JPH09293413A - Conductive paste - Google Patents
Conductive pasteInfo
- Publication number
- JPH09293413A JPH09293413A JP10740296A JP10740296A JPH09293413A JP H09293413 A JPH09293413 A JP H09293413A JP 10740296 A JP10740296 A JP 10740296A JP 10740296 A JP10740296 A JP 10740296A JP H09293413 A JPH09293413 A JP H09293413A
- Authority
- JP
- Japan
- Prior art keywords
- conductive powder
- powder
- conductive
- weight
- conductive paste
- 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.)
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Links
Landscapes
- Parts Printed On Printed Circuit Boards (AREA)
- Paints Or Removers (AREA)
- Conductive Materials (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、導電ペーストに関
する。TECHNICAL FIELD The present invention relates to a conductive paste.
【０００２】[0002]
【従来の技術】従来、プリント配線板、電子部品などの
配線導体形成用の導電ペーストには、通常、フェノール
樹脂、エポキシ樹脂、キシレン樹脂等の熱硬化性樹脂を
バインダとし、これに金、銀、銅、カーボンなどの導電
性粉末、必要に応じてそれらの樹脂の硬化剤、硬化促進
剤とエチルカルビトール、ブチルセロソルブなどの有機
溶剤が含まれ、これらを混練して導電ペーストとしてい
る（特公平５−１１３６５号公報、特公平６−１１８４
２号公報等）。2. Description of the Related Art Conventionally, a conductive paste for forming a wiring conductor of a printed wiring board, an electronic component, etc., usually contains a thermosetting resin such as phenol resin, epoxy resin or xylene resin as a binder, to which gold or silver is added. , Conductive powder such as copper and carbon, if necessary, a curing agent for those resins, a curing accelerator and an organic solvent such as ethyl carbitol and butyl cellosolve, which are kneaded to form a conductive paste. Japanese Patent Publication No. 5-11365, Japanese Patent Publication No. 6-1184
No. 2).
【０００３】銀粉を用いた導電ペーストは、導電性が良
好なことから印刷配線板や電子部品などの配線導体や電
極として使用されているが、基材である紙フェノール積
層板やガラスエポキシ積層板に対する接着性は良好であ
るが、銅箔に対する接着性がやや弱い欠点（銅箔上に導
電ペーストで所望のパターンを形成し硬化させた状態で
接着性が悪くない場合でも、このものを吸湿させた後は
んだ槽に浸漬させて急熱すると接着性が悪化する）があ
った。A conductive paste using silver powder is used as a wiring conductor or an electrode for printed wiring boards, electronic parts and the like because it has good conductivity, but it is a base material such as a paper phenol laminate or a glass epoxy laminate. Adhesiveness to is good, but the adhesiveness to copper foil is a little weak (even if the adhesiveness is not bad in the state where the desired pattern is formed on the copper foil with a conductive paste and hardened, it is allowed to absorb moisture After that, if it is immersed in a solder bath and heated rapidly, the adhesiveness deteriorates).
【０００４】[0004]
【発明が解決しようとする課題】請求項１記載の発明
は、保存安定性が良好で、熱硬化性、接着性及び導電性
が良好である配線導体を形成できる導電ペーストを提供
するものである。請求項２記載の発明は、請求項１記載
の発明の効果を奏し、より接着性が優れる導電ペースト
を提供するものである。請求項３記載の発明は、請求項
１又は２記載の発明の効果を奏し、さらに、導電性が優
れる導電ペーストを提供するものである。The invention according to claim 1 provides a conductive paste capable of forming a wiring conductor having good storage stability and good thermosetting property, adhesive property and conductivity. . The invention described in claim 2 provides the effect of the invention described in claim 1 and provides a conductive paste having more excellent adhesiveness. The invention according to claim 3 provides the effect of the invention according to claim 1 or 2, and further provides a conductive paste having excellent conductivity.
【０００５】[0005]
【課題を解決するための手段】本発明は、（Ａ）アルキ
ルエーテル化フェノール樹脂、（Ｂ）酸のアミン塩、
（Ｃ）導電粉及び（Ｄ）有機溶剤を含有してなる導電ペ
ーストに関する。また、本発明は、（Ｃ）導電粉が、扁
平状導電粉及び不定形状導電粉を含む複合導電粉である
前記導電ペーストに関する。また、本発明は、さらに、
（Ｅ）エポキシ樹脂を含む前記導電性ペーストに関す
る。The present invention comprises (A) an alkyl etherified phenolic resin, (B) an amine salt of an acid,
The present invention relates to a conductive paste containing (C) conductive powder and (D) organic solvent. The present invention also relates to the above-mentioned conductive paste, wherein (C) the conductive powder is a composite conductive powder containing flat conductive powder and irregular-shaped conductive powder. Further, the present invention further provides:
(E) The conductive paste containing an epoxy resin.
【０００６】[0006]
【発明の実施の形態】本発明の導電ペーストは、（Ａ）
アルキルエーテル化フェノール樹脂、（Ｂ）酸のアミン
塩、（Ｃ）導電粉及び（Ｄ）有機溶剤を必須成分とす
る。BEST MODE FOR CARRYING OUT THE INVENTION The conductive paste of the present invention is (A)
Alkyl etherified phenol resin, (B) amine salt of acid, (C) conductive powder and (D) organic solvent are essential components.
【０００７】本発明における（Ａ）アルキルエーテル化
フェノール樹脂は、アルコキシメチル基を有するフェノ
ール樹脂である。この樹脂は、例えば、フェノール類
（フェノール、クレゾール、キシレノール、レゾルシン
等）とアルデヒド（ホルムアルデヒド、アセトアルデヒ
ド、フルフラール等）とをトリエタノールアミン等のア
ルカリ触媒下に反応させて得られるレゾール型のフェノ
ール樹脂のメチロール基を、メタノール、エタノール、
プロパノール、イソプロパノール、ｎ−ブタノール、se
c−ブタノール、tert−ブタノール、ペンタノール、ヘ
キサノール等のアルコールを用いてアルキルエーテル化
することにより得ることができる。また、上記フェノー
ル類、アルデヒド及びアルコールを混合したものをアル
カリ触媒下に反応させることにより得ることもできる。The (A) alkyl etherified phenol resin in the present invention is a phenol resin having an alkoxymethyl group. This resin is, for example, a resol-type phenol resin obtained by reacting phenols (phenol, cresol, xylenol, resorcin, etc.) and aldehydes (formaldehyde, acetaldehyde, furfural, etc.) under an alkaline catalyst such as triethanolamine. Methylol group, methanol, ethanol,
Propanol, isopropanol, n-butanol, se
It can be obtained by alkyl etherification using an alcohol such as c-butanol, tert-butanol, pentanol or hexanol. It can also be obtained by reacting a mixture of the above-mentioned phenols, aldehydes and alcohols in the presence of an alkaline catalyst.
【０００８】この（Ａ）アルキルエーテル化フェノール
樹脂は、一般式〔Ｉ〕This (A) alkyl etherified phenol resin has the general formula [I]
【化１】 （式中、２つのＲ1は、各々独立してアルキル基又は水
素原子を示し、Ｒ2はアルキル基を示し、Ｒ3はメチレン
基又はジメチレンエーテル基を示し、ｍは０以上の整数
であり、ｎは１以上の整数である）で表すこともでき
る。一般式〔Ｉ〕において、Ｒ1のアルキル基は、通
常、炭素数が１〜６である。Ｒ2のアルキル基は、通
常、炭素数が１〜９である。耐熱性等の点から、ｍは１
以上の整数であることが好ましい。Embedded image (In the formula, two R 1 s each independently represent an alkyl group or a hydrogen atom, R 2 represents an alkyl group, R 3 represents a methylene group or a dimethylene ether group, and m is an integer of 0 or more. And n is an integer of 1 or more). In the general formula [I], the alkyl group of R 1 usually has 1 to 6 carbon atoms. The alkyl group of R 2 usually has 1 to 9 carbon atoms. In terms of heat resistance, m is 1
It is preferably an integer equal to or greater than the above.
【０００９】本発明における（Ａ）アルキルエーテル化
フェノール樹脂は、重量平均分子量（ＧＰＣ測定、標準
ポリスチレン換算）が、通常、１０，０００〜１００，
０００である。The weight average molecular weight (GPC measurement, standard polystyrene conversion) of the (A) alkyl etherified phenol resin in the present invention is usually 10,000 to 100,
000.
【００１０】本発明における（Ａ）アルキルエーテル化
フェノール樹脂のアルキルエーテル化度は、接着性、硬
化性、電気特性等の点から、１０〜９０％であることが
好ましく、２０〜８０％であることがより好ましい。こ
のアルキルエーテル化度（平均値）は、例えば、アルキ
ルエーテル化フェノール樹脂のメチロール基をアセチル
化した樹脂とアセチル化前の樹脂とを比較（ＮＭＲ等）
することにより求めることができる。一般式〔Ｉ〕で表
される樹脂においては、アルキルエーテル化度は、Ｒ1
について、（アルキル基の数）／（水素原子の数＋アル
キル基の数）で表すことができる。The degree of alkyl etherification of the (A) alkyl etherified phenol resin in the present invention is preferably 10 to 90%, and preferably 20 to 80%, from the viewpoints of adhesiveness, curability, electrical characteristics and the like. Is more preferable. This degree of alkyl etherification (average value) is obtained by comparing, for example, a resin obtained by acetylating a methylol group of an alkyl etherified phenol resin and a resin before acetylation (NMR etc.).
It can be obtained by doing. In the resin represented by the general formula [I], the alkyl etherification degree is R 1
Can be expressed by (number of alkyl groups) / (number of hydrogen atoms + number of alkyl groups).
【００１１】本発明における（Ｂ）酸のアミン塩として
は、例えば、ジノニルナフタレンジスルホン酸のアミン
塩、ドデシルベンゼンスルホン酸のアミン塩、Ｐ−トル
エンスルホン酸のアミン塩、リン酸のアミン塩などが挙
げられる。アミンとしては、例えば、トリエチルアミ
ン、ジエチルアミン、モノエチルアミン、トリエタノー
ルアミン、ジエタノールアミン、モノエタノールアミ
ン、１−アミノ−２−プロパノール、２−ジメチルアミ
ノエタノール等が挙げられる。この（Ｂ）酸のアミン塩
は、保存安定性等の点から、６５℃未満では酸を放出せ
ず、６５℃を超えると解離して酸を放出するものが好ま
しい。（Ｂ）酸のアミン塩の配合量は、（Ａ）成分１０
０重量部に対して、０．０５〜１０重量部とすることが
好ましい。この配合量が０．０５重量部未満では、硬化
性が低下し、作業性が悪くなる傾向がある。また、１０
重量部を超えると、導電性が悪くなる傾向がある。Examples of the amine salt of the acid (B) in the present invention include amine salts of dinonylnaphthalenedisulfonic acid, amine salts of dodecylbenzenesulfonic acid, amine salts of P-toluenesulfonic acid and amine salts of phosphoric acid. Is mentioned. Examples of the amine include triethylamine, diethylamine, monoethylamine, triethanolamine, diethanolamine, monoethanolamine, 1-amino-2-propanol, 2-dimethylaminoethanol and the like. From the viewpoint of storage stability and the like, it is preferable that the amine salt of the acid (B) does not release the acid below 65 ° C, and dissociates to release the acid above 65 ° C. The compounding amount of the amine salt of the acid (B) is 10 parts of the component (A).
It is preferably 0.05 to 10 parts by weight with respect to 0 parts by weight. If the amount is less than 0.05 parts by weight, the curability tends to be low and the workability tends to be poor. Also, 10
If it exceeds the weight part, the conductivity tends to deteriorate.
【００１２】本発明における（Ｃ）導電粉としては、特
に制限なく公知のものを使用できるが、導電性等の点か
ら、扁平状導電粉及び不定形状導電粉を含む複合導電粉
であることが好ましい。また、複合導電粉の場合、扁平
状導電粉のアスペクト比は、５〜２０であることが導電
性等の点から好ましく、不定形状導電粉のアスペクト比
は、１〜５であることが導電性等の点から好ましい。ま
た、その平均粒径は、扁平状導電粉では、５〜２０μｍ
であることが、印刷性、導電性等の点から好ましく、不
定形状導電粉では、１〜２０μｍであることが、印刷
性、導電性等の点から好ましい。As the conductive powder (C) in the present invention, known powders can be used without particular limitation, but from the viewpoint of conductivity, it is a composite conductive powder containing flat conductive powder and irregular-shaped conductive powder. preferable. In the case of the composite conductive powder, the flat conductive powder preferably has an aspect ratio of 5 to 20 from the viewpoint of conductivity, and the irregular conductive powder has an aspect ratio of 1 to 5. Etc. are preferable. The average particle size of the flat conductive powder is 5 to 20 μm.
From the viewpoints of printability, conductivity, etc., it is preferable for the irregular-shaped conductive powder to be 1 to 20 μm from the viewpoints of printability, conductivity, etc.
【００１３】本発明における（Ｃ）導電粉のアスペクト
比とは、導電粉の粒子の長径と短径の比率（長径／短
径）をいう。本発明においては、硬化性樹脂中に導電粉
の粒子をよく混合し、静置して粒子を沈降させるととも
にそのまま樹脂を硬化させ、得られた硬化物を垂直方向
に切断し、その切断面に現れる粒子の形状を電子顕微鏡
で拡大して観察し、少なくとも１００の粒子について、
一つ一つの粒子の長径／短径を求め、それらの平均値を
もってアスペクト比とする。ここで、短径とは、前記切
断面に現れる粒子について、その粒子の外側に接する二
つの平行線の組合せを粒子を挾むように選択し、それら
の組合せのうち最短間隔になる二つの平行線の距離であ
る。また、長径とは、前記短径を決する平行線に直角方
向の二つの平行線であって、粒子の外側に接する二つの
平行線の組合せのうち、最長間隔になる二つの平行線の
距離である。これらの四つの線で形成される長方形は、
粒子がちょうどその中に納まる大きさとなる。The aspect ratio of the conductive powder (C) in the present invention means the ratio of the major axis and the minor axis of the particles of the conductive powder (major axis / minor axis). In the present invention, the particles of the conductive powder are mixed well in the curable resin, the particles are allowed to settle and the resin is cured as it is, the obtained cured product is cut in the vertical direction, and the cut surface is cut. The appearance of particles is magnified and observed with an electron microscope, and for at least 100 particles,
The major axis / minor axis of each particle is obtained, and the average value thereof is used as the aspect ratio. Here, the minor axis is defined as a combination of two parallel lines contacting the outside of the particle with respect to the particle appearing on the cut surface so as to sandwich the particle. Distance. Further, the major axis is the distance between two parallel lines that are the longest distance among the two parallel lines that are in contact with the outside of the particle and are the two parallel lines that are perpendicular to the parallel lines that determine the minor axis. is there. The rectangle formed by these four lines is
The particles are sized just to fit inside.
【００１４】扁平状導電粉とは、形状としてほぼ平坦で
微細な小片からなる導電粉で、例えば、りん片状導電粉
等が挙げられる。不定形状導電粉とは、扁平状以外の形
状の導電粉で、球状、立方体状、四面体状、塊状、略球
状等と呼ばれる粉体、こんぺい糖のように表面に突起の
ある形状の粉体、これらの混合物等、種々の導電粉のこ
とである。種々の形状の導電粉を含むものとしては、例
えば、還元銀粉等が挙げられる。The flat conductive powder is a conductive powder composed of small pieces that are substantially flat in shape, and examples thereof include flaky conductive powder. Irregularly shaped conductive powder is a conductive powder having a shape other than flat, and is called spherical, cubic, tetrahedral, lumpy, roughly spherical, etc., powder with a projection on the surface such as sucrose. Various conductive powders such as a body and a mixture thereof. Examples of materials containing various shapes of conductive powder include reduced silver powder.
【００１５】アスペクト比が５〜２０の導電粉として
は、多くの場合、扁平状導電粉が該当し、この他に樹枝
状（デンドライト状とも呼ばれる）等と呼ばれる形状の
ものがあり、このものも併用して用いることができる。
アスペクト比が５０〜２０の導電粉としては、高導電性
のペーストが得られるという点から、アスペクト比が７
以上であることが好ましく、アスペクト比が８以上であ
ることがより好ましく、アスペクト比が１０以上である
ことが特に好ましい。In many cases, the conductive powder having an aspect ratio of 5 to 20 corresponds to a flat conductive powder, and in addition to this, there is a shape called a dendritic shape (also called a dendrite shape). It can be used in combination.
The conductive powder having an aspect ratio of 50 to 20 has an aspect ratio of 7 from the viewpoint that a highly conductive paste can be obtained.
The aspect ratio is more preferably, the aspect ratio is more preferably 8 or more, and the aspect ratio is particularly preferably 10 or more.
【００１６】以上のことから、本発明における（Ｃ）導
電粉は、高導電性、導電ペーストの粘度等の点から、ア
スペクト比が７以上の扁平状導電粉が好ましく、アスペ
クト比が８以上の扁平状導電粉がより好ましく、アスペ
クト比が１０以上の扁平状導電粉が特に好ましい。ここ
でいう平均粒子径は、レーザー散乱型粒度分布測定装置
により測定することができる。本発明においては、前記
装置として、マスターサイザー（マルバン社製）を用い
て測定した。From the above, the conductive powder (C) in the present invention is preferably a flat conductive powder having an aspect ratio of 7 or more, and an aspect ratio of 8 or more, from the viewpoints of high conductivity, viscosity of the conductive paste and the like. Flat conductive powder is more preferable, and flat conductive powder having an aspect ratio of 10 or more is particularly preferable. The average particle diameter here can be measured by a laser scattering type particle size distribution measuring device. In the present invention, Mastersizer (manufactured by Malvan Co., Ltd.) was used as the device for measurement.
【００１７】アスペクト比が１〜５の導電粉としては、
前記した不定形状導電粉等が挙げられる。また、アスペ
クト比が１〜５の導電粉としては、高導電性のペースト
が得られるという点で、アスペクト比が４以下であるこ
とが好ましく、アスペクト比が３以下であることがより
好ましく、アスペクト比が２．５以下であることがより
好ましい。As the conductive powder having an aspect ratio of 1 to 5,
The above-mentioned irregular-shaped conductive powder and the like can be mentioned. Further, as the conductive powder having an aspect ratio of 1 to 5, an aspect ratio of 4 or less is preferable, and an aspect ratio of 3 or less is more preferable, since a highly conductive paste can be obtained. More preferably, the ratio is 2.5 or less.
【００１８】本発明における（Ｃ）導電粉の材質として
は、銀、銀合金等が、導電性、耐酸化性等の点で好まし
いものとして挙げられる。上記の銀合金としては、パラ
ジウム（例えば、銀合金中に１〜５重量％程度のもの
等）、白金（例えば、銀合金中に１重量％程度のもの
等）などとの合金を使用することが好ましい。また、上
記の銀粉を作製する方法の１つとしてい液中還元法が挙
げられ、この方法により作製される銀粉は、平均粒径が
数μｍの微粉末であることから、工業的な生産方法とし
て広く利用されている。この液中還元法とは、銀を酸で
溶解した後、これをアルカリで中和し、次いで、ホルマ
リン、デンプン等の還元剤を添加し、液中で還元して微
粉末とする方法であり、これにより得られる粉末を還元
銀粉といい、その形状は、塊状に近いが、一定の形状で
はなく不規則な形状をしている。この還元銀粉は、本発
明において、不定形状導電粉として使用することができ
る。As the material of the (C) conductive powder in the present invention, silver, silver alloys and the like are preferable as the materials in terms of conductivity, oxidation resistance and the like. As the silver alloy, an alloy with palladium (for example, about 1 to 5% by weight in the silver alloy), platinum (for example, about 1% by weight in the silver alloy, etc.) should be used. Is preferred. Further, one of the methods for producing the above-mentioned silver powder is an in-liquid reduction method. Since the silver powder produced by this method is a fine powder having an average particle diameter of several μm, it is an industrial production method. Is widely used as. The in-liquid reduction method is a method of dissolving silver with an acid, neutralizing it with an alkali, then adding a reducing agent such as formalin and starch, and reducing it in the solution to obtain fine powder. The powder thus obtained is called reduced silver powder, and its shape is close to a lump, but is not a constant shape but an irregular shape. This reduced silver powder can be used as an irregularly shaped conductive powder in the present invention.
【００１９】また、本発明における（Ｃ）導電粉として
は、銀又は銀合金以外の導電体が、銀又は銀合金で被覆
されている銀被覆導電体粉であってもよい。The (C) conductive powder in the present invention may be a silver-coated conductive powder in which a conductor other than silver or a silver alloy is coated with silver or a silver alloy.
【００２０】不定形状導電粉としては、上記したように
銀被覆導電体粉であってもよいが、被覆される導電体と
しては、銀又は銀合金よりも硬度の高い導電体であるこ
とが好ましい。このような導電体としては、例えば、Ｃ
ｏ、Ｎｉ、Ｃｒ、Ｃｕ、Ｗ等の金属粉又はこれらの合金
粉を用いることができるが、この中で銅粉又は銅合金粉
を用いることが好ましい。これらを使用することによ
り、電気回路を加圧したとき、扁平状の銀粉又は銀合金
粉に不定形状導電粉がくい込み、電気回路の導電性が高
くなる傾向がある。上記の銅合金粉としては、例えば、
銅とスズ、銅と亜鉛等の合金粉が挙げられる。The irregular-shaped conductive powder may be a silver-coated conductor powder as described above, but the conductor to be coated is preferably a conductor having a hardness higher than that of silver or a silver alloy. . As such a conductor, for example, C
Metal powders such as o, Ni, Cr, Cu, and W or alloy powders thereof can be used, and among these, copper powder or copper alloy powder is preferably used. When these are used, when the electric circuit is pressurized, the irregular-shaped conductive powder is bitten into the flat silver powder or the silver alloy powder, and the electric circuit tends to have high conductivity. The copper alloy powder, for example,
Examples include alloy powders of copper and tin, copper and zinc, and the like.
【００２１】不定形状導電粉の表面に銀を被覆する方法
としては、例えば、置換めっき、電気めっき、無電解め
っき等の方法が挙げられ、その中でも、不定形状導電粉
と銀との付着力が高いこと及びランニングコストが安価
であることから、置換めっき法で被覆することが好まし
い。不定形状導電粉の表面への銀の被覆量は、コスト、
電食性の抑制効果等の点から、不定形状導電粉１００重
量部に対して、３〜５０重量部であることが好ましく、
３〜２０重量部であることがより好ましい。Examples of the method for coating the surface of the irregular-shaped conductive powder with silver include methods such as displacement plating, electroplating, and electroless plating. Among them, the adhesive force between the irregular-shaped conductive powder and silver is Since it is expensive and the running cost is low, it is preferable to perform the coating by the displacement plating method. The amount of silver coating on the surface of the irregularly shaped conductive powder is
From the viewpoint of the effect of suppressing electrolytic corrosion, it is preferably 3 to 50 parts by weight with respect to 100 parts by weight of the irregular-shaped conductive powder.
It is more preferably 3 to 20 parts by weight.
【００２２】前記した、いずれかの銀被覆導電体粉を用
いることにより、耐マイグレーション性が優れたものと
なる傾向がある。また、銀被覆導電体粉は、導電体の一
部が露出したもの（露出被覆導電体粉と略す）を用いる
こともできる。また、露出被覆導電体粉は、扁平状導電
体粉と不定形状導電粉のそれぞれに使用することができ
る。導電粉の露出面積は、良好な導電性を得る点から、
５０％以下であることが好ましく、２０％以下であるこ
とがより好ましい。By using any of the silver-coated conductor powders described above, the migration resistance tends to be excellent. Moreover, as the silver-coated conductor powder, one in which a part of the conductor is exposed (abbreviated as exposed-cover conductor powder) can be used. The exposed coated conductor powder can be used for each of the flat conductor powder and the irregular-shaped conductor powder. The exposed area of the conductive powder, from the point of obtaining good conductivity,
It is preferably 50% or less, and more preferably 20% or less.
【００２３】置換めっき後の球状の銀被覆銅粉又は銀被
覆銅合金粉は、接触点が少ないため抵抗が高くなりやす
く、そのため、置換めっき後の球状の銀被覆銅粉又は銀
被覆銅合金粉に衝撃を与え、粒子の形状を扁平状又はア
スペクト比を６以上に変形させることが好ましい。粒子
の形状を変形させる方法としては、具体的には、ボール
ミル、振動ミル等の方法が挙げられる。Since spherical silver-coated copper powder or silver-coated copper alloy powder after displacement plating has few contact points, the resistance tends to be high. Therefore, spherical silver-coated copper powder or silver-coated copper alloy powder after displacement plating is used. It is preferable that the particles are impacted to deform the particles into a flat shape or have an aspect ratio of 6 or more. Specific examples of the method for deforming the shape of the particles include a ball mill and a vibration mill.
【００２４】複合導電粉を使用する場合の扁平状導電粉
及び不定形状導電粉の配合割合は、導電性を高める点か
ら、扁平状導電粉及び不定形状導電粉の総量１００重量
部として、扁平状導電粉が、９５〜５０重量部とするこ
とが好ましく、８０〜６０重量部とすることがより好ま
しい。また、不定形状導電粉は、５〜５０重量部とする
ことが好ましく、２０〜４０重量部とすることがより好
ましい。In the case where the composite conductive powder is used, the mixing ratio of the flat conductive powder and the irregular conductive powder is 100% by weight of the flat conductive powder and the irregular conductive powder in order to improve conductivity. The conductive powder is preferably 95 to 50 parts by weight, more preferably 80 to 60 parts by weight. Further, the irregular-shaped conductive powder is preferably 5 to 50 parts by weight, more preferably 20 to 40 parts by weight.
【００２５】本発明における（Ｃ）導電粉の配合量は、
導体の抵抗、経済性、接着性等の点から、導電ペースト
中の（Ｄ）成分を除いた成分の総量１００重量部に対し
て、８５〜９３重量部とすることが好ましく、８７〜９
０重量部とすることがより好ましい。The compounding amount of the (C) conductive powder in the present invention is
From the viewpoint of resistance, economy, adhesiveness, etc. of the conductor, it is preferable that the total amount of the components excluding the component (D) in the conductive paste is 100 parts by weight, and 85 to 93 parts by weight, and 87 to 9 parts by weight.
More preferably, it is 0 parts by weight.
【００２６】本発明における（Ｄ）有機溶剤としては、
特に制限はないが、例えば、テルピネオール、エチルカ
ルビトール、カルビトールアセテート、ブチルセロソル
ブ等が挙げられる。（Ｄ）有機溶剤の配合量は、導電
性、接着性、印刷性等の点から、（Ａ）成分及び（Ｅ）
成分の総量１００重量部に対して、５０〜５００重量部
とすることが好ましく、１００〜４００重量部とするこ
とがより好ましい。As the organic solvent (D) in the present invention,
Although not particularly limited, examples thereof include terpineol, ethyl carbitol, carbitol acetate, butyl cellosolve and the like. The blending amount of the organic solvent (D) is such that the components (A) and (E) are selected from the viewpoints of conductivity, adhesiveness, printability, etc.
The total amount of the components is preferably 50 to 500 parts by weight, more preferably 100 to 400 parts by weight, based on 100 parts by weight.
【００２７】本発明の導電ペーストには、硬化性、接着
性等の点から、さらに、（Ｅ）エポキシ樹脂を含有する
ことが好ましい。本発明における（Ｅ）エポキシ樹脂と
しては、特に制限なく公知のものを使用できるが、例え
ば、ビスフェノールＡ型エポキシ樹脂、ノボラック型エ
ポキシ樹脂等が挙げられる。（Ｅ）エポキシ樹脂を使用
する場合、その使用量は、硬化性、樹脂性等の点から、
（Ａ）成分１００重量部に対して、５〜１００重量部と
することが好ましい。The conductive paste of the present invention preferably further contains (E) an epoxy resin from the viewpoint of curability, adhesiveness and the like. As the (E) epoxy resin in the present invention, known resins can be used without particular limitation, and examples thereof include bisphenol A type epoxy resin and novolac type epoxy resin. (E) When an epoxy resin is used, the amount used is in terms of curability, resinity, etc.
The amount is preferably 5 to 100 parts by weight with respect to 100 parts by weight of the component (A).
【００２８】本発明の導電ペーストには、２−エチルメ
チルイミダゾール等の有機質の接着剤成分の硬化剤、ベ
ンゾチアゾール、ベンゾイミダゾール等の腐食抑制剤、
微小黒鉛粉末、チタン系又はシラン系のカップリング剤
などを添加してもよい。The conductive paste of the present invention includes a hardening agent for organic adhesive components such as 2-ethylmethylimidazole, a corrosion inhibitor such as benzothiazole and benzimidazole,
Fine graphite powder, titanium-based or silane-based coupling agent, etc. may be added.
【００２９】本発明の導電ペーストは、前記した各成分
を、例えば、三本ロール、らいかい機等で均一に分散さ
せることにより製造することができる。The conductive paste of the present invention can be produced by uniformly dispersing each of the above-mentioned components by, for example, a three-roll mill, a ladle machine or the like.
【００３０】[0030]
【実施例】以下、本発明を実施例によって説明する。The present invention will be described below with reference to examples.
【００３１】製造例１ ブタノール２９６ｇ（４．０モル）、キシレン２０ｇ及
びクレゾール１０８ｇ（１．０モル）と８０重量％純度
のホルムアルデヒド１１２．５ｇ（３．０モル）に、ト
リエタノールアミン１４．９ｇ（０．１モル）を投入
し、８５℃で１時間、次いで、１０５℃で還流脱水をし
ながら３時間、次いで、１２５℃で脱溶剤しながら１２
時間反応させた後、カルビトールにて希釈し、固型分が
５５重量％、重量平均分子量が３０，０００、ブトキシ
化度が７０％のブチルエーテル基含有レゾール型フェノ
ール樹脂（Ｐ−１）を得た。Production Example 1 296 g (4.0 mol) of butanol, 20 g of xylene and 108 g (1.0 mol) of cresol, 112.5 g (3.0 mol) of formaldehyde having a purity of 80% by weight, and 14.9 g of triethanolamine. (0.1 mol) and charged at 85 ° C for 1 hour, then refluxed and dehydrated at 105 ° C for 3 hours, and then desolvated at 125 ° C for 12 hours.
After reacting for a time, it is diluted with carbitol to obtain a butyl ether group-containing resol-type phenol resin (P-1) having a solid content of 55% by weight, a weight average molecular weight of 30,000 and a butoxylation degree of 70%. It was
【００３２】実施例１ 製造例１で得た（Ｐ−１）８０重量部とビスフェノール
Ａ型エポキシ樹脂（油化シェルエポキシ製、商品名エピ
コート１００４）２０重量部を、予め加温溶解させた
後、室温に冷却したものに、Ｐ−トルエンスルホン酸の
アミン塩（楠本化成製、ＮＡＣＵＲＥ２５００Ｘ）２重
量部、エチルカルビトール２０重量部、ブチルセロソル
ブ２０重量部を加え、均一に混合して樹脂組成物とし
た。一方、平均粒径８μｍ、アスペクト比１０のりんぺ
ん状銀粉（徳力化学研究所製、ＴＣＧ−１）１９５重量
部と平均粒径７μｍの不定形状銀粉１０５重量部を樹脂
組成物に添加し、撹拌らいかい機及び三本ロールで均一
に分散して導電ペーストとした（導電粉の含有率は６７
重量％）。Example 1 80 parts by weight of (P-1) obtained in Production Example 1 and 20 parts by weight of a bisphenol A type epoxy resin (manufactured by Yuka Shell Epoxy, trade name Epicoat 1004) were heated and dissolved in advance. After cooling to room temperature, 2 parts by weight of an amine salt of P-toluenesulfonic acid (Kusumoto Kasei, NACURE 2500X), 20 parts by weight of ethyl carbitol, and 20 parts by weight of butyl cellosolve were added and uniformly mixed to obtain a resin composition. did. On the other hand, 195 parts by weight of phosphorus-like silver powder having an average particle size of 8 μm and an aspect ratio of 10 (manufactured by Tokuriki Kagaku Kenkyusho, TCG-1) and 105 parts by weight of irregularly shaped silver powder having an average particle size of 7 μm were added to the resin composition and stirred. Conductive paste was uniformly dispersed with a raider and a three-roll mill (content of conductive powder was 67
weight%).
【００３３】導電ペーストの保存安定性を、粘度の経時
変化で評価し、粘度の経時変化率が±２０％以内の日数
をその導電ペーストの可使時間とした。このペーストの
可使時間は、３０℃中に保存した場合、９７日間であっ
た。The storage stability of the conductive paste was evaluated by the change with time of the viscosity, and the number of days when the change rate of the viscosity with time was within ± 20% was defined as the pot life of the conductive paste. The pot life of this paste was 97 days when stored at 30 ° C.
【００３４】このペーストを銅箔貼り紙フェノール積層
板（日立化成工業(株)製、ＭＣＬ−４３７ＳＲＤ）上
に、図１に示したテストパターンの形状にスクリーン印
刷した後、加熱硬化させた。基板材料は、厚さが３５μ
ｍの銅箔をラミネートした紙フェノール積層板（日立化
成工業(株)製、ＭＣＬ−４３７ＳＲＤ、厚さ：１．６m
m）である。なお、加熱硬化条件は、６０℃で３０分間
加熱し、次いで、１４５℃で３０分間加熱した。このも
のの比抵抗は、６５μΩ・cmであった。この配線板の冷
熱衝撃試験を実施した結果、比抵抗の変化率は５％であ
った。This paste was screen-printed on a copper foil-coated paper phenol laminate (MCL-437SRD manufactured by Hitachi Chemical Co., Ltd.) in the shape of the test pattern shown in FIG. 1 and then cured by heating. The substrate material has a thickness of 35μ
Paper phenol laminated board laminated with m copper foil (manufactured by Hitachi Chemical Co., Ltd., MCL-437SRD, thickness: 1.6 m
m). The heat curing conditions were heating at 60 ° C. for 30 minutes and then at 145 ° C. for 30 minutes. The specific resistance of this product was 65 μΩ · cm. As a result of the thermal shock test of this wiring board, the rate of change in specific resistance was 5%.
【００３５】また、銅箔をラミネートした紙フェノール
積層板の銅箔上に、５０mm角に厚さ３０μｍのベタ面を
印刷、硬化させた後、４０℃で相対湿度９５％の恒温恒
湿糟に１２０時間放置し、次いで、２６０℃のはんだ糟
に５秒間浸漬させる吸湿ディップ試験を実施した後、１
mm角（１０×１０ヶ）にカッタをいれ、セロテープで引
きはがすクロスカット試験を実施したところ、はく離は
ゼロであった。なお、冷熱試験条件は、１２５℃で３０
分間〜−６５℃で３０分間を１サイクルとし、これを１
００サイクル行った。Also, after printing and curing a solid surface having a thickness of 30 μm in a 50 mm square on a copper foil of a paper phenol laminated plate laminated with a copper foil, a constant temperature and constant humidity container having a relative humidity of 95% at 40 ° C. was formed. After leaving it for 120 hours and then conducting a moisture absorption dip test of immersing it in a solder bath at 260 ° C. for 5 seconds, 1
When a crosscut test was carried out in which a cutter was placed on mm squares (10 × 10 pieces) and peeled off with cellophane tape, no peeling was found. The cold heat test condition is 125 ° C. and 30
Minute to -65 ° C for 30 minutes as one cycle,
00 cycles were performed.
【００３６】実施例２ 製造例１で得た（Ｐ−１）８０重量部と実施例１と同じ
エポキシ樹脂２０重量部を、予め加温溶解させた後、室
温に冷却したものに、リン酸のアミン塩（楠本化成製、
ＮＡＣＵＲＥ４１６７Ｘ）２重量部、エチルカルビトー
ル２０重量部、ブチルセロソルブ２０重量部を加え、均
一に混合して樹脂組成物とした。一方、実施例１と同じ
りん片状銀粉２７３重量部と実施例１と同じ不定形状銀
粉１４７重量部を、この樹脂組成物１４８重量部に添加
し、均一に混合分散して導電ペーストとした（導電粉の
含有量は７４重量％）。Example 2 80 parts by weight of (P-1) obtained in Production Example 1 and 20 parts by weight of the same epoxy resin as in Example 1 were dissolved in advance by heating and then cooled to room temperature. Amine salt of (Kusumoto Kasei,
NACURE 4167X) 2 parts by weight, ethyl carbitol 20 parts by weight, and butyl cellosolve 20 parts by weight were added and uniformly mixed to obtain a resin composition. On the other hand, 273 parts by weight of the same flaky silver powder as in Example 1 and 147 parts by weight of the irregularly shaped silver powder as in Example 1 were added to 148 parts by weight of this resin composition and uniformly mixed and dispersed to obtain a conductive paste ( The content of conductive powder is 74% by weight).
【００３７】この導電ペーストを用いて、実施例１と同
様にして、保存安定性を評価した結果、３０℃での可使
時間は９４日間であった。また、実施例１と同様にして
配線板を作製し、その特性を評価した結果、比抵抗は、
３７μΩ・cmであった。また、実施例１と同様にして、
この配線板の冷熱衝撃試験を実施した結果、比抵抗の変
化率は４％であり、吸湿ディップ試験後のクロスカット
試験の結果は、はく離ゼロであった。Using this conductive paste, the storage stability was evaluated in the same manner as in Example 1. As a result, the pot life at 30 ° C. was 94 days. A wiring board was prepared in the same manner as in Example 1 and its characteristics were evaluated.
It was 37 μΩ · cm. Also, in the same manner as in Example 1,
As a result of the thermal shock test of this wiring board, the rate of change in specific resistance was 4%, and the result of the cross-cut test after the moisture absorption dip test was zero delamination.
【００３８】比較例１ 製造例１で得た（Ｐ−１）８０重量部と実施例１と同じ
エポキシ樹脂２０重量部を、予め加温溶解させた後室温
に冷却したものにシュウ酸２重量部、エチルカルビトー
ル２０重量部、ブチルセロソルブ２０重量部を加え、均
一に混合して樹脂組成物とした。一方、実施例１と同じ
りんぺん状銀粉１９５重量部と実施例１と同じ不定形状
銀粉１０５重量部をこの樹脂組成物に添加し、撹拌らい
かい機及び三本ロールで均一に分散して導電ペーストと
した（導電粉の含有量は６８重量％）。Comparative Example 1 80 parts by weight of (P-1) obtained in Production Example 1 and 20 parts by weight of the same epoxy resin as in Example 1 were dissolved in advance by heating and then cooled to room temperature. Parts, 20 parts by weight of ethyl carbitol and 20 parts by weight of butyl cellosolve were added and uniformly mixed to obtain a resin composition. On the other hand, 195 parts by weight of the same phosphorus-like silver powder as in Example 1 and 105 parts by weight of the same irregularly shaped silver powder as in Example 1 were added to this resin composition and uniformly dispersed with a stirrer and a three-roll mill to conduct electricity. The paste was used (content of conductive powder was 68% by weight).
【００３９】このペーストを用いて、実施例１と同様に
して、保存安定性を評価した結果、３０℃での可使時間
は２５日間であった。また、実施例１と同様にして配線
板を作製し、その特性を評価した結果、比抵抗は、６７
μΩ・cmであった。また、実施例１と同様にして、この
配線板の冷熱衝撃試験を実施した結果、比抵抗の変化率
は４％であり、吸湿ディップ試験後のクロスカット試験
の結果は、はく離ゼロであった。Using this paste, the storage stability was evaluated in the same manner as in Example 1. As a result, the pot life at 30 ° C. was 25 days. A wiring board was prepared in the same manner as in Example 1, and its characteristics were evaluated. As a result, the specific resistance was 67.
μΩ · cm. Further, as a result of performing a thermal shock test on this wiring board in the same manner as in Example 1, the rate of change in resistivity was 4%, and the result of the crosscut test after the moisture absorption dip test was zero delamination. .
【００４０】[0040]
【発明の効果】請求項１記載の導電ペーストは、保存安
定性が良好で、熱硬化性、接着性及び導電性が良好であ
る配線導体を形成できる。請求項２記載の導電ペースト
は、請求項１記載の発明の効果を奏し、より接着性が優
れる。請求項３記載の導電ペーストは、請求項１又は２
記載の発明の効果を奏し、より導電性が優れる。The conductive paste according to the first aspect of the present invention can form a wiring conductor having good storage stability and good thermosetting, adhesiveness and conductivity. The conductive paste according to claim 2 has the effect of the invention according to claim 1, and is more excellent in adhesiveness. The conductive paste according to claim 3 is the conductive paste according to claim 1 or 2.
The effect of the described invention is exhibited and the conductivity is more excellent.
【図１】紙フェノール積層板に導電ペーストを印刷した
状態を示す平面図である。FIG. 1 is a plan view showing a state in which a conductive paste is printed on a paper phenol laminated plate.
Claims (3)
脂、（Ｂ）酸のアミン塩、（Ｃ）導電粉及び（Ｄ）有機
溶剤を含有してなる導電ペースト。1. A conductive paste containing (A) alkyl etherified phenolic resin, (B) amine salt of acid, (C) conductive powder and (D) organic solvent.
形状導電粉を含む複合導電粉である請求項１記載の導電
ペースト。2. The conductive paste according to claim 1, wherein the conductive powder (C) is a composite conductive powder containing flat conductive powder and irregular-shaped conductive powder.
項１又は２記載の導電性ペースト。3. The conductive paste according to claim 1, further comprising (E) an epoxy resin.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10740296A JP4019440B2 (en) | 1996-04-26 | 1996-04-26 | Conductive paste |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10740296A JP4019440B2 (en) | 1996-04-26 | 1996-04-26 | Conductive paste |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH09293413A true JPH09293413A (en) | 1997-11-11 |
| JP4019440B2 JP4019440B2 (en) | 2007-12-12 |
Family
ID=14458244
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP10740296A Expired - Lifetime JP4019440B2 (en) | 1996-04-26 | 1996-04-26 | Conductive paste |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP4019440B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103210452A (en) * | 2010-11-16 | 2013-07-17 | 旭硝子株式会社 | Conductive paste and base with conductive film |
-
1996
- 1996-04-26 JP JP10740296A patent/JP4019440B2/en not_active Expired - Lifetime
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103210452A (en) * | 2010-11-16 | 2013-07-17 | 旭硝子株式会社 | Conductive paste and base with conductive film |
| JP5880441B2 (en) * | 2010-11-16 | 2016-03-09 | 旭硝子株式会社 | Conductive paste and substrate with conductive film |
Also Published As
| Publication number | Publication date |
|---|---|
| JP4019440B2 (en) | 2007-12-12 |
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