JP4166686B2 - Metal particle-containing resin particles, metal particle-containing resin layer, and method for forming metal particle-containing resin layer - Google Patents

Metal particle-containing resin particles, metal particle-containing resin layer, and method for forming metal particle-containing resin layer Download PDF

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JP4166686B2
JP4166686B2 JP2003435760A JP2003435760A JP4166686B2 JP 4166686 B2 JP4166686 B2 JP 4166686B2 JP 2003435760 A JP2003435760 A JP 2003435760A JP 2003435760 A JP2003435760 A JP 2003435760A JP 4166686 B2 JP4166686 B2 JP 4166686B2
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resin
containing resin
metal fine
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fine particle
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JP2005194327A (en
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秀夫 青木
直子 山口
知章 田窪
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Toshiba Corp
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Priority to KR1020040111799A priority patent/KR100612170B1/en
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Description

本発明は、金属微粒子を含有する樹脂を例えば電子写真方式にて印刷した後、金属微粒子をめっき核として無電解めっきを行うことで、任意の電子回路を容易に形成することができる金属微粒子含有樹脂粒子、金属微粒子含有樹脂層および金属微粒子含有樹脂層の形成方法に関する。 The present invention includes a metal fine particle capable of easily forming an arbitrary electronic circuit by performing electroless plating using a metal fine particle as a plating nucleus after printing a resin containing the metal fine particle by, for example, electrophotography. The present invention relates to a resin particle, a resin layer containing metal fine particles, and a method for forming a resin layer containing metal fine particles .

従来の電子回路基板の製造では、金属薄膜上にレジスト塗布、露光、現像、エッチングなどの処理を行い、金属導体パターン層を形成している。この製造工程において、各層毎に露光マスクが必要となり、その設計や作成に多大な時間とコストがかかるため、回路パターンの変更や修正は、電子回路基板の製造期間やコストに大きな影響を与えていた。   In the manufacture of a conventional electronic circuit board, a metal conductor pattern layer is formed on a metal thin film by performing processes such as resist coating, exposure, development, and etching. In this manufacturing process, an exposure mask is required for each layer, and it takes a lot of time and cost to design and create the circuit. Therefore, changing or correcting the circuit pattern has a great influence on the manufacturing period and cost of the electronic circuit board. It was.

そこで、樹脂内に金属微粒子を含有する荷電粒子をトナーとして、電子写真方式によって任意のパターンを有する下地パターン層を印刷し、この印刷された下地パターン層の金属微粒子をめっき核として無電解めっきを行うことで、露光マスクを用いずに金属導体パターン層を形成する方法が開発されている（例えば、特許文献１参照。）。
特開平７−２６３８４１号公報 Therefore, a ground pattern layer having an arbitrary pattern is printed by electrophotographic method using charged particles containing fine metal particles in the resin as a toner, and electroless plating is performed using the fine metal particles of the printed ground pattern layer as a plating nucleus. As a result, a method of forming a metal conductor pattern layer without using an exposure mask has been developed (see, for example, Patent Document 1).
Japanese Patent Laid-Open No. 7-263841

この下地パターン層の無電解めっきを施す面に存在する金属微粒子は、印刷直後では樹脂に覆われており、そのままではめっき核としての機能を充分に果たさないため、その金属微粒子を覆う樹脂を機械的または化学的にエッチングして、金属微粒子を表面に露出させる必要がある。   Since the metal fine particles present on the surface of the base pattern layer to be electrolessly plated are covered with resin immediately after printing and do not function as plating nuclei as they are, the resin covering the metal fine particles is machined. It is necessary to etch the metal fine particles on the surface by performing chemical or chemical etching.

しかしながら、機械的エッチングは、基材の平坦度の問題が顕在化しやすいため、広域な面積のエッチング処理には向かない。そこで、特に、広域な面積のエッチング処理には、化学的エッチングが採用されるが、化学的エッチングの場合には、樹脂の溶解の度合いがめっき後の金属導体パターン層と基材との密着性に大きな影響を及ぼす場合がある。例えば、化学的エッチングを行っても充分に樹脂が溶解されず、金属微粒子が表面に充分に露出されない場合には、無電解めっき処理後に、めっき層がほとんど析出されないとういう問題があった。   However, mechanical etching is not suitable for etching processing over a wide area because the problem of the flatness of the substrate tends to become obvious. Therefore, chemical etching is particularly employed for etching processing over a wide area, but in the case of chemical etching, the degree of resin dissolution is the adhesion between the metal conductor pattern layer after plating and the substrate. May have a significant impact. For example, if the resin is not sufficiently dissolved even after chemical etching and the metal fine particles are not sufficiently exposed on the surface, there is a problem that the plating layer is hardly deposited after the electroless plating treatment.

本発明は、上記問題を解決するためになされたもので、パターンを形成する下地パターン層の表面にエッチングする厚さを容易にコントロールすることができる層を形成することにより、効率的な無電解めっき処理が可能となり、より均一な金属導体パターン層を形成することができる金属微粒子含有樹脂粒子、金属微粒子含有樹脂層および金属微粒子含有樹脂層の形成方法を提供することを目的とする。 The present invention has been made in order to solve the above-mentioned problems, and by forming a layer that can easily control the etching thickness on the surface of the underlying pattern layer that forms the pattern, an efficient electroless process is achieved. An object of the present invention is to provide a metal fine particle-containing resin particle, a metal fine particle-containing resin layer, and a method for forming a metal fine particle-containing resin layer, which can be plated and can form a more uniform metal conductor pattern layer.

上記目的を達成するために、本発明の一態様によれば、導体パターン形成用の金属微粒子含有樹脂粒子であって、熱硬化性樹脂からなる樹脂マトリックスと、前記樹脂マトリックスに分散された金属微粒子と、前記樹脂マトリックスに含有され、前記樹脂マトリックスを構成する樹脂材料よりも比重の小さい添加物とを具備することを特徴とする金属微粒子含有樹脂粒子が提供される。   In order to achieve the above object, according to an aspect of the present invention, resin particles containing metal fine particles for forming a conductor pattern, which are a resin matrix made of a thermosetting resin, and metal fine particles dispersed in the resin matrix And an additive having a specific gravity smaller than that of the resin material constituting the resin matrix.

また、本発明の一態様によれば、少なくとも金属微粒子を含有する熱硬化性樹脂で基材上に形成された金属微粒子含有樹脂層であって、無電解めっき処理工程前の該金属微粒子含有樹脂層の熱硬化性樹脂の硬化率が５０％以上であることを特徴とする金属微粒子含有樹脂層が提供される。   Moreover, according to one aspect of the present invention, a metal fine particle-containing resin layer formed on a substrate with a thermosetting resin containing at least metal fine particles, the metal fine particle-containing resin before the electroless plating treatment step A metal fine particle-containing resin layer is provided, wherein the curing rate of the thermosetting resin of the layer is 50% or more.

さらに、本発明の一態様によれば、感光体上に所定のパターンの静電潜像を形成する工程と、前記静電潜像が形成された感光体上に、樹脂マトリックスに分散して金属微粒子を含有し、かつ該樹脂マトリックスを構成する樹脂材料よりも比重の小さい添加物が添加された金属微粒子含有樹脂粒子を静電的に付着させて可視像を形成する工程と、前記感光体上に形成された前記金属微粒子含有樹脂粒子からなる可視像を、基材上に静電的に転写する工程と、前記基材上に転写された前記金属微粒子含有樹脂粒子を加熱または光照射により、前記樹脂マトリックスの硬化率を５０％以上に硬化し、前記基材に定着させる工程とを具備することを特徴とする金属微粒子含有樹脂層の形成方法が提供される。   Further, according to one aspect of the present invention, a process of forming an electrostatic latent image having a predetermined pattern on a photoconductor, and a metal dispersed in a resin matrix on the photoconductor on which the electrostatic latent image is formed. Forming a visible image by electrostatically adhering metal fine particle-containing resin particles containing fine particles and having an additive having a specific gravity smaller than that of a resin material constituting the resin matrix; and A step of electrostatically transferring a visible image composed of the metal fine particle-containing resin particles formed thereon onto a substrate, and heating or light irradiation of the metal fine particle-containing resin particles transferred onto the substrate Is provided with a step of curing the resin matrix to a curing rate of 50% or more and fixing the resin matrix to the substrate.

本発明の一態様による金属微粒子含有樹脂粒子、金属微粒子含有樹脂層および金属微粒子含有樹脂層の形成方法によれば、パターンを形成する下地パターン層の表面にエッチングする厚さを容易にコントロールすることができる層を形成することにより、効率的な無電解めっき処理が可能となり、より均一な金属導体パターン層を形成することができる。 According to the metal fine particle-containing resin particles, the metal fine particle-containing resin layer, and the metal fine particle-containing resin layer forming method according to one aspect of the present invention, the thickness of etching on the surface of the base pattern layer for forming the pattern can be easily controlled. By forming a layer that can be used, efficient electroless plating can be performed, and a more uniform metal conductor pattern layer can be formed.

以下、本発明の一実施の形態を、図面に基づいて説明する。   Hereinafter, an embodiment of the present invention will be described with reference to the drawings.

図１には、本発明の一実施の形態の金属微粒子含有樹脂粒子１０の断面図の概要が示されている。   FIG. 1 shows an outline of a cross-sectional view of metal particle-containing resin particles 10 according to an embodiment of the present invention.

金属微粒子含有樹脂粒子１０は、図１に示すように、樹脂マトリックス１０ａを主体とし、これに導電性の金属微粒子１０ｂがほぼ均一に分散された状態で含有されている。さらに、金属微粒子含有樹脂粒子１０には、樹脂マトリックス１０ａを構成する樹脂材料よりも比重の小さい油脂類などの添加物が添加されている。   As shown in FIG. 1, the metal fine particle-containing resin particles 10 are mainly composed of a resin matrix 10a, and the conductive metal fine particles 10b are contained in a substantially uniformly dispersed state. Furthermore, additives such as fats and oils having a specific gravity smaller than that of the resin material constituting the resin matrix 10a are added to the resin particles 10 containing fine metal particles.

この金属微粒子含有樹脂粒子１０の粒径は、微細配線パターンを形成する必要性から、小さい方が望ましく、例えば、平均粒径が４μｍ〜１０μｍの範囲で形成されている。   The particle size of the metal fine particle-containing resin particles 10 is desirably smaller in view of the necessity of forming a fine wiring pattern. For example, the average particle size is 4 μm to 10 μm.

金属微粒子含有樹脂粒子１０を構成する樹脂マトリックス１０ａは、常温で固体のＢステージの熱硬化性樹脂が用いられる。ここで、Ｂステージとは、熱硬化性樹脂の少なくとも一部は硬化しておらず、所定の熱を加えるとその硬化していない部分が溶融する状態をいう。Ｂステージの熱硬化性樹脂としては、エポキシ樹脂、ポリイミド樹脂、フェノール樹脂、ビスマレイミド樹脂、シアネートエステル樹脂、ビスマレイミドートリアジン樹脂、ベンジシクロブテン樹脂、ポリイミド樹脂、ポリベンゾオキサゾール樹脂、ブタジエン樹脂、シリコーン樹脂、ポリカルボジイミド樹脂、ポリウレタン樹脂などを使用することができる。   The resin matrix 10a constituting the metal fine particle-containing resin particles 10 is a B-stage thermosetting resin that is solid at room temperature. Here, the B stage refers to a state in which at least a part of the thermosetting resin is not cured and when the predetermined heat is applied, the uncured part is melted. B-stage thermosetting resins include epoxy resin, polyimide resin, phenolic resin, bismaleimide resin, cyanate ester resin, bismaleimide-triazine resin, benzylcyclobutene resin, polyimide resin, polybenzoxazole resin, butadiene resin, silicone Resins, polycarbodiimide resins, polyurethane resins and the like can be used.

導電性の金属微粒子１０ｂは、Ｐｔ、Ｐｄ、Ｃｕ、Ａｕ、Ｎｉ、Ａｇから成る群から選択される少なくとも一種の金属微粒子が用いられる。また、金属微粒子１０ｂの平均粒径は、０．０５μｍ〜３μｍの範囲が好ましく、さらに好ましい範囲は、０．１μｍ〜２μｍである。金属微粒子１０ｂの平均粒径が小さい方が分散性がよいからである。   As the conductive metal fine particles 10b, at least one metal fine particle selected from the group consisting of Pt, Pd, Cu, Au, Ni and Ag is used. The average particle size of the metal fine particles 10b is preferably in the range of 0.05 μm to 3 μm, and more preferably in the range of 0.1 μm to 2 μm. This is because the smaller the average particle diameter of the metal fine particles 10b, the better the dispersibility.

さらに、金属微粒子１０ｂは、金属微粒子含有樹脂粒子１０中に１５〜７０重量％の割合で含有され、無電解メッキの核となり、メッキ反応の進行に対して触媒的な作用を有する。金属微粒子含有樹脂粒子１０の含有率が１５重量％より小さい場合では、金属微粒子１０ｂのメッキ核としての機能が低下することがある。また、金属微粒子含有樹脂粒子１０の含有率が７０重量％より大きい場合では、印刷パターンが適切に形成されないことがある。さらに、金属微粒子含有樹脂粒子１０に含有される導電性の金属微粒子１０ｂのより好ましい含有率は、３０〜６０重量％である。   Furthermore, the metal fine particles 10b are contained in the metal fine particle-containing resin particles 10 in a proportion of 15 to 70% by weight, serve as nuclei for electroless plating, and have a catalytic effect on the progress of the plating reaction. When the content of the metal fine particle-containing resin particles 10 is less than 15% by weight, the function of the metal fine particles 10b as a plating nucleus may be deteriorated. In addition, when the content of the metal fine particle-containing resin particles 10 is greater than 70% by weight, the printed pattern may not be appropriately formed. Furthermore, the more preferable content rate of the electroconductive metal fine particle 10b contained in the metal fine particle containing resin particle 10 is 30 to 60 weight%.

添加物は、比重が１．１（２５℃）以下の、例えば植物性ワックスなどの油脂類で構成され、樹脂マトリックス１０ａに、樹脂マトリックス１０ａの総体積の０．５体積％以上の範囲で添加されている。添加物の添加が、０．５体積％未満では、部分的にメッキ核が露出しない場合がありメッキ析出性に影響が出る場合がある。添加物の添加量に特に上限は無いが、添加量が多すぎる場合には、エッチング処理後の印刷パターンの厚さが薄くなってしまうので少ない方が望ましい。   The additive is composed of fats and oils such as vegetable wax having a specific gravity of 1.1 (25 ° C.) or less, and is added to the resin matrix 10a in a range of 0.5% by volume or more of the total volume of the resin matrix 10a. Has been. If the addition of the additive is less than 0.5% by volume, the plating nucleus may not be partially exposed, and the plating deposition property may be affected. There is no particular upper limit to the amount of additive added, but if the amount added is too large, the thickness of the printed pattern after the etching process becomes thin, so it is desirable that the amount be small.

次に、電子写真方式による導体パターン層の形成工程について、図２および３を参照して説明する。   Next, the process of forming a conductive pattern layer by electrophotography will be described with reference to FIGS.

図２には、導体パターン層の各形成工程における断面図が示されている。また、図３には、導体パターン層を形成する製造装置の概要が示されている。   FIG. 2 is a cross-sectional view in each step of forming the conductor pattern layer. FIG. 3 shows an outline of a manufacturing apparatus for forming a conductor pattern layer.

まず、感光体ドラム１００を矢印方向に回転させながら、帯電器１０１により感光体ドラム１００の表面電位を一定電位（例えばマイナス電荷）に均一に帯電させる。次に、レーザ発生・走査装置１０２により、画像信号に応じてレーザ光１０２ａを感光体ドラム１００に照射し、照射部分のマイナス電荷を除去し、感光体ドラム１００の表面に所定パターンの電荷の像（静電潜像）を形成する。   First, while rotating the photosensitive drum 100 in the direction of the arrow, the charger 101 uniformly charges the surface potential of the photosensitive drum 100 to a constant potential (for example, negative charge). Next, the laser generation / scanning apparatus 102 irradiates the photosensitive drum 100 with laser light 102a in accordance with the image signal, removes negative charges from the irradiated portion, and forms an image of a predetermined pattern of charges on the surface of the photosensitive drum 100. (Electrostatic latent image) is formed.

次に、感光体ドラム１００上の静電潜像に、現像装置１０３に貯留された帯電した金属微粒子含有樹脂粒子１０を供給機構によって静電的に付着させ可視像を形成する。   Next, the charged metal fine particle-containing resin particles 10 stored in the developing device 103 are electrostatically attached to the electrostatic latent image on the photosensitive drum 100 by a supply mechanism to form a visible image.

続いて、感光体ドラム１００の表面に、金属微粒子含有樹脂粒子１０により形成された可視像（パターン）は、転写装置１０４によって感光体ドラム１００から所望の基材２０上に静電転写される。   Subsequently, the visible image (pattern) formed by the metal fine particle-containing resin particles 10 on the surface of the photoconductor drum 100 is electrostatically transferred from the photoconductor drum 100 onto the desired substrate 20 by the transfer device 104. .

次いで、基材２０上に転写されたＢステージの金属微粒子含有樹脂粒子１０を、加熱あるいは光照射による定着器１０５を通し、金属微粒子含有樹脂粒子１０を構成する熱硬化性樹脂を溶融し硬化させ、金属微粒子含有樹脂粒子１０が一体化された金属微粒子含有樹脂層３０を形成する（図２の（ａ））。   Next, the B stage metal fine particle-containing resin particles 10 transferred onto the base material 20 are passed through a fixing device 105 by heating or light irradiation, and the thermosetting resin constituting the metal fine particle-containing resin particles 10 is melted and cured. Then, the metal fine particle-containing resin layer 30 in which the metal fine particle-containing resin particles 10 are integrated is formed ((a) of FIG. 2).

ここで、定着器１０５で硬化処理された金属微粒子含有樹脂粒子１０には、樹脂マトリックス１０ａを構成する樹脂材料よりも比重の小さい、例えば油脂類などの添加物が含まれているので、金属微粒子含有樹脂層３０の上方の表面には、比重の影響で、添加物による表面層３０ａが形成される。   Here, the metal fine particle-containing resin particles 10 cured by the fixing device 105 contain additives such as fats and oils having a specific gravity smaller than that of the resin material constituting the resin matrix 10a. A surface layer 30 a made of an additive is formed on the surface above the containing resin layer 30 due to the influence of specific gravity.

なお、この定着器１０５では、完全に樹脂マトリックス１０ａを硬化させる必要はなく、例えば、後述する樹脂エッチング装置におけるエッチング処理の際に、樹脂マトリックス１０ａの層から金属微粒子１０ｂが欠落しない程度に硬化されるのが好ましい。   In the fixing device 105, it is not necessary to completely cure the resin matrix 10a. For example, the resin matrix 10a is cured to such an extent that the metal fine particles 10b are not lost from the layer of the resin matrix 10a during an etching process in a resin etching apparatus described later. It is preferable.

続いて、無電解メッキを効率的に行うために、樹脂エッチング装置（図示しない）において、金属微粒子含有樹脂層３０の表面をエッチング処理して、金属微粒子含有樹脂層３０の表面に金属微粒子１０ｂの少なくとも一部を露出させる（図２の（ｂ））。   Subsequently, in order to efficiently perform electroless plating, the surface of the metal fine particle-containing resin layer 30 is etched in a resin etching apparatus (not shown), and the metal fine particles 10b are formed on the surface of the metal fine particle-containing resin layer 30. At least a part is exposed (FIG. 2B).

この樹脂エッチング装置では、金属微粒子含有樹脂層３０の表面を、例えば、アセトン、イソプロピルアルコール、エタノール、または界面活性剤などに浸けることによって化学的にエッチング除去を行う。これらの溶剤は、金属微粒子含有樹脂層３０の上方の表面に形成された添加物による表面層３０ａを容易にエッチングすることができる。   In this resin etching apparatus, the surface of the metal fine particle-containing resin layer 30 is chemically removed by immersing the surface in, for example, acetone, isopropyl alcohol, ethanol, or a surfactant. These solvents can easily etch the surface layer 30 a by the additive formed on the surface above the metal fine particle-containing resin layer 30.

続いて、エッチング処理が施され、表面に金属微粒子１０ｂの少なくとも一部を露出させた金属微粒子含有樹脂層３０は、無電解めっき槽（図示しない）によって、例えばＣｕのめっき処理が施され、金属微粒子含有樹脂層３０上に露出した金属微粒子１０ｂを核としてＣｕを選択的に析出させ、導体金属層４０を形成する（図２の（ｃ））。   Subsequently, the metal fine particle-containing resin layer 30 that has been subjected to an etching process and has exposed at least a part of the metal fine particles 10b on its surface is subjected to, for example, Cu plating by an electroless plating tank (not shown), Cu is selectively deposited using the metal fine particles 10b exposed on the fine particle-containing resin layer 30 as nuclei to form the conductive metal layer 40 (FIG. 2 (c)).

なお、ここでは、無電解メッキ槽のみで構成されるメッキ槽を示したが、これに限るものではなく、無電解メッキと電解メッキの双方を行うメッキ槽を用いてもよい。   In addition, although the plating tank comprised only with an electroless plating tank was shown here, it is not restricted to this, You may use the plating tank which performs both electroless plating and electrolytic plating.

また、金属微粒子含有樹脂層３０の表面に形成される導体金属層４０の厚みは、メッキ条件により所定の厚さに設定可能である。メッキ処理後には、基材２０と金属微粒子含有樹脂層３０をより密着させ、剥離などを防止するために、定着器１０５で加熱あるいは光照射を行って、金属微粒子含有樹脂層３０を完全に硬化させることが望ましい。   The thickness of the conductive metal layer 40 formed on the surface of the metal fine particle-containing resin layer 30 can be set to a predetermined thickness depending on the plating conditions. After the plating treatment, in order to make the base material 20 and the metal fine particle-containing resin layer 30 more closely adhere to each other and prevent peeling, the metal fine particle-containing resin layer 30 is completely cured by heating or light irradiation with the fixing device 105. It is desirable to make it.

本発明の一実施の形態によれば、金属微粒子含有樹脂粒子１０を構成する樹脂マトリックス１０ａに、その樹脂マトリックス１０ａを構成する樹脂よりも比重が小さく、樹脂マトリックス１０ａと相溶性のない、例えば油脂類などの添加物を適量添加することで、金属微粒子含有樹脂層３０の表面に、エッチングが容易で、エッチングの厚さをコントロールしやすい添加物による表面層３０ａを形成することができる。これによって、無電解めっきの析出性を向上させることができ、より均一な導体パターン層を形成することができる。   According to an embodiment of the present invention, the resin matrix 10a constituting the metal fine particle-containing resin particles 10 has a specific gravity smaller than that of the resin constituting the resin matrix 10a and is not compatible with the resin matrix 10a, for example, fats and oils. By adding an appropriate amount of an additive such as a surface layer, the surface layer 30a can be formed on the surface of the metal fine particle-containing resin layer 30 with an additive that can be easily etched and the etching thickness can be easily controlled. As a result, the deposition of electroless plating can be improved, and a more uniform conductor pattern layer can be formed.

上記したような電子写真方式を用いた製造装置および製造工程は、一般の複写機やレーザプリンタなどで使用されている技術であり、デジタル化されたデータを入力することで任意の導体パターン層を形成することができる。この技術に、一実施の形態による金属微粒子含有樹脂粒子１０を採用することで、めっきの析出性に優れた導体パターン層を形成することができる。また、一実施の形態による金属微粒子含有樹脂粒子１０の用途としては、電子回路や配線基板に限られず、その他、平坦な基材上への任意の導体パターン層の形成などの幅広い応用ができる。   The manufacturing apparatus and manufacturing process using the electrophotographic method as described above are techniques used in general copying machines and laser printers, and an arbitrary conductor pattern layer can be formed by inputting digitized data. Can be formed. By adopting the metal fine particle-containing resin particles 10 according to one embodiment in this technique, it is possible to form a conductor pattern layer having excellent plating deposition properties. Further, the use of the metal fine particle-containing resin particles 10 according to the embodiment is not limited to an electronic circuit and a wiring board, and can be applied in a wide range such as formation of an arbitrary conductor pattern layer on a flat substrate.

以下に、金属微粒子含有樹脂粒子１０および無電解めっき処理の前に行われる処理に関する具体的な実施例を示す。   Below, the specific Example regarding the process performed before the metal particle containing resin particle 10 and an electroless-plating process is shown.

（実施例１）
実施例１では、図１に示す金属微粒子含有樹脂粒子１０において、エポキシ樹脂を主体とする樹脂マトリックス１０ａに添加物として比重０．９８（２５℃）の油脂類を樹脂マトリックス１０ａの総体積の１体積％添加した金属微粒子含有樹脂粒子１０と、添加物を添加しない金属微粒子含有樹脂粒子１０の２種類の金属微粒子含有樹脂粒子１０を用いて、上述したパターン形成方法により、基材上に下地パターン層（金属微粒子含有樹脂層３０）を形成し、めっき前のエッチング処理と無電解めっき処理に関する実験を行った。 (Example 1)
In Example 1, in the resin particles 10 containing fine metal particles shown in FIG. 1, fats and oils having a specific gravity of 0.98 (25 ° C.) as an additive are added to the resin matrix 10a mainly composed of an epoxy resin to 1 of the total volume of the resin matrix 10a. By using the two kinds of metal fine particle-containing resin particles 10, that is, the metal fine particle-containing resin particles 10 to which volume% is added and the metal fine particle-containing resin particles 10 to which no additive is added, an underlying pattern is formed on the substrate by the pattern forming method described above. A layer (metal fine particle-containing resin layer 30) was formed, and experiments related to the etching process and electroless plating process before plating were performed.

ここで、双方の金属微粒子含有樹脂粒子１０には、金属微粒子１０ｂとして平均粒径が０．７μｍの銅微粒子が５０％重量の割合で含有されている。また、添加物が添加された金属微粒子含有樹脂粒子１０の平均粒径は、８．２μｍであり、添加物が添加されない金属微粒子含有樹脂粒子１０の平均粒径は、８．０μｍである。また、金属微粒子含有樹脂粒子１０を構成するエポキシ樹脂を主体とする樹脂マトリックス１０ａの比重は、１．２（２５℃）である。   Here, both metal fine particle-containing resin particles 10 contain copper fine particles having an average particle diameter of 0.7 μm as metal fine particles 10b in a proportion of 50% by weight. The average particle size of the metal fine particle-containing resin particles 10 to which the additive is added is 8.2 μm, and the average particle size of the metal fine particle-containing resin particle 10 to which no additive is added is 8.0 μm. Moreover, the specific gravity of the resin matrix 10a mainly composed of an epoxy resin constituting the metal fine particle-containing resin particles 10 is 1.2 (25 ° C.).

これら２種類の下地パターン層のそれぞれに対して、溶剤に浸漬してエッチング処理を行ったものと、エッチング処理を行わなかったものについて、無電解めっき処理を行った。
その結果、エッチング処理なしでは添加物の有無にかかわらず、めっきの析出状態が疎となった。 For each of these two types of base pattern layers, an electroless plating treatment was performed on those subjected to etching treatment by immersing in a solvent and those not subjected to the etching treatment.
As a result, the deposition state of the plating became sparse regardless of the presence or absence of the additive without the etching treatment.

一方、下地パターン層を溶剤に浸漬してエッチング処理後に無電解めっき処理を行った場合、添加物を添加した下地パターン層では、めっき析出性がよく緻密な金属導体層が形成された。また、添加物を添加しない下地パターン層では、溶剤に浸漬してエッチング処理を行っても、めっきがほとんど析出せず、めっき析出状態が疎となった。   On the other hand, when the base pattern layer was immersed in a solvent and electroless plating was performed after the etching process, a dense metal conductor layer with good plating deposition was formed in the base pattern layer to which the additive was added. In addition, in the base pattern layer to which no additive was added, even when immersed in a solvent and etching treatment was performed, plating was hardly deposited and the plating deposition state became sparse.

以上の結果から、エッチング処理を施した場合であっても、添加物を添加しない下地パターン層では、その表面に銅微粒子が充分に露出していないことがわかった。また、添加物を添加した下地パターン層では、定着器１０５によって硬化される際に、樹脂の比重よりも小さい比重の添加物が下地パターン層の表面に浮出して表面層を形成し、この表面層が溶剤によりエッチングされることで、銅微粒子の露出面積を増大させ、めっき析出性を向上させることがわかった。   From the above results, it was found that even when the etching treatment was performed, the copper fine particles were not sufficiently exposed on the surface of the base pattern layer to which no additive was added. In addition, in the base pattern layer to which the additive is added, when cured by the fixing device 105, the additive having a specific gravity smaller than the specific gravity of the resin floats on the surface of the base pattern layer to form a surface layer. It has been found that etching the surface layer with a solvent increases the exposed area of the copper fine particles and improves the plating depositability.

このように、金属微粒子含有樹脂粒子１０を構成する樹脂マトリックス１０ａに、その樹脂マトリックス１０ａを構成する樹脂よりも比重が小さく、樹脂マトリックス１０ａと相溶性のない、例えば油脂類などの添加物を適量添加することで、下地パターン層の表面にエッチングが容易で、エッチングの厚さをコントロールしやすい表面層を形成することがわかった。これによって、効率的な無電解めっき処理を行うことが可能となり、より均一な導体パターン層を形成することができる。   Thus, the resin matrix 10a constituting the metal fine particle-containing resin particles 10 has an appropriate amount of an additive such as fats and oils having a specific gravity smaller than that of the resin constituting the resin matrix 10a and not compatible with the resin matrix 10a. It has been found that by adding, a surface layer can be easily formed on the surface of the underlying pattern layer and the etching thickness can be easily controlled. Thereby, an efficient electroless plating process can be performed, and a more uniform conductor pattern layer can be formed.

（実施例２）
実施例２における金属微粒子含有樹脂粒子１０は、エポキシ樹脂を主体とする樹脂マトリックス１０ａに、平均粒径が０．７μｍの銅微粒子を５０％重量の割合で含有して構成されている。また、金属微粒子含有樹脂粒子１０の平均粒径は、８．２μｍである。 (Example 2)
The metal fine particle-containing resin particles 10 in Example 2 are configured by containing copper fine particles having an average particle diameter of 0.7 μm in a proportion of 50% by weight in a resin matrix 10a mainly composed of an epoxy resin. The average particle size of the metal fine particle-containing resin particles 10 is 8.2 μm.

この金属微粒子含有樹脂粒子１０を用いて、上述したパターン形成方法により、基材上に下地パターン層（金属微粒子含有樹脂層３０）を形成し、無電解めっき前の硬化率とめっき析出性との関係について調べた。ここで、硬化率は、示差走査熱量測定（ＤＳＣ）に基づいて算出している。なお、下地パターン層には、無電解めっき前にエッチング処理が施されている。   Using this metal fine particle-containing resin particle 10, a base pattern layer (metal fine particle-containing resin layer 30) is formed on the substrate by the above-described pattern forming method, and the curing rate and electroplating property before electroless plating are determined. I investigated the relationship. Here, the curing rate is calculated based on differential scanning calorimetry (DSC). The underlying pattern layer is subjected to an etching process before electroless plating.

示差走査熱量測定（ＤＳＣ）による測定結果およびめっき析出性から、無電解めっき前における樹脂マトリックス１０ａの硬化率が５０％以上の場合には、緻密なめっき層が形成されることがわかった。一方、硬化率が５０％未満の場合には、めっき析出状態が疎となった。   From the measurement result by differential scanning calorimetry (DSC) and plating precipitation, it was found that a dense plating layer was formed when the curing rate of the resin matrix 10a before electroless plating was 50% or more. On the other hand, when the curing rate was less than 50%, the plating deposition state became sparse.

また、下地パターン層の表面状態を調べると、樹脂マトリックスの硬化率が５０％未満の場合には、所々で銅微粒子の欠落が見られた。これはアルカリ性の無電解めっき液によって、未硬化の樹脂マトリックスが侵食されるためである。   Further, when the surface state of the base pattern layer was examined, when the curing rate of the resin matrix was less than 50%, copper fine particles were missing in some places. This is because the uncured resin matrix is eroded by the alkaline electroless plating solution.

以上の結果から、無電解めっき処理前の下地パターン層の樹脂マトリックスの硬化率を５０％以上とすることで、金属微粒子の落下を防止し、無電解めっきにおけるめっき析出性を向上できることがわかった。   From the above results, it was found that by setting the curing rate of the resin matrix of the base pattern layer before the electroless plating treatment to 50% or more, the metal fine particles can be prevented from dropping and the plating deposition in electroless plating can be improved. .

本発明の一実施の形態の金属微粒子含有樹脂粒子の断面図。Sectional drawing of the metal particle containing resin particle of one embodiment of this invention. 導体パターン層の各形成工程における断面図。Sectional drawing in each formation process of a conductor pattern layer. 導体パターン層を形成する製造装置の概要図。The schematic diagram of the manufacturing apparatus which forms a conductor pattern layer.

符号の説明Explanation of symbols

１０…金属微粒子含有樹脂粒子、１０ａ…樹脂マトリックス、１０ｂ…金属微粒子。   10 ... resin particles containing metal fine particles, 10a ... resin matrix, 10b ... metal fine particles.

Claims (4)

導体パターン形成用の金属微粒子含有樹脂粒子であって、
熱硬化性樹脂からなる樹脂マトリックスと、
前記樹脂マトリックスに分散された金属微粒子と、
前記樹脂マトリックスに含有され、前記樹脂マトリックスを構成する樹脂材料よりも比重の小さい添加物と
を具備することを特徴とする金属微粒子含有樹脂粒子。 Metal particle-containing resin particles for forming a conductor pattern,
A resin matrix made of a thermosetting resin;
Metal fine particles dispersed in the resin matrix;
Metal fine particle-containing resin particles comprising: an additive contained in the resin matrix and having a specific gravity smaller than that of a resin material constituting the resin matrix. 前記添加物の比重が、１．１以下であることを特徴とする請求項１記載の金属微粒子含有樹脂粒子。   2. The metal fine particle-containing resin particles according to claim 1, wherein the specific gravity of the additive is 1.1 or less. 前記添加物が、前記樹脂マトリックスの総体積の０．５体積％以上添加されることを特徴とする請求項１または２記載の金属微粒子含有樹脂粒子。   The metal fine particle-containing resin particles according to claim 1 or 2, wherein the additive is added in an amount of 0.5% by volume or more of the total volume of the resin matrix. 感光体上に所定のパターンの静電潜像を形成する工程と、
前記静電潜像が形成された感光体上に、樹脂マトリックスに分散して金属微粒子を含有し、かつ該樹脂マトリックスを構成する樹脂材料よりも比重の小さい添加物が添加された金属微粒子含有樹脂粒子を静電的に付着させて可視像を形成する工程と、
前記感光体上に形成された前記金属微粒子含有樹脂粒子からなる可視像を、基材上に静電的に転写する工程と、
前記基材上に転写された前記金属微粒子含有樹脂粒子を加熱または光照射により、前記樹脂マトリックスの硬化率を５０％以上に硬化し、前記基材に定着させる工程と
を具備することを特徴とする金属微粒子含有樹脂層の形成方法。 Forming an electrostatic latent image of a predetermined pattern on the photoreceptor;
Metal fine particle-containing resin in which an additive having a specific gravity smaller than that of the resin material constituting the resin matrix is added to the photosensitive member on which the electrostatic latent image is formed. Forming a visible image by electrostatically attaching particles; and
A step of electrostatically transferring a visible image formed of the metal fine particle-containing resin particles formed on the photoreceptor onto a substrate;
And curing the resin matrix-containing resin particles transferred onto the base material to 50% or more by heating or light irradiation and fixing the resin matrix to the base material. Forming a fine metal particle-containing resin layer.
JP2003435760A 2003-12-26 2003-12-26 Metal particle-containing resin particles, metal particle-containing resin layer, and method for forming metal particle-containing resin layer Expired - Fee Related JP4166686B2 (en)

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