step of immersing in glycerin at 260 ° C. for 5 seconds and then immersing in trichrene at 25 ° C. for 15 seconds was repeated a predetermined number of times. Thereafter, the inside of the through hole was cut 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 2.
結 果:
この結果から明らかなように、本発明浴(1)では、一般の硫酸銅めっきと同一の結果が得られた。これに対し、他社添加剤Aを用いた場合は、クラックの発生が多く、熱ショックに弱いことが示された。 As is clear from this result, the present bath (1) yielded the same results as general copper sulfate plating. On the other hand, when the other company additive A was used, it was shown that there are many cracks and it is weak to a heat shock.
実 施 例 3
外観および均一電着性試験(2):
実施例1と同じ基本浴組成の硫酸銅めっき液に、添加剤組成に示す添加剤を加え、パルスめっき浴(本発明浴(2))を調製した。この銅めっき浴を用い、種々の孔径のスルーホール(深さ1.6mm)を有するプリント基板に、パルス硫酸銅めっきを行い、めっき後の外観および均一電着性を調べた。この結果を表3に示す。
Example 3
Appearance and throwing power test (2):
An additive shown in the additive composition was added to a copper sulfate plating solution having the same basic bath composition as in Example 1 to prepare a pulse plating bath (the present invention bath (2)). Using this copper plating bath, pulse copper sulfate plating was performed on a printed circuit board having through holes (depth: 1.6 mm) having various hole diameters, and the appearance and uniform electrodeposition after plating were examined. The results are shown in Table 3.
添加剤組成:
製造例5で得たレベリング剤5 100mg/L
SPS* 10mg/L
PEG4000 500mg/L
* ビス−(3−スルホプロピル)ジスルフィドジナトリウム
Additive composition:
Leveling agent 5 obtained in Production Example 5 100 mg / L
SPS * 10mg / L
PEG4000 500mg / L
* Bis- (3-sulfopropyl) disulfide disodium
結 果:
この結果から明らかなように、第4級アンモニウム化合物であるレベリング剤5を使用した場合でも、優れた外観および均一電着性が得られた。 As is apparent from this result, even when the leveling agent 5 which is a quaternary ammonium compound is used, an excellent appearance and uniform electrodeposition are obtained.
実 施 例 4
ホットオイル試験(2):
実施例3で硫酸銅めっきを行ったプリント基板について、実施例2と同様にホットオイル試験を行った。この結果を表4に示す。
Example 4
Hot oil test (2):
A hot oil test was performed on the printed circuit board plated with copper sulfate in Example 3 in the same manner as in Example 2. The results are shown in Table 4.
結 果:
実 施 例 5
物性試験:
実施例3で用いためっき液、めっき条件により、ステンレス板に40μmの膜厚で硫酸銅めっきを行った。次いで、得られた銅皮膜を引き剥がし、その伸び率および抗張力を測定した。この結果を表5に示す。
Example 5
Physical property test:
According to the plating solution and plating conditions used in Example 3, copper sulfate plating was performed on the stainless steel plate with a film thickness of 40 μm. Next, the obtained copper film was peeled off, and the elongation and tensile strength were measured. The results are shown in Table 5.
結 果:
実 施 例 6
外観および均一電着性試験(3):
実施例1と同じ基本浴組成の硫酸銅めっき液に、添加剤組成に示す添加剤を加え、パルスめっき浴(本発明浴(3))を調製した。この銅めっき浴を用い、種々の孔径のスルーホール(深さ1.6mm)を有するプリント基板に、パルス硫酸銅めっきを行い、めっき後の外観および均一電着性を調べた。この結果を表6に示す。
Example 6
Appearance and throwing power test (3):
The additive shown in the additive composition was added to the copper sulfate plating solution having the same basic bath composition as in Example 1 to prepare a pulse plating bath (the present invention bath (3)). Using this copper plating bath, pulse copper sulfate plating was performed on a printed circuit board having through holes (depth: 1.6 mm) having various hole diameters, and the appearance and uniform electrodeposition after plating were examined. The results are shown in Table 6.
添加剤組成:
製造例4で得たレベリング剤4 100mg/L
SPS* 10mg/L
PEG4000 500mg/L
* ビス−(3−スルホプロピル)ジスルフィドジナトリウム
Additive composition:
Leveling agent 4 obtained in Production Example 4 100 mg / L
SPS * 10mg / L
PEG4000 500mg / L
* Bis- (3-sulfopropyl) disulfide disodium
結 果:
この結果から明らかなように、第3級アミン化化合物であるレベリング剤4を使用した場合でも、優れた外観および均一電着性が得られた。 As is apparent from this result, even when the leveling agent 4 which is a tertiary amination compound is used, an excellent appearance and uniform electrodeposition are obtained.
実 施 例 7
外観および均一電着性試験(4):
実施例1と同じ基本浴組成の硫酸銅めっき液に、添加剤組成に示す添加剤を加え、パルスめっき浴(本発明浴(4))を調製した。この銅めっき浴を用い、種々の孔径のスルーホール(深さ1.6mm)を有するプリント基板に、パルス硫酸銅めっきを行い、めっき後の外観および均一電着性を調べた。この結果を表7に示す。
Example 7
Appearance and throwing power test (4):
The additive shown in the additive composition was added to the copper sulfate plating solution having the same basic bath composition as in Example 1 to prepare a pulse plating bath (the present invention bath (4)). Using this copper plating bath, pulse copper sulfate plating was performed on a printed circuit board having through holes (depth: 1.6 mm) having various hole diameters, and the appearance and uniform electrodeposition after plating were examined. The results are shown in Table 7.
添加剤組成:
製造例5で得たレベリング剤5 150mg/L
SPS* 20mg/L
* ビス−(3−スルホプロピル)ジスルフィドジナトリウム
Additive composition:
Leveling agent 5 obtained in Production Example 5 150 mg / L
SPS * 20mg / L
* Bis- (3-sulfopropyl) disulfide disodium
結 果:
この結果から明らかなように、湿潤剤(PEG4000)がない場合でも、優れた外観および均一電着性が得られた。 As is clear from this result, even when there was no wetting agent (PEG 4000), excellent appearance and uniform electrodeposition were obtained.
本発明のパルス銅めっき浴用添加剤を用い、パルスめっきで得られた銅皮膜は、優れた光沢外観と、優れた物性を有するものであり、更に、めっき浴自体の均一電着性も良いものである。 The copper film obtained by pulse plating using the additive for pulse copper plating bath of the present invention has an excellent gloss appearance and excellent physical properties, and also has a good electrodeposition property of the plating bath itself. It is.
従って、本発明のパルス銅めっき浴用添加剤は、例えば、スルーホールを有するプリント基板上の銅めっきなどで優れた効果を有するものであり、電子部品製造などの分野で広く利用することができるものである。
以 上
Therefore, the additive for pulse copper plating bath of the present invention has an excellent effect in, for example, copper plating on a printed circuit board having a through hole, and can be widely used in fields such as electronic component manufacturing. It is.
more than
Claims (9)
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JP2011207878A (en) * | 2010-03-15 | 2011-10-20 | Rohm & Haas Electronic Materials Llc | Plating bath and method |
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US8262895B2 (en) | 2010-03-15 | 2012-09-11 | Rohm And Haas Electronic Materials Llc | Plating bath and method |
JP2013500395A (en) * | 2009-07-30 | 2013-01-07 | ビーエーエスエフ ソシエタス・ヨーロピア | Metal plating composition containing an inhibitor for filling submicron structures without voids |
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JP2012512957A (en) * | 2008-12-19 | 2012-06-07 | ビーエーエスエフ ソシエタス・ヨーロピア | Composition for metal electroplating comprising a leveling agent |
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JP2020084279A (en) * | 2018-11-28 | 2020-06-04 | 住友金属鉱山株式会社 | Copper-clad laminate and manufacturing method copper-clad laminate |
JP7107189B2 (en) | 2018-11-28 | 2022-07-27 | 住友金属鉱山株式会社 | COPPER CLAD LAMINATES AND METHOD FOR MANUFACTURING COPPER CLAD LAMINATES |
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