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TWI499691B - 用於無電金屬化之安定無錫催化劑 - Google Patents

用於無電金屬化之安定無錫催化劑 Download PDF

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Publication number
TWI499691B
TWI499691B TW101129863A TW101129863A TWI499691B TW I499691 B TWI499691 B TW I499691B TW 101129863 A TW101129863 A TW 101129863A TW 101129863 A TW101129863 A TW 101129863A TW I499691 B TWI499691 B TW I499691B
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TW
Taiwan
Prior art keywords
integer
metal
chr
palladium
formula
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TW101129863A
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English (en)
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TW201319311A (zh
Inventor
劉風
瑪莉亞 安娜 齊尼克
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羅門哈斯電子材料有限公司
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
    • 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
    • C23C18/1803—Pretreatment of the material to be coated of metallic material surfaces or of a non-specific material surfaces
    • C23C18/1824—Pretreatment of the material to be coated of metallic material surfaces or of a non-specific material surfaces by chemical pretreatment
    • C23C18/1827—Pretreatment of the material to be coated of metallic material surfaces or of a non-specific material surfaces by chemical pretreatment only one step pretreatment
    • C23C18/1834—Use of organic or inorganic compounds other than metals, e.g. activation, sensitisation with polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
    • B01J23/44—Palladium
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
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    • B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
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    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
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    • 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
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    • C23C18/1803—Pretreatment of the material to be coated of metallic material surfaces or of a non-specific material surfaces
    • C23C18/1824—Pretreatment of the material to be coated of metallic material surfaces or of a non-specific material surfaces by chemical pretreatment
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    • C23C18/1831—Use of metal, e.g. activation, sensitisation with noble metals
    • 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
    • C23C18/1851—Pretreatment of the material to be coated of surfaces of non-metallic or semiconducting in organic material
    • C23C18/1872—Pretreatment of the material to be coated of surfaces of non-metallic or semiconducting in organic material by chemical pretreatment
    • C23C18/1875—Pretreatment of the material to be coated of surfaces of non-metallic or semiconducting in organic material by chemical pretreatment only one step pretreatment
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    • 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
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    • 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
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    • C23C18/2053—Pretreatment of the material to be coated of organic surfaces, e.g. resins by other methods than those of C23C18/22 - C23C18/30 by chemical pretreatment only one step pretreatment
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    • 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
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    • 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
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    • 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
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    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/40—Forming printed elements for providing electric connections to or between printed circuits
    • H05K3/42—Plated through-holes or plated via connections
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Description

用於無電金屬化之安定無錫催化劑
本發明係關於用於無電金屬化之無錫鈀催化劑的安定水溶液。更具體言之，本發明係關於用於無電金屬化之無錫鈀催化劑的安定水溶液，其中，該等催化劑係形成鈀金屬及纖維素或纖維素衍生物之奈米粒子。
無電金屬沉積係將金屬層沉積於基板表面上之周知製程。介電表面之無電鍍覆需要預先施用催化劑。催化或活化介電質(如於製造印刷電路板中使用之層壓基板之非傳導區段)的最常用方法為於酸性氯化物介質中以水性錫/鈀膠體處理該基板。該膠體之結構業經廣泛研究。通常，該膠體係包括藉由錫(II)離子之安定化層所環繞之鈀金屬芯，該安定化層基本上為用作表面安定化基之SnCl3 - 錯合物的殼體，以避免膠體於懸浮液中凝集。
於該活化製程中，錫/鈀膠體催化劑係吸附於介電基板(如含有環氧化物或聚醯亞胺之基板)上，以活化無電金屬沉積。理論上，該催化劑係作用為於該無電金屬鍍覆浴中自還原劑至金屬離子之電子傳遞路徑中的載體。儘管無電鍍覆之效能係藉由多種因素(如鍍覆溶液之添加劑組成物)所影響，活化步驟係控制無電鍍覆之速率及機制的關鍵。
近年來，隨著電子裝置尺寸之減小以及所欲之效能的增加，電子封裝工業中對於無缺陷之電子線路的要求變得更高。儘管錫/鈀膠體於商業上業經作為無電金屬鍍覆之活 化劑使用了幾十年並給出了可接受之結果，其仍具有很多缺點，而隨著對於更高品質之電子裝置的需求增加，這些缺點正在變得越發明顯。錫/鈀膠體之安定性係主要之考量。如上所述，錫/鈀膠體係藉由錫(II)離子層予以安定化，且其相對陰離子可阻止鈀凝集。該催化劑對空氣敏感並可輕易地氧化為錫(IV)，因此該膠體不能維持其膠體結構。於無電鍍覆過程中，溫度及攪動之增加會進一步促進這氧化。若錫(II)之濃度降至臨界水平，如接近零，鈀金屬粒子生長而尺寸變大、凝集並沉澱，因此變得無催化活性。結果，對於更安定之催化劑的需求增加。此外，鈀之高成本及波動之價格促使該工業之從業人員搜尋成本更低之金屬。
業經作出相當的努力以發現新的及改良之催化劑。因為鈀之高成本，在無鈀催化劑(如膠體銀催化劑)之研發有許多努力。業經進行之另一研究方向為無錫之鈀催化劑，此係由於氯化亞錫之成本高且經氧化之錫需要個別的加速步驟。於金屬化製程中，該加速步驟係額外的步驟，且該步驟往往將部分催化劑自基板剝離，尤其是玻璃纖維基板上之催化劑，於經鍍覆之基板表面上造成空洞。惟，此等無錫催化劑業經顯示，對於在印刷電路板之製造中鍍覆通孔，其活性及可靠性不足。再者，於存儲時，此等催化劑之活性典型係逐漸變小，因此使得將此等催化劑用於商業用途係不可靠和不切實際的。
業經研究了用於錫錯合物之另一種安定化部分 (moiety)，如聚乙烯基吡咯啶酮(PVP)及樹枝狀聚合物。多個研究群組業經於文獻中報導了安定且均勻之經PVP保護之奈米粒子。其他金屬膠體，如其中藉由較不昂貴之金屬部分替換鈀的銀/鈀及銅/鈀，亦業經報導於文獻中；惟，此等替代之催化劑並非為商業可接受者。離子性鈀異變體業經得以商用，但它們需要額外之還原步驟。據此，仍需要安定且可靠之無電金屬鍍覆催化劑。
水性催化劑溶液係包括一種或多種抗氧化劑、鈀金屬與選自具有式(I)之聚合物及具有式(II)之聚合物與具有式(III)或式(IV)之四級化合物之反應產物的一種或多種化合物之奈米粒子，及一種或多種交聯劑； 其中，R1 、R2 、R3 、R4 、R5 、R6 及R7 係相同或不同，且係選自-H、-CH2 COOX、-C(O)-CH3 、-C(O)-(CH2 )z -CH3 、以及 X係-H或相對陽離子； 其中，R9 、R10 、R11 、R12 、R13 、R14 及R15 係相同或不同，且係選自-H、-CH3 、-CH2 CH3 、-CH2 OH、-[CH2 CHR8 ]x -OH、-CH2 CH(OH)CH3 及-(CH2 CHR8 O)y -H，且限制條件為R9 、R10 、R11 、R12 、R13 、R14 及R15 之至少一者係-CH2 OH、-[CH2 CHR8 ]x -OH、-CH2 CH(OH)CH3 或-(CH2 CHR8 O)y -H，其中，R8 係-H或-CH3 ，x與y係至少為1之整數，且n與z係如上述者； 其中，m係自1至16之整數，Y係鹵素，Z- 係相對陰離子，R16 、R17 及R18 係相同或不同，且係-H、-CH3 或-(CH2 )p -CH3 ， 以及，R19 係-H或-CH3 ，以及，p係1至9之整數；以及，該催化劑係不含錫。
方法係包括：a)提供基板；b)將水性催化劑溶液施用至該基板，該水性催化劑溶液係包括一種或多種抗氧化劑、鈀金屬與選自具有式(I)之聚合物及具有式(II)之聚合物與具有式(III)或式(IV)之四級化合物之反應產物的一種或多種化合物之奈米粒子，及一種或多種交聯劑； 其中，R1 、R2 、R3 、R4 、R5 、R6 及R7 係相同或不同，且係選自-H、-CH2 COOX、-C(O)-CH3 、-C(O)-(CH2 )z -CH3 、以及 其中，n係至少為2之整數，z係至少為1之整數，以及，X係-H或相對陽離子； 其中，R9 、R10 、R11 、R12 、R13 、R14 及R15 係相同或不同，且係選自-H、-CH3 、-CH2 CH3 、-CH2 OH、-[CH3 CHR8 ]x -OH、-CH2 CH(OH)CH3 及-(CH2 CHR8 O)y -H，且限制條件為R9 、R10 、R11 、R12 、R13 、R14 及R15 之至少一者係-CH2 OH、-[CH2 CHR8 ]x -OH、-CH2 CH(OH)CH3 或-(CH2 CHR8 O)y -H，其中，R8 係-H或-CH3 ，x與y係至少為1之整數，且n與z係如上揭者，與具有下式之四級化合物： 其中，m係自1至16之整數，Y係鹵素，Z- 係相對陰離子，R16 、R17 及R18 係相同或不同，且係-H、-CH3 或 -(CH2 )p -CH3 ，以及，R19 係-H或-CH3 ，以及，p係1至9之整數；以及，該催化劑係不含錫；以及c)施用無電金屬鍍覆浴將金屬無電地沉積於該基板上。
該催化劑可用以將金屬無電地鍍覆於基板(包括介電質材料之基板)上，且於存儲時以及於無電金屬鍍覆過程中安定，因與傳統之錫/鈀催化劑相比，他們會輕易地氧化。纖維素安定劑係作用如同傳統錫/鈀催化劑之氯化亞錫所起之作用，但該等纖維素安定劑係生物可降解，因此，它們不像氯化亞錫一樣丟棄時對環境造成危害。該等纖維素安定劑可大量獲得，其成本僅為氯化亞錫之成本的一部分。用以做成該等安定劑之原材料可自基本上無處不在之植物中獲得。該等經纖維素安定化之鈀催化劑使得無需加速步驟之無電金屬鍍覆成為可能，且使得基板，甚至印刷電路板之通孔壁之良好金屬覆蓋成為可能。
如本說明書全文中所使用者，除了內文中明確另行指出者之外，下文給出之縮寫係具有下列意義：g=公克；mg=毫克；ml=毫升；L=公升；cm=公分；m=公尺；mm=毫米；μm=微米；nm=奈米；ppm=百萬分之份數；℃=攝氏度；g/L=每公升之公克；DI=去離子；wt%=重量百分比；以及，Tg=玻璃轉化溫度。
本說明書全文中，術語「印刷電路板」與「印刷佈線板」可互換地使用。本說明書全文中，術語「鍍覆」與「沉 積」可互換地使用。除了特別另行指明者之外，全部量係重量百分比。全部數值範圍係包括邊值且可以任何次序組合，除非邏輯上此等數值範圍之加和係設定為100%。
水性催化劑溶液係包括鈀金屬與一種或多種選自具有下式之安定化聚合物之奈米粒子： 其中，R1 、R2 、R3 、R4 、R5 、R6 及R7 係相同或不同，且係選自-H、-CH2 COOX、-C(O)-CH3 、-C(O)-(CH2 )z -CH3 、以及 其中，n係至少為2之整數，典型係自2至20，較佳係自2至15，更佳係自5至10，z係至少為1之整數，典型係自1至10，較佳係自2至5，以及，X係-H或相對陽離子，如鈉、鉀、銨離子或鹼土金屬，典型係鈉或鉀。較佳地，R1 、R2 、R3 、R4 、R5 、R6 及R7 之至少一者係-C(O)-CH3 或-CH2 COOX，更佳地，R2 、R3 、R5 、R6 及R7 之至少一者係-CH2 COOX，且較佳地，當R1 、R2 、R3 、R4 、R5 、R6 或R7 不為 -C(O)-CH3 或-CH2 COOX時，其係-H。例示性聚合物係羧甲基纖維素及醋酸纖維素。該催化劑係不含錫。
該等安定化聚合物可為具有式(II)之聚合物與具有式(III)或(IV)之四級化合物之反應產物， 其中，R9 、R10 、R11 、R12 、R13 、R14 及R15 係相同或不同，且係選自-H、-CH3 、-CH2 CH3 、-CH2 OH、-[CH2 CHR8 ]x -OH、-CH2 CH(OH)CH3 及-(CH2 CHR8 O)y -H，且條件為R9 、R10 、R11 、R12 、R13 、R14 及R15 之至少一者係-CH2 OH、-[CH2 CHR8 ]x -OH、-CH2 CH(OH)CH3 或-(CH2 CHR8 O)y -H，較佳地，R10 、R11 、R13 、R14 及R15 之至少一者係-[CH2 CHR8 ]x -OH或-(CH2 CHR8 O)y -H，其中，R8 係-H或-CH3 ，x與y係至少為1之整數，典型係自1至10，較佳係自2至5，以及，n與z係如上揭者； 其中，m係自1至16之整數，Y係鹵素，如氟、氯、溴或碘，該鹵素較佳係氯，Z- 係相對陰離子，如鹵化物如氟化物、氯化物、溴化物或碘化物，較佳係氯化物，硝酸根、亞硝酸根、磷酸根、氫氧根或羧酸根，如醋酸根或丙酸根，R16 、R17 及R18 係相同或不同且係-H、-CH3 或-(CH2 )p -CH3 ，以及，R19 係-H或-CH3 ，以及，p係1至9之整數，以及一種或多種交聯劑。該催化劑係不含錫。例示性四級化合物係氯化環氧丙基三甲基銨、氯化-2,3-環氧基丙基-N,N,N-三甲基銨、氯化3-氯-2-羥基丙基-N,N,N-三甲基銨、氯化3-氯-2-羥基丙基-N,N,N-二甲基乙醇銨及二氯化1,3-雙(3-氯-2-羥基丙基-N,N-二甲基銨)-N-丙烷。纖維素衍生物與四級銨化合物之較佳反應產物係羥乙基纖維素與氯化環氧丙基三甲基銨的反應產物。
交聯劑之實例係包括，但不限於，甲醛、經羥甲基化之氮化合物如二羥甲基脲、二羥甲基伸乙基脲以及二羥甲基咪唑啉酮；二羧酸，如馬來酸；二醛，如乙二醛；二環氧化物，如1,2,3,4-二環氧丁烷及1,2,5,6-二環氧己烷；二異氰酸酯；二乙烯基化合物，如二乙烯基碸；二鹵化合物，如二氯丙酮、二氯醋酸、1,3-二氯丙-2-醇、二氯乙烷、 2,3-二溴-1-丙醇、2,3-二氯-1-丙醇及2,2-二氯乙醚；鹵醇，如表氯醇；雙(環氧基丙基)醚；乙烯基環己烯二氧化物；乙二醇-雙(環氧基丙基)醚；乙烯基環己烯二氧化物；乙二醇-雙(環氧基丙基)醚；1,3-雙(β-羥基-Γ-氯丙氧基)醚；1,3-雙(β-羥基-Γ-氯丙氧基)乙烷；亞甲基雙(丙烯醯胺)；N,N’-二羥甲基(亞甲基雙(丙烯醯胺))；三丙烯醯氧基六氫三(triacrylolhexahydrotriazine)；丙烯醯胺基亞甲基氯乙醯胺；2,4,6-三氯嘧啶；2,4,5,6-四氯嘧啶；三聚氯氰；三烯丙基氰脲酸酯磷氧氯化物；雙(丙烯醯胺基)醋酸；二環氧化合物及鹵環氧化合物，如二氯化1,3-雙(環氧丙基二甲基銨)丙烷及表氯醇。較佳之交聯劑係該等二環氧化合物及鹵環氧化合物。
該等聚合物可藉由該技藝及文獻中之習知方法做成，且多數係可商購者。可商購之羧甲基纖維素鈉之一實例係Ashland之AQUALON，以及一種可商購之羥乙基纖維素與氯化環氧丙基三甲基銨的聚合物係可自愛美高公司(Amerchol Corporation)購得之UCARE JR-125。作成該纖維素及纖維素衍生物與四級銨化合物聚合物的方法係揭露於第5,780,616號美國專利中。
該聚合物之重量平均分子量可變。典型地，該分子量係10,000及更高之範圍，更典型係自10,000至300,000。
安定化聚合物係以足以提供奈米粒子安定之量包括於水性催化劑溶液中。多種上述之安定化聚合物的混合物可包括於水性催化劑中。可需要少量實驗以確定用以安定給 定之金屬奈米粒子所需具體安定劑或安定劑之組合的量。通常，一種或多種安定化聚合物係以10 mg/L至10 g/L，較佳自20 mg/L至1 g/L的量包括於該水性催化劑溶液中。
一種或多種抗氧化劑可包括於該水性催化劑溶液中。可包括傳統之抗氧化劑，其可以傳統之量被包括。典型地，所包括之抗氧化劑的量係0.1 g/L至10 g/L，較佳係自0.2 g/L至5 g/L。此等抗氧化劑係包括，但不限於，抗壞血酸、酚酸、聚酚類化合物，例如但不限於，羥基苯甲酸及衍生物、沒食子酸、羥基苯甲醛、兒茶酚、氫醌、兒茶素及類黃酮。
係包括一種或多種還原劑，以將鈀離子還原為鈀金屬。可使用習知以將鈀離子還原為鈀金屬之傳統還原劑。此等還原劑係包括，但不限於，二甲基胺硼烷、硼氫化鈉、抗壞血酸、異抗壞血酸、亞磷酸氫鈉、水合肼、甲酸及甲醛。所包括之還原劑的量係實質上將全部鈀離子還原為鈀金屬。該量通常係傳統之量，且為熟知該技藝之人士所習知者。
鈀金屬源係包括任何之水溶性鈀鹽。所包括之此等鹽係用以提供10ppm至5000ppm，較佳自300ppm至1500ppm量之鈀金屬。水溶性鈀鹽係包括，但不限於，氯化鈀鈉、氯化鈀、醋酸鈀、氯化鉀鈀及硝酸鈀。
組成水性催化劑之組分可以任何次序組合。可使用該技藝及文獻中習知之任何適宜之方法製備該水性催化劑溶液。儘管組分之具體參數及量可能於一種方法到另一種方 法會有變化，通常係首先將一種或多種安定化聚合物溶解於足量之水中。於劇烈攪動，將一種或多種作為水性溶液之鈀金屬源與安定劑溶液組合，以形成均勻之混合物。隨後，於劇烈攪動，將含有一種或多種還原劑之水性溶液與安定劑及鈀鹽之混合物混合，以將鈀離子還原為鈀金屬。該等製程步驟及溶液典型係於室溫進行；惟，可改變溫度以輔助溶解反應組分以及促進鈀離子至鈀金屬之還原反應。儘管未受縛於理論，該等安定劑可塗覆或環繞鈀粒子之多個部分或大部分，以安定化催化劑溶液。鈀金屬與安定劑之粒子之尺寸的範圍係1nm至1000nm或諸如自2nm至500nm。較佳地，該等粒子之尺寸的範圍係自2nm至300nm，更佳係自2nm至100nm，最佳係自2nm至10nm。
一種或多種酸可加入該催化劑中，以提供低於7，較佳係自1至6.5，更佳係自2至6之pH範圍。可以足夠之量使用無機酸或有機酸，以將pH維持於所欲之範圍。亦可使用無機酸及有機酸之混合物。無機酸之實例係鹽酸、硫酸及硝酸。有機酸係包括單羧酸及多羧酸，如二羧酸。有機酸之實例係苯甲酸及其衍生物，如羥基苯甲酸、抗壞血酸、異抗壞血酸、蘋果酸、馬來酸、沒食子酸、醋酸、檸檬酸及酒石酸。
該等催化劑可用以無電地金屬鍍覆各種已知能經無電金屬鍍覆之基板。基板係包括，但不限於，包括無機及有機物質之材質，如玻璃、陶瓷、瓷、樹脂、紙張、布及其組合。包覆及未包覆金屬之材質亦為可使用該催化劑進行 金屬鍍覆的基板。
基板亦包括印刷電路板。此等印刷電路板係包括包覆及未包覆金屬之熱固性樹脂、熱塑性樹脂及其組合，包括纖維，如玻璃纖維，以及前述者之浸漬具體例。
熱塑性樹脂係包括，但不限於，縮醛樹脂；丙烯酸系，如丙烯酸甲酯；纖維素系樹脂，如乙酸乙酯、丙酸纖維素、醋酸丁酸纖維素及硝酸纖維素；聚醚；尼龍；聚乙烯；聚苯乙烯；苯乙烯摻合物，如丙烯腈苯乙烯；及共聚物及丙烯腈-丁二烯-苯乙烯共聚物；聚碳酸酯；聚氯三氟乙烯；以及乙烯基聚合物及共聚物，如醋酸乙烯酯、乙烯基醇、乙烯基丁縮醛、氯乙烯、氯乙烯-醋酸乙烯酯共聚物、偏氯乙烯及乙烯基甲縮醛。
熱固性樹脂係包括，但不限於，酞酸烯丙酯、呋喃、蜜胺-甲醛、酚-甲醛及酚-呋喃甲醛共聚物，其係單獨使用或與丁二烯丙烯腈共聚物或丙烯腈-丁二烯-苯乙烯共聚物，聚丙烯酸酯，矽酮，脲醛，環氧樹脂，烯丙基樹脂，酞酸甘油酯及聚酯組合使用。
多孔材質係包括，但不限於，紙張、木材、玻璃纖維、布及纖維，如天然纖維及合成纖維，如棉纖維及聚酯纖維。
該等催化劑可用以鍍覆低Tg 樹脂及高Tg 樹脂兩者。低Tg 樹脂係具有低於160℃之Tg ，而高Tg 樹脂係具有160℃及更高之Tg 。典型地高Tg 樹脂係具有160℃至280℃，或諸如自170℃至240℃之Tg 。高Tg 之聚合物樹脂係包括，但不限於，聚四氟乙烯(PTFE)及聚四氟乙烯摻合物。此等摻合物 係包括，舉例而言，PTFE與聚苯醚及氰酸酯。其他類別之包括具有高Tg 之樹脂的聚合物樹脂係包括，但不限於，環氧樹脂，如二官能性及多官能性之環氧樹脂、雙馬來醯亞胺/三及環氧樹脂(BT環氧)、環氧/聚苯醚樹脂、丙烯腈丁二烯苯乙烯、聚碳酸酯(PC)、聚苯醚(PPO)、聚伸苯醚(PPE)、聚伸苯硫醚(PPS)、聚碸(PS)、聚醯胺、聚酯如聚對苯二甲酸乙二醇酯(PET)及聚對苯二甲酸丁二醇酯(PBT)、聚醚酮(PEEK)、液晶聚合物、聚氨酯、聚醚醯亞胺、環氧化物及其組合物。
催化劑可用以將金屬沉積於印刷電路板之通孔壁或導孔壁上。催化劑可用於製造印刷電路板之水平及垂直製程中。
水性催化劑可與傳統之無電金屬鍍覆浴並用。儘管預想催化劑可用於無電地沉積可經無電鍍覆之任何金屬，典型地，該金屬係選自銅、銅合金、鎳或鎳合金。更典型地，該金屬係選自銅及銅合金，最典型係使用銅。
可使用傳統之無電銅或銅合金浴。典型地，銅離子源係包括，但不限於，銅之水溶性鹵化物、硝酸鹽、醋酸鹽、硫酸鹽及其他有機及無機鹽。亦可使用一種或多種此等銅鹽之混合物，以提供銅離子。實例係包括硫酸銅如五水硫酸銅、氯化銅、硝酸銅、氫氧化銅及氨基磺酸銅。傳統量之銅鹽可用於組成物中。於組成物中，銅離子之濃度可係自0.5 g/L至30 g/L或諸如自1 g/L至20 g/L或諸如自5 g/L至10 g/L之範圍。
一種或多種合金化之金屬亦可包括於無電組成物中。此等合金化金屬係包括，但不限於，鎳及錫。銅合金之實例係包括銅/鎳及銅/錫。典型地，該銅合金係銅/鎳。
鎳及鎳合金之無電浴所用之鎳離子源可包括一種或多種鎳之傳統水溶性鹽。鎳離子源係包括，但不限於，硫酸鎳及鹵化鎳。鎳離子源可以傳統量包括於該無電合金化之組成物中。所包括之鎳離子源的量典型係0.5 g/L至10 g/L或諸如自1 g/L至5 g/L。
用於金屬化基板之方法的步驟可取決於待鍍覆之表面是否為金屬或介電質而改變。傳統之用於將金屬無電地鍍覆於基板上的步驟可與該等催化劑並用；惟，該水性且經聚合物安定化之鈀催化劑並不如多數傳統無電鍍覆製程中一樣需要加速步驟。據此，當使用該催化劑時，較佳係不包括加速步驟。通常，該催化劑係施用至待以金屬無電鍍覆之基板的表面上，之後施加金屬鍍覆浴。無電金屬鍍覆參數如溫度及時間，可係傳統者。可使用傳統之基板準備方法，如清潔或脫脂基板表面、粗糙化或微粗糙化該表面、蝕刻或微蝕刻該表面、溶劑溶脹劑應用、將通孔去油污以及各種沖洗及抗氧化處理。此等方法及製劑係該技藝中習知者且揭露於文獻中。
通常，當待鍍覆金屬之基板為介電質時，如處於印刷電路板之表面上或通孔之壁上，該等板係以水沖洗以及清潔並脫脂，之後藉由將通孔壁去油污。典型地，準備或軟化該介電質表面或將該等通孔去油污係始於溶劑溶脹劑之 應用。
可使用任何之傳統溶劑溶脹劑。具體類型可取決於介電質材料之類型而改變。介電質之實例係揭示於上。可進行少量實驗以確定何種溶劑溶脹劑係適用於特定之介電質材料。該介電質之Tg 往往決定待使用之溶劑溶脹劑之類型。溶劑溶脹劑係包括，但不限於，二醇醚及其相關之醚醋酸酯。可使用傳統量之二醇醚及其相關之醚醋酸酯。可商購之溶劑溶脹劑的實例為CIRCUPOSIT CONDITIONERTM 3302、CIRCUPOSIT HOLE PREPTM 3303及CIRCUPOSIT HOLE PREPTM 4120(可自羅門哈斯電子材料公司(Rohm and Haas Electronic Materials,Marlborough,MA)獲得)。
視需要地，以水沖洗基板及通孔。隨後施用促進劑。可使用傳統之促進劑。此等促進劑係包括硫酸、鉻酸、鹼性高錳酸鹽或電漿蝕刻。典型係使用鹼性高錳酸鹽作為促進劑。可商購之促進劑的實例係可自羅門哈斯電子材料公司購得之CIRCUPOSIT PROMOTERTM 4130。
視需要地，再次以水沖洗基板及通孔。隨後施用中和劑，以中和促進劑留下之任何殘留。可使用傳統之中和劑。典型地，該中和劑係含有一種或多種胺類或3wt%過氧化物及3wt%硫酸之溶液的水性鹼性溶液。視需要地，以水沖洗基板及通孔，隨後乾燥。
於溶劑溶脹且去油污之後，可施用酸或鹼性調節劑。可使用傳統之調節劑。此等調節劑可包括一種或多種陽離子性界面活性劑、非離子性界面活性劑、錯合劑及pH調整 劑或緩衝劑。可商購之酸調節劑的實例為可自羅門哈斯電子材料公司購得之CIRCUPOSIT CONDITIONERTM 3320及CIRCUPOSIT CONDITIONERTM 3327。適宜之鹼性調節劑係包括，但不限於，含有一種或多種四級胺類及多胺類之水性鹼性界面活性劑溶液。可商購之鹼性界面活性劑的實例係可自羅門哈斯電子材料公司購得之CIRCUPOSIT CONDITIONERTM 231、3325、813及860。視需要地，以水沖洗該基板及通孔。
調節之後可進行微蝕刻。可使用傳統之微蝕刻組成物。微蝕刻係設計為對經曝光之金屬(如，內層及表面蝕刻)提供微粗糙化之金屬表面，以加強經沉積之無電鍍覆及後來之電鍍的後續黏合。微蝕刻劑係包括，但不限於，60 g/L至120 g/L過硫酸鈉或氧單過硫酸鈉或氧單過硫酸鉀及硫酸(2%)混合物，或通用之硫酸/過氧化氫。可商購之微蝕刻組成物的實例係可自羅門哈斯電子材料公司購得之CIRCUPOSIT MICROETCHTM 3330。視需要，以水沖洗基板。
視需要地，隨後將預浸漬液(pre-dip)施用至經微蝕刻之基板及通孔上。可使用pH範圍典型係自3至5之無機或有機酸的傳統預浸漬水性溶液。無機酸溶液之實例係2%至5%鹽酸。視需要地，以冷水沖洗基板。
隨後，將安定化之奈米粒子催化劑施用至基板及通孔。可於施用該催化劑之後，視需要以水沖洗該基板及通孔。
隨後，使用無電浴將金屬如銅、銅合金、鎳或鎳合金 鍍覆於基板上及通孔壁上。典型係將銅鍍覆於通孔壁上。鍍覆時間及溫度可係傳統者。典型係於20℃至80℃，更典型自30℃至60℃之溫度進行金屬沉積。該基板可浸潤於無電鍍覆浴中，或該無電鍍覆浴可噴灑於基板上。典型地，沉積可進行5秒至30分鐘；惟，鍍覆時間可取決於該基板上金屬之厚度而改變。
視需要地，可將抗氧化劑施用至金屬。可使用傳統之抗氧化劑。可商購之抗氧化劑的實例係ANTI TARNISHTM 7130(可自羅門哈斯電子材料公司購得)。可視需要沖洗基板，隨後可乾燥該板。
進一步處理可包括藉由光圖案化進行傳統處理，以及進一步將金屬沉積於基板上，如銅、銅合金、錫及錫合金之電解金屬沉積。
催化劑可用以將金屬無電地鍍覆於基板(包括介電質材料之基板)上，且於存儲時及無電金屬鍍覆過程中係安定的，因與傳統之錫/鈀催化劑相比，該等催化劑不容易氧化。纖維素安定劑作用如同傳統錫/鈀催化劑中氯化亞錫所起之作用，但該等纖維素安定劑可生物降解，因此，它們於丟棄時不像氯化亞錫一樣對環境造成危害。該等纖維素安定劑可大量獲得，其成本僅為氯化亞錫成本之一部分。用以做成該等安定劑之原始材料可自無處不在之植物獲得。經纖維素安定化之鈀催化劑使得能進行無需加速步驟之無電金屬鍍覆的，且使得能獲得基板，甚至印刷電路板之通孔壁，之良好金屬覆蓋。
下述實施例並非欲以限制本發明之範疇，而欲以進一步闡釋本發明。
實施例1
藉由下述者製備羧甲基纖維素/鈀催化劑：於室溫將40 mg羧甲基纖維素鈉鹽溶解於含有250 ml DI水之燒杯中。於攪拌，加入溶解於10 ml DI水中之172 mg Na2 PdCl4 ，劇烈混合該混合物。於非常強烈之攪動，將溶解於10 ml DI水中之250 mg NaBH4 加入溶液混合物中。該溶液迅速從黃色變為黑色，表明鈀離子被還原為鈀金屬。該鈀金屬之平均粒子尺寸為5nm。該等粒子係以穿式射電子顯微鏡量測之。使用來自費雪科技(Fisher Scientific)之ACCUMET AB15 pH計量測，如此合成之催化劑溶液具有介於8與9之間的pH。將含有水性催化劑溶液之燒杯於50℃水浴中放置12小時，以測試其安定性。12小時之後，觀察該溶液，未見可觀察之沉澱，表明該催化劑仍安定。
使用該催化劑溶液作為母液，並將8份分裝樣本稀釋至奈米粒子濃度為25ppm。以抗壞血酸將等分量之pH調整至3.5。
測試六種不同之層壓體(laminate)：NP-175、370 HR、TUC-752、SY-1141、SY-1000-2及FR-408。NP-175係自南亞科技公司(Nanya)獲得，370 HR及FR-408係自Isola獲得，TUC-752係自臺耀科技(Taiwan Union Technology Corporation)獲得，而SY-1141及SY-1000係自Shengyi獲得。Tg 值係自140℃至180℃之範圍。每一層壓體係5cm ×12cm。每一層壓體之表面係處理如下：1.將每一層壓體於80℃溶劑溶脹劑中浸潤7分鐘，該溶劑係包括體積和體積之比為1：2的乙二醇二甲醚及水；2.隨後，將每一層壓體自該溶劑溶脹劑移除，以冷自來水沖洗4分鐘；3.隨後，於80℃以高錳酸鹽水性溶液處理每一層壓體10分鐘，該溶液係包括1%高錳酸鉀且其pH高於10；4.隨後，以冷自來水沖洗每一層壓體4分鐘；5.隨後，於室溫以3wt%過氧化物及3wt%硫酸之中和劑溶液處理每一層壓體2分鐘；6.隨後，以冷自來水沖洗每一層壓體4分鐘；7.隨後，將每一層壓體於含有3% CIRCUPOSIT CONDITIONERTM 231水性酸調節劑之水性浴中於40℃浸潤5分鐘；8.隨後，以冷自來水沖洗每一層壓體4分鐘；9.隨後，於室溫對每一層壓體施用MICROETCHTM 748溶液2分鐘，以微蝕刻該等層壓體；10.隨後，以冷自來水沖洗每一層壓體4分鐘；11.隨後，以一份或多份上述製備之羧甲基纖維素/鈀催化劑分裝量於40℃打底(prime)層壓體6分鐘；12.隨後，以冷自來水沖洗層壓體5分鐘；13.隨後，於40℃將層壓體於pH為13之CIRCUPOSITTM 880無電銅鍍覆浴中浸潤18分鐘，且將銅沉積於該基板上；14.隨後，以冷水沖洗鍍覆有銅之層壓體2分鐘；15.隨後，將每一鍍覆有銅之層壓體置於傳統烘箱中，並於105℃乾燥20分鐘；16.乾燥之後，將每一鍍覆有銅之層壓體於傳統之實驗室乾燥器中放置20分鐘，或直至其冷卻至室溫；以及17.隨後，使用傳統之斯科奇膠帶測試(Scotch tape test)方法測試每一銅層壓體之黏著性。
鍍覆有銅之層壓體全部通過斯科奇膠帶測試。自銅層壓體移除該膠帶之後，不存在可觀察之黏貼於斯科奇膠帶上的銅金屬。
實施例2
如實施例1中揭示者製備25 ppm水性羧甲基纖維素/鈀催化劑。以抗壞血酸將該催化劑溶液之pH調整至pH 3.5。該鈀金屬之平均粒子尺寸係確定為5nm。提供各自具有複數個通孔之六種類型的上述層壓體。藉由與實施例1中描述之層壓體之表面處理相同的製程步驟將該等通孔作成導電性。於施用該催化劑之後，以與實施例1中描述者相同之無電銅浴來無電地鍍覆該等通孔。
鍍覆之後，縱向切割每一板以曝露該等通孔之鍍覆有銅的壁。自每一板之經切割之通孔壁取得多個厚度為1mm之橫切面，以確定該板之通孔壁覆蓋量。使用歐洲背光等 級表(European Backlight Grading Scale)。將來自每一板之1mm切片置於傳統之50X放大之光學顯微鏡下。藉由自該顯微鏡下觀察到之光的量，來確定銅沉積物之品質。若未觀察到光，則切片完全為黑色且其背光等級係定為5，表明該通孔之完整銅覆蓋。若光穿行通過整個切片而無任何暗域，則表明壁上存在極少的銅金屬沉積至甚至沒有銅金屬沉積，且切片背光等級定為0。若切片具有一些暗域及光域，則將它們的等級定為介於0與5之間。在5等中，六片層壓體上之25 ppm羧甲基纖維素/鈀催化劑的背光等級為4.5或更高，其表明，對於以工業標準商用，該催化劑係通常可接受者。

Claims (10)

  1. 一種水性催化劑溶液，係包含一種或多種抗氧化劑、鈀金屬與選自具有式(I)之聚合物及具有式(II)之聚合物與具有式(III)或式(IV)之四級化合物之反應產物的一種或多種化合物之奈米粒子，以及一種或多種交聯劑； 其中，R1 、R2 、R3 、R4 、R5 、R6 及R7 係相同或不同，且係選自-H、-CH2 COOX、-C(O)-CH3 、-C(O)-(CH2 )z -CH3 以及 其中，n係至少為2之整數，z係至少為1之整數，且X係-H或相對陽離子； 其中，R9 、R10 、R11 、R12 、R13 、R14 及R15 係相同或不同，且係選自-H、-CH3 、-CH2 CH3 、-CH2 OH、-[CH2 CHR8 ]x -OH、-CH2 CH(OH)CH3 及-(CH2 CHR8 O)y -H，且限制條件為R9 、R10 、R11 、R12 、R13 、R14 及R15 之至少一者係-CH2 OH、-[CH2 CHR8 ]x -OH、-CH2 CH(OH)CH3 或-(CH2 CHR8 O)y -H，其中，R8 係-H或-CH3 ，x與y係至少為1之整數，以及n與z係如上述者； 其中，m係1至16之整數，Y係鹵素，Z- 係相對陰離子，R16 、R17 及R18 係相同或不同且係-H、-CH3 或-(CH2 )p -CH3 ，R19 係-H或-CH3 ，p係1至9之整數，該催化劑係不含錫。
  2. 如申請專利範圍第1項所述之水性催化劑，其中，R2 、R3 、R5 、R6 與R7 之至少一者係-CH2 COOX或-C(O)-CH3 。
  3. 如申請專利範圍第1項所述之水性催化劑，其中，該奈米粒子係1nm至1000nm。
  4. 如申請專利範圍第1項所述之水性催化劑，其中，該交 聯劑係選自鹵環氧化合物及二環氧化合物之一者或多者。
  5. 一種無電金屬化之方法，係包含：a)提供基板；b)將水性催化劑溶液施用至該基板，該水性催化劑溶液係包含一種或多種抗氧化劑、鈀金屬與選自具有式(I)之聚合物及具有式(II)之聚合物與具有式(III)或式(IV)之四級化合物之反應產物的一種或多種化合物之奈米粒子，以及一種或多種交聯劑； 其中，R1 、R2 、R3 、R4 、R5 、R6 及R7 係相同或不同，且係選自-H、-CH2 COOX、-C(O)-CH3 、-C(O)-(CH2 )z -CH3 以及 其中，n係至少為2之整數，z係至少為1之整數， 且X係-H或相對陽離子； 其中，R9 、R10 、R11 、R12 、R13 、R14 及R15 係相同或不同，且係選自-H、-CH3 、-CH2 CH3 、-CH2 OH、-[CH2 CHR8 ]x -OH、-CH2 CH(OH)CH3 及-(CH2 CHR8 O)y -H，且限制條件為R9 、R10 、R11 、R12 、R13 、R14 及R15 之至少一者係-CH2 OH、-[CH2 CHR8 ]x -OH、-CH2 CH(OH)CH3 或-(CH2 CHR8 O)y -H，其中，R8 係-H或-CH3 ，x與y係至少為1之整數，以及n與z係如上揭者； 其中，m係1至16之整數，Y係鹵素，Z- 係相對陰 離子，R16 、R17 及R18 係相同或不同且係-H、-CH3 或-(CH2 )p -CH3 ，R19 係-H或-CH3 ，p係1至9之整數，該水性催化劑溶液係不含錫；以及c)使用無電金屬鍍覆浴將金屬無電地沉積於該基板上。
  6. 如申請專利範圍第5項所述之方法，其中，該基板係包含複數個通孔。
  7. 如申請專利範圍第5項所述之方法，其中，該無電金屬鍍覆浴係選自銅、銅合金、鎳及鎳合金浴。
  8. 如申請專利範圍第5項所述之方法，其中，R2 、R3 、R5 、R6 與R7 之至少一者係-CH2 COOX或-C(O)-CH3 。
  9. 如申請專利範圍第5項所述之方法，其中，該交聯劑係選自鹵環氧化合物及二環氧化合物之一者或多者。
  10. 如申請專利範圍第5項所述之方法，其中，該奈米粒子係1nm至1000nm。
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