JP2007314695A - Solder resist composition for flexible board, flexible board and production method therefor - Google Patents

Solder resist composition for flexible board, flexible board and production method therefor Download PDF

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JP2007314695A
JP2007314695A JP2006146993A JP2006146993A JP2007314695A JP 2007314695 A JP2007314695 A JP 2007314695A JP 2006146993 A JP2006146993 A JP 2006146993A JP 2006146993 A JP2006146993 A JP 2006146993A JP 2007314695 A JP2007314695 A JP 2007314695A
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epoxy resin
type epoxy
solder resist
biphenyl type
resist composition
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JP4871646B2 (en
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Yoshikazu Daiko
義和 大胡
Shigeru Ushiki
滋 宇敷
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Taiyo Holdings Co Ltd
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Taiyo Ink Mfg Co Ltd
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Priority to JP2006146994A priority patent/JP4864545B2/en
Priority to TW096115966A priority patent/TW200811236A/en
Priority to CN2007101061106A priority patent/CN101077956B/en
Priority to KR1020070050656A priority patent/KR100830810B1/en
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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
    • G03F7/0045—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
    • 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
    • G03F7/0047—Photosensitive materials characterised by additives for obtaining a metallic or ceramic pattern, e.g. by firing

Abstract

<P>PROBLEM TO BE SOLVED: To provide a solder resist for a flexible board, having excellent heat resistance as well as excellent flexibility (softness). <P>SOLUTION: The solder resist composition for a flexible board, contains (A) a hydrogenated biphenyl type epoxy resin and (B) a rubbery compound having a functional group reactive to an epoxy group. <P>COPYRIGHT: (C)2008,JPO&INPIT

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。
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 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.
JP-A-1-121364, claims, etc. JP-A-50-69563, claims and specification

本発明は、上記事情に鑑みてなされたもので、その目的とするところは、可撓性（柔らかさ）とともに耐熱性が優れた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。   This invention is made | formed in view of the said situation, The place made into the objective is to provide the soldering resist composition of the flexible substrate excellent in heat resistance with flexibility (softness).

上記課題を解決するために本発明は以下の構成を有する。   In order to solve the above problems, the present invention has the following configuration.

（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）とを含有することを特徴とするフレキシブル基板用ソルダーレジスト組成物。 (1) A solder resist composition for a flexible substrate comprising a hydrogenated biphenyl type epoxy resin (A) and a rubbery compound (B) having a functional group that reacts with an epoxy group.

（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ソルダーレジスト組成物。 (2) The solder resist composition for flexible substrates according to (1), wherein the hydrogenated biphenyl type epoxy resin (A) has an average hydrogenation rate of 5 to 95%.

（３）さらに、ビフェニル型エポキシ樹脂（Ｃ）を含有し、水添ビフェニル型エポキシ樹脂（Ａ）とビフェニル型エポキシ樹脂（Ｃ）との総和（（Ａ）＋（Ｃ））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ソルダーレジスト組成物。 (3) Furthermore, when it contains a biphenyl type epoxy resin (C) and the sum ((A) + (C)) of the hydrogenated biphenyl type epoxy resin (A) and the biphenyl type epoxy resin (C) is used as a reference The soldering resist composition for a flexible substrate according to (1) or (2), wherein the average hydrogenation ratio is from 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（Ｃ）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ソルダーレジスト組成物。 (4) 2.5 to 950 parts by mass of biphenyl type epoxy resin (C) with respect to 50 parts by mass of the hydrogenated biphenyl type epoxy resin (A) (1) to (3) The solder resist composition for flexible substrates as described in any one of 1).

（５）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あ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ソルダーレジスト組成物。 (5) The solder resist composition for a flexible substrate according to any one of (1) to (4), wherein the rubbery compound (B) is a carboxyl group-terminated butadiene acrylonitrile.

（６）前記ゴム状化合物（Ｂ）は、（１）〜（５）のいずれかのソルダーレジスト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）が０．５〜３．０当量となるように配合されていることを特徴とするフレキシブル基板用ソルダーレジスト組成物。 (6) The rubbery compound (B) is a functional group (carboxyl terminal) that reacts with an epoxy group per equivalent of an epoxy group of the epoxy resin blended in the solder resist of any one of (1) to (5). In the case of butadiene acrylonitrile, the solder resist composition for flexible substrates is blended so that the carboxyl group) is 0.5 to 3.0 equivalents.

（７）基板上に、（１）〜（６）のいずれかに記載された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ることを特徴とするフレキシブル基板。 (7) A flexible substrate obtained by forming a solder resist made of the solder resist composition described in any one of (1) to (6) on a substrate.

（８）基板上に、（１）〜（６）のいずれかに記載された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。 (8) A method for producing a flexible substrate, comprising applying a solder resist comprising the solder resist composition described in any one of (1) to (6) 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 the hydrogen to the aromatic ring of the epoxy resin as a raw material to form a cyclohexane ring (M) as 100%, and adding it (X ) From (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).

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。   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.

（組成物）
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を有し、更に必要によりビフェニル型エポキシ樹脂を含有する。 (Composition)
The composition according to the present invention has a hydrogenated biphenyl type epoxy resin and a rubber having a functional group that reacts with the epoxy resin, 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 ring-close 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低い結晶性（言い換えると、ゴム状化合物との相溶性）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。   The average hydrogenation rate of the hydrogenated biphenyl type epoxy resin according to the present invention is that the hydrogenated biphenyl type epoxy resin has low crystallinity (in other words, compatibility with a rubbery compound) and good heat resistance. It is decided in consideration. 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.

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常温で液状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、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。 When biphenyl type epoxy resin is blended, the average hydrogenation rate based on the sum of hydrogenated biphenyl type epoxy resin and biphenyl epoxy resin is good when liquidated biphenyl type epoxy resin is liquid at room temperature. It is determined in consideration of maintaining 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.

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）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使用できる。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。 (4) 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 may be used. These organic solvents can be used alone or in combination of two or more.

これら有機溶剤の配合量は、特に限定されるものでないが、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。   Although the compounding quantity of these organic solvents is not specifically limited, in order to ensure coating property and the film thickness of a cured coating film, it is a ratio used as 50 mass% or less in a composition, Preferably it is 30 mass% or less.

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、また、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. When the particle size is larger than the above range, the filler protruding from the coating film deteriorates the surface state of the coating film, and moisture and the like enter through the filler interface to lower the electrical characteristics.

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等は、低減されるが、フレキ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 the 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., if necessary. colorants, hydro key non, hydroquinone monomethyl ether, t- butyl catechol, pyrogallol, conventionally well-known thermal polymerization inhibitors such as phenothiazine, fine silica powder, organic bentonite, thickeners conventionally well-known, such as montmorillonite, silicone-based, fluorine-based Well-known and conventional additives such as a defoaming agent and / or a leveling agent such as a polymer, and a silane coupling agent such as an imidazole, thiazole, and triazole 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塗膜の特性
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 resulting cured coating film The above-described solder resist composition for a flexible substrate according to the present invention is generally applied to a flexible printed wiring board on which a circuit is formed. It is applied by screen printing using a ~ 250 mesh screen platemaking. 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.

表１に記載された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 described in Table 1 were pattern-printed on a circuit-formed FR-4 substrate by screen printing so that the dried coating film was about 30 μm, and the temperature was set at 170 ° C. for 60 minutes. Cured.

（評価方法）
（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 methods)
(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 2007314695
The components and evaluation of each composition are summarized in Table 1 below.
Figure 2007314695

表１から明らかなように、実施例１〜３のソルダーレジストは、屈曲性、耐溶剤性、鉛筆硬度、電気絶縁性が優れ、しかも、耐熱性も優れており、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 is clear from Table 1, the solder resists of Examples 1 to 3 have excellent flexibility, solvent resistance, pencil hardness, electrical insulation, excellent heat resistance, and excellent characteristics for flexible substrates. It can be seen that

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とを配合したものである。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, without mix | blending a hydrogenated biphenyl type epoxy resin. Since the biphenyl type epoxy resin was crystalline, the blending was poor.

比較例２は、水添ビフェニル型エポキシ樹脂に代えて水添ビスフェノールＡ型エポキシ樹脂を用い、これと液状ＣＴＢＮとを配合したものである。比較例２のソルダーレジストは、屈曲性、耐溶剤性、鉛筆硬度、電気絶縁性に優れているが、耐熱性に劣ることがわかる。   In Comparative Example 2, a hydrogenated bisphenol A type epoxy resin is used in place of the hydrogenated biphenyl type epoxy resin, and this is mixed with liquid CTBN. It can be seen that the solder resist of Comparative Example 2 is excellent in flexibility, solvent resistance, pencil hardness, and electrical insulation, but inferior in heat resistance.

比較例３は、水添ビフェニル型エポキシ樹脂に代えて水添ビスフェノールＦ型エポキシ樹脂を用い、これと液状ＣＴＢＮとを配合したものである。比較例３のソルダーレジストは、屈曲性、耐溶剤性、鉛筆硬度、電気絶縁性に優れているが、耐熱性に劣ることがわかる。   In Comparative Example 3, a hydrogenated bisphenol F type epoxy resin is used in place of the hydrogenated biphenyl type epoxy resin, and this is mixed with liquid CTBN. It can be seen that the solder resist of Comparative Example 3 is excellent in flexibility, solvent resistance, pencil hardness, and electrical insulation, but inferior in heat resistance.

比較例４は、水添ビフェニル型エポキシ樹脂に代えてビスフェノールＡ型エポキシ樹脂を用い、これと液状ＣＴＢＮとを配合したものである。このものは撹拌時にゲル化してしまった。   In Comparative Example 4, a bisphenol A type epoxy resin is used instead of the hydrogenated biphenyl type epoxy resin, and this is mixed with liquid CTBN. This product gelled during stirring.

比較例５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ビスフェノール型エポキシ樹脂もゴムも配合しない例である。このものは、屈曲性、鉛筆硬度、電気絶縁性優れているが、耐溶剤性、耐熱性に劣ることがわかる。   Comparative Example 5 is an example in which neither a hydrogenated biphenyl type epoxy resin, a biphenyl type epoxy resin, a bisphenol type epoxy resin nor a rubber is blended. This is excellent in flexibility, pencil hardness, and electrical insulation, but inferior in solvent resistance and heat resistance.

Claims (8)

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）とを含有することを特徴とするフレキシブル基板用ソルダーレジスト組成物。 A solder resist composition for a flexible substrate comprising a hydrogenated biphenyl type epoxy resin (A) and a rubbery compound (B) having a functional group that reacts with an epoxy group. 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ソルダーレジスト組成物。 2. The 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（Ｃ）を含有し、水添ビフェニル型エポキシ樹脂（Ａ）とビフェニル型エポキシ樹脂（Ｃ）との総和（（Ａ）＋（Ｃ））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, it contains biphenyl type epoxy resin (C), and the average water based on the sum ((A) + (C)) of hydrogenated biphenyl type epoxy resin (A) and biphenyl type epoxy resin (C) The soldering resist composition for a flexible substrate according to claim 1 or 2, wherein the additive rate is 5 to 95%. 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（Ｃ）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ソルダーレジスト組成物。 The biphenyl type epoxy resin (C) is contained in an amount of 2.5 to 950 parts by mass with respect to 50 parts by mass of the hydrogenated biphenyl type epoxy resin (A). Solder resist composition for flexible substrates. 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あることを特徴とする請求項１〜４のいずれか記載のフレキシブル基板用ソルダーレジスト組成物。 The solder resist composition for a flexible substrate according to any one of claims 1 to 4, wherein the rubbery compound (B) is a carboxyl group-terminated butadiene acrylonitrile. 前記ゴム状化合物（Ｂ）は、請求項１〜５のいずれかのソルダーレジスト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官能基が０．５〜３．０当量となるように配合されていることを特徴とするフレキシブル基板用ソルダーレジスト組成物。 The rubbery compound (B) has a functional group that reacts with an epoxy group in an amount of 0.5 to 3.0 equivalents per equivalent of an epoxy group of the epoxy resin blended in the solder resist of any one of claims 1 to 5. It is mix | blended so that it may become. The soldering resist composition for flexible substrates characterized by the above-mentioned. 基板上に、請求項１〜６のいずれかに記載された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ることを特徴とするフレキシブル基板。 A flexible substrate obtained by forming a solder resist comprising the solder resist composition according to any one of claims 1 to 6 on a substrate. 基板上に、請求項１〜６のいずれかに記載された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。 The manufacturing method of the flexible substrate characterized by apply | coating the soldering resist which consists of a soldering resist composition in any one of Claims 1-6 on a board | substrate.
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