JP2003209341A - Method for forming conductive pattern on insulation board - Google Patents
Method for forming conductive pattern on insulation boardInfo
- Publication number
- JP2003209341A JP2003209341A JP2002006890A JP2002006890A JP2003209341A JP 2003209341 A JP2003209341 A JP 2003209341A JP 2002006890 A JP2002006890 A JP 2002006890A JP 2002006890 A JP2002006890 A JP 2002006890A JP 2003209341 A JP2003209341 A JP 2003209341A
- Authority
- JP
- Japan
- Prior art keywords
- conductive pattern
- forming
- solvent
- ultrafine
- dispersion
- 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.)
- Granted
Links
- 238000000034 method Methods 0.000 title claims abstract description 68
- 238000009413 insulation Methods 0.000 title abstract 3
- 239000006185 dispersion Substances 0.000 claims abstract description 100
- 239000011882 ultra-fine particle Substances 0.000 claims abstract description 57
- 239000007788 liquid Substances 0.000 claims abstract description 49
- 229910052751 metal Inorganic materials 0.000 claims abstract description 40
- 239000002184 metal Substances 0.000 claims abstract description 40
- 239000002245 particle Substances 0.000 claims abstract description 34
- 239000002923 metal particle Substances 0.000 claims description 58
- 239000002904 solvent Substances 0.000 claims description 57
- 239000000758 substrate Substances 0.000 claims description 33
- 238000010304 firing Methods 0.000 claims description 20
- 150000003973 alkyl amines Chemical class 0.000 claims description 19
- 125000004432 carbon atom Chemical group C* 0.000 claims description 18
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- 238000009713 electroplating Methods 0.000 claims description 11
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- 239000011777 magnesium Substances 0.000 claims description 9
- 239000006228 supernatant Substances 0.000 claims description 9
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- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 7
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- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims description 6
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- SEAWWISVQGCBOW-GRVYQHKQSA-L manganese(2+);(9z,12z)-octadeca-9,12-dienoate Chemical compound [Mn+2].CCCCC\C=C/C\C=C/CCCCCCCC([O-])=O.CCCCC\C=C/C\C=C/CCCCCCCC([O-])=O SEAWWISVQGCBOW-GRVYQHKQSA-L 0.000 description 1
- SGGOJYZMTYGPCH-UHFFFAOYSA-L manganese(2+);naphthalene-2-carboxylate Chemical compound [Mn+2].C1=CC=CC2=CC(C(=O)[O-])=CC=C21.C1=CC=CC2=CC(C(=O)[O-])=CC=C21 SGGOJYZMTYGPCH-UHFFFAOYSA-L 0.000 description 1
- YWFWDNVOPHGWMX-UHFFFAOYSA-N n,n-dimethyldodecan-1-amine Chemical compound CCCCCCCCCCCCN(C)C YWFWDNVOPHGWMX-UHFFFAOYSA-N 0.000 description 1
- SFBHPFQSSDCYSL-UHFFFAOYSA-N n,n-dimethyltetradecan-1-amine Chemical compound CCCCCCCCCCCCCCN(C)C SFBHPFQSSDCYSL-UHFFFAOYSA-N 0.000 description 1
- XTAZYLNFDRKIHJ-UHFFFAOYSA-N n,n-dioctyloctan-1-amine Chemical compound CCCCCCCCN(CCCCCCCC)CCCCCCCC XTAZYLNFDRKIHJ-UHFFFAOYSA-N 0.000 description 1
- DIOQZVSQGTUSAI-UHFFFAOYSA-N n-butylhexane Natural products CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 1
- UWHRNIXHZAWBMF-UHFFFAOYSA-N n-dodecyl-n-methyldodecan-1-amine Chemical compound CCCCCCCCCCCCN(C)CCCCCCCCCCCC UWHRNIXHZAWBMF-UHFFFAOYSA-N 0.000 description 1
- GKCGAKGJCYKIIS-UHFFFAOYSA-N n-dodecyldodecanamide Chemical compound CCCCCCCCCCCCNC(=O)CCCCCCCCCCC GKCGAKGJCYKIIS-UHFFFAOYSA-N 0.000 description 1
- JLKNUWMHLAWPRV-UHFFFAOYSA-N n-methyl-n-tridecyltetradecan-1-amine Chemical compound CCCCCCCCCCCCCCN(C)CCCCCCCCCCCCC JLKNUWMHLAWPRV-UHFFFAOYSA-N 0.000 description 1
- ZOLJFBQEKSZVCB-UHFFFAOYSA-N n-phenyloctadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(=O)NC1=CC=CC=C1 ZOLJFBQEKSZVCB-UHFFFAOYSA-N 0.000 description 1
- NTNWKDHZTDQSST-UHFFFAOYSA-N naphthalene-1,2-diamine Chemical compound C1=CC=CC2=C(N)C(N)=CC=C21 NTNWKDHZTDQSST-UHFFFAOYSA-N 0.000 description 1
- DDLUSQPEQUJVOY-UHFFFAOYSA-N nonane-1,1-diamine Chemical compound CCCCCCCCC(N)N DDLUSQPEQUJVOY-UHFFFAOYSA-N 0.000 description 1
- LYRFLYHAGKPMFH-UHFFFAOYSA-N octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(N)=O LYRFLYHAGKPMFH-UHFFFAOYSA-N 0.000 description 1
- 229940038384 octadecane Drugs 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- FATBGEAMYMYZAF-KTKRTIGZSA-N oleamide Chemical compound CCCCCCCC\C=C/CCCCCCCC(N)=O FATBGEAMYMYZAF-KTKRTIGZSA-N 0.000 description 1
- 125000001117 oleyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])/C([H])=C([H])\C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000002895 organic esters Chemical class 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 150000003141 primary amines Chemical class 0.000 description 1
- AOHJOMMDDJHIJH-UHFFFAOYSA-N propylenediamine Chemical compound CC(N)CN AOHJOMMDDJHIJH-UHFFFAOYSA-N 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 150000003335 secondary amines Chemical class 0.000 description 1
- 150000003377 silicon compounds Chemical class 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000003760 tallow Substances 0.000 description 1
- RJSZFSOFYVMDIC-UHFFFAOYSA-N tert-butyl n,n-dimethylcarbamate Chemical compound CN(C)C(=O)OC(C)(C)C RJSZFSOFYVMDIC-UHFFFAOYSA-N 0.000 description 1
- AKRQMTFHUVDMIL-UHFFFAOYSA-N tetrakis(prop-2-enyl)silane Chemical compound C=CC[Si](CC=C)(CC=C)CC=C AKRQMTFHUVDMIL-UHFFFAOYSA-N 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- FLTJDUOFAQWHDF-UHFFFAOYSA-N trimethyl pentane Natural products CCCCC(C)(C)C FLTJDUOFAQWHDF-UHFFFAOYSA-N 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Landscapes
- Ink Jet (AREA)
- Electrodes Of Semiconductors (AREA)
- Manufacturing Of Printed Wiring (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、絶縁基板上に導電
パターンを形成する方法に関し、特に、金属超微粒子独
立分散液からなるインク（インクジェット用インク）を
用いて、絶縁基板上に微細な導電パターンを形成する方
法に関する。この形成方法は、プリント基板上の導電回
路の形成、ディスプレイ電極の形成、ＰＤＰの電磁波シ
ールド等の電気・電子分野において利用できる。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for forming a conductive pattern on an insulating substrate, and more particularly, to a fine conductive film on an insulating substrate using an ink (inkjet ink) composed of an independent dispersion of ultrafine metal particles. The present invention relates to a method of forming a pattern. This forming method can be used in the electric and electronic fields such as forming a conductive circuit on a printed circuit board, forming a display electrode, and electromagnetic wave shielding of a PDP.
【０００２】[0002]
【従来の技術】従来から、石英、セラミックス、樹脂等
の絶縁体基板上にＬ／Ｓが３０μｍ以下の微細な導電パ
ターンを形成する場合、真空蒸着、スパッタリング等の
物理蒸着により密着力の良い膜が得られている。上記物
理蒸着による膜の形成では、膜厚がミクロンオーダーの
膜を形成する場合、成膜速度が遅く、産業レベルでの量
産には向かない。また、蒸着により直接パターニングを
行う方法がなかったので、フォトリソグラフィー工程に
よりパターニングを行うことが必要であった。2. Description of the Related Art Conventionally, when a fine conductive pattern having an L / S of 30 μm or less is formed on an insulating substrate made of quartz, ceramics, resin or the like, a film having a good adhesion by physical vapor deposition such as vacuum vapor deposition and sputtering. Has been obtained. In the case of forming a film by physical vapor deposition, when forming a film having a film thickness on the order of micron, the film forming speed is slow and it is not suitable for mass production on an industrial level. Further, since there was no method for directly patterning by vapor deposition, it was necessary to perform patterning by a photolithography process.
【０００３】また、成膜速度の速い方法として電界及び
無電界メッキ法があるが、電解メッキの場合には、下地
に電極としてのシード層が必要になる。このシード層を
形成するために、上記の物理蒸着法が用いられるが、こ
の場合も、パターニングにはフォトリソグラフィー工程
が必要である。さらに、絶縁基板上に導電パターンを直
接形成可能な方法として、導電ペーストを用いた印刷法
があるが、この方法により微細なパターンを形成するこ
とは、現状では困難である。Further, there are an electric field and electroless plating method as a method of forming a film at a high speed, but in the case of electrolytic plating, a seed layer as an electrode is required as an underlayer. The physical vapor deposition method described above is used to form this seed layer, but in this case as well, patterning requires a photolithography process. Further, there is a printing method using a conductive paste as a method of directly forming a conductive pattern on an insulating substrate, but it is difficult to form a fine pattern by this method at present.
【０００４】[0004]
【発明が解決しようとする課題】上記従来技術の方法で
は、印刷法以外では、必ずフォトリソグラフィー工程を
必要とするので、工数が多くなるという問題がある。ま
た、この方法は、省資源の観点からも好ましくない。ま
た、従来の印刷法の場合には、絶縁基板上に直接パター
ニングは可能であるが、パターンの微細化には限界があ
る。従って、本発明の課題は、上記従来技術の問題点を
解消し、フォトリソグラフィー工程を必要とせず、微細
なパターニングが可能な導電パターン形成方法を提供す
ることにある。The method of the prior art described above has a problem that the number of steps is increased because a photolithography process is always required except for the printing method. Further, this method is not preferable from the viewpoint of resource saving. Further, in the case of the conventional printing method, it is possible to directly pattern on the insulating substrate, but there is a limit to the miniaturization of the pattern. Therefore, an object of the present invention is to solve the above-mentioned problems of the prior art, and to provide a conductive pattern forming method capable of fine patterning without requiring a photolithography process.
【０００５】[0005]
【課題を解決するための手段】本発明者らは、金属超微
粒子が独立状態で分散している分散液、すなわち、超微
粒子の凝集が発生せず、流動性が保たれていると共に、
インク特性にも優れた金属超微粒子独立分散液からなる
インクを用いて行うインクジェット法により、上記従来
技術の問題点を解決することができることを見出し、本
発明を完成するに至った。DISCLOSURE OF THE INVENTION The present inventors have found that a dispersion liquid in which ultrafine metal particles are dispersed in an independent state, that is, the ultrafine particles do not aggregate and the fluidity is maintained,
The inventors have found that the problems of the above-mentioned conventional techniques can be solved by an inkjet method using an ink composed of an independent dispersion liquid of ultrafine metal particles having excellent ink characteristics, and have completed the present invention.
【０００６】本発明の導電パターン形成方法は、金属超
微粒子及び分散剤を含む金属超微粒子独立分散液からな
るインクを用いて、インクジェット法により、直接、絶
縁基板上に下地導電パターンを形成し、焼成した後、電
解メッキ処理して該下地電導パターン上にさらに導電パ
ターンを形成することからなる。本発明で用いる金属超
微粒子独立分散液は、金属超微粒子が個々に独立して均
一に分散しており、流動性が保たれており、導電パター
ンを形成するためのインクジェット用インクとしては有
用である。The conductive pattern forming method of the present invention comprises forming an underlying conductive pattern directly on an insulating substrate by an ink jet method using an ink comprising an ultrafine metal particle independent dispersion liquid containing ultrafine metal particles and a dispersant. After firing, electroplating is performed to further form a conductive pattern on the underlying conductive pattern. The ultrafine metal particle independent dispersion liquid used in the present invention is such that ultrafine metal particles are dispersed independently and uniformly, and the fluidity is maintained, and it is useful as an inkjet ink for forming a conductive pattern. is there.
【０００７】上記金属超微粒子の粒径は通常１００ｎｍ
以下である。また、金属超微粒子独立分散液の粘度は、
１〜１００ｍＰａ・ｓであり、その表面張力は、２５〜
８０ｍＮ／ｍである。このような特性は、インクジェッ
ト用インクとして用いるためのインク特性を満足してい
る。上記分散剤は、アルキルアミン、カルボン酸アミ
ド、及びアミノカルボン酸塩から選ばれた１種又は複数
のものでありう。特に、アルキルアミンは、その主鎖の
炭素数が４〜２０であり、第１級アルキルアミンである
ことが好ましい。この分散剤の含有量は、金属超微粒子
重量基準で通常０．１〜１０重量％である。The particle size of the ultrafine metal particles is usually 100 nm.
It is the following. In addition, the viscosity of the ultrafine metal independent dispersion is
The surface tension is 25 to 100 mPa · s.
It is 80 mN / m. Such characteristics satisfy the ink characteristics for use as an inkjet ink. The dispersant may be one or more selected from alkylamines, carboxylic acid amides, and aminocarboxylic acid salts. In particular, the alkylamine has preferably 4 to 20 carbon atoms in its main chain and is preferably a primary alkylamine. The content of this dispersant is usually 0.1 to 10% by weight based on the weight of ultrafine metal particles.
【０００８】分散液はまた、分散媒として、主鎖の炭素
数６〜２０の非極性炭化水素、水、及び炭素数が１５以
下のアルコール系溶剤から選ばれた少なくとも１種の溶
剤を含んでいても良い。上記金属超微粒子独立分散液
は、さらに、ケイ素、マンガン、クロム、ニッケル、チ
タン、マグネシウム、アルミニウム、ゲルマニウム、タ
ンタル、ニオブ及びバナジウムから選ばれた少なくとも
１種の金属を含んでいることが好ましい。これにより、
基板に対する密着性がさらに向上する。The dispersion liquid also contains, as a dispersion medium, a non-polar hydrocarbon having 6 to 20 carbon atoms in the main chain, water, and at least one solvent selected from alcohol solvents having 15 or less carbon atoms. You may stay. It is preferable that the ultrafine metal particle independent dispersion liquid further contains at least one metal selected from silicon, manganese, chromium, nickel, titanium, magnesium, aluminum, germanium, tantalum, niobium, and vanadium. This allows
The adhesion to the substrate is further improved.
【０００９】本発明で用いるインクは、ガス雰囲気中で
かつ第１溶剤の蒸気の存在下で金属を蒸発させることに
より溶剤中に金属超微粒子が分散した金属超微粒子分散
液を得る第１工程と、該第１工程で得られた分散液に低
分子量の極性溶剤である第２溶剤を加えて該金属超微粒
子を沈降させ、その上澄み液を取り除くことにより該第
１溶剤を実質的に除去する第２工程と、このようにして
得られた沈降物に第３溶剤を加えて金属超微粒子の独立
分散液を得る第３工程とにより製造され得る。この製造
工程において、分散剤は、第１工程及び／又は第３工程
のいずれで加えても良い。第３溶剤としては、主鎖の炭
素数が６〜２０の非極性炭化水素、水、及び炭素数が１
５以下のアルコール系溶剤から選ばれた少なくとも１種
を用いることができる。The ink used in the present invention comprises a first step of obtaining an ultrafine metal particle dispersion liquid in which ultrafine metal particles are dispersed in a solvent by evaporating a metal in a gas atmosphere and in the presence of vapor of a first solvent. The second solvent, which is a low molecular weight polar solvent, is added to the dispersion obtained in the first step to precipitate the ultrafine metal particles, and the supernatant is removed to substantially remove the first solvent. It can be produced by the second step and the third step of adding a third solvent to the precipitate thus obtained to obtain an independent dispersion liquid of ultrafine metal particles. In this manufacturing process, the dispersant may be added in any of the first step and / or the third step. As the third solvent, a non-polar hydrocarbon having 6 to 20 carbon atoms in the main chain, water, and 1 carbon atoms
At least one selected from alcohol solvents of 5 or less can be used.
【００１０】本発明の導電パターン形成方法はまた、ケ
イ素、マンガン、クロム、ニッケル、チタン、マグネシ
ウム、アルミニウム、ゲルマニウム、タンタル、ニオブ
及びバナジウムから選ばれた少なくとも１種の金属を含
有する有機化合物の分散液を用いて、インクジェット法
により、直接、絶縁基板上に第一下地導電パターンを形
成し、焼成した後、上記金属超微粒子独立分散液からな
るインクを用いて、インクジェット法により、直接、該
第一下地導電パターン上に第二下地導電パターンを形成
し、次いで、焼成した後、電解メッキ処理して該第二下
地電導パターン上にさらに導電パターンを形成するもの
であっても良い。このように２層の下地導電パターンの
膜を形成することにより、さらに、基板と導電パターン
との密着性が向上すると共に、膜質も良好になる。The conductive pattern forming method of the present invention also comprises dispersing an organic compound containing at least one metal selected from silicon, manganese, chromium, nickel, titanium, magnesium, aluminum, germanium, tantalum, niobium and vanadium. The first underlayer conductive pattern is directly formed on the insulating substrate by using the liquid by an inkjet method, and after firing, the ink is formed by the inkjet method using the ink containing the metal ultrafine particle independent dispersion liquid. A second underlying conductive pattern may be formed on the first underlying conductive pattern, followed by firing, followed by electrolytic plating to form an additional conductive pattern on the second underlying conductive pattern. By thus forming the two-layer film of the underlying conductive pattern, the adhesion between the substrate and the conductive pattern is further improved and the film quality is improved.
【００１１】[0011]
【発明の実施の形態】以下、本発明の実施の形態につい
て、特に、本発明で用いるインクを主体に説明する。本
発明の導電パターン形成方法で用いるインク中に含まれ
る金属超微粒子は、上記したように低真空ガス中蒸発法
で製造され得るものであり、この製造方法によれば粒径
１００ｎｍ以下、好ましくは１０ｎｍ以下の粒度の揃っ
た金属超微粒子を製造することができる。このような金
属超微粒子を原料として、インクジェットプリンタ用イ
ンクとしての用途に適したようにするために、以下説明
するように、最終工程(第３工程)で溶剤置換を行ってお
り、また、この超微粒子の分散安定性を増すために、所
定の工程で分散剤を添加している。このために、金属超
微粒子が個々に独立して均一に分散され、かつ、流動性
のある状態が保持されて、インクジェット用インクに適
した分散液が得られる。BEST MODE FOR CARRYING OUT THE INVENTION Embodiments of the present invention will be described below mainly with respect to the ink used in the present invention. The ultrafine metal particles contained in the ink used in the conductive pattern forming method of the present invention can be manufactured by the low vacuum gas evaporation method as described above, and according to this manufacturing method, the particle size is 100 nm or less, preferably Ultrafine metal particles having a uniform particle size of 10 nm or less can be produced. In order to make the metal ultrafine particles as a raw material suitable for use as an ink for an ink jet printer, solvent replacement is performed in the final step (third step) as described below. In order to increase the dispersion stability of ultrafine particles, a dispersant is added in a predetermined process. Therefore, the ultrafine metal particles are independently and uniformly dispersed, and the fluid state is maintained, whereby a dispersion suitable for an inkjet ink can be obtained.
【００１２】インクジェット用インクの場合、インクの
供給安定性やインクの液滴形成飛翔安定性やプリンタヘ
ッドの高速応答性等を実現するためには、通常の動作時
における温度（０〜５０℃）において、所定の粘度、表
面張力を有することが要求される。本発明の方法で用い
るインクは、上記したように、その粘度が通常１〜１０
０ｍＰａ・ｓ、好ましくは１〜１０ｍＰａ・ｓ、その表
面張力が通常２５〜８０ｍＮ／ｍ、好ましくは３０〜６
０ｍＮ／ｍであるので、インク特性を満足するものであ
る。In the case of ink-jet ink, in order to realize stability of ink supply, stability of ink droplet formation and flight, high-speed response of the printer head, etc., the temperature during normal operation (0 to 50 ° C.) In, it is required to have a predetermined viscosity and surface tension. The ink used in the method of the present invention has a viscosity of usually 1 to 10 as described above.
0 mPa · s, preferably 1 to 10 mPa · s, and the surface tension thereof is usually 25 to 80 mN / m, preferably 30 to 6
Since it is 0 mN / m, the ink characteristics are satisfied.
【００１３】本発明の方法で用いるインクとして、低真
空ガス中蒸発法により得られた金属超微粒子を利用して
所期の金属超微粒子分散液を製造する場合、まず、第１
工程において、真空室中でかつＨｅ等の不活性ガスの圧
力を１０Ｔｏｒｒ以下とする雰囲気の下で金属を蒸発さ
せ、蒸発した金属の蒸気を冷却捕集する際に、該真空室
中に、１種以上の第１溶剤の蒸気を導入し、金属が粒成
長する段階においてその表面を該第１溶剤蒸気と接触せ
しめ、得られる一次粒子が独立してかつ均一に第１溶剤
中にコロイド状に分散した分散液を得、次の第２工程で
第１溶剤を除去する。このように第１溶剤を除去するの
は、第１工程において蒸発した金属蒸気が凝縮する際
に、共存する第１溶剤が変性されて生じる副生成物を除
くためである。また、インクの用途によって、第１工程
で使い難い低沸点溶剤や水、アルコール系溶剤等に分散
した超微粒子独立分散液を使用する必要がある場合に、
そのような分散液を製造するためでもある。When a desired ultrafine metal particle dispersion liquid is produced by using ultrafine metal particles obtained by the evaporation method in a low vacuum gas as the ink used in the method of the present invention, first,
In the step, when the metal is evaporated in a vacuum chamber and under an atmosphere where the pressure of an inert gas such as He is 10 Torr or less and the vapor of the evaporated metal is collected by cooling, 1 At least one kind of vapor of the first solvent is introduced, and the surface of the metal is brought into contact with the vapor of the first solvent at the stage of grain growth of the metal, and the obtained primary particles are independently and uniformly colloidal in the first solvent. The dispersed liquid is obtained, and the first solvent is removed in the next second step. The reason for removing the first solvent in this manner is to remove by-products generated by modifying the coexisting first solvent when the metal vapor evaporated in the first step is condensed. Further, depending on the use of the ink, when it is necessary to use an ultrafine particle independent dispersion liquid dispersed in a low boiling point solvent, water, an alcohol solvent or the like which is difficult to use in the first step,
It is also for producing such a dispersion.
【００１４】上記第２工程において、第１工程で得られ
た分散液に低分子量の極性溶剤である第２溶剤を加えて
該分散液中に含まれた金属超微粒子を沈降させ、その上
澄み液を静置法やデカンテーション等により除去して第
１工程で使用した第１溶剤を除去する。この第２工程を
複数回繰り返して、第１溶剤を実質的に除去する。そし
て、第３工程において、第２工程で得られた沈降物に新
たな第３溶剤を加えて、溶剤置換を行い、所期の金属超
微粒子分散液を得る。これにより、粒径１００ｎｍ以下
の金属超微粒子が独立状態で分散している金属超微粒子
独立分散液が得られる。上記の場合、必要に応じ、第１
工程及び／又は第３工程で分散剤を加えることができ
る。第３工程で添加する場合には、第１工程で使用する
溶剤に溶解しないような分散剤でも使用可能である。In the second step, the second solvent, which is a low molecular weight polar solvent, is added to the dispersion obtained in the first step to precipitate the ultrafine metal particles contained in the dispersion, and the supernatant is obtained. Are removed by a static method or decantation to remove the first solvent used in the first step. This second step is repeated a plurality of times to substantially remove the first solvent. Then, in the third step, a new third solvent is added to the precipitate obtained in the second step to carry out solvent replacement to obtain the desired ultrafine metal particle dispersion. Thereby, an ultrafine metal particle independent dispersion liquid in which ultrafine metal particles having a particle diameter of 100 nm or less are dispersed in an independent state is obtained. In the above case, if necessary, the first
A dispersant can be added in the step and / or the third step. When added in the third step, a dispersant that does not dissolve in the solvent used in the first step can be used.
【００１５】上記製造方法で使用可能な分散剤として
は、特に限定されないが、アルキルアミン、カルボン酸
アミド、及びアミノカルボン酸塩から選ばれた１種又は
複数のものが用いられる。特に、アルキルアミンとして
は、第１〜３級アミンであっても、モノアミン、ジアミ
ン、トリアミンであっても良い。主鎖の炭素数が４〜２
０であるアルキルアミンが好ましく、主鎖の炭素数が８
〜１８であるアルキルアミンが安定性、ハンドリング性
の点からはさらに好ましい。アルキルアミンの主鎖の炭
素数が４より短かいと、アミンの塩基性が強過ぎて金属
超微粒子を腐食する傾向があり、最終的には金属超微粒
子を溶かしてしまうという問題がある。また、アルキル
アミンの主鎖の炭素数が２０よりも長いと、金属超微粒
子分散液の濃度を高くしたときに、分散液の粘度が上昇
してハンドリング性がやや劣るようになり、また、焼成
後の金属膜中に炭素が残留しやすくなって、比抵抗値が
上昇するという問題がある。また、全ての級数のアルキ
ルアミンが分散剤として有効に働くが、第１級のアルキ
ルアミンが安定性、ハンドリング性の点からは好適に用
いられる。The dispersant which can be used in the above production method is not particularly limited, but one or more selected from alkylamines, carboxylic acid amides, and aminocarboxylic acid salts are used. In particular, the alkylamine may be a primary to tertiary amine, monoamine, diamine or triamine. Main chain has 4 to 2 carbon atoms
An alkylamine having 0 is preferable, and the main chain has 8 carbon atoms.
Alkylamines of -18 are more preferable in terms of stability and handling properties. If the number of carbon atoms in the main chain of the alkylamine is shorter than 4, the basicity of the amine is too strong, and the ultrafine metal particles tend to corrode, and eventually the ultrafine metal particles are dissolved. When the number of carbon atoms in the main chain of the alkylamine is longer than 20, when the concentration of the ultrafine metal particle dispersion liquid is increased, the viscosity of the dispersion liquid increases and the handling property becomes slightly inferior. There is a problem that carbon tends to remain in the subsequent metal film and the specific resistance value increases. Further, all series alkylamines work effectively as a dispersant, but primary alkylamines are preferably used from the viewpoint of stability and handleability.
【００１６】上記アルキルアミンの具体例としては、例
えば、ブチルアミン、オクチルアミン、ドデシルアミ
ン、ヘクサドデシルアミン、オクタデシルアミン、ココ
アミン、タロウアミン、水素化タロウアミン、オレイル
アミン、ラウリルアミン、及びステアリルアミン等のよ
うな第１級アミン、ジココアミン、ジ水素化タロウアミ
ン、及びジステアリルアミン等のような第２級アミン、
並びにドデシルジメチルアミン、ジドデシルモノメチル
アミン、テトラデシルジメチルアミン、オクタデシルジ
メチルアミン、ココジメチルアミン、ドデシルテトラデ
シルジメチルアミン、及びトリオクチルアミン等のよう
な第３級アミンや、その他に、ナフタレンジアミン、ス
テアリルプロピレンジアミン、オクタメチレンジアミ
ン、及びノナンジアミン等のようなジアミンがある。Specific examples of the above-mentioned alkylamines include butylamine, octylamine, dodecylamine, hexadodecylamine, octadecylamine, cocoamine, tallowamine, hydrogenated tallowamine, oleylamine, laurylamine, and stearylamine. Secondary amines such as primary amines, dicocoamine, dihydrogenated tallow amines, and distearyl amines;
And tertiary amines such as dodecyldimethylamine, didodecylmonomethylamine, tetradecyldimethylamine, octadecyldimethylamine, cocodimethylamine, dodecyltetradecyldimethylamine, and trioctylamine, and others, naphthalenediamine, stearyl. There are diamines such as propylene diamine, octamethylene diamine, and nonane diamine.
【００１７】上記カルボン酸アミドやアミノカルボン酸
塩の具体例としては、例えば、ステアリン酸アミド、パ
ルミチン酸アミド、ラウリン酸ラウリルアミド、オレイ
ン酸アミド、オレイン酸ジエタノールアミド、オレイン
酸ラウリルアミド、ステアラニリド、オレイルアミノエ
チルグリシン等がある。これらのアルキルアミン、カル
ボン酸アミド、及びアミノカルボン酸塩は、１種以上を
使用することができ、それにより安定な分散剤として作
用する。Specific examples of the above-mentioned carboxylic acid amide and aminocarboxylic acid salt include, for example, stearic acid amide, palmitic acid amide, lauric acid laurylamide, oleic acid amide, oleic acid diethanolamide, oleic acid laurylamide, stearanilide and oleyl. Aminoethylglycine and the like are available. One or more of these alkylamines, carboxylic acid amides, and aminocarboxylic acid salts can be used, thereby acting as a stable dispersant.
【００１８】上記アルキルアミンの含有量は、金属超微
粒子重量基準で、通常、およそ０．１〜１０重量％、好
ましくは０．２〜７重量％の範囲である。含有量が０．
１重量％未満であると、金属超微粒子が独立状態で分散
せずに、その凝集体が発生し、分散安定性が悪くなると
いう問題があり、また、１０重量％を超えると、得られ
る分散液の粘度が高くなり、最終的にはゲル状物が形成
されるという問題がある。また、上記溶剤については、
ガラス基板、プラスチック基板、セラミック基板等の被
処理基板の性質に合わせて、水、アルコール系等の極性
溶剤や非極性炭化水素系溶剤を選択する必要がある等の
ように、得られる膜の用途の違いにより溶剤の選択条件
がきまってくる場合がある。The content of the alkylamine is usually about 0.1 to 10% by weight, preferably 0.2 to 7% by weight, based on the weight of ultrafine metal particles. The content is 0.
If it is less than 1% by weight, there is a problem that ultrafine metal particles are not dispersed in an independent state and aggregates thereof are generated, resulting in poor dispersion stability. There is a problem that the viscosity of the liquid becomes high and finally a gel-like material is formed. Further, for the solvent,
Use of the resulting film, such as the need to select a polar solvent such as water or alcohol, or a non-polar hydrocarbon solvent according to the properties of the substrate to be processed such as glass substrate, plastic substrate, ceramic substrate, etc. Depending on the difference, the solvent selection conditions may be dictated.
【００１９】例えば、第１溶剤は、ガス中蒸発法の際に
用いる金属超微粒子生成用の溶剤であって、金属超微粒
子を冷却捕集する際に容易に液化できるように、比較的
沸点の高い溶剤である。この第１溶剤としては、炭素数
が５以上のアルコール類、例えば、テルピネオール、シ
トロネオール、ゲラニオール、フェネチルアルコール等
から選ばれた１種以上を含有する溶剤、又は有機エステ
ル類、例えば、酢酸ベンジル、ステアリン酸エチル、オ
レイン酸メチル、フェニル酢酸エチル、グリセリド等か
ら選ばれた１種以上を含有する溶剤であれば良く、使用
する金属超微粒子の構成元素、又は分散液の用途によっ
て適宜選択できる。For example, the first solvent is a solvent for producing ultrafine metal particles used in the gas evaporation method, and has a relatively high boiling point so that it can be easily liquefied when the ultrafine metal particles are collected by cooling. It is a high solvent. Examples of the first solvent include alcohols having 5 or more carbon atoms, for example, solvents containing one or more selected from terpineol, citroneol, geraniol, phenethyl alcohol and the like, or organic esters such as benzyl acetate and stearin. Any solvent containing at least one selected from ethyl acidate, methyl oleate, ethyl phenylacetate, glyceride, etc. may be used, and can be appropriately selected depending on the constituent elements of the ultrafine metal particles used or the application of the dispersion liquid.
【００２０】第２溶剤は、第１工程で得られた分散液中
に含まれた金属超微粒子を沈降させ、第１溶剤を抽出・
分離して除去できるものであれば良く、例えば、低分子
量の極性溶剤であるアセトン等がある。第３溶剤として
は、主鎖の炭素数が６〜２０の非極性炭化水素、水及び
炭素数が１５以下のアルコール等のような常温で液体の
ものを適宜選択し、使用することができる。非極性炭化
水素の場合、炭素数が６未満であると、乾燥が早すぎて
分散液のハンドリング上で問題があり、また、炭素数が
２０を超えると、分散液の粘度が上昇し易く、また、焼
成する場合には炭素が残留し易いという問題がある。ア
ルコールの場合も、炭素数が１５を超えると分散液の粘
度が上昇し易く、また、焼成する場合には炭素が残留し
易いという問題がある。The second solvent precipitates the ultrafine metal particles contained in the dispersion obtained in the first step and extracts the first solvent.
Any substance that can be separated and removed may be used, and examples thereof include low molecular weight polar solvent such as acetone. As the third solvent, those which are liquid at room temperature, such as non-polar hydrocarbons having 6 to 20 carbon atoms in the main chain, water and alcohols having 15 or less carbon atoms, can be appropriately selected and used. In the case of a non-polar hydrocarbon, if the carbon number is less than 6, drying is too fast and there is a problem in handling the dispersion, and if the carbon number exceeds 20, the viscosity of the dispersion tends to increase, Further, there is a problem that carbon tends to remain when firing. Also in the case of alcohol, there is a problem that the viscosity of the dispersion liquid tends to increase when the number of carbon atoms exceeds 15, and carbon tends to remain when firing.
【００２１】第３溶剤としては、例えば、ヘキサン、ヘ
プタン、オクタン、ノナン、デカン、ウンデカン、ドデ
カン、トリデカン、テトラデカン、ペンタデカン、ヘキ
サデカン、オクタデカン、ノナデカン、エイコサン、ト
リメチルペンタン等の長鎖アルカンや、シクロヘキサ
ン、シクロヘプタン、シクロオクタン等の環状アルカ
ン、ベンゼン、トルエン、キシレン、トリメチルベンゼ
ン、ドデシルベンゼン等の芳香族炭化水素、ヘキサノー
ル、ヘプタノール、オクタノール、デカノール、シクロ
ヘキサノール、テルピネオール等のアルコールを用いる
ことができる。これらの溶剤は、単独で用いても、混合
溶剤の形で用いても良い。例えば、長鎖アルカンの混合
物であるミネラルスピリットであっても良い。Examples of the third solvent include long-chain alkanes such as hexane, heptane, octane, nonane, decane, undecane, dodecane, tridecane, tetradecane, pentadecane, hexadecane, octadecane, nonadecane, eicosane, trimethylpentane, cyclohexane, and the like. Cyclic alkanes such as cycloheptane and cyclooctane, aromatic hydrocarbons such as benzene, toluene, xylene, trimethylbenzene and dodecylbenzene, and alcohols such as hexanol, heptanol, octanol, decanol, cyclohexanol and terpineol can be used. These solvents may be used alone or in the form of a mixed solvent. For example, it may be mineral spirit which is a mixture of long chain alkanes.
【００２２】第３溶剤の場合、第１工程で使ったものと
異なる溶剤（たとえ同一であっても、純度が違う等の溶
剤）を使わねばならない場合があるが、本発明はそのよ
うな場合に好適である。上記溶剤の使用量は、金属超微
粒子分散液の用途に応じて適宜設定すれば良い。なお、
金属超微粒子濃度は、分散液製造後に真空中加熱等によ
り随時調整可能である。In the case of the third solvent, it may be necessary to use a solvent different from the one used in the first step (even if the solvent is the same, but the purity is different). Suitable for The amount of the solvent used may be set appropriately according to the use of the ultrafine metal particle dispersion. In addition,
The ultrafine metal particle concentration can be adjusted at any time by heating in a vacuum after the dispersion is manufactured.
【００２３】本発明の方法で用いるインク中の金属超微
粒子の構成元素としては、導電性金属であれば特に制限
はなく、目的・用途に合わせて適宜選定すれば良い。例
えば、金、銀、銅、パラジウム、錫、白金、タングステ
ン、ニッケル、タンタル、インジウム、亜鉛、チタン、
クロム、鉄、コバルトその他の多くの導電性金属から選
ばれた少なくとも１種の金属、又はこれらの金属の合金
若しくは酸化物があげられる。酸化物の場合は、焼成時
の雰囲気に酸素やＨ２Ｏ、ＣＯ、水素及びその混合ガス
を用いることで金属膜を作ることができる。これらの元
素で構成された金属超微粒子のいずれに対しても、上記
アルキルアミン、カルボン酸アミド、及びアミノカルボ
ン酸塩から選ばれた１種又は複数のものが分散剤として
作用し、所期の金属超微粒子分散液が得られる。The constituent element of the ultrafine metal particles in the ink used in the method of the present invention is not particularly limited as long as it is a conductive metal, and may be appropriately selected according to the purpose and application. For example, gold, silver, copper, palladium, tin, platinum, tungsten, nickel, tantalum, indium, zinc, titanium,
At least one metal selected from chromium, iron, cobalt and many other conductive metals, or alloys or oxides of these metals can be mentioned. In the case of an oxide, a metal film can be formed by using oxygen, H 2 O, CO, hydrogen, or a mixed gas thereof in an atmosphere during baking. For any of the ultrafine metal particles composed of these elements, one or more selected from the above alkylamines, carboxylic acid amides, and aminocarboxylic acid salts act as a dispersant. An ultrafine metal particle dispersion is obtained.
【００２４】本発明の方法で用いるインク中の金属超微
粒子の濃度は、通常、１０重量％〜７０重量％、好まし
くは１０重量％〜５０重量％である。１０重量％未満だ
と粘度、表面張力等のインク特性は十分に満たすが、焼
成後の膜の電気抵抗が導電回路として十分な値ではな
く、また、７０重量％を超えると粘度、表面張力等のイ
ンク特性を満たさなくなるため、導電回路を形成するた
めのインクジェット用インクとして使用できない。The concentration of ultrafine metal particles in the ink used in the method of the present invention is usually 10% by weight to 70% by weight, preferably 10% by weight to 50% by weight. If it is less than 10% by weight, ink properties such as viscosity and surface tension are sufficiently satisfied, but the electric resistance of the film after firing is not a sufficient value for a conductive circuit, and if it exceeds 70% by weight, viscosity, surface tension, etc. Therefore, the ink cannot be used as an inkjet ink for forming a conductive circuit because the ink properties of No. 1 are not satisfied.
【００２５】また、本発明において、液相還元法等の化
学還元法で得られた金属超微粒子を用いて分散液を製造
する場合、金属超微粒子を製造するための原料として
は、例えば、ビスヘキサフルオロアセチルアセトネート
銅、ビスアセチルアセトネートニッケル、ビスアセチル
アセトネートコバルト等の金属含有有機化合物である還
元用原料を使用することができる。上記還元法は、例え
ば、次のようにして行われる。上記原料に上記分散剤を
添加した状態で、所定の温度で原料を加熱分解させ、金
属超微粒子を発生させる。発生した金属超微粒子のほぼ
全量を独立分散状態で回収する。この金属超微粒子の粒
径は約１００ｎｍ以下である。この金属超微粒子を前記
したような分散金属超微粒子生成用溶剤である第３溶剤
に置換すれば、所期の金属超微粒子分散液が得られる。
得られた分散液は、真空中での加熱により最高濃度８０
重量％程度になるまで濃縮しても、安定な分散状態を維
持している。In the present invention, when a dispersion is produced using ultrafine metal particles obtained by a chemical reduction method such as a liquid phase reduction method, the raw material for producing the ultrafine metal particles may be, for example, bismuth. A reducing raw material which is a metal-containing organic compound such as copper hexafluoroacetylacetonate, nickel bisacetylacetonate, and cobalt bisacetylacetonate can be used. The reduction method is performed as follows, for example. With the dispersant added to the raw material, the raw material is thermally decomposed at a predetermined temperature to generate ultrafine metal particles. Almost all of the generated ultrafine metal particles are collected in an independently dispersed state. The particle size of the ultrafine metal particles is about 100 nm or less. By replacing the ultrafine metal particles with the third solvent which is the solvent for producing dispersed ultrafine metal particles as described above, a desired ultrafine metal particle dispersion can be obtained.
The dispersion obtained has a maximum concentration of 80 when heated in vacuum.
Even if it is concentrated to about wt%, it maintains a stable dispersed state.
【００２６】下地導電パターンである金属膜の密着性を
改良するために、上記金属超微粒子分散液に対して、有
機ケイ素化合物、有機マンガン化合物等の金属含有有機
化合物（含金属有機化合物）を添加しても良い。有機ケ
イ素化合物としては、常温で液体の主溶剤（第３溶剤）
である非極性炭化水素等に可溶であり、分解温度が１５
０〜２５０℃程度のものであれば適宜使用可能であり、
例えば、ジフェニルシラン、テトラアリルシラン、デカ
メチルテトラシロキサン等を用いることができる。その
添加量としては、ケイ素重量として、金属(例えば、銅)
超微粒子重量に対して０．５ｗｔ％〜１０ｗｔ％程度で
あればよい。０．５ｗｔ％未満であると密着性の改良に
はならず、また、この添加量が多いほど密着性は上がる
が、１０ｗｔ％程度を越えると、膜の抵抗値が上昇し、
メッキのつきが悪くなる。また、有機マンガン化合物と
しては、例えば、オクタン酸マンガン、ナフテン酸マン
ガン、リノール酸マンガン等を用いることができる。そ
の添加量としては、マンガン重量として、金属(銅)超微
粒子重量に対して、０．５〜１０ｗｔ％を用いることが
できる。０．５ｗｔ％未満であると密着性の改良にはな
らず、１０ｗｔ％を超えると、膜の抵抗値が上昇し、メ
ッキのつきが悪くなる。In order to improve the adhesion of the metal film which is the underlying conductive pattern, a metal-containing organic compound (metal-containing organic compound) such as an organic silicon compound or an organic manganese compound is added to the above ultrafine metal particle dispersion. You may. As an organosilicon compound, a main solvent that is liquid at room temperature (third solvent)
It is soluble in non-polar hydrocarbons and has a decomposition temperature of 15
If it is about 0 to 250 ° C., it can be appropriately used,
For example, diphenylsilane, tetraallylsilane, decamethyltetrasiloxane, etc. can be used. As the amount of addition, as a silicon weight, a metal (for example, copper)
It may be about 0.5 wt% to 10 wt% with respect to the weight of the ultrafine particles. If it is less than 0.5 wt%, the adhesiveness will not be improved. Further, if the amount of addition is large, the adhesiveness will increase, but if it exceeds about 10 wt%, the resistance value of the film will increase,
Plating will be poor. Further, as the organic manganese compound, for example, manganese octoate, manganese naphthenate, manganese linoleate or the like can be used. As the addition amount, 0.5 to 10 wt% can be used as the manganese weight with respect to the metal (copper) ultrafine particle weight. If it is less than 0.5 wt%, the adhesion will not be improved, and if it exceeds 10 wt%, the resistance value of the film will increase and the plating will be poor.
【００２７】上記有機ケイ素化合物、有機マンガン化合
物の他に、密着性確保のために効果がある含金属有機化
合物として、例えば、ケイ素、マンガン、クロム、ニッ
ケル、チタン、マグネシウム、アルミニウム、ゲルマニ
ウム、タンタル、ニオブ及びバナジウムから選ばれた少
なくとも１種の金属を含有する有機化合物である脂肪酸
塩がある。これらの金属の脂肪酸塩のうち、分解温度の
低いもの（３００℃以下程度）であれば効果がある。例
えば、マグネシウム、アルミニウムを含む化合物とし
て、(Ｃ１７Ｈ３５ＣＯＯ)２Ｍｇ、(Ｃ１７Ｈ３５ＣＯ
Ｏ)３Ａｌをあげることができる。In addition to the above-mentioned organosilicon compounds and organomanganese compounds, examples of metal-containing organic compounds which are effective for ensuring adhesion are, for example, silicon, manganese, chromium, nickel, titanium, magnesium, aluminum, germanium, tantalum, There is a fatty acid salt which is an organic compound containing at least one metal selected from niobium and vanadium. Of these fatty acid salts of metals, those having a low decomposition temperature (about 300 ° C. or lower) are effective. For example, as a compound containing magnesium and aluminum, (C 17 H 35 COO) 2 Mg, (C 17 H 35 CO
O) 3 Al can be mentioned.
【００２８】本発明によれば、上記した含金属有機化合
物を添加した金属超微粒子独立分散液を用いる方法とは
別に、上記含金属有機化合物のみの分散液を用いて、イ
ンクジェット法により、直接、絶縁基板上に第一下地導
電パターンを形成し、焼成した後、含金属有機化合物が
添加されていても良い上記金属超微粒子独立分散液から
なるインクを用いて、インクジェット法により、直接、
第一下地絶導電パターン上に第二下地導電パターンを形
成し、次いで、焼成することにより下地導電パターンを
２層膜とする導電パターン形成方法もまた、被処理基板
と導電パターンとの密着性を確保するためには有用であ
る。例えば、被処理基板上に、まず、オクタン酸マンガ
ン溶液（溶剤：テトラデカン）をインクジェット塗布
し、これを大気中で、例えば、２３０℃×１０分の条件
で焼成し、膜厚約０．１μｍの膜を得る。この膜上に、
金属超微粒子独立分散液を上記と同条件でインクジェッ
ト塗布し、これを焼成した後、電解メッキ処理をする。
得られた導電パターンの比抵抗値は２μｍΩ・ｃｍ程度
であり、密着性及び膜質は、含金属有機化合物が添加さ
れた銅超微粒子独立分散液を用いる１層の下地膜のみの
場合より良好である。According to the present invention, in addition to the above-mentioned method of using the metal ultrafine particle independent dispersion liquid to which the metal-containing organic compound is added, a dispersion liquid of only the metal-containing organic compound is directly used by an ink jet method. After forming the first underlying conductive pattern on the insulating substrate and firing, using an ink comprising the metal ultrafine particle independent dispersion liquid which may contain a metal-containing organic compound, by an inkjet method, directly,
A method of forming a second underlying conductive pattern on a first underlying conductive pattern and then firing the conductive underlying pattern to form a two-layer film is also a method for forming a conductive pattern. Is useful to secure. For example, first, a manganese octoate solution (solvent: tetradecane) is applied onto a substrate to be processed by ink jet printing, and this is baked in the air at, for example, 230 ° C. × 10 minutes to obtain a film thickness of about 0.1 μm. Get the membrane. On this membrane,
The metallic ultrafine particle independent dispersion liquid is applied by inkjet under the same conditions as above, and after firing, electrolytic plating treatment is performed.
The specific resistance value of the obtained conductive pattern was about 2 μmΩ · cm, and the adhesiveness and film quality were better than those of only one-layer base film using the copper ultrafine particle independent dispersion liquid to which the metal-containing organic compound was added. is there.
【００２９】[0029]
【実施例】以下、本発明で用いるインクの製造例及び本
発明の実施例を説明する。これらの例は単なる例示であ
って、本発明を何ら限定するものではない。
（製造例１）ビスヘキサフルオロアセチルアセトネート
銅にオレイルアミンとステアリン酸エチルとを添加した
状態で急激に加熱して銅(Ｃｕ)を還元し、Ｃｕ超微粒子
を発生させ、分散液を得た。オレイルアミンはＣｕ超微
粒子１ｇ当たり０．１ｇの割合で添加した。発生したＣ
ｕ超微粒子のほぼ全量が独立分散状態で回収された。こ
のＣｕ超微粒子の粒径は約１０ｎｍであった。このＣｕ
超微粒子分散液をアセトンで１０倍希釈してステアリン
酸エチルを抽出し、Ｃｕ超微粒子を沈降させて、上澄み
を除く工程を３回繰り返すことにより、ステアリン酸エ
チルを実質的に取り除いて、トルエン溶剤に置換したと
ころ、得られたＣｕ超微粒子分散液は、真空中加熱によ
り濃度８０重量％になるまで濃縮しても安定な分散状態
を維持した。この分散液について、安定性の昇温加速試
験を行った結果、６０℃保温で２週間以上にわたって粒
子は独立して分散した状態を維持し、安定であった。EXAMPLES Examples of producing the ink used in the present invention and examples of the present invention will be described below. These examples are merely illustrative and do not limit the present invention in any way. (Production Example 1) Bishexafluoroacetylacetonate Copper (Cu) was reduced by rapidly heating with oleylamine and ethyl stearate added to copper to generate Cu ultrafine particles and obtain a dispersion liquid. Oleylamine was added at a rate of 0.1 g per 1 g of Cu ultrafine particles. Occurred C
Almost all of the u ultrafine particles were recovered in an independently dispersed state. The particle size of the Cu ultrafine particles was about 10 nm. This Cu
The process of diluting the ultrafine particle dispersion with acetone by 10 times to extract ethyl stearate, precipitating the Cu ultrafine particles, and repeating the step of removing the supernatant three times to substantially remove the ethyl stearate, and remove the toluene solvent When replaced with, the obtained Cu ultrafine particle dispersion liquid maintained a stable dispersion state even when concentrated in a vacuum to a concentration of 80% by weight by heating. As a result of conducting a temperature rising acceleration test on the stability of this dispersion, the particles were stable at a temperature of 60 ° C. for 2 weeks or more, in which the particles were independently dispersed.
【００３０】また、ビスヘキサフルオロアセチルアセト
ネート銅とステアリン酸エチルを急激に加熱してＣｕを
還元し、Ｃｕ超微粒子を発生させた後、これにオレイル
アミンをＣｕ超微粒子１ｇ当たり０．１ｇの割合で添加
してＣｕ超微粒子分散液を回収した。得られた分散液を
前記と同様にして、アセトン処理した後トルエンに置換
したところ、Ｃｕ超微粒子の大部分が独立状態であった
が、一部は凝集した形で回収された。かくして、第一工
程後であって第三工程前における分散剤の添加はあまり
好ましくない。Also, after copper bishexafluoroacetylacetonate and ethyl stearate are rapidly heated to reduce Cu to generate Cu ultrafine particles, oleylamine is added to this in an amount of 0.1 g per 1 g of Cu ultrafine particles. And the ultrafine Cu particle dispersion was recovered. When the obtained dispersion was treated with acetone and replaced with toluene in the same manner as described above, most of the Cu ultrafine particles were in an independent state, but some were collected in an aggregated form. Thus, the addition of dispersant after the first step and before the third step is less preferred.
【００３１】（製造例２）Ｈｅガス圧力０．５Ｔｏｒｒ
の条件で金（Ａｕ）を蒸発させ、ガス中蒸発法によりＡ
ｕの超微粒子を生成する際に、生成過程のＡｕ超微粒子
にオレイン酸メチルの蒸気を接触させ、冷却捕集して回
収し、回収した液中のＡｕ超微粒子１ｇ当たり０．０７
ｇの割合でラウリルアミンを添加し、Ａｕの一次粒子が
単独でかつ均一にオレイン酸メチル中にコロイド状に分
散した分散液を得た。このようにして得られた分散液自
体は、Ａｕ超微粒子が独立状態で分散されている金属超
微粒子分散液であった。次いで、この分散液をアセトン
で１０倍希釈してオレイン酸メチルを抽出し、Ａｕ超微
粒子を沈降させて、上澄みを除く工程を３回繰り返すこ
とにより、オレイン酸メチルを実質的に取り除いた。そ
の後、ミネラルスピリットを添加して、粒子同士が独立
した状態で分散しているＡｕ超微粒子分散液を得た。(Production Example 2) He gas pressure 0.5 Torr
Gold (Au) was evaporated under the conditions of
When ultra-fine particles of u are produced, vapor of methyl oleate is brought into contact with Au ultra-fine particles in the production process, and is collected by cooling and collected, and 0.07 per 1 g of Au ultra-fine particles in the recovered liquid.
Laurylamine was added at a rate of g to obtain a dispersion liquid in which primary particles of Au were dispersed alone and uniformly in methyl oleate in a colloidal state. The dispersion liquid thus obtained was an ultrafine metal particle dispersion liquid in which Au ultrafine particles were dispersed in an independent state. Next, this dispersion was diluted 10 times with acetone to extract methyl oleate, the ultrafine Au particles were allowed to settle, and the step of removing the supernatant was repeated three times to substantially remove methyl oleate. Then, mineral spirit was added to obtain an Au ultrafine particle dispersion liquid in which particles were dispersed in an independent state.
【００３２】得られた分散液中のＡｕ粒子は約８ｎｍの
粒径を持ち、粒子同士が完全に独立した状態で溶剤中に
分散していた。この分散液は、Ａｕ超微粒子を２５重量
％含有するＡｕ超微粒子分散液であり、その粘度は室温
で８ｍＰａ・ｓであった。上記したようにしてオレイン
酸メチルを除去して得た分散液を真空中加熱して、Ａｕ
超微粒子の濃度が８０重量％になるまで濃縮した。得ら
れた分散液の粘度は室温で４０ｍＰａ・ｓを示し、Ａｕ
粒子は約８ｎｍの粒径を持ち、粒子同士は独立して分散
した状態を示していた。また、このＡｕ超微粒子分散液
に対して安定性の昇温加速試験を行った結果、６０℃保
温で２週間以上にわたって粒子は独立して分散した状態
を維持し、安定であった。The Au particles in the obtained dispersion had a particle size of about 8 nm, and the particles were dispersed in the solvent in a completely independent state. This dispersion was an Au ultrafine particle dispersion containing 25% by weight of Au ultrafine particles and had a viscosity of 8 mPa · s at room temperature. The dispersion obtained by removing methyl oleate as described above is heated in a vacuum to remove Au.
The ultrafine particles were concentrated to a concentration of 80% by weight. The viscosity of the obtained dispersion is 40 mPa · s at room temperature,
The particles had a particle size of about 8 nm, and the particles were in a state of being dispersed independently. Further, as a result of conducting a temperature rising acceleration test on this Au ultrafine particle dispersion, the particles remained stable at a temperature of 60 ° C. for 2 weeks or more, maintaining the independent dispersion state.
【００３３】（製造例３）ヘリウムガス圧力０．５Ｔｏ
ｒｒの条件下でＡｕを蒸発させるガス中蒸発法によりＡ
ｕの超微粒子を生成する際に、生成過程のＡｕ超微粒子
にα−テルピネオールとオクチルアミンとの２０：１
（容量比）の蒸気を接触させ、冷却捕集して回収し、α
−テルピネオール溶剤中に独立した状態で分散している
平均粒子径８ｎｍのＡｕ超微粒子を２５重量％含有する
Ａｕ超微粒子独立分散液を調製した。この分散液１容量
に対しアセトンを５容量加えて攪拌した。極性のアセト
ンの作用により分散液中の超微粒子は沈降した。２時間
静置後、上澄みを除去し、再び最初と同じ量のアセトン
を加えて攪拌し、２時間静置後、上澄みを除去した。こ
の操作を５回繰り返して十分にα−テルピネオールを除
去した。この沈降物に新たに非極性炭化水素であるドデ
カンを加えて攪拌した。沈降していたＡｕ超微粒子は再
び均一に分散した。得られた分散液中のＡｕ粒子は約８
ｎｍの粒径を持ち、粒子同士が完全に独立した状態でド
デカン中に分散していた。この分散液は非常に安定であ
って、常温で１ヶ月経過後でも沈降分離は見られなかっ
た。この分散液中のＡｕの含量は２３重量％、分散液粘
度は８ｍＰａ・ｓであり、表面張力は３５ｍＮ／ｍであ
った。(Production Example 3) Helium gas pressure 0.5 To
A by a gas evaporation method that evaporates Au under the condition of rr
When ultra-fine particles of u are produced, the ultra-fine particles of Au in the production process are mixed with 20: 1 of α-terpineol and octylamine.
(Volume ratio) steam is brought into contact, cooled, collected, and recovered.
An Au ultrafine particle independent dispersion liquid containing 25% by weight of Au ultrafine particles having an average particle size of 8 nm dispersed independently in a terpineol solvent was prepared. To 1 volume of this dispersion, 5 volumes of acetone were added and stirred. The ultrafine particles in the dispersion liquid settled due to the action of polar acetone. After standing for 2 hours, the supernatant was removed, the same amount of acetone as that used at the beginning was again added and stirred, and after standing for 2 hours, the supernatant was removed. This operation was repeated 5 times to sufficiently remove α-terpineol. A new non-polar hydrocarbon, dodecane, was added to this precipitate and stirred. The ultrafine Au particles that had settled were uniformly dispersed again. The Au particles in the obtained dispersion were about 8
It had a particle size of nm, and the particles were dispersed in dodecane in a completely independent state. This dispersion was very stable and no sedimentation was observed even after 1 month at room temperature. The content of Au in this dispersion was 23% by weight, the viscosity of the dispersion was 8 mPa · s, and the surface tension was 35 mN / m.
【００３４】（製造例４）製造例３におけるＡｕの代わ
りに銀(Ａｇ)を用いて、製造例３の方法を繰り返した。
得られた分散液中のＡｇ粒子は約８ｎｍの粒径を持ち、
粒子同士が完全に独立した状態でドデカン中に分散して
いた。この分散液は非常に安定であって、常温で１ヶ月
経過後でも沈降分離は見られなかった。この分散液中の
Ａｇの含量は２３重量％、分散液粘度は８ｍＰａ・ｓで
あり、表面張力は３５ｍＮ／ｍであった。Production Example 4 The method of Production Example 3 was repeated using silver (Ag) instead of Au in Production Example 3.
Ag particles in the obtained dispersion have a particle size of about 8 nm,
The particles were completely independent and dispersed in dodecane. This dispersion was very stable and no sedimentation was observed even after 1 month at room temperature. The content of Ag in this dispersion was 23% by weight, the viscosity of the dispersion was 8 mPa · s, and the surface tension was 35 mN / m.
【００３５】（製造例５）上記と同様にして、α−テル
ピネオール溶剤中に独立した状態で分散している平均粒
子径７ｎｍのＣｕ超微粒子を２７重量％含有するＣｕ超
微粒子独立分散液を調製した。この分散液に対して上記
と同様にアセトン処理して、Ｃｕ超微粒子を沈降せし
め、この沈降物に新たに非極性炭化水素であるテトラデ
カンを加えて攪拌した。沈降していたＣｕ超微粒子は、
約７ｎｍの粒径を持ち、粒子同士が完全に独立した状態
でテトラデカン中に分散していたことが確かめられた。
この分散液は非常に安定であって、常温で１ヶ月経過後
でも沈降分離は見られなかった。この分散液中のＣｕの
含量は２５重量％、分散液粘度は９ｍＰａ・ｓであり、
表面張力は３７ｍＮ／ｍであった。(Production Example 5) In the same manner as described above, a Cu ultrafine particle independent dispersion liquid containing 27% by weight of Cu ultrafine particles having an average particle size of 7 nm dispersed independently in an α-terpineol solvent was prepared. did. This dispersion was treated with acetone in the same manner as above to precipitate Cu ultrafine particles, and tetradecane, which is a nonpolar hydrocarbon, was newly added to this precipitate and stirred. The Cu ultrafine particles that had settled
It was confirmed that the particles had a particle size of about 7 nm and were dispersed in tetradecane in a completely independent state.
This dispersion was very stable and no sedimentation was observed even after 1 month at room temperature. The content of Cu in this dispersion was 25% by weight, the viscosity of the dispersion was 9 mPa · s,
The surface tension was 37 mN / m.
【００３６】（製造例６）ヘリウムガス圧力０．５Ｔｏ
ｒｒの条件下でＡｇを蒸発させるガス中蒸発法によりＡ
ｇの超微粒子を生成する際に、生成過程のＡｇ超微粒子
にα−テルピネオールの蒸気を接触させ、冷却捕集して
回収し、α−テルピネオール溶剤中に独立した状態で分
散している平均粒子径１０ｎｍのＡｇ超微粒子を２０重
量％含有するＡｇ超微粒子独立分散液を調製した。この
分散液１容量に対しアセトンを５容量加えて攪拌した。
極性のアセトンの作用により分散液中の超微粒子は沈降
した。２時間静置後、上澄みを除去し、再び最初と同じ
量のアセトンを加えて攪拌し、２時間静置後、上澄みを
除去した。この操作を５回繰り返して十分にα−テルピ
ネオールを除去した。この沈降物に新たにブチルアミン
を加え、さらにオクタノールとキシレンとの混合溶剤を
加えて攪拌した。沈降していたＡｇ超微粒子は再び均一
に分散した。得られた分散液中のＡｇ粒子は約１０ｎｍ
の粒径を持ち、粒子同士が完全に独立した状態で該混合
溶剤中に分散していた。この分散液は非常に安定であっ
て、常温で１ヶ月経過後でも沈降分離は見られなかっ
た。この分散液中のＡｇの含量は１８重量％、分散液粘
度は７ｍＰａ・ｓであり、表面張力は３２ｍＮ／ｍであ
った。(Production Example 6) Helium gas pressure 0.5 To
A by a gas evaporation method in which Ag is evaporated under the condition of rr
In producing g ultrafine particles, average particles dispersed by contacting vapor of α-terpineol to Ag ultrafine particles in the production process, collecting by cooling, and independently dispersing in α-terpineol solvent. An Ag ultrafine particle independent dispersion liquid containing 20% by weight of Ag ultrafine particles having a diameter of 10 nm was prepared. To 1 volume of this dispersion, 5 volumes of acetone were added and stirred.
The ultrafine particles in the dispersion liquid settled due to the action of polar acetone. After standing for 2 hours, the supernatant was removed, the same amount of acetone as that used at the beginning was again added and stirred, and after standing for 2 hours, the supernatant was removed. This operation was repeated 5 times to sufficiently remove α-terpineol. Butylamine was newly added to this precipitate, a mixed solvent of octanol and xylene was further added, and the mixture was stirred. The precipitated Ag ultrafine particles were uniformly dispersed again. Ag particles in the obtained dispersion are about 10 nm.
And the particles were dispersed in the mixed solvent in a completely independent state. This dispersion was very stable and no sedimentation was observed even after 1 month at room temperature. The content of Ag in this dispersion was 18% by weight, the viscosity of the dispersion was 7 mPa · s, and the surface tension was 32 mN / m.
【００３７】（実施例１）上記製造例５で得られたＣｕ
超微粒子独立分散液に、ジフェニルシランを、ケイ素重
量がＣｕ超微粒子重量に対して２ｗｔ％になるように添
加したものをインクとして用い、インクジェットプリン
タで、ガラス基板上に、焼成後に線幅５０μｍ、膜厚１
μｍとなるようなラインを描画した。その後、０．１Ｔ
ｏｒｒの酸素雰囲気下で、３５０℃×１０分焼成し、引
き続き、１０−６Ｔｏｒｒ以下の真空中で４００℃×１
０分焼成した。(Example 1) Cu obtained in the above Production Example 5
An ink obtained by adding diphenylsilane to the ultrafine particle independent dispersion so that the weight of silicon is 2 wt% with respect to the weight of Cu ultrafine particles is used as an ink on an ink jet printer on a glass substrate and a line width of 50 μm after firing. Film thickness 1
A line was drawn so that the thickness would be μm. After that, 0.1T
In an oxygen atmosphere of orr, the material is baked at 350 ° C. for 10 minutes, and subsequently, in a vacuum of 10 −6 Torr or less, 400 ° C. × 1.
It was baked for 0 minutes.
【００３８】焼成後、得られた膜の比抵抗値を測定した
ところ、５μΩ・ｃｍの比抵抗値が得られた。焼成後の
膜の基板に対する密着性をテープテストにより調べたと
ころ剥離は無く、また、メタルピンセットでのスクラッ
チテストでも剥離は無く、高い密着性を示した。なお、
上記ジフェニルシランを添加しなかったインクの場合、
テープテストはパスしたが、スクラッチテストでは剥離
した。上記のようにして得られたラインに対して、硫酸
銅水溶液を用いた銅電解メッキ処理（ラインを陰極、電
気銅を陽極とした。）を、電流密度０．１Ａ／ｃｍ２で
１０分間行い、膜厚１０μｍの微細な導電パターンを形
成した。得られた膜の比抵抗値は２μΩ・ｃｍであり、
また、上記と同様の剥離テストで剥離は観測されず、高
い密着性を示した。かくして得られた膜は、ＰＤＰの電
磁波シールドとして有用であった。After firing, the specific resistance value of the obtained film was measured, and a specific resistance value of 5 μΩ · cm was obtained. When the adhesion of the film after firing to the substrate was examined by a tape test, there was no peeling, and there was no peeling even in a scratch test with metal tweezers, indicating high adhesion. In addition,
In the case of the ink in which the above diphenylsilane was not added,
It passed the tape test, but peeled off in the scratch test. The line obtained as described above was subjected to copper electrolytic plating treatment using a copper sulfate aqueous solution (the line was used as a cathode and electrolytic copper was used as an anode) at a current density of 0.1 A / cm 2 for 10 minutes. A fine conductive pattern having a film thickness of 10 μm was formed. The specific resistance value of the obtained film is 2 μΩ · cm,
No peeling was observed in the peeling test similar to the above, and high adhesion was exhibited. The film thus obtained was useful as an electromagnetic wave shield for PDPs.
【００３９】（実施例２）上記製造例５で得られたＣｕ
超微粒子独立分散液をインクとして用い、インジェット
プリンタで、セラミックス（高純度、高密度アルミナ）
基板上に、線幅５０μｍ、膜厚０．２μｍのラインを描
画した。その後、１０〜１００Ｔｏｒｒの酸素雰囲気下
で３５０℃×１０分焼成し、この膜を密着性確保のため
の下地酸化物層とした。この膜上に、さらに、実施例１
と同様の方法でＣｕ超微粒子独立分散液を塗布し、焼成
して、膜厚１μｍの膜を形成した。(Example 2) Cu obtained in the above Production Example 5
Ceramics (high-purity, high-density alumina) with an ink jet printer using ultrafine particle independent dispersion liquid
A line having a line width of 50 μm and a film thickness of 0.2 μm was drawn on the substrate. Then, it was baked at 350 ° C. for 10 minutes in an oxygen atmosphere of 10 to 100 Torr, and this film was used as a base oxide layer for securing adhesion. On this film, further, Example 1
The Cu ultrafine particle independent dispersion liquid was applied in the same manner as in (1) and baked to form a film having a thickness of 1 μm.
【００４０】焼成後、得られた膜の比抵抗値を測定した
ところ、２μΩ・ｃｍの比抵抗値が得られた。また、焼
成後の膜の基板に対する密着性を実施例１と同じ方法で
調べたところ、同様の高い密着性を示した。上記のよう
にして得られたラインに対して、実施例１と同様の方法
で銅電解メッキ処理を行い、膜厚１０μｍの微細な導電
パターンを形成した。得られた膜の比抵抗値測定及び剥
離テストを実施例１の場合と同様に行ったところ、同様
の結果を示した。かくして得られた膜を有する基板は、
高周波回路用プリント基板として有用であった。なお、
セラミックス基板の代わりにガラス基板を用いて上記方
法を繰り返した場合も、同様の結果が得られた。After firing, the specific resistance value of the obtained film was measured, and a specific resistance value of 2 μΩ · cm was obtained. Further, when the adhesion of the film after firing to the substrate was examined by the same method as in Example 1, the same high adhesion was exhibited. Copper electroplating treatment was performed on the line obtained as described above in the same manner as in Example 1 to form a fine conductive pattern having a film thickness of 10 μm. When the specific resistance value measurement and the peeling test of the obtained film were performed in the same manner as in Example 1, the same result was shown. The substrate having the film thus obtained is
It was useful as a printed circuit board for high frequency circuits. In addition,
Similar results were obtained when the above method was repeated using a glass substrate instead of a ceramic substrate.
【００４１】（実施例３）上記製造例５で得られたＣｕ
超微粒子独立分散液に、オクタン酸マンガンを、マンガ
ン重量がＣｕ超微粒子重量に対して５ｗｔ％になるよう
に添加したものをインクとして用い、インクジェットプ
リンタで、ポリイミド基板上に、線幅５０μｍ、膜厚１
μｍのラインを描画した。その後、０．０５Ｔｏｒｒの
酸素雰囲気下で３００℃×３０分焼成した。焼成後、得
られた膜の比抵抗値を測定したところ、４μΩ・ｃｍの
比抵抗値が得られた。また、焼成後の膜の基板に対する
密着性を実施例１と同じ方法で調べたところ、同様の高
い密着性を示した。(Example 3) Cu obtained in the above Production Example 5
An ultrafine particle independent dispersion containing manganese octoate added so that the weight of manganese was 5 wt% with respect to the weight of Cu ultrafine particles was used as an ink, and an ink jet printer was used to form a film having a line width of 50 μm and a film on a polyimide substrate. Thickness 1
A μm line was drawn. Then, it was baked at 300 ° C. for 30 minutes in an oxygen atmosphere of 0.05 Torr. When the specific resistance value of the obtained film was measured after firing, a specific resistance value of 4 μΩ · cm was obtained. Further, when the adhesion of the film after firing to the substrate was examined by the same method as in Example 1, the same high adhesion was exhibited.
【００４２】上記のようにして得られたラインに対し
て、実施例１と同様の方法で銅電解メッキ処理を行い、
膜厚１０μｍの微細な導電パターンを形成した。得られ
た膜の比抵抗値測定及び剥離テストを実施例１の場合と
同様に行ったところ、同様の結果を示した。かくして得
られた膜を有する基板は、プリント基板として有用であ
った。The line obtained as described above is subjected to copper electrolytic plating in the same manner as in Example 1,
A fine conductive pattern having a film thickness of 10 μm was formed. When the specific resistance value measurement and the peeling test of the obtained film were performed in the same manner as in Example 1, the same result was shown. The substrate having the film thus obtained was useful as a printed circuit board.
【００４３】（実施例４）オクタン酸マンガン溶液（溶
剤：テトラデカン）をインクとして用い、インクジェッ
トプリンタで、ポリイミド基板上に、線幅５０μｍ、膜
厚０．１μｍのラインを描画した。その後、１０〜１０
０Ｔｏｒｒの酸素雰囲気下で２３０℃×１０分焼成し、
この膜を密着性確保のための下地層（第一下地膜）とし
た。この膜上に、さらに、上記製造例５で得られたＣｕ
超微粒子独立分散液をインクとして用い、インクジェッ
トプリンタで描画し、実施例３と同様の方法で焼成を行
い、膜厚１μｍの膜（第二下地膜）を形成した。Example 4 Using a manganese octanoate solution (solvent: tetradecane) as an ink, a line having a line width of 50 μm and a film thickness of 0.1 μm was drawn on a polyimide substrate with an ink jet printer. Then 10-10
Bake at 230 ° C for 10 minutes in an oxygen atmosphere of 0 Torr,
This film was used as a base layer (first base film) for securing adhesion. On this film, the Cu obtained in Production Example 5 was further added.
Using the ultrafine particle independent dispersion liquid as an ink, drawing was performed with an inkjet printer, and baking was performed in the same manner as in Example 3 to form a film (second base film) having a film thickness of 1 μm.
【００４４】焼成後、得られた膜の比抵抗値を測定した
ところ、２μΩ・ｃｍの比抵抗値が得られた。また、焼
成後の膜の基板に対する密着性を実施例１と同じ方法で
調べたところ、実施例３の場合より高い密着性を示し
た。上記のようにして得られた膜に対して、実施例１と
同様の方法で銅電解メッキ処理を行い、膜厚１０μｍの
微細な導線パターンを形成した。得られた膜の比抵抗値
測定及び剥離テストを実施例１の場合と同様に行ったと
ころ、高い密着性を示した。なお、膜質に関しては、実
施例３の場合より良好であった。ポリイミド基板の代わ
りにガラス基板を用いて上記方法を行った場合も、同様
の結果が得られた。After firing, the specific resistance of the obtained film was measured, and a specific resistance of 2 μΩ · cm was obtained. Further, when the adhesion of the film after firing to the substrate was examined by the same method as in Example 1, the adhesion was higher than that of Example 3. The film obtained as described above was subjected to copper electrolytic plating in the same manner as in Example 1 to form a fine conductor pattern having a film thickness of 10 μm. When the specific resistance value and the peeling test of the obtained film were performed in the same manner as in Example 1, high adhesion was exhibited. The film quality was better than that of Example 3. Similar results were obtained when the above method was performed using a glass substrate instead of the polyimide substrate.
【００４５】（実施例５）実施例３のオクタン酸マンガ
ンの代わりに、マグネシウム又はアルミニウムを含有す
る有機化合物として、(Ｃ１７Ｈ３５ＣＯＯ)２Ｍｇ又は
(Ｃ１７Ｈ３５ＣＯＯ)３Ａｌを添加したＣｕ超微粒子独
立分散液を調製し、実施例３の方法を繰り返したとこ
ろ、得られた膜の基板との密着性も同様に良好であり、
その比抵抗は２．１μΩ・ｃｍであった。[0045] Instead of (Example 5) Example 3 octanoate manganese, as an organic compound containing magnesium or aluminum, (C 17 H 35 COO) 2 Mg , or
An independent dispersion of Cu ultrafine particles containing (C 17 H 35 COO) 3 Al was prepared and the method of Example 3 was repeated, and the adhesion of the obtained film to the substrate was similarly good,
The specific resistance was 2.1 μΩ · cm.
【００４６】[0046]
【発明の効果】本発明によれば、従来の電解メッキ法の
ネックである下地電極の形成を、直接パターニングが可
能な金属超微粒子独立分散液をインクとして用いて、イ
ンクジェット法で行った後、その上にメッキを施してい
るので、フォトリソグラフィー工程が不要となり、かな
りの工程及びコストの削減が可能となると共に、被処理
基板に対する高い密着性が達成される。According to the present invention, the formation of the base electrode, which is a bottleneck of the conventional electrolytic plating method, is carried out by the ink jet method after using the metal ultrafine particle independent dispersion liquid capable of direct patterning as the ink. Since plating is applied on top of this, a photolithography step is not required, and it is possible to considerably reduce the steps and costs, and at the same time, high adhesion to the substrate to be processed is achieved.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 小田 正明 千葉県山武郡山武町横田516 株式会社ア ルバック・コーポレートセンター内 Ｆターム(参考） 2C056 EA24 FB01 4M104 BB04 BB05 BB06 BB07 BB08 BB09 BB13 BB14 BB17 BB18 DD51 DD52 DD78 FF13 5E343 AA02 AA22 AA39 BB16 BB22 BB24 BB28 BB35 BB38 BB44 BB71 BB80 CC22 CC32 DD12 DD43 ER42 GG11 ─────────────────────────────────────────────────── ─── Continued front page (72) Inventor Masaaki Oda 516 Yokota, Sanmu-cho, Sanbu-gun, Chiba Prefecture Inside Rubac Corporate Center F-term (reference) 2C056 EA24 FB01 4M104 BB04 BB05 BB06 BB07 BB08 BB09 BB13 BB14 BB17 BB18 DD51 DD52 DD78 FF13 5E343 AA02 AA22 AA39 BB16 BB22 BB24 BB28 BB35 BB38 BB44 BB71 BB80 CC22 CC32 DD12 DD43 ER42 GG11
Claims (12)
粒子独立分散液からなるインクを用いて、インクジェッ
ト法により、直接、絶縁基板上に下地導電パターンを形
成し、焼成した後、電解メッキ処理して該下地電導パタ
ーン上にさらに導電パターンを形成することを特徴とす
る導電パターンの形成方法。1. An undercoating conductive pattern is directly formed on an insulating substrate by an ink jet method using an ink composed of an ultrafine metal particle independent dispersion liquid containing ultrafine metal particles and a dispersant, followed by electrolytic plating treatment. Then, a conductive pattern is further formed on the underlying conductive pattern.
であり、前記金属超微粒子独立分散液の粘度が１〜１０
０ｍＰａ・ｓ、その表面張力が２５〜８０ｍＮ／ｍであ
ることを特徴とする請求項１記載の導電パターンの形成
方法。2. The ultrafine metal particles have a particle diameter of 100 nm or less, and the independent dispersion liquid of ultrafine metal particles has a viscosity of 1 to 10.
The method for forming a conductive pattern according to claim 1, wherein the surface tension is 0 mPa · s and the surface tension is 25 to 80 mN / m.
酸アミド、及びアミノカルボン酸塩から選ばれた１種又
は複数のものであることを特徴とする請求項１又は２記
載の導電パターンの形成方法。3. The method for forming a conductive pattern according to claim 1, wherein the dispersant is one or more selected from alkylamines, carboxylic acid amides, and aminocarboxylic acid salts. .
〜２０であることを特徴とする請求項３項記載の導電パ
ターンの形成方法。4. The main chain of the alkylamine has 4 carbon atoms.
4. The method for forming a conductive pattern according to claim 3, wherein the conductive pattern is 20 to 20.
ミンであることを特徴とする請求項３又は４項記載の導
電パターンの形成方法。5. The method for forming a conductive pattern according to claim 3, wherein the alkylamine is a primary alkylamine.
量基準で０．１〜１０重量％であることを特徴とする請
求の範囲第１〜５項のいずれかに記載の導電パターンの
形成方法。6. The conductive pattern according to claim 1, wherein the content of the dispersant is 0.1 to 10% by weight based on the weight of ultrafine metal particles. Forming method.
素数６〜２０の非極性炭化水素、水、及び炭素数が１５
以下のアルコール系溶剤から選ばれた少なくとも１種の
溶剤を含んでいることを特徴とする請求項１〜６項のい
ずれかに記載の導電パターンの形成方法。7. The dispersion liquid, as a dispersion medium, a non-polar hydrocarbon having 6 to 20 carbon atoms in the main chain, water, and 15 carbon atoms.
7. The method for forming a conductive pattern according to claim 1, further comprising at least one solvent selected from the following alcohol solvents.
に、ケイ素、マンガン、クロム、ニッケル、チタン、マ
グネシウム、アルミニウム、ゲルマニウム、タンタル、
ニオブ及びバナジウムから選ばれた少なくとも１種の金
属を含んでいることを特徴とする請求項１〜７のいずれ
かに記載の導電パターンの形成方法。8. The metal ultrafine particle independent dispersion liquid further comprises silicon, manganese, chromium, nickel, titanium, magnesium, aluminum, germanium, tantalum,
The method for forming a conductive pattern according to claim 1, further comprising at least one metal selected from niobium and vanadium.
溶剤の蒸気の存在下で金属を蒸発させることにより溶剤
中に金属超微粒子が分散した金属超微粒子分散液を得る
第１工程と、該第１工程で得られた分散液に低分子量の
極性溶剤である第２溶剤を加えて該金属超微粒子を沈降
させ、その上澄み液を取り除くことにより該第１溶剤を
実質的に除去する第２工程と、このようにして得られた
沈降物に第３溶剤を加えて金属超微粒子の独立分散液を
得る第３工程とにより製造されたものであることを特徴
とする請求項１〜８のいずれかに記載の導電パターンの
形成方法。9. The ink according to claim 1,
A first step of obtaining an ultrafine metal particle dispersion in which ultrafine metal particles are dispersed in a solvent by evaporating a metal in the presence of solvent vapor; and a low molecular weight polar solvent in the dispersion obtained in the first step. The second solvent is added to precipitate the ultrafine metal particles, and the supernatant is removed to substantially remove the first solvent, and the precipitate thus obtained is subjected to a third step. The method for forming a conductive pattern according to any one of claims 1 to 8, which is manufactured by the third step of adding a solvent to obtain an independent dispersion liquid of ultrafine metal particles.
工程と第３工程との両工程のいずれかで分散剤を加える
ことを特徴とする請求項９項記載の導電パターンの形成
方法。10. The first step, the third step, or the first step
The method for forming a conductive pattern according to claim 9, wherein a dispersant is added in either of the step and the third step.
の非極性炭化水素、水、及び炭素数が１５以下のアルコ
ール系溶剤から選ばれた少なくとも１種であることを特
徴とする請求項９又は１０記載の導電パターンの形成方
法。11. The third solvent comprises a main chain having 6 to 20 carbon atoms.
11. The method for forming a conductive pattern according to claim 9 or 10, wherein the conductive pattern is at least one selected from the nonpolar hydrocarbons, water, and alcohol solvents having 15 or less carbon atoms.
チタン、マグネシウム、アルミニウム、ゲルマニウム、
タンタル、ニオブ及びバナジウムから選ばれた少なくと
も１種の金属を含有する有機化合物の分散液を用いて、
インクジェット法により、直接、絶縁基板上に第一下地
導電パターンを形成し、焼成した後、請求項１〜１１の
いずれかに記載の金属超微粒子独立分散液からなるイン
クを用いて、インクジェット法により、直接、該第一下
地導電パターン上に第二下地導電パターンを形成し、次
いで、焼成した後、電解メッキ処理して該第二下地電導
パターン上にさらに導電パターンを形成することを特徴
とする導電パターンの形成方法。12. Silicon, manganese, chromium, nickel,
Titanium, magnesium, aluminum, germanium,
Using a dispersion liquid of an organic compound containing at least one metal selected from tantalum, niobium and vanadium,
The first underlying conductive pattern is directly formed on an insulating substrate by an inkjet method, and after firing, the inkjet method is performed using the ink composed of the independent dispersion of ultrafine metal particles according to any one of claims 1 to 11. By directly forming a second underlying conductive pattern on the first underlying conductive pattern, and then firing and then electrolytic plating to form a further conductive pattern on the second underlying conductive pattern. And a method for forming a conductive pattern.
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|---|---|---|---|
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| JP2016000842A (en) * | 2014-06-11 | 2016-01-07 | Dic株式会社 | Manufacturing method of plating |
| US10076028B2 (en) | 2015-01-22 | 2018-09-11 | Sumitomo Electric Industries, Ltd. | Substrate for printed circuit board, printed circuit board, and method for producing printed circuit board |
| CN106132102A (en) * | 2016-07-12 | 2016-11-16 | 北京梦之墨科技有限公司 | Liquid metal odt circuit manufacture method and compound circuit manufacture method |
| JP2022175248A (en) * | 2021-05-13 | 2022-11-25 | Jsr株式会社 | Wiring board, method for manufacturing the same, and surface treatment agent |
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