JP4751773B2 - Photocurable composition and fired product pattern formed using the same - Google Patents

Photocurable composition and fired product pattern formed using the same Download PDF

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JP4751773B2
JP4751773B2 JP2006160614A JP2006160614A JP4751773B2 JP 4751773 B2 JP4751773 B2 JP 4751773B2 JP 2006160614 A JP2006160614 A JP 2006160614A JP 2006160614 A JP2006160614 A JP 2006160614A JP 4751773 B2 JP4751773 B2 JP 4751773B2
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composition
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photocurable composition
powder
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JP2007326987A (en
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和信 福島
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Taiyo Holdings Co Ltd
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Taiyo Holdings Co Ltd
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/0042—Photosensitive materials with inorganic or organometallic light-sensitive compounds not otherwise provided for, e.g. inorganic resists
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/0047—Photosensitive materials characterised by additives for obtaining a metallic or ceramic pattern, e.g. by firing
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/20—Conductive material dispersed in non-conductive organic material
    • H01B1/22—Conductive material dispersed in non-conductive organic material the conductive material comprising metals or alloys

Description

本発明は、プラズマディスプレイパネル（以下、ＰＤＰと略称する）のガラス基板や、電気回路配線基板用のセラミクス基板等に精細な電極回路を形成するのに有用な光硬化性組成物、及びそれを用いて電極、電気回路を形成した焼成物パターンに関するものである。   The present invention relates to a photocurable composition useful for forming fine electrode circuits on a glass substrate of a plasma display panel (hereinafter abbreviated as PDP) or a ceramic substrate for an electric circuit wiring board, and the like. The present invention relates to a fired product pattern in which electrodes and electric circuits are formed.

ガラス基板上に導電体のパターン層を形成する方法として、銀粉末を含有した光硬化性組成物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）   As a method for forming a conductive pattern layer on a glass substrate, a method for forming a conductive pattern using a photolithographic technique using a photocurable composition containing silver powder has been proposed. (See Patent Document 1)

しかしながら、銀粉末を含有した光硬化性組成物の場合、焼成により銀イオンの拡散が起こりガラス基板が黄色く変色してしまうという問題があった。
特開２００３−１６２０４９号公報 However, in the case of a photocurable composition containing silver powder, there is a problem that silver ions diffuse due to firing and the glass substrate turns yellow.
JP 2003-162049 A

本発明は、このような従来技術が抱える課題を解決するためになされたものであり、その主たる目的は、焼成後にガラス基板の黄変が少ない光硬化性組成物を提供することにある。また、この光硬化性組成物を用いることによって、導電性焼成物パターンを形成したガラス基板を提供することにある。   The present invention has been made in order to solve such problems of the prior art, and a main object thereof is to provide a photocurable composition in which the glass substrate is less yellowed after firing. Another object of the present invention is to provide a glass substrate on which a conductive fired product pattern is formed by using this photocurable composition.

前記目的を達成するために、本発明の焼成導電体パターン形成用光硬化性組成物の基本的な第一の態様は、（Ａ）低融点合金粉末、（Ｂ）有機バインダー、（Ｃ）光重合性モノマー、及び（Ｄ）光重合開始剤を含有する光硬化性組成物であって、前記低融点合金粉末（Ａ）を構成する合金の成分組成が、錫（Ｓｎ）を６０〜９８質量％、銀（Ａｇ）を２０質量％未満含む組成であり、この低融点合金粉末（Ａ）の配合量は、前記光硬化性組成物中の６０〜９０質量％であることを特徴としている。
このような本発明の光硬化性組成物は、ペースト状形態であってもよく、また予めフィルム状に製膜したドライフイルムの形態であってもよい。
さらに本発明によれば、このような光硬化性組成物を用いて形成された導電性焼成物パターンが提供される。 In order to achieve the above object, the basic first aspect of the photocurable composition for forming a fired conductor pattern of the present invention is as follows: (A) low melting point alloy powder, (B) organic binder, (C) light A photocurable composition containing a polymerizable monomer and (D) a photopolymerization initiator , wherein the component composition of the alloy constituting the low melting point alloy powder (A) is tin (Sn) in an amount of 60 to 98 mass. %, And a composition containing less than 20% by mass of silver (Ag), and the amount of the low-melting-point alloy powder (A) is 60 to 90% by mass in the photocurable composition .
Such a photocurable composition of the present invention may be in the form of a paste, or may be in the form of a dry film previously formed into a film.
Furthermore, according to this invention, the conductive baked material pattern formed using such a photocurable composition is provided.

本発明の光硬化性組成物によれば、焼成後にガラス基板の黄変が少ない焼成物パターンの形成が可能となり、例えばＰＤＰの前面板では、表示画面の色彩が黄色くなるなどの問題を減らすことが可能となり極めて有用である。また、高価な銀粉末を使用することが無くコスト的にも極めて有用である。   According to the photocurable composition of the present invention, it becomes possible to form a fired product pattern with less yellowing of the glass substrate after firing. For example, in the case of a front panel of a PDP, it is possible to reduce problems such as a yellow display screen color. Is possible and extremely useful. Further, it is extremely useful in terms of cost without using expensive silver powder.

発明者は、前記目的の実現に向けて鋭意研究した結果、光硬化性導電組成物に低融点合金粉末を使用すると焼成後にガラス基板の黄変が少ない焼成物パターンの形成が可能となることを見出した。   As a result of intensive research aimed at realizing the above object, the inventors have found that when a low melting point alloy powder is used for the photocurable conductive composition, it is possible to form a fired product pattern with less yellowing of the glass substrate after firing. I found it.

このような本発明の光硬化性組成物において、前記低融点合金粉末（Ａ）は２種類以上の金属からなる合金であり、代表的なものとしては鉛（Ｐｂ）、錫（Ｓｎ）系合金およびこれに少量のビスマス（Ｂｉ）などの低融点金属を含む合金などがあげられるが、環境面から考えると有害とされる鉛成分を含まない低融点合金がより好ましく、錫（Ｓｎ）、銀（Ａｇ）、銅（Ｃｕ）、ビスマス（Ｂｉ）亜鉛（Ｚｎ）を主成分にニッケル（Ｎｉ）、ゲルマニウム（Ｇｅ）、インジウム（Ｉｎ）などを少量含む合金を用いることができる。これら金属の中で、錫（Ｓｎ）が主成分としてより好ましく、含有量としては６０〜９８質量％であることが好ましい。含有量が上記範囲よりも少ない場合、融点が高くなり、粉末の融着が起こり難くなることから抵抗値が高くなり好ましくない。一方、上記範囲を超えて多くなるとラインのよれが発生しやすく好ましくない。
また、黄変の原因となる銀（Ａｇ）の含有量としては２０質量％未満であることが好ましい。２０質量％以上となると焼成後のガラス基板の黄変が発生しやすくなり、好ましくない。 In the photocurable composition of the present invention, the low-melting-point alloy powder (A) is an alloy composed of two or more kinds of metals, and representative examples include lead (Pb) and tin (Sn) -based alloys. And an alloy containing a low melting point metal such as bismuth (Bi), etc., and a low melting point alloy containing no lead component, which is considered harmful from the viewpoint of the environment, is more preferable, and tin (Sn), silver An alloy containing (Ag), copper (Cu), bismuth (Bi) zinc (Zn) as a main component and a small amount of nickel (Ni), germanium (Ge), indium (In), or the like can be used. Among these metals, tin (Sn) is more preferable as a main component, and the content is preferably 60 to 98% by mass. When the content is less than the above range, the melting point becomes high, and it becomes difficult for the powder to be fused. On the other hand, if the amount is larger than the above range, the line is liable to be distorted, which is not preferable.
The content of silver (Ag) that causes yellowing is preferably less than 20% by mass. If it is 20% by mass or more, yellowing of the glass substrate after firing tends to occur, which is not preferable.

低融点合金粉末の平均粒径（Ｄ５０）としては１〜２０μｍ、好ましくは１〜１５μｍであることが好ましい。平均粒径（Ｄ５０）が上記範囲よりも小さい場合、光の透過性が悪くなりパターン形成が困難になる。一方、上記範囲を超えて大きくなると、ラインの直線性が得られ難くなり好ましくない。また、一次粒子径（ＳＥＭ写真より任意に選んだ１０個の粒子の平均粒子径）としては１〜１５μｍ、好ましくは１〜１０μｍであることが好ましい。一次粒子径が上記範囲よりも小さい場合、焼成中に酸化され易くなり好ましくない。一方、上記範囲を超えて大きくなると、ラインのよれが発生し易くなり好ましくない。   The average particle diameter (D50) of the low melting point alloy powder is 1 to 20 μm, preferably 1 to 15 μm. When the average particle diameter (D50) is smaller than the above range, the light transmittance is deteriorated and pattern formation becomes difficult. On the other hand, if it exceeds the above range, it is difficult to obtain line linearity, which is not preferable. The primary particle size (average particle size of 10 particles arbitrarily selected from the SEM photograph) is 1 to 15 μm, preferably 1 to 10 μm. When the primary particle diameter is smaller than the above range, it is not preferable because it is easily oxidized during firing. On the other hand, if the value is larger than the above range, the line is liable to be distorted, which is not preferable.

このような低融点合金粉末の配合量は、光硬化性組成物中の６０〜９０質量％、好ましくは７５〜９０質量％の割合とする。導電性粉末の配合量が上記範囲よりも少ない場合、導電回路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、印刷に必要な流動性が得られ難くなり好ましくない。   The blending amount of such a low melting point alloy powder is 60 to 90% by mass, preferably 75 to 90% by mass in the photocurable composition. When the blending amount of the conductive powder is less than the above range, sufficient conductivity of the conductive circuit pattern cannot be obtained. On the other hand, when the amount exceeds the above range, it is difficult to obtain the fluidity necessary for printing. Absent.

次に、有機バインダー（Ｂ）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。
この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、単独でまたは混合して用いてもよいが、いずれの場合でもこれらは合計で組成物全量の１〜３５質量％の割合で配合することが好ましい。これらのポリマーの配合量が上記範囲より少ない場合、形成する皮膜中の上記樹脂の分布が不均一になり易く、充分な光硬化性およ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、上記範囲よりも多い場合、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。 Next, as the organic binder (B), a carboxyl group-containing resin, specifically, a carboxyl group-containing photosensitive resin itself having an ethylenically unsaturated double bond and an ethylenically unsaturated double bond. Any carboxyl group-containing resin can be used.
These carboxyl group-containing photosensitive resins and carboxyl group-containing resins may be used alone or in combination, but in any case, they may be blended in a proportion of 1 to 35% by mass of the total amount of the composition. preferable. When the blending amount of these polymers is less than the above range, the distribution of the resin in the film to be formed tends to be non-uniform, and it is difficult to obtain sufficient photocurability and photocuring depth, and patterning by selective exposure and development. It becomes difficult. On the other hand, when the amount is larger than the above range, it is not preferable because the pattern is distorted or the line width is easily shrunk during firing.

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が１，０００〜１００，０００、好ましくは５，０００〜７０，０００であり、かつ酸価が５０〜２５０ｍｇＫＯＨ／ｇであることが好ましい。さらに、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３５０〜２，０００ｇ／当量、好ましくは４００〜１，５００ｇ／当量のものが好適に用いることができる。上記樹脂の重量平均分子量が１，０００未満の場合、現像時の皮膜の密着性に悪影響を与え、一方、１００，０００を超えた場合、現像不良を生じ易いので好ましくない。また、酸価が５０ｍｇＫＯＨ／ｇ未満の場合、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を超えた場合、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。   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 50 to 250 mgKOH / It is preferable that it is g. Furthermore, in the case of a carboxyl group-containing photosensitive resin, those having a double bond equivalent of 350 to 2,000 g / equivalent, preferably 400 to 1,500 g / equivalent can be suitably used. When the weight average molecular weight of the resin is less than 1,000, it adversely affects the adhesion of the film during development. On the other hand, when it exceeds 100,000, development failure tends to occur, which is not preferable. When the acid value is less than 50 mg KOH / g, the solubility in an alkaline aqueous solution is insufficient and the development is likely to be poor. On the other hand, when the acid value exceeds 250 mg KOH / g, the adhesion of the film is deteriorated during development or the photocured part ( This is not preferable because dissolution of the exposed portion occurs.

本発明において光重合性モノマー（Ｃ）は、組成物の光硬化性の促進及び現像性を向上させるために用いる。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、こはく酸、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。   In the present invention, the photopolymerizable monomer (C) is used for promoting the photocurability of the composition and improving the developability. Examples of the photopolymerizable monomer (C) include 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, polyethylene glycol diacrylate, polyurethane diacrylate, trimethylolpropane triacrylate, penta Erythritol triacrylate, pentaerythritol tetraacrylate, trimethylolpropane ethylene oxide modified triacrylate, trimethylolpropane propylene oxide modified triacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, and methacrylates corresponding to the above acrylates; phthalic acid , Adipic acid, maleic acid, octopus Examples include mono-, di-, tri- or higher polyesters of polybasic acids such as acids, succinic acid, trimellitic acid, terephthalic acid, and hydroxyalkyl (meth) acrylate, but are limited to specific ones. These are not intended, 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.

このような光重合性モノマー（Ｃ）の配合量は、前記有機バインダー（カルボキシル基含有感光性樹脂及び／又はカルボキシル基含有樹脂）（Ｂ）１００質量部当り、２０〜２５０質量部が適当である。光重合性モノマー（Ｃ）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面部の光硬化が早くなるため硬化むらを生じ易くなる。   The amount of such photopolymerizable monomer (C) is suitably 20 to 250 parts by mass per 100 parts by mass of the organic binder (carboxyl group-containing photosensitive resin and / or carboxyl group-containing resin) (B). . When the blending amount of the photopolymerizable monomer (C) 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 surface is larger than the deep part of the film. Since the photo-curing of the part is accelerated, uneven curing is likely to occur.

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ン−１−オン、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、２−（ジメチルアミノ）−２−［（４−メチルフェニル）メチル］−１−［４−（４−モルホリニル）フェニル］−１−ブタノン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、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、これら公知慣用の光重合開始剤を単独で又は２種以上を組み合わせて用いることができる。
これらの光重合開始剤（Ｄ）の配合割合は、前記有機バインダー（カルボキシル基含有感光性樹脂及び／又はカルボキシル基含有樹脂）（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。 Specific examples of the photopolymerization initiator (D) include 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, Acetophenones such as 2-diethoxy-2-phenylacetophenone and 1,1-dichloroacetophenone; 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl-2- Dimethylamino-1- (4-morpholinophenyl) -butanone-1,2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1 -Aminoacetophenones such as butanone; 2-methyla Anthraquinones such as traquinone, 2-ethylanthraquinone, 2-t-butylanthraquinone, 1-chloroanthraquinone; 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-diisopropylthioxanthone, etc. Thioxanthones; 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 (2,4,4) 6-trimethylbenzoyl) -phenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, ethyl-2,4,6-trimethylbenzoylphenylphosphine Phosphine oxide such as preparative; various peroxides and the like can be used alone or in combination of two or more of these conventionally known photopolymerization initiator.
The mixing ratio of these photopolymerization initiators (D) is suitably 1 to 30 parts by mass per 100 parts by mass of the organic binder (carboxyl group-containing photosensitive resin and / or carboxyl group-containing resin) (B), Preferably, it is 5-20 mass parts.

また、上記のような光重合開始剤（Ｄ）は、Ｎ，Ｎ−ジメチルアミノ安息香酸エチルエステル、Ｎ，Ｎ−ジメチルアミノ安息香酸イソアミルエステル、ペンチル−４−ジメチルアミノベンゾエート、トリエチルアミン、トリエタノールアミン等の三級アミン類のような光増感剤の１種あるいは２種以上と組み合わせて用いることができる。
さらに、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・ケミカルズ社製イルガキュアー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。 The photopolymerization initiator (D) is composed of N, N-dimethylaminobenzoic acid ethyl ester, N, N-dimethylaminobenzoic acid isoamyl ester, pentyl-4-dimethylaminobenzoate, triethylamine, triethanolamine. It can be used in combination with one or more photosensitizers such as tertiary amines.
Furthermore, 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 dyes are cured as necessary. It can be used in combination as an auxiliary agent.

本発明の光硬化性組成物は、必要に応じて軟化点４００〜６００℃のガラス粉末を、本発明の光硬化性樹脂組成物の特性を損なわない量的割合で配合することができる。
ガラス粉末は、焼成後の導体回路との密着性向上のために、導電粉末（Ｂ）１００質量部当り、５０質量部以下、好ましくは１０質量部以下の割合で添加できる。この理由は、その配合量が上記範囲よりも多いと焼成後に充分な導通が得られず、好ましくない。このガラス粉末としては、そのガラス転移点（Ｔｇ）３００〜５００℃、ガラス軟化点（Ｔｓ）４００〜６００℃のものが好ましい。ガラス粉末の軟化点が４００℃より低いと、有機バインダーを包み込み易くなり、残存する有機バインダーが分解することによって組成物中にブリスターが生じ易くなるので好ましくない。また、解像度の点からは、平均粒径１０μｍ以下、好ましくは３μｍ以下のガラス粉末を用いることが好ましい。 The photocurable composition of this invention can mix | blend the glass powder of the softening point 400-600 degreeC with the quantitative ratio which does not impair the characteristic of the photocurable resin composition of this invention as needed.
The glass powder can be added at a ratio of 50 parts by mass or less, preferably 10 parts by mass or less per 100 parts by mass of the conductive powder (B) in order to improve the adhesion with the conductor circuit after firing. The reason is that if the blending amount is larger than the above range, sufficient conduction cannot be obtained after firing, which is not preferable. The glass powder preferably has a glass transition point (Tg) of 300 to 500 ° C. and a glass softening point (Ts) of 400 to 600 ° C. When the softening point of the glass powder is lower than 400 ° C., the organic binder is likely to be encapsulated, and the remaining organic binder is decomposed, so that blisters are easily generated in the composition. From the viewpoint of resolution, it is preferable to use glass powder having an average particle size of 10 μm or less, preferably 3 μm or less.

上記ガラス粉末としては、酸化鉛、酸化ビスマス、又は酸化亜鉛などを主成分とする非結晶性フリットが好適に使用できる。   As the glass powder, an amorphous frit mainly composed of lead oxide, bismuth oxide, zinc oxide or the like can be preferably used.

本発明においては、光硬化性組成物に多量の無機粉末を配合した場合、得られる組成物の保存安定性が悪く、ゲル化や流動性の低下により塗布作業性が悪くなる傾向がある。従って、本発明の組成物では、組成物の保存安定性向上のため、無機粉末の成分である金属あるいは酸化物粉末との錯体化あるいは塩形成などの効果のある化合物を、安定剤として添加することができる。安定剤としては、硝酸、硫酸、塩酸、ホウ酸等の各種無機酸；ギ酸、酢酸、アセト酢酸、クエン酸、ステアリン酸、マレイン酸、フマル酸、フタル酸、ベンゼンスルホン酸、スルファミン酸等の各種有機酸；リン酸、亜リン酸、次亜リン酸、リン酸メチル、リン酸エチル、リン酸ブチル、リン酸フェニル、亜リン酸エチル、亜リン酸ジフェニル、モノ（２−メタクリロイルオキシエチル）アシッドホスフェート等の各種リン酸化合物（無機リン酸、有機リン酸）などの酸が挙げられ、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。   In the present invention, when a large amount of inorganic powder is blended with the photocurable composition, the storage stability of the resulting composition is poor, and the coating workability tends to be poor due to gelation and fluidity deterioration. Therefore, in the composition of the present invention, in order to improve the storage stability of the composition, a compound having an effect of complexing or forming a salt with a metal or oxide powder which is a component of the inorganic powder is added as a stabilizer. be able to. Stabilizers include various inorganic acids such as nitric acid, sulfuric acid, hydrochloric acid, and boric acid; various types such as formic acid, acetic acid, acetoacetic acid, citric acid, stearic acid, maleic acid, fumaric acid, phthalic acid, benzenesulfonic acid, and sulfamic acid Organic acids: phosphoric acid, phosphorous acid, hypophosphorous acid, methyl phosphate, ethyl phosphate, butyl phosphate, phenyl phosphate, ethyl phosphite, diphenyl phosphite, mono (2-methacryloyloxyethyl) acid Acids, such as various phosphoric acid compounds (inorganic phosphoric acid, organic phosphoric acid), such as a phosphate, are mentioned, It can use individually or in combination of 2 or more types.

本発明においては、組成物を希釈することによりペースト化し、容易に塗布工程を可能とし、次いで乾燥させて造膜し、接触露光を可能とさせるために、適宜の量の有機溶剤を配合することができる。具体的には、メチルエチルケトン、シクロヘキサノンなどのケトン類；トルエン、キシレン、テトラメチルベンゼンなどの芳香族炭化水素類；セロソルブ、メチルセロソルブ、カルビトール、メチルカルビトール、ブチルカルビトール、プロピレングリコールモノメチルエーテル、ジプロピレングリコールモノメチルエーテル、ジプロピレングリコールモノエチルエーテル、トリエチレングリコールモノエチルエーテルなどのグリコールエーテル類；酢酸エチル、酢酸ブチル、セロソルブアセテート、ブチルセロソルブアセテート、カルビトールアセテート、ブチルカルビトールアセテート、プロピレングリコールモノメチルエーテルアセテート、２，２，４−トリメチル−１，３−ペンタンジオールモノイソブチレートなどのエステル類；エタノール、プロパノール、エチレングリコール、プロピレングリコール、テルピネオールなどのアルコール類；オクタン、デカンなどの脂肪族炭化水素；石油エーテル、石油ナフサ、水添石油ナフサ、ソルベントナフサなどの石油系溶剤、２，２，４−トリメチル−１，３−ペンタンジオールモノイソブチレート等が挙げられ、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。   In the present invention, the composition is made into a paste by diluting, enabling an easy coating process, then drying to form a film, and blending an appropriate amount of an organic solvent to enable contact exposure. Can do. Specifically, ketones such as methyl ethyl ketone and cyclohexanone; aromatic hydrocarbons such as toluene, xylene and tetramethylbenzene; cellosolve, methyl cellosolve, carbitol, methyl carbitol, butyl carbitol, propylene glycol monomethyl ether, di Glycol ethers such as propylene glycol monomethyl ether, dipropylene glycol monoethyl ether, triethylene glycol monoethyl ether; ethyl acetate, butyl acetate, cellosolve acetate, butyl cellosolve acetate, carbitol acetate, butyl carbitol acetate, propylene glycol monomethyl ether acetate , Esters such as 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate; Alcohols such as ethanol, propanol, ethylene glycol, propylene glycol and terpineol; aliphatic hydrocarbons such as octane and decane; petroleum solvents such as petroleum ether, petroleum naphtha, hydrogenated petroleum naphtha and solvent naphtha, 2,2,4 -Trimethyl- 1, 3-pentanediol monoisobutyrate etc. are mentioned, These can be used individually or in combination of 2 or more types.

さらに、必要に応じて、ハイドロキノン、ハイドロキノンモノメチルエーテル、ｔｅｒｔ−ブチルカテコール、ピロガロール、フェノチアジンなどの公知慣用の熱重合禁止剤、微粉シリカ、有機ベントナイト、モンモリロナイト、脂肪酸アミドなどの公知慣用のチクソ性付与剤、シリコーン系、フッ素系、高分子系などの消泡剤及び／又はレベリング剤、イミダゾール系、チアゾール系、トリアゾール系、シランカップリング剤などの公知慣用の密着性付与剤、分散助剤のような添加剤類を配合することができる。   Further, if necessary, known and conventional thermal polymerization inhibitors such as hydroquinone, hydroquinone monomethyl ether, tert-butylcatechol, pyrogallol and phenothiazine, and known and conventional thixotropic agents such as fine silica, organic bentonite, montmorillonite and fatty acid amide. , Antifoaming agents and / or leveling agents such as silicones, fluorines and polymers, imidazole, thiazoles, triazoles, silane coupling agents and other well-known and commonly used adhesion promoters, dispersion aids, etc. Additives can be blended.

本発明の光硬化性組成物は、予めフィルム状に成膜されている場合には基板上にラミネートすればよいが、ペースト状組成物の場合、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で基板、例えばＰＤＰの前面基板となるガラス基板に塗布し、次いで指触乾燥性を得るために熱風循環式乾燥炉、遠赤外線乾燥炉等で例えば約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。その後、選択的露光、現像、焼成を行なって所定のパターンの電極回路を形成する。   The photocurable composition of the present invention may be laminated on a substrate when it has been formed into a film in advance, but in the case of a paste-like composition, a screen printing method, a bar coater, a blade coater, etc. It is applied to a substrate, for example, a glass substrate that is a front substrate of a PDP by a coating method, and then, for example, in a hot air circulation drying furnace, a far infrared drying furnace, etc., for example, at about 60 to 120 ° C. for 5 to 40 minutes in order to obtain touch dryness The organic solvent is evaporated by drying to a certain degree to obtain a tack-free coating film. Thereafter, selective exposure, development, and baking are performed to form an electrode circuit having a predetermined pattern.

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及び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、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。 As the exposure step, contact exposure and non-contact exposure using a negative mask having a predetermined exposure pattern are possible. As the exposure light source, a halogen lamp, a high-pressure mercury lamp, a laser beam, a metal halide 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、水洗を行なうことが好ましい。   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. Moreover, it is preferable to wash with water in order to remove an unnecessary developer after development.

焼成工程においては、現像後の基板を空気中又は窒素雰囲気下で約５００〜６２０℃の加熱処理を行ない、所望のパターンを形成する。
焼成後のパターンの膜厚は、１〜３０μｍであることが好ましく、焼成膜厚が上記範囲よりも薄くなるとパターンの断線、ピンホールなどが起こりやすく充分な導通を得ることが難しく、焼成膜厚が上記範囲を超えて厚くなるとパターン形成が難しくなり好ましくない。 In the baking step, the substrate after development is subjected to heat treatment at about 500 to 620 ° C. in air or in a nitrogen atmosphere to form a desired pattern.
The film thickness of the pattern after firing is preferably 1 to 30 μm. When the fired film thickness is thinner than the above range, pattern disconnection, pinholes and the like are likely to occur, and it is difficult to obtain sufficient conduction, and the fired film thickness If the thickness exceeds the above range, pattern formation becomes difficult, which is not preferable.

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。   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.

下記の表１に示す熱硬化成分、有機バインダー、及び導電性粉末を用いて、組成物例１〜５並びに比較組成物例１〜２を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なった。   Using the thermosetting component, organic binder, and conductive powder shown in Table 1 below, Composition Examples 1 to 5 and Comparative Composition Examples 1 and 2 were blended in the composition ratios shown below, and after stirring with a stirrer Pasting was carried out by kneading with a three-roll mill.

・低融点合金粉末は、レーザー解析散乱法粒度分布測定装置による平均粒径（Ｄ５０）＝１２μｍ、（Ｄ１０）＝９．５μｍ、（Ｄ９０）＝１５．４３μｍ、ＳＥＭ写真（２０００倍）の写真により任意に選んだ１０個の粒子の平均粒径が５．６μｍ、組成比率（質量％）錫９６．５％、銀３％、銅０．５％、の粉末を使用した。
・有機バインダーは、三菱レイヨン社製のカルボキシル基含有樹脂ＰＢ−３８３（Ｔｇ＝６３℃、酸価＝１７６ｍｇＫＯＨ／ｇ、重量平均分子量＝２６，０００）を２，２，４−トリメチル−１，３ペンタンジオールモノイソブチレートへ溶解させ、固形分４０ｗｔ％としたものを用いた。
・ 銀粉末は、平均粒径（Ｄ５０）＝１．７μｍ、銀９９質量％の粉末を使用した。 ・ The low melting point alloy powder is obtained by a photograph of an average particle diameter (D50) = 12 μm, (D10) = 9.5 μm, (D90) = 15.43 μm, SEM photograph (2000 times) by a laser analysis scattering method particle size distribution measuring device. A powder having an average particle diameter of 5.6 μm, composition ratio (mass%) tin 96.5%, silver 3%, copper 0.5% was used.
The organic binder is a carboxyl group-containing resin PB-383 (Tg = 63 ° C., acid value = 176 mgKOH / g, weight average molecular weight = 26,000) manufactured by Mitsubishi Rayon Co., 2,2,4-trimethyl-1,3 What was dissolved in pentanediol monoisobutyrate to give a solid content of 40 wt% was used.
-The silver powder used the average particle diameter (D50) = 1.7micrometer and the powder of silver 99 mass%.

（組成物例１）
有機バインダー ２５０部
トリメチロールプロパントリアクリレート ７４部
EO変性トリメチロールプロパントリアクリレート １００部
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ン−１−オン １０部
低融点合金粉末 １４８１部
消泡・レベリング剤（ＸＬ４９０−５０：伊藤製油社製） ５部 (Composition Example 1)
Organic binder 250 parts Trimethylolpropane triacrylate 74 parts
EO-modified trimethylolpropane triacrylate 100 parts 2-methyl-1- [4- (methylthio) phenyl]-
2-morpholinopropan-1-one 10 parts Low melting point alloy powder 1481 parts Antifoaming / leveling agent (XL490-50: manufactured by Ito Oil Co., Ltd.) 5 parts

（組成物例２）
低融点合金粉末の配合量を２２２２部としたこと以外は組成物例１と同様の組成物。 (Composition Example 2)
A composition similar to that of Composition Example 1 except that the blending amount of the low melting point alloy powder is 2222 parts.

（組成物例３）
低融点合金粉末の配合量を２９６３部としたこと以外は組成物例１と同様の組成物。 (Composition Example 3)
A composition similar to that of Composition Example 1 except that the blending amount of the low melting point alloy powder is 2963 parts.

（比較組成物例１）
低融点合金粉末を銀粉末に置き換え、配合量を７５０部としたこと以外は組成物例１と同様の組成物。 (Comparative composition example 1)
A composition similar to that of Composition Example 1 except that the low melting point alloy powder is replaced with silver powder and the blending amount is 750 parts.

（比較組成物例２）
低融点合金粉末の配合量を６００部としたこと以外は組成物例１と同様の組成物。 (Comparative composition example 2)
A composition similar to that of Composition Example 1 except that the blending amount of the low melting point alloy powder is 600 parts.

（比較組成物例３）
低融点合金粉末の配合量を４５００部としたこと以外は組成物例１と同様の組成物。 (Comparative composition example 3)
A composition similar to that of Composition Example 1 except that the blending amount of the low melting point alloy powder is 4500 parts.

ガラス基板の黄変試験用基板作成
ガラス基板上に、評価用ペーストを２００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８０℃で２０分間乾燥して指触乾燥性の良好な皮膜を形成した。その後、ライン／スペース＝１００／１００μｍとなるネガフィルムを用いて組成物上の積算光量が９００ｍＪ／ｃｍ２となるように露光した後、液温３０℃の０．４ｗｔ％Ｎａ２ＣＯ３水溶液を用いて現像を行ない、水洗した。最後に空気雰囲気下にて１０℃／分で昇温し、５６０℃で１０分間焼成して試験片を作製した。 Preparation of substrate for yellowing test of glass substrate On the glass substrate, the paste for evaluation was applied to the entire surface using a 200 mesh polyester screen, and then dried at 80 ° C. for 20 minutes in a hot air circulating drying oven to touch. A film having good drying properties was formed. Then, after the integrated quantity of light on the composition using a negative film as a line / space = 100/100 [mu] m was exposed to a 900 mJ / cm 2, the 0.4wt% Na 2 CO 3 aqueous solution temperature 30 ° C. It was used for development and washed with water. Finally, the temperature was raised at 10 ° C./min in an air atmosphere and baked at 560 ° C. for 10 minutes to prepare a test piece.

抵抗値測定用基板作成
１００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８０℃で２０分間乾燥して指触乾燥性の良好な皮膜を形成した。その後、パターン寸法４ｍｍ×１００ｍｍのラインが形成できるネガマスクを用いて、組成物上の積算光量が９００ｍＪ／ｃｍ２となるように露光した後、液温３０℃の０．４ｗｔ％Ｎａ２ＣＯ３水溶液を用いて現像を行ない、水洗した。最後に空気雰囲気下にて１０℃／分で昇温し、５６０℃で１０分間焼成して基板を作製した。 Create a resistance measurement board
The film was coated on the entire surface using a 100 mesh polyester screen, and then dried at 80 ° C. for 20 minutes in a hot air circulating drying oven to form a film having good touch drying properties. Then, using the negative mask capable of forming a line pattern dimensions 4 mm × 100 mm, after the accumulated amount of the composition was exposed so as to 900mJ / cm 2, 0.4wt% Na 2 CO 3 aqueous solution temperature 30 ° C. Development was carried out using and washed with water. Finally, the substrate was heated at 10 ° C./min in an air atmosphere and baked at 560 ° C. for 10 minutes to produce a substrate.

ガラス基板の黄変：
上記試験片を光学顕微鏡により目視観察してスペース部分が黄色く変色しているか否かを評価した。 Yellowing of glass substrate:
The test piece was visually observed with an optical microscope to evaluate whether or not the space portion had turned yellow.

膜厚：
上記試験片を用いて表面粗さ計（小坂研究所社製 ＳＥ−３０Ｈ）により膜厚を測定した。 Film thickness:
The film thickness was measured with a surface roughness meter (SE-30H manufactured by Kosaka Laboratory Ltd.) using the above test piece.

抵抗値：
上記試験片を用いてテスター（ＨＩＯＫＩ ３５４０ ｍΩ ＨＩＴＥＳＴＥＲ）により抵抗値を測定した。
Resistance value:
The resistance value was measured with a tester (HIOKI 3540 mΩ HITESTER) using the test piece.

これらの評価結果を、表１に示す。


These evaluation results are shown in Table 1.


表１に示す結果から明らかなように、本発明の組成物に係るペーストは、比較組成物のペーストに比べてガラス基板の黄変が充分に少ないパターンを形成できることが判った。

As is clear from the results shown in Table 1, it was found that the paste according to the composition of the present invention can form a pattern with sufficiently less yellowing of the glass substrate than the paste of the comparative composition.

Claims (3)

（Ａ）低融点合金粉末、（Ｂ）有機バインダー、（Ｃ）光重合性モノマー、及び（Ｄ）光重合開始剤を含有する光硬化性組成物であって、前記低融点合金粉末（Ａ）を構成する合金の成分組成が、錫（Ｓｎ）を６０〜９８質量％、銀（Ａｇ）を２０質量％未満含む組成であり、この低融点合金粉末（Ａ）の配合量は、前記光硬化性組成物中の６０〜９０質量％であることを特徴とする焼成導電体パターン形成用光硬化性組成物。 (A) a low-melting-point alloy powder, (B) an organic binder, (C) a photopolymerizable monomer, and (D) a photo-curable composition containing a photopolymerization initiator , wherein the low-melting-point alloy powder (A) The composition of the alloy constituting the alloy is a composition containing 60 to 98% by mass of tin (Sn) and less than 20% by mass of silver (Ag), and the blending amount of the low melting point alloy powder (A) A photocurable composition for forming a fired conductor pattern, which is 60 to 90% by mass in the conductive composition. 前記低融点合金粉末（Ａ）を構成する合金の成分組成が、鉛（Ｐｂ）を含まないことを特徴とする請求項１に記載の焼成導電体パターン形成用光硬化性組成物。 2. The photocurable composition for forming a fired conductor pattern according to claim 1, wherein the component composition of the alloy constituting the low melting point alloy powder (A) does not contain lead (Pb). ガラス基板上に、前記請求項１または２に記載の光硬化性組成物のパターンを形成し、焼成して得られる焼成物パターン。 A fired product pattern obtained by forming and firing a pattern of the photocurable composition according to claim 1 or 2 on a glass substrate.
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