JP2005276573A - Photosensitive conductive paste and conductor pattern formed using it - Google Patents

Photosensitive conductive paste and conductor pattern formed using it Download PDF

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JP2005276573A
JP2005276573A JP2004086592A JP2004086592A JP2005276573A JP 2005276573 A JP2005276573 A JP 2005276573A JP 2004086592 A JP2004086592 A JP 2004086592A JP 2004086592 A JP2004086592 A JP 2004086592A JP 2005276573 A JP2005276573 A JP 2005276573A
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conductive paste
photosensitive conductive
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JP4411113B2 (en
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Kazunobu Fukushima
和信 福島
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Taiyo Holdings Co Ltd
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Taiyo Ink Mfg Co Ltd
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Abstract

<P>PROBLEM TO BE SOLVED: To provide a photosensitive conductive paste which is superior in forming characteristics of a highly precise fine pattern, and in such storage stability that conductive powder such as silver powder is not sedimented even if it is stored over a long period. <P>SOLUTION: The photosensitive conductive paste is a paste containing (A) the conductive powder, (B) an organic binder, (C) a photopolymerizable monomer, (D) a photopolymerization initiator, and (E) a sedimentation inhibitor, and the sedimentation inhibitor (E) is a modified urea solution (isocyanate monomer or reaction product of these aducts and organic amine). <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

本発明は、感光性導電ペースト及びそれを用いて形成した導電体パターンに関し、特に、フォトリソグラフィー技術にて形成されるパターン塗膜の焼成により得られる導電体の材料として好適に用いられる感光性導電ペーストに関するものである。   The present invention relates to a photosensitive conductive paste and a conductor pattern formed using the same, and in particular, a photosensitive conductive material suitably used as a conductor material obtained by baking a pattern coating film formed by a photolithography technique. It relates to paste.

従来、プラズマディスプレイパネルやCCDセンサ、イメージセンサ等の部品において、無アルカリガラスやその他の各種ガラス基板上に電極を形成する方法として、蒸着法が知られている。
しかしながら、この蒸着法は、真空容器内に電極形成部材を収納して金属の蒸着膜を形成するものであり、装置が大がかりで高価であるばかりでなく、部材の出し入れがわずらわしく、真空引きに時間を要するなど作業性が悪いという欠点があった。
Conventionally, vapor deposition is known as a method for forming electrodes on non-alkali glass and other various glass substrates in components such as plasma display panels, CCD sensors, and image sensors.
However, in this vapor deposition method, an electrode forming member is housed in a vacuum vessel to form a metal vapor deposition film. Not only is the apparatus large and expensive, it is also troublesome to put in and out of the member, and it takes time to evacuate. There was a drawback that workability was poor.

これに対し、上記欠点を解消できる、基板上に導電体のパターン層を形成する他の方法として、感光性導電ペーストを用いフォトリソグラフィー技術を利用した導電体パターンの形成方法が提案されている(特許文献1参照)。   On the other hand, as another method of forming a conductor pattern layer on a substrate that can eliminate the above-mentioned drawbacks, a method of forming a conductor pattern using a photosensitive conductive paste and using a photolithography technique has been proposed ( Patent Document 1).

しかしながら、かかる形成方法に用いる感光性導電ペーストは、長期間保存すると、銀粉末などの導電粉末が沈降するという問題があった。
特開平10−269848号公報
However, the photosensitive conductive paste used in such a forming method has a problem in that conductive powder such as silver powder settles when stored for a long period of time.
Japanese Patent Laid-Open No. 10-269848

そこで本発明は、従来技術が抱える上記課題を解消するためになされたものであり、その主たる目的は、高精細パターンの形成性に優れ、かつ長期間にわたって保存しても銀粉末などの導電粉末が沈降しない保存安定性に優れる感光性導電ペーストを提供することにある。   Accordingly, the present invention has been made to solve the above-described problems of the prior art, and its main purpose is excellent in the formation of a high-definition pattern and a conductive powder such as silver powder even when stored for a long period of time. An object of the present invention is to provide a photosensitive conductive paste that does not settle and has excellent storage stability.

発明者は、上記目的の実現に向け鋭意研究した結果、以下に示すような内容を要旨構成とする発明を完成させるに至った。   As a result of earnest research for the realization of the above object, the inventor has completed an invention having the following contents as the gist.

すなわち、本発明の感光性導電ペーストは、(A)導電粉末、(B)有機バインダー、(C)光重合性モノマー、(D)光重合開始剤、(E)沈降防止剤を含有するペーストであって、前記沈降防止剤(E)が変性ウレア溶液であることを特徴とする。
ここで、本発明において、変性ウレア溶液とは、イソシアネート単量体あるいはこれらのアダクト体と有機アミンとの反応物(官報公示整理番号 化審法7−885)をいう。
That is, the photosensitive conductive paste of the present invention is a paste containing (A) conductive powder, (B) an organic binder, (C) a photopolymerizable monomer, (D) a photopolymerization initiator, and (E) an anti-settling agent. The anti-settling agent (E) is a modified urea solution.
Here, in the present invention, the modified urea solution refers to a reaction product of an isocyanate monomer or an adduct thereof and an organic amine (Gazette Official Notice No. 7-885).

また、本発明の導電体パターンは、上述した本発明の感光性導電ペーストを用いて焼成物パターンを形成してなることを特徴とする。
なお、この導電体パターンは、基材上に、本発明の感光性導電ペーストを塗布・乾燥して乾燥塗膜を形成し、次いで、露光・現像した後、得られた感光性導電ペーストの乾燥塗膜パターンを、好ましくは480℃〜620℃の温度で焼成して有機分を脱バインダーすることにより、形成することが好ましい。
The conductor pattern of the present invention is characterized in that a fired product pattern is formed using the above-described photosensitive conductive paste of the present invention.
The conductive pattern is formed by applying and drying the photosensitive conductive paste of the present invention on a substrate to form a dry coating film, then exposing and developing, and then drying the resulting photosensitive conductive paste. The coating pattern is preferably formed by baking at a temperature of 480 ° C. to 620 ° C. to remove the organic component.

本発明によれば、高精細パターンの形成性に優れ、かつ長期間にわたって保存しても銀粉末などの導電粉末が沈降しない保存安定性に優れる感光性導電ペーストを提供することができる。その結果、620℃以下の温度での焼成によっても導電性と解像性が共に優れる導電体パターンを複雑な工程を経ることなく容易に形成することができる。   ADVANTAGE OF THE INVENTION According to this invention, the photosensitive electrically conductive paste which is excellent in the formation stability of a high-definition pattern, and is excellent in the storage stability which conductive powders, such as silver powder, do not settle even if preserve | saved over a long period of time can be provided. As a result, it is possible to easily form a conductor pattern that is excellent in both conductivity and resolution even through firing at a temperature of 620 ° C. or less without going through complicated steps.

以下、本発明の感光性導電ペーストについて説明する。
本発明の感光性導電ペーストは、沈降防止剤(E)として変性ウレア(イソシアネート単量体あるいはこれらのアダクト体と有機アミンとの反応物)を含有することを特徴とする。この変性ウレア溶液によれば、主にペースト中で三次元構造を形成し、擬塑性及びチクソトロピー性を付与させるものと考えられる。また、この変性ウレア溶液によれば、一般的に沈降防止剤として用いられる脂肪酸アミドやアミノ酸塩などに比べ、理由は明らかではないが、焼成後の比抵抗値が低く導電性に優れる。
このような変性ウレア溶液としては、BYK−410、BYK−411、BYK−420等が挙げられる。
Hereinafter, the photosensitive conductive paste of the present invention will be described.
The photosensitive conductive paste of the present invention is characterized by containing a modified urea (isocyanate monomer or a reaction product of these adducts and an organic amine) as an anti-settling agent (E). According to this modified urea solution, it is considered that a three-dimensional structure is mainly formed in the paste and pseudoplasticity and thixotropy are imparted. Further, according to this modified urea solution, the specific resistance value after firing is low and the conductivity is excellent, although the reason is not clear as compared with fatty acid amides and amino acid salts generally used as an anti-settling agent.
Examples of such a modified urea solution include BYK-410, BYK-411, BYK-420, and the like.

この沈降防止剤(E)の配合量は、前記有機バインダー(B)100質量部当り0.1〜10質量部、好ましくは0.5〜5質量部が適当である。沈降防止剤(E)の配合量が上記範囲よりも少ない場合、充分な沈降防止効果が得られ難くなり、一方、上記範囲を超えて多量になると、焼成収縮が大きくなるので好ましくない。   The amount of the antisettling agent (E) is suitably 0.1 to 10 parts by mass, preferably 0.5 to 5 parts by mass per 100 parts by mass of the organic binder (B). When the amount of the anti-settling agent (E) is less than the above range, it is difficult to obtain a sufficient anti-settling effect. On the other hand, when the amount exceeds the above range, firing shrinkage increases, which is not preferable.

次に、本発明の感光性導電ペーストにおけるその他の構成について説明する。
本発明の感光性導電ペーストを構成する導電粉末(A)としては、比抵抗値が1×10Ω・cm以下の導電粉末であれば幅広く用いることができる。例えば、銀、金、ニッケル、銅、アルミニウム、錫、亜鉛、鉄、白金、イリジウム、オスニウム、パラジウム、ロジウム、ルテニウム、タングステン、モリブデンなどの単体とその合金の他、酸化錫、酸化インジウム、ITO、酸化ルテニウムなどが挙げられる。これらは、単独で又は2種類以上の混合粉として用いることができる。
この導電粉末(A)は、球状、フレーク状、デントライト状など種々の形状のものを用いることができるが、特に光特性や分散性を考慮すると球状のものを用いることが好ましい。
この導電粉末(A)は、電子顕微鏡(SEM)を用いて10,000倍にて観察したランダムな10個の銀粉末の平均粒径で、0.1〜5μm、好ましくは0.4〜2.0μmの大きさのものを用いることが好ましい。この平均粒径が0.1μm未満の場合、光の透過性が悪くなり高精細なパターンが描き難くなり、一方、平均粒径が5μmを超える場合、ラインエッジの直線性が得られ難くなるので好ましくない。
なお、この導電粉末(A)は、レーザー回折散乱式粒度分布測定装置またはレーザードップラー法を利用した粒度分布測定装置を用いて測定した平均粒径が0.5〜3.5μmであるものを用いることが好ましい。
また、この導電粉末(A)は、比表面積が0.01〜2.0m/g、好ましくは0.1〜1.0m/gのものを用いることが好ましい。この比表面積が0.01m/g未満の場合、保存時に沈降を引き起こし易く、一方、比表面積が2.0m/gを超える場合、吸油量が大きくなってペーストの流動性が損なわれるため好ましくない。
特に銀粉末については、X線解析パターンにおけるAg(111)面ピークの半価幅が0.15°以上、好ましくは0.19°以上の値を示すものを用いることが望ましい。この半価幅が0.15未満の銀粉末では、銀粉末の結晶化度が高く、粒子間の焼結が起こりにくいため、620℃以下の焼成温度では抵抗値が下がらないため好ましくない。
Next, the other structure in the photosensitive electrically conductive paste of this invention is demonstrated.
As the conductive powder (A) constituting the photosensitive conductive paste of the present invention, any conductive powder having a specific resistance value of 1 × 10 3 Ω · cm or less can be widely used. For example, in addition to simple substances such as silver, gold, nickel, copper, aluminum, tin, zinc, iron, platinum, iridium, osmium, palladium, rhodium, ruthenium, tungsten, molybdenum and their alloys, tin oxide, indium oxide, ITO, Examples include ruthenium oxide. These can be used alone or as a mixed powder of two or more.
The conductive powder (A) can be used in various shapes such as a spherical shape, a flake shape, and a dentlite shape, but it is preferable to use a spherical shape particularly considering optical characteristics and dispersibility.
This conductive powder (A) has an average particle diameter of 10 random silver powders observed at 10,000 times using an electron microscope (SEM), and is 0.1 to 5 μm, preferably 0.4 to 2 μm. It is preferable to use one having a size of 0.0 μm. If this average particle size is less than 0.1 μm, light transmission is poor and it becomes difficult to draw a high-definition pattern. On the other hand, if the average particle size exceeds 5 μm, it is difficult to obtain line edge linearity. It is not preferable.
The conductive powder (A) has a mean particle size of 0.5 to 3.5 μm measured using a laser diffraction / scattering particle size distribution measuring device or a particle size distribution measuring device utilizing a laser Doppler method. It is preferable.
The conductive powder (A) preferably has a specific surface area of 0.01 to 2.0 m 2 / g, preferably 0.1 to 1.0 m 2 / g. When this specific surface area is less than 0.01 m 2 / g, sedimentation is likely to occur during storage. On the other hand, when the specific surface area exceeds 2.0 m 2 / g, the oil absorption increases and the fluidity of the paste is impaired. It is not preferable.
In particular, regarding silver powder, it is desirable to use a silver (111) plane peak in the X-ray analysis pattern having a half width of 0.15 ° or more, preferably 0.19 ° or more. The silver powder having a half width of less than 0.15 is not preferable because the crystallinity of the silver powder is high and sintering between particles hardly occurs, and the resistance value does not decrease at a firing temperature of 620 ° C. or lower.

このような導電粉末(A)の配合量は、感光性導電ペースト100質量部に対して50〜90質量部が適当である。導電性粉末の配合量が上記範囲よりも少ない場合、かかるペーストから得られる導電体パターンの充分な導電性が得られず、一方、上記範囲を超えて多量になると、基材との密着性が悪くなるので好ましくない。   The blending amount of the conductive powder (A) is appropriately 50 to 90 parts by mass with respect to 100 parts by mass of the photosensitive conductive paste. When the blending amount of the conductive powder is less than the above range, sufficient conductivity of the conductor pattern obtained from such a paste cannot be obtained. On the other hand, when the amount exceeds the above range, the adhesion to the substrate is poor. It is not preferable because it gets worse.

次に、本発明の感光性導電ペーストを構成する有機バインダー(B)は、焼成前における各成分の結合材、または組成物の光硬化性や現像性の付与として機能するものである。
この有機バインダーとしては、カルボキシル基を有する樹脂、具体的にはそれ自体がエチレン性不飽和二重結合を有するカルボキシル基含有感光性樹脂及びエチレン性不飽和二重結合を有さないカルボキシル基含有樹脂のいずれも使用可能である。好適に使用できる樹脂(オリゴマー及びポリマーのいずれでもよい)としては、以下のようなものが挙げられる。
(1)(a)不飽和カルボン酸と(b)不飽和二重結合を有する化合物を共重合させることによって得られるカルボキシル基含有樹脂、
(2)(a)不飽和カルボン酸と(b)不飽和二重結合を有する化合物の共重合体にエチレン性不飽和基をペンダントとして付加させることによって得られるカルボキシル基含有感光性樹脂、
(3)(c)エポキシ基と不飽和二重結合を有する化合物と(b)不飽和二重結合を有する化合物の共重合体に、(d)不飽和モノカルボン酸を反応させ、生成した2級の水酸基に(e)多塩基酸無水物を反応させて得られるカルボキシル基含有感光性樹脂
(4)(f)不飽和二重結合を有する酸無水物と(b)不飽和二重結合を有する化合物の共重合体に、(g)水酸基を有する化合物を反応させて得られるカルボキシル基含有樹脂、
(5)(f)不飽和二重結合を有する酸無水物と(b)不飽和二重結合を有する化合物の共重合体に、(h)水酸基と不飽和二重結合を有する化合物を反応させて得られるカルボキシル基含有感光性樹脂、
(6)(i)多官能エポキシ化合物と(d)不飽和モノカルボン酸を反応させ、生成した2級の水酸基に(e)多塩基酸無水物を反応させて得られるカルボキシル基含有感光性樹脂、
(7)(b)不飽和二重結合を有する化合物と(c)エポキシ基と不飽和二重結合を有する化合物の共重合体のエポキシ基に、(j)1分子中に1つのカルボキシル基を有し、エチレン性不飽和結合を持たない有機酸を反応させ、生成した2級の水酸基に(d)多塩基酸無水物を反応させて得られるカルボキシル基含有樹脂、
(8)(k)水酸基含有ポリマーに(d)多塩基酸無水物を反応させて得られるカルボキシル基含有樹脂、
(9)(k)水酸基含有ポリマーに(d)多塩基酸無水物を反応させて得られるカルボキシル基含有樹脂に、(c)エポキシ基と不飽和二重結合を有する化合物をさらに反応させて得られるカルボキシル基含有感光性樹脂などが挙げられる。
Next, the organic binder (B) constituting the photosensitive conductive paste of the present invention functions as a binder for each component before firing, or imparting photocurability and developability of the composition.
As this organic binder, a carboxyl group-containing resin, specifically, a carboxyl group-containing photosensitive resin itself having an ethylenically unsaturated double bond and a carboxyl group-containing resin not having an ethylenically unsaturated double bond Either of these can be used. Examples of the resin (which may be either an oligomer or a polymer) that can be suitably used include the following.
(1) a carboxyl group-containing resin obtained by copolymerizing (a) an unsaturated carboxylic acid and (b) a compound having an unsaturated double bond,
(2) a carboxyl group-containing photosensitive resin obtained by adding an ethylenically unsaturated group as a pendant to a copolymer of (a) an unsaturated carboxylic acid and (b) a compound having an unsaturated double bond,
(3) produced by reacting (d) an unsaturated monocarboxylic acid with a copolymer of (c) a compound having an epoxy group and an unsaturated double bond and (b) a compound having an unsaturated double bond (E) a carboxyl group-containing photosensitive resin obtained by reacting a polybasic acid anhydride with a secondary hydroxyl group (4) (f) an acid anhydride having an unsaturated double bond and (b) an unsaturated double bond (G) a carboxyl group-containing resin obtained by reacting a compound having a hydroxyl group with a copolymer of the compound having
(5) (h) a copolymer of an acid anhydride having an unsaturated double bond and (b) a compound having an unsaturated double bond is reacted with a compound having (h) a hydroxyl group and an unsaturated double bond. Carboxyl group-containing photosensitive resin obtained by
(6) A carboxyl group-containing photosensitive resin obtained by reacting (i) a polyfunctional epoxy compound with (d) an unsaturated monocarboxylic acid and reacting the resulting secondary hydroxyl group with (e) a polybasic acid anhydride. ,
(7) (j) One carboxyl group in one molecule is added to the epoxy group of a copolymer of (b) a compound having an unsaturated double bond and (c) an epoxy group and a compound having an unsaturated double bond. A carboxyl group-containing resin obtained by reacting an organic acid having no ethylenically unsaturated bond and reacting the resulting secondary hydroxyl group with (d) a polybasic acid anhydride,
(8) (k) a carboxyl group-containing resin obtained by reacting a hydroxyl group-containing polymer with (d) a polybasic acid anhydride,
(9) Obtained by further reacting (c) a compound having an unsaturated double bond with a carboxyl group-containing resin obtained by reacting (k) a hydroxyl group-containing polymer with (d) a polybasic acid anhydride. And carboxyl group-containing photosensitive resin.

このようなカルボキシル基含有感光性樹脂及びカルボキシル基含有樹脂は、単独で又は混合して用いてもよいが、いずれの場合でも合計量で組成物全量の5〜50質量%の割合で配合することが好ましい。これらの樹脂の配合量が上記範囲よりも少な過ぎる場合、形成する塗膜中の上記樹脂の分布が不均一になり易く、充分な光硬化性及び光硬化深度が得られ難く、選択的露光、現像によるパターニングが困難となる。一方、上記範囲よりも多過ぎると、焼成時のパターンのよれや線幅収縮を生じ易くなるので好ましくない。   Such a carboxyl group-containing photosensitive resin and a carboxyl group-containing resin may be used alone or in combination, but in any case, they should be blended in a proportion of 5 to 50% by mass of the total amount of the composition. Is preferred. When the blending amount of these resins is less than the above range, the distribution of the resin in the coating film to be formed tends to be non-uniform, it is difficult to obtain sufficient photocurability and photocuring depth, selective exposure, Patterning by development becomes difficult. On the other hand, if it is more than the above range, it is not preferable because the pattern during baking and the line width shrinkage are likely to occur.

また、上記カルボキシル基含有感光性樹脂及びカルボキシル基含有樹脂としては、それぞれ重量平均分子量1,000〜100,000、好ましくは5,000〜70,000、及び酸価30〜250mgKOH/g、かつ、カルボキシル基含有感光性樹脂の場合、その二重結合当量が350〜2,000、好ましくは400〜1,500のものを好適に用いることができる。
上記樹脂の分子量が1,000より低い場合、現像時の皮膜の密着性に悪影響を与え、一方、100,000よりも高い場合、現像不良を生じ易いので好ましくない。また、酸価が30mgKOH/gより低い場合、アルカリ水溶液に対する溶解性が不充分で現像不良を生じ易く、一方、250mgKOH/gより高い場合、現像時に皮膜の密着性の劣化や光硬化部(露光部)の溶解が生じるので好ましくない。さらに、カルボキシル基含有感光性樹脂の場合、感光性樹脂の二重結合当量が350よりも小さいと、焼成時に残渣が残り易くなり、一方、2,000よりも大きいと、現像時の作業余裕度が狭く、また光硬化時に高露光量を必要とするので好ましくない。
The carboxyl group-containing photosensitive resin and the carboxyl group-containing resin each have a weight average molecular weight of 1,000 to 100,000, preferably 5,000 to 70,000, and an acid value of 30 to 250 mgKOH / g, and In the case of a carboxyl group-containing photosensitive resin, those having a double bond equivalent of 350 to 2,000, preferably 400 to 1,500 can be suitably used.
When the molecular weight of the resin is lower than 1,000, the adhesion of the film during development is adversely affected. On the other hand, when the molecular weight is higher than 100,000, development defects are liable to occur. On the other hand, when the acid value is lower than 30 mgKOH / g, the solubility in an alkaline aqueous solution is insufficient, and development failure tends to occur. Part) is not preferable. Further, in the case of a carboxyl group-containing photosensitive resin, if the double bond equivalent of the photosensitive resin is less than 350, a residue is likely to remain at the time of baking, whereas if it is greater than 2,000, a work margin at the time of development. Is narrow, and a high exposure amount is required at the time of photocuring.

本発明の感光性導電性ペーストを構成する光重合性モノマー(C)は、組成物の光硬化性の付与促進及び現像性を向上させるために用いられる。このような光重合性モノマー(C)としては、例えば、2−ヒドロキシエチルアクリレート,2−ヒドロキシプロピルアクリレート、ジエチレングリコールジアクリレート、トリエチレングリコールジアクリレート、ポリエチレングリコールジアクリレート、ポリウレタンジアクリレート、トリメチロールプロパントリアクリレート、ペンタエリスリトールトリアクリレート、ペンタエリスリトールテトラアクリレート、トリメチロールプロパンエチレンオキサイド変性トリアクリレート、トリメチロールプロパンプロピレンオキサイド変性トリアクリレート、ジペンタエリスリトールペンタアクリレート、ジペンタエリスリトールヘキサアクリレート及び上記アクリレートに対応する各メタクリレート類;フタル酸、アジピン酸、マレイン酸、イタコン酸、コハク酸、トリメリット酸、テレフタル酸等の多塩基酸とヒドロキシアルキル(メタ)アクリレートとのモノ−、ジ−、トリ−又はそれ以上のポリエステルなどが挙げられるが、特定のものに限定されるものではなく、またこれらを単独で又は2種以上を組み合わせて用いることができる。これらの光重合性モノマーの中でも、1分子中に2個以上のアクリロイル基又はメタクリロイル基を有する多官能モノマーが好ましい。   The photopolymerizable monomer (C) constituting the photosensitive conductive paste of the present invention is used for promoting the imparting of photocurability of the composition and improving the developability. Examples of such a photopolymerizable monomer (C) include 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, polyethylene glycol diacrylate, polyurethane diacrylate, trimethylol propane tri Acrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, trimethylolpropane ethylene oxide modified triacrylate, trimethylolpropane propylene oxide modified triacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate and each methacrylate corresponding to the above acrylate Phthalic acid, adipic acid, malein Mono-, di-, tri- or higher polyesters of polybasic acids such as itaconic acid, succinic acid, trimellitic acid, terephthalic acid and the like and hydroxyalkyl (meth) acrylates. It is not limited and these can be used alone or in combination of two or more. Among these photopolymerizable monomers, polyfunctional monomers having two or more acryloyl groups or methacryloyl groups in one molecule are preferable.

この光重合性モノマー(C)の配合量は、前記有機バインダー(B)100質量部当り20〜100質量部が適当である。光重合性モノマーの配合量が上記範囲よりも少ない場合、組成物の充分な光硬化性が得られ難くなり、一方、上記範囲を超えて多量になると、皮膜の深部に比べて表層部の光硬化が早くなるため硬化むらを生じ易くなる。   The blending amount of the photopolymerizable monomer (C) is suitably 20 to 100 parts by mass per 100 parts by mass of the organic binder (B). When the amount of the photopolymerizable monomer is less than the above range, it is difficult to obtain sufficient photocurability of the composition. On the other hand, when the amount exceeds the above range, the amount of light in the surface layer portion is larger than that in the deep portion of the film. Since curing becomes faster, uneven curing tends to occur.

本発明の感光性導電性ペーストを構成する光重合開始剤(D)は、光反応を開始させる成分で、主に紫外線を吸収しラジカルを発生させる、前記光重合開始剤(D)の具体例としては、ベンゾイン、ベンゾインメチルエーテル、ベンゾインエチルエーテル、ベンゾインイソプロピルエーテル等のベンゾインとベンゾインアルキルエーテル類;アセトフェノン、2,2−ジメトキシー2−フェニルアセトフェノン、2,2−ジエトキシー2−フェニルアセトフェノン、1,1−ジクロロアセトフェノン等のアセトフェノン類;2−メチル−1−[4−(メチルチオ)フェニル]−2−モルフォリノプロパノン−1、2−ベンジル−2−ジメチルアミノ−1−(4−モルフォリノフェニル)−ブタノン−1等のアミノアセトフェノン類;2−メチルアントラキノン、2−エチルアントラキノン、2−t−ブチルアントラキノン、1−クロロアントラキノン等のアントラキノン類;2,4−ジメチルチオキサントン、2,4−ジエチルチオキサントン、2−クロロチオキサントン、イソプロピルチオキサントン、2,4−ジイソプロピルチオキサントン等のチオキサントン類;アセトフェノンジメチルケタール、ベンジルジメチルケタール等のケタール類;ベンゾフェノン等のベンゾフェノン類;又はキサントン類;(2,6−ジメトキシベンゾイル)−2,4,4−ペンチルホスフィンオキサイド、ビス(2,4,6−トリメチルベンゾイル)−フェニルフォスフィンオキサイド、2,4,6−トリメチルベンゾイルジフェニルフォスフィンオキサイド、エチル−2,4,6−トリメチルベンゾイルフェニルフォスフィネイト等のフォスフィンオキサイド類;各種パーオキサイド類などが挙げられるが、特定のものに限定されるものではなく、また、これらを単独あるいは2種類以上を組み合わせて使用することができる。   The photopolymerization initiator (D) constituting the photosensitive conductive paste of the present invention is a component that initiates a photoreaction, and is a specific example of the photopolymerization initiator (D) that mainly absorbs ultraviolet rays and generates radicals. Benzoin and benzoin alkyl ethers such as benzoin, benzoin methyl ether, benzoin ethyl ether and benzoin isopropyl ether; acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1 -Acetophenones such as dichloroacetophenone; 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropanone-1, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl)- Aminoacetophenones such as butanone-1; 2-methi Anthraquinones such as anthraquinone, 2-ethylanthraquinone, 2-t-butylanthraquinone, 1-chloroanthraquinone; 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, isopropylthioxanthone, 2,4-diisopropyl Thioxanthones such as thioxanthone; ketals such as acetophenone dimethyl ketal and benzyl dimethyl ketal; benzophenones such as benzophenone; or xanthones; (2,6-dimethoxybenzoyl) -2,4,4-pentylphosphine oxide, bis (2 , 4,6-trimethylbenzoyl) -phenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, ethyl-2,4,6-trimethyl Phosphine oxides such as benzoylphenyl phosphinate; various peroxides and the like are mentioned, but it is not limited to specific ones, and these can be used alone or in combination of two or more. .

また、この光重合開始剤(D)のペースト中の配合割合は、前記有機バインダー(B)100質量部当り1〜30質量部が適当であり、好ましくは5〜20質量部である。上記範囲より少ない場合、ペーストの充分な光硬化性が得られ難くなり、一方、上記範囲を超えて多量になると、光の透過が阻害され深部の光硬化性が得られ難くなる。   Moreover, 1-30 mass parts is suitable per 100 mass parts of said organic binder (B), and, as for the mixture ratio in the paste of this photoinitiator (D), Preferably it is 5-20 mass parts. When the amount is less than the above range, it is difficult to obtain sufficient photocurability of the paste. On the other hand, when the amount exceeds the above range, light transmission is inhibited and it is difficult to obtain deep photocurability.

また、より深い光硬化深度を要求される場合、必要に応じて、可視領域でラジカル重合を開始するチバ・スペシャルティー・ケミカルズ社製イルガキュア784等のチタノセン系光重合開始剤、ロイコ染料等を硬化助剤として組み合わせて用いることができる。   In addition, when a deeper photocuring depth is required, a titanocene photopolymerization initiator such as Irgacure 784 manufactured by Ciba Specialty Chemicals, which starts radical polymerization in the visible region, and leuco dye are cured as necessary. It can be used in combination as an auxiliary agent.

なお、本発明の感光性導電ペーストは、ガラス基板への密着性、焼成膜の強度を上げる目的で低融点ガラスを配合することができる。この低融点ガラスとしては、鉛系、ビスマス系、リン酸系、リチウム系等のガラス転移点(Tg)が300〜500℃、軟化点(Ts)が400〜600℃の低融点ガラス粉末を用いることが好ましい。また、解像性の観点から粒径は10μm以下の粉末が好ましく、結晶性、非結晶性の何れであっても良い。   In addition, the photosensitive electrically conductive paste of this invention can mix | blend low melting glass for the purpose of raising the adhesiveness to a glass substrate and the intensity | strength of a baked film. As the low melting point glass, a low melting point glass powder having a glass transition point (Tg) of 300 to 500 ° C. and a softening point (Ts) of 400 to 600 ° C. such as lead, bismuth, phosphoric acid and lithium is used. It is preferable. Further, from the viewpoint of resolution, a powder having a particle size of 10 μm or less is preferable, and may be either crystalline or non-crystalline.

さらに必要に応じて、本発明の感光性導電ペーストは、保存安定性を確保するためのリン酸、リン酸エステル、カルボン酸含有化合物等の酸性化合物、シリコーン系、アクリル系等の消泡・レベリング剤、流動性を調整するためのチクソ性付与剤、皮膜の密着性向上のためのシランカップリング剤、等の他の添加剤を配合することもできる。さらにまた、必要に応じて、導電性粉の酸化を防止するための公知慣用の酸化防止剤や、保存時の熱的安定性を向上させるための熱重合禁止剤、焼成時における基板との結合成分としての金属酸化物、ケイ素酸化物、ホウ素酸化物、低融点ガラスなどの微粒子を添加することもできる。また、焼成収縮を調整する目的でシリカ、酸化ビスマス、酸化アルミニウム、酸化チタン等の無機粉末、有機金属化合物、金属有機酸塩、金属アルコキシド等を添加することもできる。   Further, if necessary, the photosensitive conductive paste of the present invention is an acid compound such as phosphoric acid, phosphate ester, carboxylic acid-containing compound, silicone-based, acrylic-based defoaming and leveling to ensure storage stability. Other additives such as an agent, a thixotropic agent for adjusting fluidity, and a silane coupling agent for improving the adhesion of the film can also be blended. Furthermore, if necessary, a known and commonly used antioxidant for preventing oxidation of the conductive powder, a thermal polymerization inhibitor for improving the thermal stability during storage, and bonding with the substrate during firing. Fine particles such as metal oxides, silicon oxides, boron oxides, and low-melting glass as components can be added. In addition, inorganic powders such as silica, bismuth oxide, aluminum oxide, and titanium oxide, organic metal compounds, metal organic acid salts, metal alkoxides, and the like can be added for the purpose of adjusting firing shrinkage.

また、色調を調整する目的で、Fe、Co、Cu、Cr、Mn、Al、Ru、Niの1種又は2種類以上を主成分として含む金属酸化物又は複合金属酸化物からなる黒色顔料、四三酸化コバルト(Co)、酸化ルテニウム、ランタン複合酸化物等の黒色材料を添加することもできる。 Further, for the purpose of adjusting the color tone, a black pigment made of a metal oxide or a composite metal oxide containing one or more of Fe, Co, Cu, Cr, Mn, Al, Ru, Ni as a main component, four Black materials such as cobalt trioxide (Co 3 0 4 ), ruthenium oxide, and lanthanum composite oxide can also be added.

本発明の感光性導電ペーストは、上述したような必須成分と任意成分を所定の割合で配合し、三本ロールやブレンダー等の混練機にて均一分散して得られる。こうして得られた本発明の感光性導電ペーストは、例えば、以下のような工程を経て基材上の導電体パターンとして形成される。   The photosensitive conductive paste of the present invention is obtained by blending the above-described essential components and optional components in a predetermined ratio and uniformly dispersing them in a kneader such as a three roll or blender. The photosensitive conductive paste of the present invention thus obtained is formed as a conductor pattern on a substrate through, for example, the following steps.

(1)まず、本発明の感光性導電ペーストは、スクリーン印刷法、バーコーター、ブレードコーターなど適宜の塗布方法にて、基材、例えばプラズマディスプレイパネル(PDP)の前面基板となるガラス基板等に塗布し、次いで指触乾燥性を得るために、熱風循環式乾燥炉や遠赤外線乾燥炉などで例えば約60〜120℃で5〜40分程度乾燥させて有機溶剤を蒸発させ、タックフリーの塗膜を得る。
ここで、基材としては、特定のものに限定されるものではないが、例えば、ガラス基板やセラミック基板などの耐熱性基板を用いることができる。
なお、ペーストを予めフィルム状に成膜することもでき、この場合には基材上にフィルムをラミネートすればよい。
(1) First, the photosensitive conductive paste of the present invention is applied to a base material such as a glass substrate serving as a front substrate of a plasma display panel (PDP) by an appropriate coating method such as a screen printing method, a bar coater, or a blade coater. In order to obtain a touch-drying property, the organic solvent is evaporated by drying at about 60 to 120 ° C. for about 5 to 40 minutes in a hot air circulating drying furnace or a far infrared drying furnace, and a tack-free coating is applied. Get a membrane.
Here, the base material is not limited to a specific one, but for example, a heat resistant substrate such as a glass substrate or a ceramic substrate can be used.
Note that the paste can be formed into a film in advance. In this case, the film may be laminated on the substrate.

(2)次に、基材上に形成した乾燥塗膜をパターン露光して現像する。
露光工程としては、所定の露光パターンを有するネガマスクを用いた接触露光又は非接触露光が可能である。露光光源としては、ハロゲンランプ、高圧水銀灯、レーザー光、メタルハライドランプ、ブラックランプ、無電極ランプなどが使用される。露光量としては50〜1000mJ/cm2程度が好ましい。
(2) Next, the dry coating film formed on the substrate is subjected to pattern exposure and developed.
As the exposure step, contact exposure or non-contact exposure using a negative mask having a predetermined exposure pattern is possible. As the exposure light source, a halogen lamp, a high-pressure mercury lamp, a laser beam, a metal halide lamp, a black lamp, an electrodeless lamp, or the like is used. The exposure amount is preferably about 50 to 1000 mJ / cm 2 .

現像工程としてはスプレー法、浸漬法等が用いられる。現像液としては、水酸化ナトリウム、水酸化カリウム、炭酸ナトリウム、炭酸カリウム、珪酸ナトリウムなどの金属アルカリ水溶液や、モノエタノールアミン、ジエタノールアミン、トリエタノールアミンなどのアミン水溶液、特に約1.5質量%以下の濃度の希アルカリ水溶液が好適に用いられるが、組成物中のカルボキシル基含有樹脂のカルボキシル基がケン化され、未硬化部(未露光部)が除去されればよく、上記のような現像液に限定されるものではない。また、現像後に不要な現像液の除去のため、水洗や酸中和を行うことが好ましい。   As the development process, a spray method, an immersion method, or the like is used. Developers include aqueous alkali metal solutions such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate and sodium silicate, and aqueous amine solutions such as monoethanolamine, diethanolamine and triethanolamine, especially about 1.5% by mass or less. A dilute alkaline aqueous solution having a concentration of 1 is preferably used, as long as the carboxyl group of the carboxyl group-containing resin in the composition is saponified and the uncured part (unexposed part) is removed. It is not limited to. Further, it is preferable to perform washing with water and acid neutralization in order to remove an unnecessary developer after development.

(3)そして、得られた感光性導電ペーストのパターンを焼成してペースト中に含まれる有機分を脱バインダーすることにより、所定の導電体パターンを形成する。 (3) A predetermined conductor pattern is formed by baking the pattern of the obtained photosensitive conductive paste to remove the organic component contained in the paste.

以下、本発明を実施例に基づいて具体的に説明するが、本発明が下記実施例に限定されるものでないことはもとよりである。なお、以下において「部」は、特に断りのない限りすべて質量部であるものとする。
(合成例1)
温度計、攪拌機、滴下ロート、及び還流冷却器を備えたフラスコに、メチルメタクリレートとメタクリル酸を0.87:0.13のモル比で仕込み、溶媒としてジプロピレングリコールモノメチルエーテル、触媒としてアゾビスイソブチロニトリルを入れ、窒素雰囲気下、80℃で2〜6時間攪拌し、樹脂溶液を得た。この樹脂溶液中の有機バインダーA(共重合樹脂)は、重量平均分子量が約10,000、酸価が74mgKOH/gであった。
なお、得られた樹脂溶液中の有機バインダーAの重量平均分子量は、島津製作所製ポンプLC−6ADと昭和電工製カラムShodex(登録商標)KF−804、KF−803、KF−802を三本つないだ高速液体クロマトグラフィーを用いて測定した。
EXAMPLES Hereinafter, although this invention is demonstrated concretely based on an Example, it cannot be overemphasized that this invention is not limited to the following Example. In the following, “parts” are all parts by mass unless otherwise specified.
(Synthesis Example 1)
A flask equipped with a thermometer, stirrer, dropping funnel, and reflux condenser is charged with methyl methacrylate and methacrylic acid in a molar ratio of 0.87: 0.13, dipropylene glycol monomethyl ether as a solvent, and azobisiso as a catalyst. Butyronitrile was added and stirred at 80 ° C. for 2 to 6 hours under a nitrogen atmosphere to obtain a resin solution. The organic binder A (copolymer resin) in this resin solution had a weight average molecular weight of about 10,000 and an acid value of 74 mgKOH / g.
In addition, the weight average molecular weight of the organic binder A in the obtained resin solution connects three Shimadzu pump LC-6AD and Showa Denko column Shodex (registered trademark) KF-804, KF-803, and KF-802. It was measured using high performance liquid chromatography.

このようにして得られた有機バインダーAを含む樹脂溶液を用い、以下に示す組成比にて配合し、攪拌機により攪拌後、3本ロールミルにより練肉してペースト化を行い、感光性導電ペーストを作製した。なお、低融点ガラス粉末としては、Bi23が50%、B23が15%、ZnOが15%、SiO2が6%、BaOが17%を粉砕し、熱膨張係数α300=85×10-7 /℃、ガラス転移点460℃、平均粒径1.6μmとしたものを使用した。 The resin solution containing the organic binder A thus obtained was blended at the composition ratio shown below, stirred with a stirrer, kneaded with a three-roll mill to form a paste, and a photosensitive conductive paste was prepared. Produced. As the low melting point glass powder, Bi 2 O 3 is pulverized 50%, B 2 O 3 is 15%, ZnO is 15%, SiO 2 is 6%, BaO is 17%, and the thermal expansion coefficient α 300 = 85 × 10 −7 / ° C., glass transition point 460 ° C., and average particle size 1.6 μm were used.

(組成物例1)
有機バインダーA 100.0部
トリメチロールプロパントリアクリレート 50.0部
2−ベンジル−2−ジメチルアミノ−1−
(4−モルフォリノフェニル)−ブタノン−1 10.0部
2,4−ジエチルチオキサントン 1.0部
ジプロピレングリコールモノメチルエーテル 90.0部
銀粉 (平均粒径(D50):2.5μm) 700.0部
沈降防止剤(BYK-410:ビックケミー・ジャパン製) 5.0部
ガラス粉末 35.0部
リン酸エステル 2.0部
消泡剤(BYK-354:ビックケミー・ジャパン製) 1.0部
(Composition Example 1)
Organic binder A 100.0 parts Trimethylolpropane triacrylate 50.0 parts 2-Benzyl-2-dimethylamino-1-
(4-morpholinophenyl) -butanone-1 10.0 parts 2,4-diethylthioxanthone 1.0 part dipropylene glycol monomethyl ether 90.0 parts Silver powder (average particle size (D50): 2.5 μm) 700.0 Part Antisettling agent (BYK-410: manufactured by Big Chemie Japan) 5.0 parts Glass powder 35.0 parts Phosphate ester 2.0 parts Antifoam agent (BYK-354: manufactured by Big Chemie Japan) 1.0 part

(比較組成物例1)
有機バインダーA 100.0部
トリメチロールプロパントリアクリレート 50.0部
2−ベンジル−2−ジメチルアミノ−1−
(4−モルフォリノフェニル)−ブタノン−1 10.0部
2,4−ジエチルチオキサントン 1.0部
ジプロピレングリコールモノメチルエーテル 90.0部
銀粉 (平均粒径(D50):2.5μm) 700.0部

ガラス粉末 35.0部
リン酸エステル 2.0部
消泡剤(BYK-354:ビックケミー・ジャパン製) 1.0部
(Comparative composition example 1)
Organic binder A 100.0 parts Trimethylolpropane triacrylate 50.0 parts 2-Benzyl-2-dimethylamino-1-
(4-morpholinophenyl) -butanone-1 10.0 parts 2,4-diethylthioxanthone 1.0 part dipropylene glycol monomethyl ether 90.0 parts Silver powder (average particle size (D50): 2.5 μm) 700.0 Part

Glass powder 35.0 parts Phosphate ester 2.0 parts Antifoam (BYK-354: manufactured by Big Chemie Japan) 1.0 part

このようにして得られた組成物例1、比較組成物例1の各感光性導電ペーストを80ps(E型粘度計の測定値)になるようにジプロピレングリコールモノメチルエーテルで粘度調整を行った。こうして得られた各ペーストについて、解像性、比抵抗値、密着性、焼成収縮、銀粉末の沈降を評価した。その評価方法は以下のとおりである。
試験片作成:
ガラス基板上に、評価用の各感光性導電ペーストを180メッシュのポリエステルスクリーンを用いて全面に塗布し、次いで、熱風循環式乾燥炉にて90℃で20分間乾燥して指触乾燥性の良好な塗膜を形成した。次に、光源としてメタルハライドランプを用い、ネガマスクを介して、乾燥塗膜上の積算光量が300mJ/cm2となるようにパターン露光した後、液温30℃の0.5wt%Na2CO3水溶液を用いて現像を行い、水洗した。そして、こうして塗膜パターンを形成した基板を、空気雰囲気下にて5℃/分で550℃まで昇温して570℃で30分間焼成し、導電体パターンを形成した試験片を作成した。
The viscosity of each of the photosensitive conductive pastes of Composition Example 1 and Comparative Composition Example 1 thus obtained was adjusted with dipropylene glycol monomethyl ether so as to be 80 ps (measured value of an E-type viscometer). Each paste thus obtained was evaluated for resolution, specific resistance, adhesion, firing shrinkage, and silver powder sedimentation. The evaluation method is as follows.
Specimen creation:
Each photosensitive conductive paste for evaluation was applied on the entire surface of a glass substrate using a 180 mesh polyester screen, and then dried at 90 ° C. for 20 minutes in a hot-air circulating drying oven to provide good touch drying properties. A good coating was formed. Next, using a metal halide lamp as a light source, pattern exposure was performed through a negative mask so that the integrated light amount on the dried coating film was 300 mJ / cm 2, and then a 0.5 wt% Na 2 CO 3 aqueous solution having a liquid temperature of 30 ° C. Development was carried out using and washed with water. And the board | substrate which formed the coating film pattern in this way was heated up to 550 degreeC by 5 degree-C / min in air atmosphere, and baked at 570 degreeC for 30 minutes, and the test piece which formed the conductor pattern was created.

(解像性)
上記方法によって作成した試験片の最小ライン幅を評価した。
(比抵抗値)
上記方法によって4mm×10cmのパターンを有する試験片を作成し、パターン抵抗値と膜厚を測定して比抵抗値を算出した。
(密着性)
上記法保によって作成した試験片について、粘着テープピーリングを行い、パターンの剥離がないかどうかで評価した。
(銀粉の沈降)
ペーストを350mlの容器に300g入れ密閉した後、10℃の保冷庫で3ヶ月間放置した後、ペーストに金属へらを差し込み容器の底部に沈降があるか確認した。
これらの評価結果を表1に示す。
(Resolution)
The minimum line width of the test piece prepared by the above method was evaluated.
(Specific resistance value)
A test piece having a pattern of 4 mm × 10 cm was prepared by the above method, and the specific resistance value was calculated by measuring the pattern resistance value and the film thickness.
(Adhesion)
About the test piece created by the above-mentioned Hobo, adhesive tape peeling was performed and evaluated whether there was no peeling of a pattern.
(Sedimentation of silver powder)
After 300 g of the paste was put in a 350 ml container and sealed, it was allowed to stand in a 10 ° C. cool box for 3 months, and then a metal spatula was inserted into the paste to confirm whether there was sedimentation at the bottom of the container.
These evaluation results are shown in Table 1.

Figure 2005276573
Figure 2005276573

この表1に示す結果から明らかなように、本発明の感光性導電ペーストによれば、高精細な導電体パターンを容易に形成することができる。しかも、本発明の感光性導電ペーストは、長期間にわたって保存しても銀粉末などの導電粉末が沈降しない保存安定性に優れるものであることがわかる。
As is clear from the results shown in Table 1, according to the photosensitive conductive paste of the present invention, a high-definition conductor pattern can be easily formed. Moreover, it can be seen that the photosensitive conductive paste of the present invention is excellent in storage stability in which conductive powder such as silver powder does not settle even when stored for a long period of time.

Claims (2)

(A)導電粉末、(B)有機バインダー、(C)光重合性モノマー、(D)光重合開始剤、(E)沈降防止剤を含有するペーストであって、前記沈降防止剤(E)が変性ウレア溶液であることを特徴とする感光性導電ペースト。 A paste containing (A) conductive powder, (B) an organic binder, (C) a photopolymerizable monomer, (D) a photopolymerization initiator, and (E) an anti-settling agent, wherein the anti-settling agent (E) is A photosensitive conductive paste, which is a modified urea solution. 前記請求項1に記載の感光性導電ペーストを用いて焼成物パターンを形成してなることを特徴とする導電体パターン。

A conductor pattern obtained by forming a fired product pattern using the photosensitive conductive paste according to claim 1.

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