JPS62205284A - Catalytic solution for electroless plating - Google Patents
Catalytic solution for electroless platingInfo
- Publication number
- JPS62205284A JPS62205284A JP4725786A JP4725786A JPS62205284A JP S62205284 A JPS62205284 A JP S62205284A JP 4725786 A JP4725786 A JP 4725786A JP 4725786 A JP4725786 A JP 4725786A JP S62205284 A JPS62205284 A JP S62205284A
- Authority
- JP
- Japan
- Prior art keywords
- soln
- stabilizer
- solution
- catalyst
- hydrochloric acid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 238000007772 electroless plating Methods 0.000 title claims abstract description 14
- 230000003197 catalytic effect Effects 0.000 title abstract description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 28
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 26
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 21
- 150000003839 salts Chemical class 0.000 claims abstract description 21
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 13
- 150000001875 compounds Chemical class 0.000 claims abstract description 7
- 239000003054 catalyst Substances 0.000 claims description 43
- 239000007788 liquid Substances 0.000 claims description 25
- 229910000510 noble metal Inorganic materials 0.000 claims description 9
- 239000003929 acidic solution Substances 0.000 claims description 4
- 239000013043 chemical agent Substances 0.000 claims 1
- 239000003381 stabilizer Substances 0.000 abstract description 37
- 239000000084 colloidal system Substances 0.000 abstract description 15
- -1 phosphoric acid compound Chemical class 0.000 abstract description 11
- 239000002253 acid Substances 0.000 abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 5
- 239000010409 thin film Substances 0.000 abstract description 4
- 150000007513 acids Chemical class 0.000 abstract description 3
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 abstract description 3
- 239000002244 precipitate Substances 0.000 abstract description 3
- HWGNBUXHKFFFIH-UHFFFAOYSA-I pentasodium;[oxido(phosphonatooxy)phosphoryl] phosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O HWGNBUXHKFFFIH-UHFFFAOYSA-I 0.000 abstract description 2
- 235000019832 sodium triphosphate Nutrition 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 37
- 238000007747 plating Methods 0.000 description 18
- 230000004913 activation Effects 0.000 description 11
- 239000000758 substrate Substances 0.000 description 11
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 8
- 239000010408 film Substances 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 239000000203 mixture Substances 0.000 description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 4
- 230000002378 acidificating effect Effects 0.000 description 4
- 229910052802 copper Inorganic materials 0.000 description 4
- 239000010949 copper Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 229910052763 palladium Inorganic materials 0.000 description 4
- 238000003860 storage Methods 0.000 description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 3
- 239000003945 anionic surfactant Substances 0.000 description 3
- 239000012298 atmosphere Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 3
- 229910052737 gold Inorganic materials 0.000 description 3
- 239000010931 gold Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 150000003016 phosphoric acids Chemical class 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 230000001133 acceleration Effects 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000005238 degreasing Methods 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 150000002941 palladium compounds Chemical class 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical class [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 150000003606 tin compounds Chemical class 0.000 description 2
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 description 1
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 229930182843 D-Lactic acid Natural products 0.000 description 1
- JVTAAEKCZFNVCJ-UWTATZPHSA-N D-lactic acid Chemical compound C[C@@H](O)C(O)=O JVTAAEKCZFNVCJ-UWTATZPHSA-N 0.000 description 1
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 235000003332 Ilex aquifolium Nutrition 0.000 description 1
- 235000002296 Ilex sandwicensis Nutrition 0.000 description 1
- 235000002294 Ilex volkensiana Nutrition 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 210000000481 breast Anatomy 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 description 1
- 229910000397 disodium phosphate Inorganic materials 0.000 description 1
- 235000019800 disodium phosphate Nutrition 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical class [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 125000005341 metaphosphate group Chemical group 0.000 description 1
- 229910052762 osmium Inorganic materials 0.000 description 1
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical class [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Chemical class 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical class [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000001509 sodium citrate Substances 0.000 description 1
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 description 1
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 1
- GCLGEJMYGQKIIW-UHFFFAOYSA-H sodium hexametaphosphate Chemical compound [Na]OP1(=O)OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])O1 GCLGEJMYGQKIIW-UHFFFAOYSA-H 0.000 description 1
- 235000019982 sodium hexametaphosphate Nutrition 0.000 description 1
- 229910001379 sodium hypophosphite Inorganic materials 0.000 description 1
- 239000001488 sodium phosphate Substances 0.000 description 1
- 229910000162 sodium phosphate Inorganic materials 0.000 description 1
- 235000011008 sodium phosphates Nutrition 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- YWPOLRBWRRKLMW-UHFFFAOYSA-M sodium;naphthalene-2-sulfonate Chemical compound [Na+].C1=CC=CC2=CC(S(=O)(=O)[O-])=CC=C21 YWPOLRBWRRKLMW-UHFFFAOYSA-M 0.000 description 1
- 235000011150 stannous chloride Nutrition 0.000 description 1
- 239000001119 stannous chloride Substances 0.000 description 1
- RCIVOBGSMSSVTR-UHFFFAOYSA-L stannous sulfate Chemical compound [SnH2+2].[O-]S([O-])(=O)=O RCIVOBGSMSSVTR-UHFFFAOYSA-L 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 description 1
- UDEJEOLNSNYQSX-UHFFFAOYSA-J tetrasodium;2,4,6,8-tetraoxido-1,3,5,7,2$l^{5},4$l^{5},6$l^{5},8$l^{5}-tetraoxatetraphosphocane 2,4,6,8-tetraoxide Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]P1(=O)OP([O-])(=O)OP([O-])(=O)OP([O-])(=O)O1 UDEJEOLNSNYQSX-UHFFFAOYSA-J 0.000 description 1
- 229910000375 tin(II) sulfate Inorganic materials 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/18—Pretreatment of the material to be coated
- C23C18/20—Pretreatment of the material to be coated of organic surfaces, e.g. resins
- C23C18/28—Sensitising or activating
Abstract
Description
【発明の詳細な説明】
本発明は、無電解めっき用の触媒液に関するものであり
、特には触媒液の活性付与能を低下させることなくその
安定性を向上させる安定剤を含有する無電解めっき用触
媒液に関する。Detailed Description of the Invention The present invention relates to a catalyst solution for electroless plating, and in particular to an electroless plating solution containing a stabilizer that improves the stability of the catalyst solution without reducing its activation ability. This invention relates to a catalyst liquid for use.
本発明は、装飾、耐食性、導宛性付与等の各種工業用途
向けの無電解めっき用触媒液として有用であり、特には
銅張り基板、接着剤付基板、セラミック基板、多層配線
板等の電子デバイス用途の製造工程において更にはコン
デンサの製造工程において有用である。The present invention is useful as a catalyst solution for electroless plating for various industrial applications such as decoration, corrosion resistance, and conductivity imparting, and is particularly useful for electronic plating such as copper-clad substrates, adhesive-coated substrates, ceramic substrates, and multilayer wiring boards. It is useful in the manufacturing process of device applications and furthermore in the manufacturing process of capacitors.
発明の背景
無電解めっきは、電子工業を始めとする産業の発展にと
もない急速な進歩をとげ、金属表面処理法の重要な手段
の一つとしての地位を確立している。種々の基板表面に
無’Ｉｔ解めっきを施すに際して、基板表面が触媒作用
を持たない場合には、めっき金属の成長核となり、めっ
き反応の触媒として働く微粒子を基板表面に付着させる
活性化処理が必要であることは知られている。例えば回
路用基板のようなプラスチックに無電解めっきを行うと
きには、プラスチック自体に触ｇ＃ｉ′！かないため、
表面に触媒粒子を吸着させ、無電解めっき反応に対して
活性を持たせる活性化処理が行われている。BACKGROUND OF THE INVENTION Electroless plating has made rapid progress with the development of industries including the electronics industry, and has established itself as one of the important means for metal surface treatment. When performing IT-free plating on various substrate surfaces, if the substrate surface does not have a catalytic effect, an activation treatment is performed to attach fine particles to the substrate surface that act as growth nuclei for the plating metal and act as a catalyst for the plating reaction. It is known that it is necessary. For example, when performing electroless plating on plastic such as a circuit board, touch the plastic itself. Because it is fleeting,
Activation treatment is performed to adsorb catalyst particles on the surface and make it active for electroless plating reaction.
触媒としては、現在では塩酸酸性貴金属−スズー液型即
ち混合型触媒液が広く用いられている。この−液源触媒
液中に基板を浸漬するごとにより、表面に責金松、コロ
イドを収着させたままでは、賀金ｈｓコ四イドの表面を
スズ化合物が覆っており、めっき液に対して不活性であ
る。このため、上記触媒液に浸漬後、統いて基板を酸ま
たはアルカリ溶液に浸漬して、被覆スズ化合物を取除き
、めっき反応に対しての活性を促進する操作が必要であ
り、これは促進化（アクセレレーション）処理と呼ばれ
ている。活性化処理と促進化処理とを併せて触媒付与と
呼ぶこともある。Currently, as a catalyst, a hydrochloric acid acidic noble metal-tin liquid type, that is, a mixed type catalyst liquid is widely used. Each time the substrate is immersed in this liquid source catalyst solution, if the surface of the colloid is still sorbed, the surface of the colloid will be covered with a tin compound, and it will not be exposed to the plating solution. Inert. Therefore, after being immersed in the above catalyst solution, it is necessary to immerse the substrate in an acid or alkaline solution to remove the coating tin compound and promote the activity for the plating reaction. This is called (acceleration) processing. The activation treatment and the acceleration treatment are sometimes collectively referred to as catalyst application.
従来技術とその間ｍ点
上記のような触々に液はｉｔｌ工程の液の持ち込みや空
気酸化による保護コロイドの破壊により安定性を損いや
すく、液面に貴金属コロイドが凝集して薄い膜を影＠１
したりまたコｑイドが沈殿したりして、触媒液の寿命を
矧くする。Between the conventional technology and the m point above, the liquid tends to lose stability due to the introduction of the liquid from the ITL process and the destruction of the protective colloid due to air oxidation, and the noble metal colloid aggregates on the liquid surface and causes a thin film to be affected. @1
Otherwise, coqoids may precipitate, shortening the life of the catalyst solution.
こうした欠点を改善する為に、従来安定剤として比較的
分子量が大きく、極性基を持つ有機試剤が主として使用
された。例えば特公昭５２−１６８５２９は、β−ナフ
タリンスルホン酸ナトリウム、ドデシルベンゼンスルホ
ン酸ナトリウムのような陰イオン界面活性剤を安定剤と
して添加している。特公昭５２−３７９７１号は、有機
モノール、ジオ−Ａ・及びポリオールやフッ素化炭化水
素湿胸剤を安定剤として用いている。こうした有機安定
剤は、触媒液の安定性を向上させはするが、同時に触媒
液の活性付与能を低下させ、場合によってはめっきの際
につきむらが生じることもある。めっきのつきむらは、
電子工業用印刷回路板製造の為の基板の無電解めっきに
おいては殊に重要な問題である。電子デバイスの動作の
高い信頼性を得るためには、つきむらのない無電解めっ
き部を生成することが必要であり、そのためにはめつき
に先立っての被めっき表面の充分なる活性化が必要とさ
れる。In order to improve these drawbacks, organic agents with relatively large molecular weights and polar groups have conventionally been mainly used as stabilizers. For example, Japanese Patent Publication No. 52-168529 discloses that anionic surfactants such as sodium β-naphthalene sulfonate and sodium dodecylbenzenesulfonate are added as stabilizers. Japanese Patent Publication No. 52-37971 uses organic monols, Di-A, polyols, and fluorinated hydrocarbon wet breast preparations as stabilizers. Although such organic stabilizers improve the stability of the catalyst solution, they also reduce the ability of the catalyst solution to impart activation, and in some cases may cause unevenness during plating. The unevenness of plating is
This is a particularly important problem in the electroless plating of substrates for the production of printed circuit boards for the electronic industry. In order to obtain high reliability in the operation of electronic devices, it is necessary to generate electroless plated areas with no unevenness, and for this purpose, sufficient activation of the surface to be plated is required prior to plating. be done.
発明の概要
本発明は、触媒液中の貴金属コロイドの安定性を改善し
、貴金属コロイド凝集によるＵ膜形成や沈殿を防止し、
なおかつ触媒液本来の持っている活性付与能を損なわな
い無ｉ１！解めっき用触媒液を開発することを目的とす
る。Summary of the Invention The present invention improves the stability of noble metal colloids in a catalyst solution, prevents U film formation and precipitation due to noble metal colloid aggregation, and
In addition, it does not impair the activation ability inherent in the catalyst liquid! The purpose is to develop a catalyst solution for deplating.
従来、安定剤は柊性基を多数持つものが好ましいとの観
点の下で比較的分子量が大きく極性基を持つ前述したよ
うな有機安定剤が主として使用されてきた。しかしなが
ら、本発明者等の研究の結果、こうした有機安定剤の添
加によって触媒液中の貴金属コロイドが被毒し、これが
活性付与能の劣化の原因であることが判明した。Conventionally, the above-mentioned organic stabilizers having relatively large molecular weights and polar groups have been mainly used, based on the viewpoint that stabilizers having a large number of holly groups are preferable. However, as a result of research conducted by the present inventors, it has been found that the noble metal colloid in the catalyst solution is poisoned by the addition of such an organic stabilizer, and this is the cause of the deterioration of the activation ability.
本発明者等は、こうした貴金属コロイドの被指を生じな
い安定剤として塩す酸性液中でも負に電離する酸及び化
合物に注目し、それらの中から好適なものを選定するべ
く探究を重ねた。その結果、硫酸及びリン酸並びにその
化合物は安定剤として有効であり、特に綜合リン酸化合
物は安定剤として非常に優れたものであることが見出さ
れた。The present inventors have focused on acids and compounds that negatively ionize even in salty acidic solutions as stabilizers that do not cause the formation of such noble metal colloids, and have conducted extensive research to select suitable ones from among them. As a result, it was found that sulfuric acid, phosphoric acid, and their compounds are effective as stabilizers, and that combined phosphoric acid compounds are particularly excellent as stabilizers.
斯くして、本発明は、塩酸酸性の水溶液にｍｊ５金属塩
、（量）第一スズ塩並びに（ｉｉ）塩酸酸性液中で負に
電離する、硫酸、リン酸及びそれらの水溶性化合物から
選択される安定剤を添加して成る無電解めっき用触媒液
を提供する。Thus, the present invention provides the following methods: mj5 metal salts, stannous salts, and (ii) selected from sulfuric acid, phosphoric acid, and water-soluble compounds thereof, which are negatively ionized in hydrochloric acid acidic solutions. To provide a catalyst liquid for electroless plating, which comprises a stabilizer added thereto.
発明の詳細な説明
本発明は、銅、ニッケル、パラジウム、コバルト、銀及
び金のような金！ｆＪＳを、電導性表面、非電導性表面
或いは両者が併存する表面に無ｔＸｔ Ｐｙ’ｆめっき
するに先立って、これら表面を活性化する触媒液を提供
する。DETAILED DESCRIPTION OF THE INVENTION The present invention utilizes copper, nickel, palladium, cobalt, silver and gold like gold! Prior to fJS plating without tXt Py'f on a conductive surface, a non-conductive surface, or a surface where both coexist, a catalyst liquid is provided to activate these surfaces.
被めっき表面は、脱脂、酸洗等の浄化工程を経て本発明
による触媒付与工程に供される。The surface to be plated is subjected to a purification process such as degreasing and pickling, and then subjected to a catalyst application process according to the present invention.
本発明に従う触媒液は、基本的に、塩酸酸性の水溶液に
貴金属塩及び第一スズ塩を添加して成るものである。貴
金属塩としては、元素周期表の１′１及びＩＢ族の第５
及び第６周期から違択した金属の水溶性塩、例えばパラ
ジウム、白金、金、ロジウム、オスミウム、イリジウム
等の水溶性無機及び有機酸塩が使用しうるが、特に水溶
性パラジウム化合物の使用が望ましい。水溶性パラジウ
ム化合物としては、ハロゲン化パラジウム、硫酸パラジ
ウム、硝酸パラジウム等が使用しつるが、塩化パラジウ
ムが特に好ましい。触媒効果とコストとを勘案して一般
に（ＬＯＯ０５〜２αＯｉ／ｌの濃度で使用される。水
溶性第一スズ塩としては、ハ四ゲン化第−スズ、硫酸第
一スズ、亜スズ酸塩等が使用しつるが、塩化第一スズの
使用が望ましい。The catalyst liquid according to the present invention is basically formed by adding a noble metal salt and a stannous salt to an acidic aqueous solution of hydrochloric acid. Noble metal salts include 1'1 of the periodic table of elements and 5th of group IB.
and water-soluble salts of metals selected from the sixth period, such as water-soluble inorganic and organic salts of palladium, platinum, gold, rhodium, osmium, iridium, etc., but it is particularly preferred to use water-soluble palladium compounds. . As the water-soluble palladium compound, palladium halides, palladium sulfate, palladium nitrate, etc. are used, and palladium chloride is particularly preferred. In consideration of catalytic effect and cost, it is generally used at a concentration of 05 to 2αOi/l (LOO). Examples of water-soluble stannous salts include stannous halide, stannous sulfate, stannous salts, etc. However, the use of stannous chloride is preferred.
第−スズ塩の濃度は一般に１．０〜１０００Ｊ？／／。The concentration of stannous salt is generally 1.0 to 1000 J? //.
の範囲である。これら貴金属塩と第一スズ塩とは塩酸溶
液中に溶解される。塩酸濃度は一般に１０〜８００ ｒ
ｕｔ／ｌ の範ＵＨをとる。is within the range of These noble metal salts and stannous salts are dissolved in a hydrochloric acid solution. Hydrochloric acid concentration is generally 10-800 r
Take the range UH of ut/l.
本発明に従えば、触媒液の活性付与能を低下させること
なく触媒液の安定性を向上させる安定剤として、塩酸酸
性液中でも負に電離する戯及びその化合物の中から、硫
酸、硫酸ナトリウムのような硫酸塩、硫酸・水素す）
ＩＪウムのような硫酸水素塩、その他の水溶性硫酸化合
物並びにリン酸、リン酸水素ナトリウムのようなリン酸
水緊塩、三リン酸ナトリウムのような縮合リン酸化合物
その他の水溶性リン酸化合物が単独で或いは捏合して使
用される。これらの安定剤のうち縮合リン酸化合物の安
定剤としての効果はきわめて優秀であり、２０日間以上
触媒液の安定性を保持しうる。縮合リン酸化合物として
は、三すン酸五ナトリウム（Ｎ ＦＬ＊ Ｐｓ Ｏ＋ｏ
） 、ヘキサメタリン市ナトリウム、テトラメタリン
酸ナトリウム、ウルトラポリリン酸す） ＩＪウム等が
代表的に挙げられる。According to the present invention, sulfuric acid and sodium sulfate are used as stabilizers to improve the stability of the catalyst liquid without reducing the activation ability of the catalyst liquid. (such as sulfates, sulfuric acid/hydrogen)
Hydrogen sulfates such as IJum, other water-soluble sulfuric acid compounds, phosphoric acid, phosphoric acid aqueous salts such as sodium hydrogen phosphate, condensed phosphoric acid compounds such as sodium triphosphate, and other water-soluble phosphoric acid compounds are used alone or in combination. Among these stabilizers, the condensed phosphoric acid compound is extremely effective as a stabilizer, and can maintain the stability of the catalyst solution for 20 days or more. As a condensed phosphoric acid compound, pentasodium trisstate (NFL* Ps O+o
), sodium hexametaline, sodium tetrametaphosphate, ultrapolyphosphate, etc. are representative examples.
これら安定剤は、安定剤として効力を発抑する６度以上
添加され、溶解度上限まで添加して差支えない。一般的
な添加濃度は０．０１〜５モ／Ｉ／／ｌである。These stabilizers are added at least 6 times to suppress their effectiveness as stabilizers, and may be added up to the upper limit of solubility. Typical addition concentrations are 0.01 to 5 mo/I//l.
本発明の触媒液の好ましい調製方法は次の通りである：
貴会Ｍ塩及び第一スズ塩が別々に塩酸溶液中に溶解され
、その後両者混合されそして例えば室温で放置すること
により熟成される。熟成によって混合溶液の色は緑色か
ら黒褐色に変化する。熟成ずみの溶液に安定剤を添加し
て溶解せしめ、この溶液を塩酸溶液に加え、所定ｊ度の
触媒液とする。A preferred method for preparing the catalyst solution of the present invention is as follows: The Kikai M salt and the stannous salt are dissolved separately in a hydrochloric acid solution, then both are mixed and aged, for example by standing at room temperature. . The color of the mixed solution changes from green to blackish brown as it ages. A stabilizer is added to the aged solution and dissolved, and this solution is added to a hydrochloric acid solution to obtain a catalyst solution of a predetermined degree.
本触媒液は従来態様で用いられる。被めっき部材が、触
媒液中に数秒〜数十分、通常３〜２０分浸漬され、水洗
後酸或いはアルカリにより促ｉｆｆ化される。The catalyst liquid is used in conventional manner. The member to be plated is immersed in the catalyst solution for several seconds to several tens of minutes, usually 3 to 20 minutes, and after washing with water, it is accelerated with acid or alkali.
この後、被めっき部材は従来からの慣用的な無電解めっ
き条件の下でめっきされる。Thereafter, the member to be plated is plated under conventional electroless plating conditions.
発明の効果
１、 触媚金風コロイドが安定であり、貯り１詩のコロ
イドの沈殿そして使用時のコロイドの凝集による薄膜の
形成が起きない。Advantages of the invention 1. The tactile gold-like colloid is stable and does not cause precipitation of the colloid during storage or the formation of a thin film due to aggregation of the colloid during use.
２、 触媒液の活性付与能が低下せず、めっきのつきむ
らが生じない。2. The activation ability of the catalyst liquid does not decrease and uneven plating does not occur.
五 安定剤として縮合リン酸化合物を使用することによ
り長期貯蔵が可能である。(v) Long-term storage is possible by using a condensed phosphoric acid compound as a stabilizer.
４、 特殊な有機安定剤を使用しないので、安定剤のコ
スト、取扱い等の負担が軽減される。4. Since no special organic stabilizer is used, the cost and handling burden of the stabilizer is reduced.
５、 寿命の侵いしかも活性付与能の低下のない触ａ１
′、液の使用により電子工業用各種基板を含め様々の無
電解めっき物品の品質の信頼性を向上する。5. Touch a1 that does not shorten its lifespan or reduce its activation ability.
', The use of liquid improves the reliability of the quality of various electroless plated products, including various substrates for the electronic industry.
実施例１及び比較例
塩化パラジウム０．５９を塩酸（３６％）５ｄに溶解さ
せた（これをＡ液とする）。次に別の容器に５ｎＣ１２
−２Ｈ２０２０ｇをとり、塩酸（３６％）７ｄｍｌを加
えて溶解させた（これをＢ液とする）。Example 1 and Comparative Examples 0.59 g of palladium chloride was dissolved in 5 d of hydrochloric acid (36%) (this was referred to as liquid A). Next, put 5nC12 in another container.
-2020 g of 2H was taken and dissolved by adding 7 dml of hydrochloric acid (36%) (this is referred to as Solution B).
■３液にＡ液を攪拌しながら加え、熟成した。液の色が
黒褐色に変化した時点で、液に安定剤として４ｉｉ＋合
リンｒ古化合物である三すン薗ナトリウム（トリポリリ
ン（ｙｐルナトリウム２．ＯＦ／ｌ を加え、溶解せし
めた。この液を坦飽（３６％）２００ｄと水７２５ＪＩ
ｌ−の混合液に加え触媒液を調合した。(2) Solution A was added to Solution 3 while stirring, and the mixture was aged. When the color of the liquid changed to blackish brown, 2.OF/l of tripolyline (sodium yp) was added to the liquid as a stabilizer and dissolved in 2.OF/l of tripolyline. Danku (36%) 200d and water 725JI
A catalyst solution was prepared in addition to the mixed solution of 1-.
この触媒液を大気中で２０日保管したが、Ｐｄコロイド
の薄膜及び沈殿は全く生成せず、安定性は良好であった
。This catalyst solution was stored in the atmosphere for 20 days, but no thin film or precipitate of Pd colloid was formed, and the stability was good.
次いで、脱脂等の前処理を行ったガラスエポキシ樹脂基
板を上記触媒液に５分間浸漬し、水洗しそして１０％硫
酸溶液で５分間促進化した。この後、下記の無１！Ｎめ
つき液に浸漬したところ、良好なめつき皮膜が得られた
。Next, the glass epoxy resin substrate, which had been pretreated such as degreasing, was immersed in the above catalyst solution for 5 minutes, washed with water, and accelerated with a 10% sulfuric acid solution for 5 minutes. After this, there will be no 1 below! When immersed in N plating solution, a good plating film was obtained.
無電解銅めっき液組成
ＣｕＳＯ４−５Ｈ２０１０９／Ｉ
ＥＤＴＡ ３０ ！／／１２゜２１−ジ
ピリジル 適 作
界面活性剤 Ｊｌ”Ｖ 舟ＮａＯＨｐＩ１
１２．８
温度 ７２’Ｃ，浸漬時間３０分
綜合リン飲化合物安定剤として、上記玉リン酸ナトリウ
ムに代えて、ヘキサメタリン酸ナトリウム２Ｆｌ／を及
びウルトラポリリン［孜ナトリウム（酸性メタリン酸ナ
トリウム）２１／ｌをそれぞれ使用する試験を行った。Electroless copper plating solution composition CuSO4-5H20109/I EDTA 30! //12゜21-dipyridyl suitable surfactant Jl”V FunaOHpI1
12.8 Temperature: 72'C, immersion time: 30 minutes As a phosphorus compound stabilizer, in place of the above-mentioned sodium phosphate, sodium hexametaphosphate 2Fl/L and ultrapolyline [sodium acidic acid metaphosphate] 21/L A test was conducted using each.
いずれも安定剤として有効な結果を示し、また無′亀解
銅めつき試験の結果析出ムラのない良好なめつき皮膜が
生成された。All of them showed effective results as stabilizers, and a good plating film with no uneven precipitation was produced as a result of a copper plating test.
比較試験として、安定剤を添加しない場合と、安定剤と
して陰イオン界面活性剤１９／ｌを添加する場合の２つ
について、上記の同一の試験を繰返した。液の安定性は
いずれも悪く、陰イオン界面活性剤使用の場合は無電解
銅めつき広開に析出ムラが生じた。これら試験の結果を
表Ｉにまとめて示す。As a comparative test, the same test described above was repeated for two cases: one without the addition of a stabilizer and one with the addition of 19/l of an anionic surfactant as a stabilizer. The stability of the solutions was poor in all cases, and when an anionic surfactant was used, uneven deposition occurred over a wide area during electroless copper plating. The results of these tests are summarized in Table I.
実施例２
実施例１の縮合リン酸化合物含有触媒液を用いてニッケ
ルの無電解めっき試験を行った。めっき液の組成及び条
件は次の通りである：
Ｎｌ５Ｏ，・６Ｈ，Ｏ１５１／ｌ
クエン酸ナトリウム ４５１／を次亜リン酸ナ
トリウム １ａｌ／１乳 酸
３ ｔｒｔｌ／１ｐＨ８，０（Ｎｕ、ＯＨ）
温度４３℃、浸漬時間３０分
非常に均一な、つきむらのないＮｉ皮膜が得られた。Example 2 A nickel electroless plating test was conducted using the condensed phosphoric acid compound-containing catalyst liquid of Example 1. The composition and conditions of the plating solution are as follows: Nl5O, 6H, O151/l Sodium citrate 451/L Sodium hypophosphite 1al/1 Lactic acid
3 trtl/1 pH 8.0 (Nu, OH) Temperature: 43°C, immersion time: 30 minutes A very uniform Ni film with no unevenness was obtained.
実施例５
安定剤として、硫酸、硫酸す） ＩＪウム及び硫酸水嵩
す） ＩＪウムを使用して触媒液の安定性を判定する試
験を行った。Example 5 A test was conducted to determine the stability of the catalyst liquid using sulfuric acid, sulfuric acid, sulfuric acid, and sulfuric acid as stabilizers.
触媒液としては次の基本組成を持つものを使用し、これ
に上記３棺の安定剤を添加し、大気中に室温で放置して
液表面に凝集膜が生じるまでの日数を調べた。A catalyst solution having the following basic composition was used, to which the above-mentioned three stabilizers were added, and the solution was left in the atmosphere at room temperature to determine the number of days until a cohesive film was formed on the surface of the solution.
酸性触媒液基本組成 結果を表■に示す。Basic composition of acidic catalyst liquid The results are shown in Table ■.
表■
これら安定剤は、短期貯蔵触媒液用の安定剤として有効
である。Table ■ These stabilizers are effective as stabilizers for short-term storage catalyst fluids.
実施例４
リン酸及びリン散水素ナトリウムについて実施例３と同
様にしてその安定剤としての効力を調べた。結果を表■
に示す。Example 4 Phosphoric acid and sodium phosphorus hydrogen dispersion were examined for their effectiveness as stabilizers in the same manner as in Example 3. Display the results■
Shown below.
表■ これらも短期貯蔵用安定剤として有効である。Table ■ These are also effective as short-term storage stabilizers.
実施例５
安定剤の混合利用について評価を行うべく、以下のよう
な組成の触媒液を調製し、大気中に放置して触媒コロイ
ド凝集膜の生成の互勲を観察した。Example 5 In order to evaluate the mixed use of stabilizers, a catalyst liquid having the following composition was prepared and left in the atmosphere to observe the interaction between the formation of a catalyst colloid agglomerated film.
（Ｉ）、［Ｆ］）、０１ｌ）液とも２０日後まで！、）
Ｉ媒コロイド凝集膜の生成は、圧察されず、触媒液の安
定性は良好であった。(I), [F]), 01l) until 20 days later! ,)
No formation of medium I colloid agglomerated film was observed, and the stability of the catalyst liquid was good.
、１ 代理人の氏名 倉 内 基 弘 ： 同 風 間 弘 志 。,1 Agent's name Motohiro Kurauchi: Same as Hiroshi Kaze.
手続浦正書
昭和６１年１１月４ 日
特許庁長官 黒 １）明 雄 殿
事件の表示 昭和６１年 特願第 ４７２５７ 号発
明の名作 無電解めっき用触媒液
補正をする者
事件との関係 特許出願人名称
日本鉱業株式会社Procedures Urasa Book November 4, 1985 Commissioner of the Patent Office Black 1) Indication of the Aki Yu Tono case 1985 Patent Application No. 47257 Masterpiece of invention Relationship with the case of the person correcting the catalyst solution for electroless plating Patent application person name
Japan Mining Co., Ltd.
Claims (1)
スズ塩並びに（ｉｉ）塩酸酸性液中で負に電離する、硫
酸、リン酸及びそれらの水溶性化合物から選択される安
定剤を添加して成る無電解めつき用触媒液。1) In an acidic solution of hydrochloric acid, a stable compound selected from (1) noble metal salts, (i) stannous salts, and (ii) sulfuric acid, phosphoric acid, and water-soluble compounds thereof, which are negatively ionized in an acidic solution of hydrochloric acid, is added. Catalyst liquid for electroless plating made by adding a chemical agent.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4725786A JPS62205284A (en) | 1986-03-06 | 1986-03-06 | Catalytic solution for electroless plating |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4725786A JPS62205284A (en) | 1986-03-06 | 1986-03-06 | Catalytic solution for electroless plating |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS62205284A true JPS62205284A (en) | 1987-09-09 |
Family
ID=12770225
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP4725786A Pending JPS62205284A (en) | 1986-03-06 | 1986-03-06 | Catalytic solution for electroless plating |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS62205284A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004513229A (en) * | 2000-11-01 | 2004-04-30 | アトーテヒ ドイッチュラント ゲゼルシャフト ミット ベシュレンクテル ハフツング | Method for electroless metal plating |
| JP2004190042A (en) * | 2002-03-05 | 2004-07-08 | Daiwa Fine Chemicals Co Ltd (Laboratory) | Pretreatment solution for providing catalyst for electroless plating, pretreatment method using the solution, and electroless plated film and/or plated object produced by use of the method |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5216852A (en) * | 1975-07-29 | 1977-02-08 | Aiko Kojima | Drainage treatment device |
| JPS5232727A (en) * | 1975-09-05 | 1977-03-12 | Toppan Printing Co Ltd | Method of binding books |
| JPS5315744A (en) * | 1976-07-28 | 1978-02-14 | Hitachi Ltd | Panel positioning device for colore picture tube |
-
1986
- 1986-03-06 JP JP4725786A patent/JPS62205284A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5216852A (en) * | 1975-07-29 | 1977-02-08 | Aiko Kojima | Drainage treatment device |
| JPS5232727A (en) * | 1975-09-05 | 1977-03-12 | Toppan Printing Co Ltd | Method of binding books |
| JPS5315744A (en) * | 1976-07-28 | 1978-02-14 | Hitachi Ltd | Panel positioning device for colore picture tube |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004513229A (en) * | 2000-11-01 | 2004-04-30 | アトーテヒ ドイッチュラント ゲゼルシャフト ミット ベシュレンクテル ハフツング | Method for electroless metal plating |
| JP2004190042A (en) * | 2002-03-05 | 2004-07-08 | Daiwa Fine Chemicals Co Ltd (Laboratory) | Pretreatment solution for providing catalyst for electroless plating, pretreatment method using the solution, and electroless plated film and/or plated object produced by use of the method |
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