JPWO2017090680A1 - 硬化性組成物及び電子部品の製造方法 - Google Patents
硬化性組成物及び電子部品の製造方法 Download PDFInfo
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- JPWO2017090680A1 JPWO2017090680A1 JP2016570123A JP2016570123A JPWO2017090680A1 JP WO2017090680 A1 JPWO2017090680 A1 JP WO2017090680A1 JP 2016570123 A JP2016570123 A JP 2016570123A JP 2016570123 A JP2016570123 A JP 2016570123A JP WO2017090680 A1 JPWO2017090680 A1 JP WO2017090680A1
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- acrylic monomer
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- titanium oxide
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Images
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
- C08F265/02—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of acids, salts or anhydrides
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- 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
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Abstract
Description
本発明に係る硬化性組成物は、光の照射により硬化されて用いられることが好ましい。本発明に係る硬化性組成物は、現像処理により硬化被膜を形成するために用いられることが好ましく、現像処理によりレジスト膜を形成するために用いられることがより好ましい。本発明に係る硬化性組成物は、現像型レジスト硬化性組成物であることが好ましい。本発明に係る硬化性組成物においては、レジスト膜を形成するために現像が行われなくてもよく、本発明に係る硬化性組成物は、非現像型レジスト硬化性組成物であってもよい。本発明に係る硬化性組成物は、ソルダーレジスト用硬化性組成物であることが好ましい。
(A)カルボキシル基含有樹脂は、カルボキシル基を有する重合性重合体であることが好ましい。カルボキシル基を有する重合性重合体は、重合性を有し、重合可能である。(A)カルボキシル基含有樹脂は、(メタ)アクリロイル基を3つ以上有するアクリルモノマー以外の樹脂であり、式(1)で表されるアクリルモノマー以外の樹脂である。(A)カルボキシル基含有樹脂は、1種のみが用いられてもよく、2種以上が併用されてもよい。
(B)第1のアクリルモノマーは、(メタ)アクリロイル基を3つ以上有する。(B)第1のアクリルモノマーの(メタ)アクリロイル基の数は6以下であってもよく、5以下であってもよい。(B)第1のアクリルモノマーは、1種のみが用いられてもよく、2種以上が併用されてもよい。
上記硬化性組成物は、(D)光重合開始剤を含むので、光の照射により硬化性組成物を硬化させることができる。(D)光重合開始剤は、1種のみが用いられてもよく、2種以上が併用されてもよい。
上記硬化性組成物が(E)酸化チタンを含むので、反射率が高いレジスト膜などの硬化物を形成できる。(E)酸化チタンを用いることによって、(E)酸化チタン以外の他の無機フィラーを用いた場合と比較して、反射率が高い硬化物を形成できる。(E)酸化チタンは、1種のみが用いられてもよく、2種以上が併用されてもよい。
上記硬化性組成物は、(F)酸化チタンとは異なる無機フィラーを含んでいてもよい。(F)無機フィラーは、酸化チタンとは異なる無機フィラーである。(F)無機フィラーは1種のみが用いられてもよく、2種以上が併用されてもよい。
硬化物の切り出し加工性を高めることなどを目的として、上記硬化性組成物は、(G)エポキシ化合物を含むことが好ましい。また、(G)エポキシ化合物の使用により、硬化性組成物の硬化性も良好になる。(G)エポキシ化合物は、(A)カルボキシル基含有樹脂以外のエポキシ化合物である。(G)エポキシ化合物は、1種のみが用いられてもよく、2種以上が併用されてもよい。
上記硬化性組成物は、(H)溶剤を含んでいてもよい。(H)溶剤は、1種のみが用いられてもよく、2種以上が併用されてもよい。
硬化物の高温下での変色をより一層抑える観点からは、上記硬化性組成物は、(I)酸化防止剤を含んでいてもよい。(I)酸化防止剤は、ルイス塩基性部位を有することが好ましい。硬化物の高温下での変色をより一層抑える観点からは、(I)酸化防止剤は、フェノール系酸化防止剤、リン系酸化防止剤又はアミン系酸化防止剤であることが好ましく、フェノール系酸化防止剤であることがより好ましい。
上記硬化性組成物は、着色剤、充填剤、消泡剤、硬化剤、硬化促進剤、離型剤、表面処理剤、難燃剤、粘度調節剤、分散剤、分散助剤、表面改質剤、可塑剤、抗菌剤、防黴剤、レベリング剤、安定剤、カップリング剤、タレ防止剤又は蛍光体等を含んでいてもよい。
本発明に係る電子部品の製造方法は、電子部品本体の表面上に、上記硬化性組成物を塗布して、組成物層を形成する工程と、上記組成物層に光を照射して、硬化被膜形成する工程とを備える。本発明に係る電子部品の製造方法では、上記硬化被膜を形成するために、上記組成物層を現像してもよい。上記組成物層がレジスト層であることが好ましく、上記硬化被膜がレジスト膜であることが好ましい。
(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、溶剤であるエチルカルビトールアセテートと、触媒であるアゾビスイソブチロニトリルとを入れ、窒素雰囲気下で80℃に加熱し、メタクリル酸とメチルメタクリレートとを30:70のモル比で混合したモノマーを2時間かけて滴下した。滴下後、1時間攪拌し、温度を120℃に上げた。その後、冷却した。得られた樹脂の全てのモノマー単位の総量のモル量に対するモル比が10となる量のグリシジルアクリレートを加え、触媒として臭化テトラブチルアンモニウムを用い100℃で30時間加熱して、グリシジルアクリレートとカルボキシル基とを付加反応させた。冷却後、フラスコから取り出して、固形分酸価60mgKOH/g、重量平均分子量15000、二重結合当量1000のカルボキシル基含有樹脂を50重量%(不揮発分)含む溶液を得た。以下、この溶液をアクリルポリマー1と呼ぶ。
、新中村化学工業社製)
合成例1で得られたアクリルポリマー1を15重量部と、DPHA(第1のアクリルモノマー、ジペンタエリスリトールヘキサアクリレート、ダイセル・オルネクス社製)5重量部と、A−200(第2のアクリルモノマー、ポリエチレングリコールジアクリレート、新中村化学工業社製)1重量部と、157S(ビスフェノールAノボラック型エポキシ樹脂、三菱化学社製、25℃で固体)8重量部と、TPO(光ラジカル発生剤である光重合開始剤、BASFジャパン社製)2重量部と、CR−50(酸化チタン、石原産業社製)40重量部と、FH105(タルク、富士タルク社製)10重量部と、KS−7710(コンパウンド型シリコーンオイル、ポリジメチルシロキサン、信越化学工業社製)1重量部と、ジプロピレングリコールモノメチルエーテル(MFDG、溶剤、日本乳化剤社製)30重量部とを配合し、混合機(シンキー社製「練太郎ARE−310」)にて3分間混合した後、3本ロールにて混合し、混合物を得た。その後、ARE−310を用いて、得られた混合物を3分間脱泡することにより、硬化性組成物であるレジスト材料を得た。
使用した材料の種類及び配合量を下記の表1,2に示すように変更したこと以外は、実施例1と同様にして、硬化性組成物であるレジスト材料を得た。
(1)測定サンプルの作製
80mm×90mm、厚さ0.8mmのFR−4基板を用意した。この基板上に、スクリーン印刷法により、100メッシュのポリエステルバイアス製の版を用いて、ベタパターンでレジスト材料を印刷した。印刷後、80℃のオーブン内で20分間乾燥させ、レジスト材料層を基板上に形成した。次に、所定のパターンを有するフォトマスクを介して、紫外線照射装置を用い、レジスト材料層に波長365nmの紫外線を、照射エネルギーが400mJ/cm2となるように100mW/cm2の紫外線照度で4秒間照射した。その後、未露光部のレジスト材料層を除去してパターンを形成するために、炭酸ナトリウムの1重量%水溶液(25℃)にレジスト材料層を30秒間浸漬して現像し、基板上にレジスト膜を形成した。その後、150℃のオーブン内で1時間加熱しレジスト膜を後硬化させることにより、測定サンプルとしてのレジスト膜を得た。得られたレジスト膜の厚みは20μmであった。
測定サンプルを加熱オーブン内に入れ、270℃で5分間加熱した。
○:ΔE*abが0.5以下
△:ΔE*abが0.5を超え、1以下
×:ΔE*abが1を超える
○○:b*の変化量が1.0下
○:b*が1.0を超え、1.5以下
△:b*が1.5を超え、2.0以下
×:b*が2.0を超える
測定サンプルを加熱オーブン内に入れ、270℃で5分間加熱した。270℃で5分間加熱した後の測定サンプルにおいて、レジスト膜におけるクラックの発生状態を確認した。また、測定サンプルを加熱オーブン内に入れ、270℃で10分間加熱した。270℃で10分間加熱した後の測定サンプルにおいて、レジスト膜におけるクラックの発生状態を確認した。
○○:クラックが発生していない
○:最大長さが500μm未満のわずかなクラックが発生している
△:最大長さが500μm以上、1000μm未満のクラックが発生している
×:最大長さが1000μm以上のクラックが発生している
測定サンプルの未露光部のレジスト残渣、即ちレジスト材料層が除去され、パターン形成された銅表面に残っているレジスト残渣を観察した。この残渣から、現像性を以下の基準で判定した。
○○:銅表面にレジスト材料層が全く残っておらず、銅色がはっきりと見える
○:銅表面にごくわずかにレジスト材料層が残っているが、銅色がはっきりと見える
△:銅表面にわずかにレジスト材料層が残っており、銅色が白くかすんでいる
×:銅表面にレジスト材料層が残っており、銅色が見えない
2,2X…レジスト膜
11…塗布対象部材(電子部品本体)
11A…基板
11B…電極
12,12X…レジスト層
13…マスク
使用した材料の種類及び配合量を書きの表1,2に示すように変更したこと以外は、実施例1と同様にして、硬化性組成物であるレジスト材料を得た。
Claims (7)
- エポキシ化合物を含む、請求項1に記載の硬化性組成物。
- 前記エポキシ化合物が、25℃で固体状である、請求項2に記載の硬化性組成物。
- 前記第1のアクリルモノマーの含有量の前記第2のアクリルモノマーの含有量に対する比が、重量基準で、0.05以上、20以下である、請求項1〜3のいずれか1項に記載の硬化性組成物。
- 現像処理によりレジスト膜を形成するために用いられる現像型レジスト硬化性組成物である、請求項1〜4のいずれか1項に記載の硬化性組成物。
- 電子部品本体の表面上に、請求項1〜5のいずれか1項に記載の硬化性組成物を塗布して、組成物層を形成する工程と、
前記組成物層に光を照射して、硬化被膜を形成する工程とを備え、
前記硬化被膜を形成するために、前記組成物層を現像する、電子部品の製造方法。 - 前記組成物層がレジスト層であり、前記硬化被膜がレジスト膜である、請求項6に記載の電子部品の製造方法。
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