JP4864545B2 - Thermosetting solder resist composition for flexible substrate, flexible substrate and method for producing flexible substrate - Google Patents

Thermosetting solder resist composition for flexible substrate, flexible substrate and method for producing flexible substrate Download PDF

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JP4864545B2
JP4864545B2 JP2006146994A JP2006146994A JP4864545B2 JP 4864545 B2 JP4864545 B2 JP 4864545B2 JP 2006146994 A JP2006146994 A JP 2006146994A JP 2006146994 A JP2006146994 A JP 2006146994A JP 4864545 B2 JP4864545 B2 JP 4864545B2
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solder resist
flexible substrate
epoxy resin
resist composition
type epoxy
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JP2007317945A (en
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義和 大胡
滋 宇敷
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Taiyo Holdings Co Ltd
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Priority to CN2007101061106A priority patent/CN101077956B/en
Priority to KR1020070050656A priority patent/KR100830810B1/en
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    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03FPHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004Photosensitive materials
    • G03F7/0045Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03FPHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004Photosensitive materials
    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03FPHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004Photosensitive materials
    • G03F7/0042Photosensitive materials with inorganic or organometallic light-sensitive compounds not otherwise provided for, e.g. inorganic resists
    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03FPHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004Photosensitive materials
    • G03F7/0047Photosensitive materials characterised by additives for obtaining a metallic or ceramic pattern, e.g. by firing

Description

本発明は、柔軟な屈曲性が要求されるフレキシブル基板に使用されるソルダーレジストインキ、例えばモバイルノートパソコン、携帯電話などの小型電子機器のプリント配線板製造用のソルダーレジストインキとして用いられるフレキシブル基板用ソルダーレジスト組成物に関する。   The present invention relates to a solder resist ink used for a flexible substrate requiring flexible flexibility, for example, a flexible substrate used as a solder resist ink for manufacturing a printed wiring board of a small electronic device such as a mobile notebook computer or a mobile phone. The present invention relates to a solder resist composition.

フレキシブルプリント配線板やテープキャリアパッケージの製造に用いられるソルダーレジストとしては、カバーレイフィルムと呼ばれるポリイミドフィルムをパターンにあわせた金型で打ち抜いた後、接着剤を用いて貼り付けるタイプや、可撓性を有する被膜を形成する紫外線硬化型、熱硬化型のソルダーレジストインキ又は液状ポリイミドインキをスクリーン印刷により塗布するタイプや、可撓性を有する被膜を形成する液状フォトソルダーレジストインキのタイプがある。   Solder resist used in the manufacture of flexible printed wiring boards and tape carrier packages is a type that can be applied with an adhesive after punching a polyimide film called a coverlay film with a mold that matches the pattern. There are a type in which an ultraviolet curable type, thermosetting type solder resist ink or liquid polyimide ink is formed by screen printing to form a coating film having liquid crystal, and a liquid photo solder resist ink type in which a flexible film is formed.

カバーレイフィルムでは、銅箔との追随性が無く、高精度なパターンを形成することができないという問題がある。一方、紫外線硬化型ソルダーレジストインキ及び液状フォトソルダーレジストインキでは、基材のポリイミドとの密着性が悪く、十分な可撓性が得られない。また、ソルダーレジストインキの硬化収縮及び硬化後の冷却収縮が大きいため反りが生じてしまうという問題がある。液状ポリイミドインキでは、可溶性芳香族ポリイミドが用いられるが(特許文献1参照)、高価であること、また、印刷時にニジミが生じてしまい、十分な作業性が得られないという問題がある。   The coverlay film has a problem that it cannot follow a copper foil and cannot form a highly accurate pattern. On the other hand, in the ultraviolet curable solder resist ink and the liquid photo solder resist ink, the adhesiveness with the polyimide of the base material is poor, and sufficient flexibility cannot be obtained. Moreover, since the curing shrinkage of the solder resist ink and the cooling shrinkage after curing are large, there is a problem that warpage occurs. In the liquid polyimide ink, soluble aromatic polyimide is used (see Patent Document 1), but there are problems that it is expensive and blurring occurs during printing, and sufficient workability cannot be obtained.

また、従来の熱硬化型ソルダーレジストインキとしては、メラミン樹脂等を用いたものが提案されている(例えば、特許文献2参照)。しかし、これらは、塗膜表面のみ脱水反応により硬化しており、塗膜内部は、未硬化の部分を有していることによりフレキシブル性が得られている。このため、はんだ耐熱性試験などを繰り返すと完全硬化し、塗膜がもろくなる。また、硬化触媒として、酸触媒を用いているため、電気特性などが劣るという問題もあった。   Further, as a conventional thermosetting solder resist ink, one using a melamine resin or the like has been proposed (for example, see Patent Document 2). However, these are cured only by the dehydration reaction on the surface of the coating film, and flexibility is obtained by having an uncured portion inside the coating film. For this reason, if a solder heat resistance test etc. are repeated, it will harden completely and a coating film will become brittle. In addition, since an acid catalyst is used as a curing catalyst, there is a problem that electrical characteristics and the like are inferior.

特に、最近の急速な軽薄短小化に技術により、携帯電話等に用いられるビルドアップ基板のコア材も薄くなり、ソルダーレジストの硬化収縮による反りが解決すべき課題となっている。   In particular, due to the recent rapid reduction in thickness, the core material of the build-up substrate used for mobile phones and the like has become thinner, and the warpage due to the hardening shrinkage of the solder resist has become an issue to be solved.

さらに、携帯電話に用いられる基板は、プッシュボタンの照明に用いられる発光ダイオードや表示装置から発熱する熱が蓄積する傾向があり、放熱特性が求められている。
特開平1−121364、特許請求の範囲など 特開昭50−69563、特許請求の範囲、明細書
Furthermore, a substrate used for a mobile phone tends to accumulate heat generated from a light emitting diode or a display device used for illumination of a push button, and heat dissipation characteristics are required.
JP-A-1-121364, claims, etc. JP-A-50-69563, claims and specification

本発明は、上記課題を解決すべくなされたもので、その目的とするところは、未硬化部分を残すことなくしっかりとした硬化反応で架橋をおこなっても強靭かつ柔軟であり、耐熱性にも優れ、更に、熱伝導率を高めるためにフィラーの充填率を高めても、割れにくく、柔軟性を維持することができるフレキシブル基板のソルダーレジスト組成物を提供することにある。   The present invention has been made to solve the above-mentioned problems, and its purpose is tough and flexible even when crosslinking is performed with a firm curing reaction without leaving an uncured part, and heat resistance is also improved. Further, it is to provide a solder resist composition for a flexible substrate that is resistant to cracking and can maintain flexibility even when the filler filling rate is increased in order to increase thermal conductivity.

(1)水添ビフェニル型エポキシ樹脂(A)と、エポキシ基と反応する官能基を有するゴム状化合物(B)と、酸化アルミニウム粒子(C)とを含有し、前記ゴム状化合物(B)はカルボキシル基末端ブタジエンアクリロニトリルで、かつ、ソルダーレジスト組成物中に配合されるエポキシ樹脂のエポキシ基1当量当たり、エポキシ基と反応するカルボキシル基が0.5〜3.0当量となるように配合することを特徴とするフレキシブル基板用熱硬化型ソルダーレジスト組成物。 (1) A hydrogenated biphenyl type epoxy resin (A), a rubbery compound (B) having a functional group that reacts with an epoxy group, and aluminum oxide particles (C) , wherein the rubbery compound (B) is It is a carboxyl group-terminated butadiene acrylonitrile and is blended so that the carboxyl group that reacts with the epoxy group is 0.5 to 3.0 equivalents per equivalent of the epoxy group of the epoxy resin blended in the solder resist composition. A thermosetting solder resist composition for a flexible substrate.

(2)前記水添ビフェニル型エポキシ樹脂(A)は、平均水添率が5〜95%であることを特徴とする(1)記載のフレキシブル基板用熱硬化型ソルダーレジスト組成物。 (2) The hydrogenated biphenyl type epoxy resin (A) has an average hydrogenation rate of 5 to 95%. The thermosetting solder resist composition for a flexible substrate as described in (1).

(3)さらに、ビフェニル型エポキシ樹脂(D)を含有し、水添ビフェニル型エポキシ樹脂とビフェニル型エポキシ樹脂(D)との総和((A)+(D))を基準としたときの平均水添率が5〜95%であることを特徴とする(1)又は(2)記載のフレキシブル基板用熱硬化型ソルダーレジスト組成物。 (3) Further, the average water containing the biphenyl type epoxy resin (D) and based on the sum ((A) + (D)) of the hydrogenated biphenyl type epoxy resin and the biphenyl type epoxy resin (D) The thermosetting solder resist composition for flexible substrates according to (1) or (2), wherein the addition ratio is 5 to 95%.

(4)前記水添ビフェニル型エポキシ樹脂(A)50質量部に対し、ビフェニル型エポキシ樹脂を2.5〜950質量部含有していることを特徴とする(1)〜(3)のいずれか記載のフレキシブル基板用熱硬化型ソルダーレジスト組成物。 (4) The hydrogenated biphenyl type epoxy resin (A) contains 2.5 to 950 parts by mass of a biphenyl type epoxy resin with respect to 50 parts by mass of any one of (1) to (3) The thermosetting solder resist composition for flexible substrates as described.

(5)フレキシブル基板用ソルダーレジスト組成物の硬化物100容量部中に、酸化アルミニウム粒子(C)を60〜95容量部含有していることを特徴とする(1)〜(4)のいずれか記載のフレキシブル基板用熱硬化型ソルダーレジスト組成物。 (5) In any one of (1) to (4) , 60 to 95 parts by volume of aluminum oxide particles (C) are contained in 100 parts by volume of the cured product of the solder resist composition for flexible substrates. The thermosetting solder resist composition for flexible substrates as described.

(6)酸化アルミニウム粒子(C)は、熱伝導率15W/m・K以上の粒径30μm以下の球状の酸化アルミニウム粒子であることを特徴とする(1)〜(5)のいずれか記載のフレキシブル基板用熱硬化型ソルダーレジスト組成物。 (6) The aluminum oxide particles (C) are spherical aluminum oxide particles having a thermal conductivity of 15 W / m · K or more and a particle size of 30 μm or less, according to any one of (1) to (5) Thermosetting solder resist composition for flexible substrates.

(7)酸化アルミニウム粒子(C)は、粒径20〜5μmの範囲内にある第1の酸化アルミニウム粒子100質量部に対し、この第1の酸化アルミニウム粒子の平均粒径の1/2〜1/10の範囲内にある第2の酸化アルミニウム粒子を20〜100質量部配合していることを特徴とする(1)〜(6)のいずれか記載のフレキシブル基板用熱硬化型ソルダーレジスト組成物。 (7) The aluminum oxide particles (C) are 1/2 to 1 of the average particle diameter of the first aluminum oxide particles with respect to 100 parts by mass of the first aluminum oxide particles having a particle diameter of 20 to 5 μm. The thermosetting solder resist composition for flexible substrates according to any one of (1) to (6) , wherein 20 to 100 parts by mass of second aluminum oxide particles in the range of / 10 are blended .

(8)基板上に(1)〜(7)のいずれかに記載されたフレキシブル基板用熱硬化型ソルダーレジスト組成物からなるソルダーレジストを形成してなり、このソルダーレジストの硬化物100容量部中に酸化アルミニウム粒子が60〜95容量部含有していることを特徴とするフレキシブル基板。 (8) A solder resist composed of the thermosetting solder resist composition for flexible substrate described in any one of (1) to (7) is formed on a substrate, and 100 parts by volume of the cured product of the solder resist. A flexible substrate comprising 60 to 95 parts by volume of aluminum oxide particles.

(9)基板上に、(1)〜(7)のいずれかに記載されたフレキシブル基板用熱硬化型ソルダーレジスト組成物からなるソルダーレジストを塗布することを特徴とするフレキシブル基板の製造方法。 (9) A method for producing a flexible substrate, comprising applying a solder resist comprising a thermosetting solder resist composition for a flexible substrate described in any one of (1) to (7) on a substrate.

尚、本発明において、「平均水添率」とは、原料となるエポキシ樹脂の芳香環に、全て水素添加して、シクロヘキサン環になる付加量(M)を100%とし、実際に付加した値(X)から、(X)/(M)として、求めた。   In the present invention, the “average hydrogenation rate” is a value obtained by adding all hydrogen to the aromatic ring of the epoxy resin used as a raw material and setting the addition amount (M) to be a cyclohexane ring as 100%. From (X), it was determined as (X) / (M).

平均水添率は、UV分光光度計で、276nmの吸光度から求めた。   The average hydrogenation rate was determined from the absorbance at 276 nm with a UV spectrophotometer.

また、混合物における平均水添率は、原料となる全てのエポキシ樹脂の芳香環に、全て水素添加して、シクロヘキサン環になる付加量(M)を100%とし、実際に付加した値(X)から、(X)/(M)として、求めた。   Moreover, the average hydrogenation rate in the mixture is the value (X) that is actually added to the aromatic ring of all epoxy resins as raw materials by adding all hydrogen to 100% as the addition amount (M) that becomes a cyclohexane ring. Therefore, it was determined as (X) / (M).

「平均粒径」とは、一次粒子と二次粒子(凝集粒子)の混合物を透過型電子顕微鏡(TEM)で任意の範囲で観察される微粒子の平均粒子径を示す。   The “average particle diameter” refers to the average particle diameter of fine particles obtained by observing a mixture of primary particles and secondary particles (aggregated particles) with a transmission electron microscope (TEM) in an arbitrary range.

「球形」とは、鉱物又は合成品を粉砕処理した後、熱処理した結果、形状が丸くなった状態を意味する。真球を意味するものではない。   “Spherical shape” means a state in which a shape is rounded as a result of heat treatment after pulverizing mineral or synthetic product. It does not mean a true sphere.

一般的にゴム状化合物(ソルダーレジスト硬化物のフレキシブル性を付与する)と液状のビスフェノールA型エポキシ樹脂は相溶するが、耐熱性に劣る。またビフェニル型エポキシ樹脂(正確にはビキシレノール型エポキシ樹脂)は耐熱性に優れているが、結晶性が高い粉体のエポキシ樹脂であり、均一分散しても均一な硬化物が得られず、結果として、柔軟性に乏しい硬化物が得られる。   In general, a rubbery compound (providing flexibility of a cured solder resist) and a liquid bisphenol A type epoxy resin are compatible but have poor heat resistance. Biphenyl type epoxy resin (exactly bixylenol type epoxy resin) is excellent in heat resistance, but it is a powdery epoxy resin with high crystallinity, and a uniform cured product cannot be obtained even if dispersed uniformly. As a result, a cured product having poor flexibility is obtained.

これに対し、本発明ではこれらの樹脂に代えて水添ビフェニル型エポキシ樹脂を用いている。水添ビフェニル型エポキシ樹脂は耐熱性に優れ、また結晶性が低いためにゴム状化合物と相溶性が良く、柔軟性に優れた硬化物が得られる。このように柔軟性に優れた硬化物が得られることから、熱伝度率を高める(放熱特性を向上する)ためにフィラーの充填率を高めても、割れにくく、柔軟性を維持することができる。   On the other hand, in the present invention, hydrogenated biphenyl type epoxy resin is used instead of these resins. The hydrogenated biphenyl type epoxy resin is excellent in heat resistance and has low crystallinity, so that it has good compatibility with the rubbery compound and a cured product excellent in flexibility can be obtained. Since a cured product with excellent flexibility is obtained in this way, even if the filler filling rate is increased to increase the thermal conductivity (improving heat dissipation characteristics), it is difficult to break and maintain flexibility. it can.

本発明に係る組成物は、水添ビフェニル型エポキシ樹脂と、エポキシ樹脂と反応する官能基を有するゴムと、酸化アルミニウム粒子とを含有し、更に必要によりビフェニル型エポキシ樹脂を含有する。   The composition according to the present invention contains a hydrogenated biphenyl type epoxy resin, a rubber having a functional group that reacts with the epoxy resin, and aluminum oxide particles, and further contains a biphenyl type epoxy resin as necessary.

(1)水添ビフェニル型エポキシ樹脂(A)
水添ビフェニル型エポキシ樹脂としては、任意の水添ビフェニル型エポキシ樹脂を用いることができる。例えば、特開平11−335439号公報に記載されているように、ビフェノール化合物(ビフェノール、2,2’−ジメチルビフェノール、ビキシレノール、2,2’−ジアリルビフェノール、2,2’,6,6’−テトラアリルビフェノール等)を、三フッ化ホウ素または三フッ化ホウ素錯体を触媒として、水素添加した後、ハエピハロヒドリンを反応させて得られる水添ビフェニル型エポキシ樹脂を使用することができる。しかし、このように、酸性のフェノール性水酸基を中性のアルコール性水酸基にした場合、エピハロヒドリンとの反応では、β開裂だけでなく、α開裂も起こり、エポキシ基に閉環しない化合物が生成することから、得られた反応生成物は、分子中にハロゲン原子を比較的多く含んだ化合物となる。
(1) Hydrogenated biphenyl type epoxy resin (A)
Any hydrogenated biphenyl type epoxy resin can be used as the hydrogenated biphenyl type epoxy resin. For example, as described in JP-A-11-335439, biphenol compounds (biphenol, 2,2′-dimethylbiphenol, bixylenol, 2,2′-diallylbiphenol, 2,2 ′, 6,6 ′ Hydrogenated biphenyl type epoxy resin obtained by reacting haepihalohydrin after hydrogenation of tetraallylbiphenol or the like) using boron trifluoride or boron trifluoride complex as a catalyst can be used. However, when an acidic phenolic hydroxyl group is changed to a neutral alcoholic hydroxyl group in this way, not only β-cleavage but also α-cleavage occurs in the reaction with epihalohydrin, and a compound that does not cyclize to the epoxy group is generated. The obtained reaction product is a compound containing a relatively large number of halogen atoms in the molecule.

これに対して、例えば、特開2000−226380号公報に記載してあるような工法により、ビフェニル型エポキシ樹脂やビキシレノール型エポキシ樹脂のベンゼン環のみにルテニウム坦持触媒等を用いて選択的に水素添加して得られるエポキシ樹脂は、上記工法と異なり分子中のハロゲン原子少なく、電気特性に優れており、好ましい。市販品としては、ジャパンエポキシレジン(株)社製の商品名YL6800などが挙げられる。   In contrast, for example, by a method as described in JP-A-2000-226380, a ruthenium-supported catalyst or the like is selectively used only on the benzene ring of a biphenyl type epoxy resin or a bixylenol type epoxy resin. The epoxy resin obtained by hydrogenation is preferable because it has few halogen atoms in the molecule unlike the above method and has excellent electrical characteristics. As a commercial item, Japan Epoxy Resin Co., Ltd. brand name YL6800 etc. are mentioned.

本発明に係る水添ビフェニル型エポキシ樹脂の平均水添率は、水添ビフェニル型エポキシ樹脂を、結晶性の低い状態に維持すること(言い換えると、ゴム状化合物との相溶性を維持すること)と、良好な耐熱性を維持することとを考慮して決められる。具体的には、平均水添率は5〜95%、好ましくは25〜75%、より好ましくは35〜65%である。平均水添率が下限値より低いと結晶性が強くなり、ゴム状化合物との相溶性が低下する。上限値より高い場合も同様に、結晶性が強くなり、ゴム状化合物との相溶性が低下すると共に、耐熱性が低下する。なお、結晶性の低い水添ビフェニル型エポキシ樹脂は、一般に常温で液体であるが、ゴム状化合物との相溶性のある水添ビフェニル型エポキシ樹脂は、常温で液体であることを必須とするものではない。   The average hydrogenation rate of the hydrogenated biphenyl type epoxy resin according to the present invention is to maintain the hydrogenated biphenyl type epoxy resin in a low crystallinity state (in other words, to maintain compatibility with the rubber-like compound). And maintaining good heat resistance. Specifically, the average hydrogenation rate is 5 to 95%, preferably 25 to 75%, more preferably 35 to 65%. When the average hydrogenation rate is lower than the lower limit, the crystallinity becomes strong and the compatibility with the rubbery compound is lowered. Similarly, when it is higher than the upper limit value, the crystallinity becomes strong, the compatibility with the rubbery compound is lowered, and the heat resistance is lowered. In addition, hydrogenated biphenyl type epoxy resins with low crystallinity are generally liquid at room temperature, but hydrogenated biphenyl type epoxy resins compatible with rubber-like compounds must be liquid at room temperature. is not.

水添ビフェニル型エポキシ樹脂の結晶性は、水添率のみで一義的に決められるものではなく、他の条件、例えば原料のビフェニル化合物に付いた置換基(アリル基等)なども水添ビフェニル型エポキシ樹脂の結晶性を決定するための重要な因子であるので、これらをゴム状化合物との相溶性を考慮して適宜設定する。   The crystallinity of the hydrogenated biphenyl type epoxy resin is not uniquely determined only by the hydrogenation rate. Other conditions such as substituents (allyl groups, etc.) attached to the raw material biphenyl compound are also hydrogenated biphenyl type. Since these are important factors for determining the crystallinity of the epoxy resin, these are appropriately set in consideration of compatibility with the rubber-like compound.

例えば、水添ビフェニル型エポキシ樹脂の数平均分子量は300〜1,000、特に380〜450が好ましい。この範囲内にすることにより、結晶性を低減できると共に、ゴム状化合物との相溶性が良くなり、耐熱性にも優れている。   For example, the number average molecular weight of the hydrogenated biphenyl type epoxy resin is preferably 300 to 1,000, particularly preferably 380 to 450. By making it within this range, crystallinity can be reduced, compatibility with the rubbery compound is improved, and heat resistance is also excellent.

(2)ビフェニル型エポキシ樹脂(C)など他のエポキシ樹脂
本発明では、硬化物のフレキシブル性を阻害する等、塗膜に悪影響を及ぼさない範囲で、周知慣用のエポキシ樹脂、例えばビスフェノールA型エポキシ樹脂、ビスフェノールF型エポキシ樹脂、ビスフェノールS型エポキシ樹脂、臭素化ビスフェノールA型エポキシ樹脂、水添ビスフェノールA型エポキシ樹脂、ビフェノール型エポキシ樹脂、ビキシレノール型エポキシ樹脂、フェノールノボラック型エポキシ樹脂、クレゾールノボラック型エポキシ樹脂、臭素化フェノールノボラック型エポキシ樹脂、ビスフェノールAのノボラック型エポキシ樹脂などのグリシジルエーテル化合物;テレフタル酸ジグリシジルエステル、ヘキサヒドロフタル酸ジグリシジルエステル、ダイマー酸ジグリシジルエステルなどのグリシジルエステル化合物;トリグリシジルイソシアヌレート、N,N,N’,N’−テトラグリシジルメタキシレンジアミン、N,N,N’,N’−テトラグリシジルビスアミノメチルシクロヘキサン、N,N−ジグリシジルアニリンなどのグリシジルアミン化合物、脂環式エポキシ化合物、エポキシ化ポリブタジエンなどを配合することができる。
(2) Other epoxy resins such as biphenyl type epoxy resin (C) In the present invention, well-known and commonly used epoxy resins such as bisphenol A type epoxy are used as long as they do not adversely affect the coating film, such as inhibiting the flexibility of the cured product. Resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, brominated bisphenol A type epoxy resin, hydrogenated bisphenol A type epoxy resin, biphenol type epoxy resin, bixylenol type epoxy resin, phenol novolac type epoxy resin, cresol novolak type Glycidyl ether compounds such as epoxy resin, brominated phenol novolac epoxy resin, bisphenol A novolac epoxy resin; terephthalic acid diglycidyl ester, hexahydrophthalic acid diglycidyl ester, dimer Glycidyl ester compounds such as acid diglycidyl ester; triglycidyl isocyanurate, N, N, N ′, N′-tetraglycidylmetaxylenediamine, N, N, N ′, N′-tetraglycidylbisaminomethylcyclohexane, N, Glycidylamine compounds such as N-diglycidylaniline, alicyclic epoxy compounds, epoxidized polybutadiene, and the like can be blended.

ビフェニル型エポキシ樹脂(ビフェノール型エポキシ樹脂、ビキシレノールエポキシ樹脂などの総称)として、例えば、ジャパンエポキシレジン(株)製の商品名YX4000が挙げられる。   Examples of the biphenyl type epoxy resin (generic name for biphenol type epoxy resin, bixylenol epoxy resin, etc.) include trade name YX4000 manufactured by Japan Epoxy Resin Co., Ltd.

ビフェニル型エポキシ樹脂を配合した場合、水添ビフェニル型エポキシ樹脂とビフェニルエポキシ樹脂との総和を基準としたときの平均水添率は、水添ビフェニル型エポキシ樹脂を結晶性の低い状態(すなわち、ゴム状化合物との相溶性に優れている状態)とすることと良好な耐熱性を維持することを考慮して決められる。具体的には、平均水添率5〜95%、好ましくは25〜75%、より好ましくは35〜65%である。平均水添率が下限値より低いと結晶性が強くなり液状化が困難になる。上限値より高い場合も同様に、結晶性が強くなり液状化が困難になる。更に加えて、耐熱性が低下する。   When the biphenyl type epoxy resin is blended, the average hydrogenation rate based on the sum of the hydrogenated biphenyl type epoxy resin and the biphenyl epoxy resin is a state in which the hydrogenated biphenyl type epoxy resin has low crystallinity (that is, rubber In a state excellent in compatibility with the glassy compound) and maintaining good heat resistance. Specifically, the average hydrogenation rate is 5 to 95%, preferably 25 to 75%, more preferably 35 to 65%. When the average hydrogenation rate is lower than the lower limit, the crystallinity becomes strong and liquefaction becomes difficult. Similarly, when it is higher than the upper limit, the crystallinity becomes strong and liquefaction becomes difficult. In addition, heat resistance is reduced.

ビフェニル型エポキシ樹脂の配合割合は、耐熱性向上と結晶性の観点から、水添ビフェニル型エポキシ50質量部に対し、2.5〜950質量部、好ましくは10〜300質量部、特に好ましくは30〜100質量部とするのがよい。   The blending ratio of the biphenyl type epoxy resin is 2.5 to 950 parts by mass, preferably 10 to 300 parts by mass, particularly preferably 30 to 50 parts by mass of the hydrogenated biphenyl type epoxy from the viewpoint of heat resistance improvement and crystallinity. It is good to set it to -100 mass parts.

ビフェニル型エポキシ樹脂の数平均分子量は300〜1,000、特に380〜450が好ましい。この範囲内にすることにより、結晶性を低減できると共に、ゴム状化合物との相溶性が良くなり、耐熱性にも優れている。   The number average molecular weight of the biphenyl type epoxy resin is preferably 300 to 1,000, particularly 380 to 450. By making it within this range, crystallinity can be reduced, compatibility with the rubbery compound is improved, and heat resistance is also excellent.

(3)エポキシ基と反応する官能基を有するゴム状化合物(B)
ゴム状化合物は、ソルダーレジスト硬化物に柔軟性を付与する成分である。
(3) Rubber-like compound having a functional group that reacts with an epoxy group (B)
The rubbery compound is a component that imparts flexibility to the cured solder resist.

エポキシ基と反応する官能基としては、カルボキシル基、酸無水物基、水酸基、アミノ基などが挙げられる。これらの官能基を有するゴム状化合物としては、例えば、ポリブタジエンと無水マレイン酸の反応させたマレイン化ポリブダジエン、更にこのマレイン化ポリブタジエンに一級アルコールを反応させ、遊離カルボキシル基を持つマレイン化ポリブタシエンハーフエステル、カルボキシル基末端ブタジエンアクリロニトリル、アミノ基含有ブタジエンアクリロニトニルなどが挙げられる。   Examples of the functional group that reacts with the epoxy group include a carboxyl group, an acid anhydride group, a hydroxyl group, and an amino group. Examples of the rubber-like compound having these functional groups include maleated polybutadiene obtained by reacting polybutadiene and maleic anhydride, and further reacting a primary alcohol with the maleated polybutadiene to provide maleated polybutadiene having a free carboxyl group. Examples include half esters, carboxyl group-terminated butadiene acrylonitrile, amino group-containing butadiene acrylonitrile.

これらの中で、特にCTBNと呼ばれるカルボキシル基末端ブタジエンアクリロニトリルが好ましい。カルボキシル基末端ブタジエンアクリロニトリルは、分子量が2000〜5000のものが好適である。市販品としては、宇部興産(株)製のハイカーCTBN2000×162、CTBN1300×31、CTBN1300×8、CTBN1300×13、CTBNX1300×9などが挙げられる。   Among these, carboxyl group-terminated butadiene acrylonitrile called CTBN is particularly preferable. The carboxyl group-terminated butadiene acrylonitrile preferably has a molecular weight of 2000 to 5000. Examples of commercially available products include Hiker CTBN2000 × 162, CTBN1300 × 31, CTBN1300 × 8, CTBN1300 × 13, and CTBNX1300 × 9 manufactured by Ube Industries.

これらのゴム状化合物(B)の配合割合は、硬化物の電気絶縁性、柔軟性の観点から、ソルダーレジスト中に配合されるエポキシ樹脂(水添ビフェニル型エポキシ樹脂及び必要により添加されるその他のエポキシ樹脂の総和)のエポキシ基1当量当たり、エポキシ基と反応する官能基(カルボキシル基末端ブタジエンアクリロニトリルの場合はカルボキシル基)0.5〜3.0当量、好ましくは0.8〜2.0当量配合されているのがよい。   The blending ratio of these rubber-like compounds (B) is an epoxy resin (hydrogenated biphenyl type epoxy resin and other additives added as necessary) from the viewpoint of electrical insulation and flexibility of the cured product. Functional group that reacts with the epoxy group (carboxyl group in the case of carboxyl-terminated butadiene acrylonitrile) 0.5 to 3.0 equivalents, preferably 0.8 to 2.0 equivalents per equivalent of epoxy group It is good that it is blended.

(4)酸化アルミニウム粒子
酸化アルミニウム粒子(C)は、熱伝導率15W/m・K以上の粒径が30μm以下、好ましくは20μm以下のものを用いる。粒径の下限は0.01μmが好ましい。0.01μmよりも小さいと組成物の粘度が高くなりすぎて、分散が困難であり、被塗布物への塗布も困難となる。30μmより大きいと塗膜への頭出しが発生することと、沈降速度が速くなり保存安定性が悪化する。
(4) Aluminum oxide particles The aluminum oxide particles (C) having a thermal conductivity of 15 W / m · K or more and a particle size of 30 μm or less, preferably 20 μm or less are used. The lower limit of the particle size is preferably 0.01 μm. If it is smaller than 0.01 μm, the viscosity of the composition becomes too high, so that it is difficult to disperse and application to an object to be coated becomes difficult. If it is larger than 30 μm, cueing to the coating film occurs and the sedimentation speed is increased, so that the storage stability is deteriorated.

熱伝導率が15W/m・K以上の酸化アルミニウム粒子(C)は、純度92%以上とすることにより得られる。   Aluminum oxide particles (C) having a thermal conductivity of 15 W / m · K or more can be obtained by setting the purity to 92% or more.

酸化アルミニウム粒子の配合量は、放熱特性と柔軟性を勘案して、ソルダーレジスト硬化物を基準としたとき、ソルダーレジスト硬化物100容量部中に、60〜95容量部、好ましくは70〜90容量部とするのがよい。   The blending amount of the aluminum oxide particles is 60 to 95 parts by volume, preferably 70 to 90 parts by volume in 100 parts by volume of the solder resist cured product in consideration of heat dissipation characteristics and flexibility. Good part.

更に、酸化アルミニウム粒子は、最密充填となるような粒度分布を持つ2種類以上の平均粒子径のものを配合するこしにより、より高充填にすることができ、保存安定性、熱伝導率の両側面から好ましい。最密充填となるような粒度分布を例示すれば、粒径20〜5μmの範囲内にある第1の酸化アルミニウム粒子100質量部に対し、この第1の酸化アルミニウム粒子の平均粒径の1/2〜1/10の範囲内にある第2の酸化アルミニウム粒子を20〜100質量部配合したものである。   Furthermore, the aluminum oxide particles can be made to have a higher packing by blending two or more types having an average particle size with a particle size distribution that results in the closest packing, and the storage stability and thermal conductivity are improved. Preferred from both sides. For example, a particle size distribution that provides close-packing is 1/100 of the average particle size of the first aluminum oxide particles with respect to 100 parts by mass of the first aluminum oxide particles in the range of 20 to 5 μm. 20-100 mass parts of 2nd aluminum oxide particles in the range of 2/1/10 are mix | blended.

本発明に用いられる球状の酸化アルミニウム粒子(C)の代表的な市販品としては、DAW−05(電気化学工業社製、平均粒径5μm)、DAW−10(電気化学工業社製、平均粒径10μm)、AS−40(昭和電工社製、平均粒径12μm)、AS−50(昭和電工社製、平均粒径9μm)等が挙げられる。   As typical commercial products of spherical aluminum oxide particles (C) used in the present invention, DAW-05 (manufactured by Denki Kagaku Kogyo Co., Ltd., average particle size 5 μm), DAW-10 (manufactured by Denki Kagaku Kogyo Co., Ltd., average particle size) Diameters 10 μm), AS-40 (manufactured by Showa Denko KK, average particle size 12 μm), AS-50 (manufactured by Showa Denko KK, average particle size 9 μm), and the like.

(5)その他の配合成分
本発明に係るフレキシブル基板用ソルダーレジスト組成物は、組成物の調整や粘度調整のために、有機溶剤を添加しても良い。有機溶剤としては、例えば、メチルエチルケトン、シクロヘキサノン等のケトン類;トルエン、キシレン、テトラメチルベンゼン等の芳香族炭化水素類;セロソルブ、メチルセロソルブ、ブチルセロソルブ、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ジエチルエーテル、トリプロピレングリコールモノメチルエーテル等のグリコールエーテル類;酢酸エチル、酢酸ブチル、乳酸ブチル、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、ジプロピレングリコールモノメチルエーテルアセテート、炭酸プロピレン等のエステル類;オクタン、デカン等の脂肪族炭化水素類;石油エーテル、石油ナフサ、ソルベントナフサ等の石油系溶剤などの有機溶剤が用いることができる。これらの有機溶剤は、単独で又は二種類以上を組み合わせて使用することができる。
(5) Other compounding components The solder resist composition for a flexible substrate according to the present invention may contain an organic solvent for adjusting the composition and adjusting the viscosity. Examples of the organic solvent include ketones such as methyl ethyl ketone and cyclohexanone; aromatic hydrocarbons such as toluene, xylene, and tetramethylbenzene; cellosolve, methyl cellosolve, butyl cellosolve, carbitol, methyl carbitol, butyl carbitol, propylene glycol Glycol ethers such as monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol diethyl ether, tripropylene glycol monomethyl ether; ethyl acetate, butyl acetate, butyl lactate, cellosolve acetate, butyl cellosolve acetate, carbitol acetate, butyl carbitol acetate, Propylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether acetate DOO, esters such as propylene carbonate; octane, aliphatic hydrocarbons decane; petroleum ether, petroleum naphtha, and organic solvents such as petroleum-based solvents such as solvent naphtha used. These organic solvents can be used alone or in combination of two or more.

これらの有機溶剤の配合量は、特に限定されるものではないが、コーティング性や硬化塗膜の膜厚確保のため、組成物中に50質量%以下、好ましくは30質量%以下となる割合である。   The blending amount of these organic solvents is not particularly limited, but in order to ensure the coating properties and the film thickness of the cured coating film, it is 50% by mass or less, preferably 30% by mass or less in the composition. is there.

本発明に係るフレキシブル基板用ソルダーレジスト組成物は、塗膜に悪影響を及ぼさない範囲で周知慣用の無機フィラー又は有機フィラーを用いることができる。   In the solder resist composition for a flexible substrate according to the present invention, a well-known and commonly used inorganic filler or organic filler can be used as long as it does not adversely affect the coating film.

これらフィラーを例示すれば、硫酸バリウム、タルク、シリカ、酸化アルミニウム、水酸化アルミニウムなどの無機フィラー、及びベンゾグアナミン樹脂などの有機フィラーが挙げられる。このようなフィラーの粒径としては、電気特性を良好に維持する観点から、20μm以下、好ましくは10μm以下とするのがよい。上記範囲より粒径が大きいと、塗膜から突出したフィラーにより塗膜の表面状態が悪くなり、フィラー界面を通して水分などが入り、電気特性を低下させるので、好ましくない。   Examples of these fillers include inorganic fillers such as barium sulfate, talc, silica, aluminum oxide, and aluminum hydroxide, and organic fillers such as benzoguanamine resin. The particle size of such a filler is 20 μm or less, preferably 10 μm or less, from the viewpoint of maintaining good electrical characteristics. If the particle size is larger than the above range, the surface state of the coating film is deteriorated by the filler protruding from the coating film, moisture and the like enter through the filler interface, and electrical characteristics are deteriorated.

これらのフィラーの配合量としては、組成物中に、50質量%以下、好ましくは30質量%以下の範囲とするのがよい。上記範囲より多いと塗膜の硬化収縮による反りなどは低減されるが、フレキシブル性が損なわれるので、好ましくない。   The blending amount of these fillers is 50% by mass or less, preferably 30% by mass or less in the composition. When the amount is more than the above range, warpage due to curing shrinkage of the coating film is reduced, but flexibility is impaired, which is not preferable.

本発明に係るフレキシブル基板用ソルダーレジスト組成物は、更に必要に応じて、フタロシアニン・ブルー、フタロシアニン・グリーン、アイオジン・グリーン、ジスアゾイエロー、クリスタルバイオレット、酸化チタン、カーボンブラック、ナフタレンブラックなどの周知慣用の着色剤、ハイドロキノン、ハイドロキノンモノメチルエーテル、t−ブチルカテコール、ピロガロール、フェノチアジン等の周知慣用の熱重合禁止剤、微粉シリカ、有機ベントナイト、モンモリロナイトなどの周知慣用の増粘剤、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、トリアゾール系等のシランカップリング剤などの周知慣用の添加剤類を配合することができる。   The solder resist composition for a flexible substrate according to the present invention is a known and commonly used phthalocyanine blue, phthalocyanine green, iodin green, disazo yellow, crystal violet, titanium oxide, carbon black, naphthalene black, etc. Colorants, hydroquinone, hydroquinone monomethyl ether, t-butylcatechol, pyrogallol, phenothiazine and other well-known and conventional thermal polymerization inhibitors, finely-silica, organic bentonite, montmorillonite and other well-known and conventional thickeners, silicone-based, fluorine-based, high Well-known and conventional additives such as molecular-type antifoaming agents and / or leveling agents, imidazole-based, thiazole-based, triazole-based silane coupling agents, and the like can be blended.

(5)この組成物によるソルダーレジストの塗布方法および得られる硬化被膜の特性
以上のような本発明に係るフレキシブル基板用ソルダーレジスト組成物は、回路形成されたフレキシブルプリント配線板に、通常、80〜250メッシュのスクリーン製版を用いて、スクリーン印刷法により塗布する。塗布した基板は、例えば120〜200℃の温度に加熱して、20〜120分間、熱硬化させる。必要に応じて、温度、時間を変えて、二段硬化しても良い。
(5) Solder resist coating method using this composition and properties of the cured film obtained The solder resist composition for a flexible substrate according to the present invention as described above is usually applied to a flexible printed wiring board on which a circuit is formed. Coating is performed by a screen printing method using a 250 mesh screen plate making. The coated substrate is heated to a temperature of 120 to 200 ° C., for example, and cured for 20 to 120 minutes. If necessary, two-stage curing may be performed by changing the temperature and time.

このようにして得られた硬化塗膜は、硬化収縮及び冷却収縮による反りがなく、基材に対する密着性、耐屈曲性、耐折性、柔軟性、耐めっき性、PCT耐性、はんだ耐熱性、電気絶縁性等に優れている。   The cured coating film thus obtained is free from warping due to curing shrinkage and cooling shrinkage, and adheres to the substrate, flex resistance, folding resistance, flexibility, plating resistance, PCT resistance, solder heat resistance, Excellent electrical insulation.

以下、本発明を実施例により具体的に説明するが本発明はこれら実施例に限定されるものではない。なお、以下において特に断りのない限り、「部」は質量部を意味するものである。   EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples. In the following description, “part” means part by mass unless otherwise specified.

実施例及び比較例の熱硬化組成物を、回路形成されたFR−4基板上にスクリーン印刷で乾燥塗膜が約30μmとなるようにパターン印刷し、170℃で60分間硬化させた。   The thermosetting compositions of Examples and Comparative Examples were pattern printed on a circuit-formed FR-4 substrate by screen printing so that the dried coating film was about 30 μm, and cured at 170 ° C. for 60 minutes.

(評価)
(1)耐溶剤性
得られた基板をプロピレングリコールモノメチルエーテルアセテートに30分間浸漬し、乾燥後、セロハン粘着テープによるピールテストを行い、塗膜の剥がれ・変色について評価した。
(Evaluation)
(1) Solvent resistance The obtained substrate was immersed in propylene glycol monomethyl ether acetate for 30 minutes, dried, and then subjected to a peel test using a cellophane adhesive tape to evaluate peeling and discoloration of the coating film.

○:剥がれや変色のないもの
×:剥がれ又は変色のあるもの
(2)耐熱性
実施例及び比較例の熱硬化組成物を用いて耐溶剤性と同様の方法で得られた基板にロジン系フラックスを塗布して260℃のはんだ槽で30秒間フローさせて、プロピレングリコールモノメチルエーテルアセテートにより洗浄・乾燥後、セロハン粘着テープによるピールテストを行い、塗膜の剥がれが発生しない最大回数。
○: No peeling or discoloration ×: Separation or discoloration (2) Heat resistance Rosin flux on a substrate obtained by the same method as solvent resistance using the thermosetting compositions of Examples and Comparative Examples Is applied for 30 seconds in a solder bath at 260 ° C., washed and dried with propylene glycol monomethyl ether acetate, then peel-tested with a cellophane adhesive tape, and the maximum number of times the film does not peel off.

(3)鉛筆硬度
実施例及び比較例の熱硬化組成物を用いて耐溶剤性と同様の方法で得られた基板に、Bから9Hの鉛筆の芯を先が平らになるように研ぎ、約45°の角度で押し付けて、塗膜の下の銅箔が見えない鉛筆の最大硬さを記録した。
(3) Pencil hardness Using a thermosetting composition of Examples and Comparative Examples, sharpen a B to 9H pencil core so that the tip is flat on a substrate obtained by the same method as the solvent resistance. Pressing at an angle of 45 °, the maximum hardness of the pencil where the copper foil under the coating was not visible was recorded.

(4)電気絶縁性
実施例及び比較例の熱硬化組成物を、IPC規格8パターンのくし形電極が形成されたFR−4基板上にスクリーン印刷で乾燥塗膜が約30μmとなるようにパターン印刷し、170℃で60分間硬化させた。得られた基板の電極間の絶縁抵抗値を印加電圧500Vにて測定した。
(4) Electrical insulation The thermosetting compositions of Examples and Comparative Examples were patterned so that the dried coating film was about 30 μm by screen printing on an FR-4 substrate on which comb-shaped electrodes of IPC standard 8 patterns were formed. Printed and cured at 170 ° C. for 60 minutes. The insulation resistance value between the electrodes of the obtained substrate was measured at an applied voltage of 500V.

(5)耐屈曲性
実施例及び比較例の熱硬化組成物を、それぞれカプトン材(厚さ50μm)上にスクリーン印刷で全面印刷し、170℃で60分間硬化させた(乾燥膜厚20μm)。その硬化塗膜の耐屈曲性をIPC−SM−849B TM2.4.29に従って直径1/8インチ、10サイクルの条件にて以下の基準で評価した。
(5) Flexibility The thermosetting compositions of Examples and Comparative Examples were each printed on the entire surface of a Kapton material (thickness 50 μm) by screen printing and cured at 170 ° C. for 60 minutes (dry film thickness 20 μm). The bending resistance of the cured coating film was evaluated according to the following criteria under conditions of 1/8 inch diameter and 10 cycles in accordance with IPC-SM-849B TM2.4.29.

○:硬化塗膜にクラックのないもの
△:硬化塗膜に若干クラックがあるもの
×:硬化塗膜にクラックがあるもの
合成例1
温度計、攪拌器、滴下ロート、及び還流冷却器を備えたフラスコに、カルビトールアセテート214.3部、アゾビスイソブチロニトリル24.0部を入れ、窒素雰囲気下で70℃に加熱せしめた。そこに、アクリル酸18.0部、i−ブチルメタクリレート162.5部、及び2−エチルヘキシルメタクリレート319.5部の混合モノマーを3時間かけて滴下した。その後さらに4時間撹拌・反応させ、不揮発分70%、固形分酸価28.1mgKOH/g、質量平均分子量16,000、FOXの式によるTgの計算値=9.7℃のポリカルボン酸樹脂溶液を得た。以下、このポリカルボン酸樹脂溶液をAワニスと称す。
○: The cured coating film has no cracks Δ: The cured coating film has some cracks ×: The cured coating film has cracks Synthesis Example 1
A flask equipped with a thermometer, a stirrer, a dropping funnel and a reflux condenser was charged with 214.3 parts of carbitol acetate and 24.0 parts of azobisisobutyronitrile and heated to 70 ° C. under a nitrogen atmosphere. . Thereto was added dropwise a mixed monomer of 18.0 parts of acrylic acid, 162.5 parts of i-butyl methacrylate, and 319.5 parts of 2-ethylhexyl methacrylate over 3 hours. The mixture was further stirred and reacted for 4 hours, and the polycarboxylic acid resin solution had a non-volatile content of 70%, a solid content acid value of 28.1 mgKOH / g, a mass average molecular weight of 16,000, and a calculated Tg value of FOX = 9.7 ° C Got. Hereinafter, this polycarboxylic acid resin solution is referred to as A varnish.

各組成物の成分及び評価を下記表1にまとめる。

Figure 0004864545
The components and evaluation of each composition are summarized in Table 1 below.
Figure 0004864545

表1からあきらかなように、実施例1、2のソルダーレジストは、屈曲性、耐溶剤性、耐熱性、鉛筆硬度、電気絶縁性が優れ、しかも、放熱性も優れており、フレキシブル基板用として優れた特性を有することがわかる。   As clearly shown in Table 1, the solder resists of Examples 1 and 2 are excellent in flexibility, solvent resistance, heat resistance, pencil hardness, electrical insulation, heat dissipation, and for flexible substrates. It turns out that it has the outstanding characteristic.

これに対し、比較例1は、水添ビフェニル型エポキシ樹脂を配合せずに、ビフェニル型エポキシ樹脂と液状CTBNとを酸化アルミニウム(アルミナ)配合したものである。比較例1は、ビフェニル型エポキシ樹脂は結晶性のため、配合不良となった。   On the other hand, the comparative example 1 mix | blends a biphenyl type epoxy resin and liquid CTBN with aluminum oxide (alumina), without mix | blending hydrogenated biphenyl type epoxy resin. In Comparative Example 1, the biphenyl type epoxy resin had poor blending due to crystallinity.

比較例2は、水添ビフェニル型エポキシ樹脂もビフェニル型エポキシ樹脂もゴムも配合せずに酸化アルミニウムを配合した例である。このものは、屈曲性、耐溶剤性、耐熱性に劣ることがわかる。   Comparative Example 2 is an example in which aluminum oxide was blended without blending hydrogenated biphenyl type epoxy resin, biphenyl type epoxy resin, or rubber. It can be seen that this product is inferior in flexibility, solvent resistance and heat resistance.

比較例3は、比較例2と配合成分は同じであるが、酸化アルミニウムの配合量を比較例2より多くしたものである。この例ではインキ化することができなかった。   Comparative Example 3 has the same blending components as Comparative Example 2, but the amount of aluminum oxide blended is larger than that of Comparative Example 2. In this example, ink could not be formed.

Claims (9)

水添ビフェニル型エポキシ樹脂(A)と、エポキシ基と反応する官能基を有するゴム状化合物(B)と、酸化アルミニウム粒子(C)とを含有し、前記ゴム状化合物(B)はカルボキシル基末端ブタジエンアクリロニトリルで、かつ、ソルダーレジスト組成物中に配合されるエポキシ樹脂のエポキシ基1当量当たり、エポキシ基と反応するカルボキシル基が0.5〜3.0当量となるように配合することを特徴とするフレキシブル基板用熱硬化型ソルダーレジスト組成物。 It contains a hydrogenated biphenyl type epoxy resin (A), a rubbery compound (B) having a functional group that reacts with an epoxy group, and aluminum oxide particles (C), and the rubbery compound (B) has a carboxyl group terminal. It is characterized by being blended so that the carboxyl group that reacts with the epoxy group is 0.5 to 3.0 equivalents per equivalent of epoxy group of the epoxy resin blended with butadiene acrylonitrile and in the solder resist composition. A thermosetting solder resist composition for flexible substrates. 前記水添ビフェニル型エポキシ樹脂(A)は、平均水添率が5〜95%であることを特徴とする請求項1記載のフレキシブル基板用熱硬化型ソルダーレジスト組成物。 The thermosetting solder resist composition for a flexible substrate according to claim 1, wherein the hydrogenated biphenyl type epoxy resin (A) has an average hydrogenation rate of 5 to 95%. さらに、ビフェニル型エポキシ樹脂(D)を含有し、水添ビフェニル型エポキシ樹脂とビフェニル型エポキシ樹脂(D)との総和((A)+(D))を基準としたときの平均水添率が5〜95%であることを特徴とする請求項1又は2記載のフレキシブル基板用ソルダーレジスト組成物。 Furthermore, the biphenyl type epoxy resin (D) is contained, and the average hydrogenation rate when the sum ((A) + (D)) of the hydrogenated biphenyl type epoxy resin and the biphenyl type epoxy resin (D) is used as a standard is It is 5-95%, The soldering resist composition for flexible substrates of Claim 1 or 2 characterized by the above-mentioned. 前記水添ビフェニル型エポキシ樹脂(A)50質量部に対し、ビフェニル型エポキシ樹脂を2.5〜950質量部含有していることを特徴とする請求項1〜3のいずれか記載のフレキシブル基板用熱硬化型ソルダーレジスト組成物。 The flexible substrate according to any one of claims 1 to 3, wherein 2.5 to 950 parts by mass of a biphenyl type epoxy resin is contained with respect to 50 parts by mass of the hydrogenated biphenyl type epoxy resin (A). Thermosetting solder resist composition. フレキシブル基板用ソルダーレジスト組成物の硬化物100容量部中に、酸化アルミニウム粒子(C)を60〜95容量部含有していることを特徴とする請求項1〜のいずれか記載のフレキシブル基板用熱硬化型ソルダーレジスト組成物。 The cured product 100 parts by volume of the flexible substrate for a solder resist composition, for a flexible substrate according to any one of claims 1-4, characterized by containing 60 to 95 parts by volume of aluminum oxide particles (C) Thermosetting solder resist composition. 酸化アルミニウム粒子(C)は、熱伝導率15W/m・K以上の粒径30μm以下の球状の酸化アルミニウム粒子であることを特徴とする請求項1〜のいずれか記載のフレキシブル基板用熱硬化型ソルダーレジスト組成物。 The aluminum oxide particles (C) are spherical aluminum oxide particles having a thermal conductivity of 15 W / m · K or more and a particle size of 30 µm or less, and the thermosetting for a flexible substrate according to any one of claims 1 to 5. Type solder resist composition. 酸化アルミニウム粒子(C)は、粒径20〜5μmの範囲内にある第1の酸化アルミニウム粒子100質量部に対し、この第1の酸化アルミニウム粒子の平均粒径の1/2〜1/10の範囲内にある第2の酸化アルミニウム粒子を20〜100質量部配合していることを特徴とする請求項1〜のいずれか記載のフレキシブル基板用熱硬化型ソルダーレジスト組成物。 The aluminum oxide particles (C) are ½ to 1/10 of the average particle diameter of the first aluminum oxide particles with respect to 100 parts by mass of the first aluminum oxide particles having a particle diameter of 20 to 5 μm. The thermosetting solder resist composition for a flexible substrate according to any one of claims 1 to 6 , wherein 20 to 100 parts by mass of second aluminum oxide particles within the range are blended. 基板上に、請求項1〜のいずれかに記載されたフレキシブル基板用熱硬化型ソルダーレジスト組成物からなるソルダーレジストを形成してなり、このソルダーレジストの硬化物100容量部中に酸化アルミニウム粒子が60〜95容量部含有していることを特徴とするフレキシブル基板。 A solder resist made of the thermosetting solder resist composition for a flexible substrate according to any one of claims 1 to 7 is formed on a substrate, and aluminum oxide particles are contained in 100 parts by volume of the cured product of the solder resist. Contains 60 to 95 volume parts of a flexible substrate. 基板上に、請求項1〜のいずれかに記載されたフレキシブル基板用熱硬化型ソルダーレジスト組成物からなるソルダーレジストを塗布することを特徴とするフレキシブル基板の製造方法。 A method for producing a flexible substrate, comprising: applying a solder resist comprising the thermosetting solder resist composition for a flexible substrate according to any one of claims 1 to 7 on the substrate.
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