JP2005311233A - Solder resist composition and printed wiring board including solder resist formed therefrom - Google Patents
Solder resist composition and printed wiring board including solder resist formed therefrom Download PDFInfo
- Publication number
- JP2005311233A JP2005311233A JP2004129558A JP2004129558A JP2005311233A JP 2005311233 A JP2005311233 A JP 2005311233A JP 2004129558 A JP2004129558 A JP 2004129558A JP 2004129558 A JP2004129558 A JP 2004129558A JP 2005311233 A JP2005311233 A JP 2005311233A
- Authority
- JP
- Japan
- Prior art keywords
- solder resist
- resist composition
- printed wiring
- wiring board
- pigment
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
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- 229910000679 solder Inorganic materials 0.000 title claims abstract description 76
- 239000000203 mixture Substances 0.000 title claims abstract description 53
- 239000000049 pigment Substances 0.000 claims abstract description 29
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- 239000012463 white pigment Substances 0.000 claims abstract description 13
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- 238000005476 soldering Methods 0.000 claims description 5
- 238000000016 photochemical curing Methods 0.000 abstract description 12
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- Materials For Photolithography (AREA)
- Non-Metallic Protective Coatings For Printed Circuits (AREA)
Abstract
Description
本発明は、プリント配線板の回路パターン隠蔽性に優れたソルダーレジスト組成物及びそれから形成されたソルダーレジストを有するプリント配線板に関する。 The present invention relates to a solder resist composition excellent in circuit pattern concealability of a printed wiring board and a printed wiring board having a solder resist formed therefrom.
一般に、民生用乃至産業用プリント配線板においては、電子部品実装時のはんだ供給に当たって、不要部分へのはんだ不着防止や回路保護を目的として、ソルダーレジストが形成される。このソルダーレジスト用の樹脂組成物としては、熱硬化型、光硬化型、光硬化・熱硬化型など種々の組成物が従来から知られているが、微細なパターンが容易に形成できることからフォトリソ法にてパターンを形成する現像型ソルダーレジスト組成物が普及しており、なかでも環境への配慮、コストの面から希アルカリ水溶液を用いるアルカリ現像タイプのソルダーレジスト組成物が主として用いられている（特許文献１〜３参照）。 In general, in consumer or industrial printed wiring boards, a solder resist is formed for the purpose of preventing solder non-sticking to unnecessary portions and circuit protection when supplying solder when mounting electronic components. As a resin composition for this solder resist, various compositions such as thermosetting type, photocuring type, photocuring / thermosetting type have been conventionally known. However, since a fine pattern can be easily formed, a photolithography method is used. The development-type solder resist composition that forms a pattern is widely used, and in particular, an alkali development-type solder resist composition that uses a dilute aqueous alkali solution is mainly used in consideration of the environment and cost (patents) References 1-3).
従来、プリント配線板のソルダーレジストにおいては、その色調は一般的に作業者の視覚に刺激を与えないように緑色とされ、その色素（もしくは着色顔料）としてはフタロシアニングリーンが多用されている。
しかしながら、近年の電子機器の小型化、高機能化の要求に応えるためにプリント配線板の回路パターンの微細化が進んでおり、また、それに伴ってソルダーレジスト層もより一層薄膜化されつつある。その結果、ソルダーレジスト層を通して回路パターンが見えてしまうという問題がある。すなわち、プリント配線板の重要な構成部分である回路パターンについて、第三者が容易に模倣、盗用し易い状況となっている。そこで、本発明者らは、例えば黒などの有色顔料を多量に配合して回路パターンを隠蔽しようと試みたが、ソルダーレジスト層の薄膜化と回路パターンの隠蔽を同時に達成することはできなかった。
Conventionally, in a solder resist of a printed wiring board, its color tone is generally green so as not to irritate an operator's vision, and phthalocyanine green is frequently used as a coloring matter (or coloring pigment).
However, in order to meet the recent demand for downsizing and high functionality of electronic devices, the circuit pattern of the printed wiring board has been miniaturized, and accordingly, the solder resist layer is becoming thinner. As a result, there is a problem that the circuit pattern can be seen through the solder resist layer. That is, the circuit pattern, which is an important component of the printed wiring board, can be easily imitated or stolen by a third party. Therefore, the present inventors tried to conceal the circuit pattern by blending a large amount of colored pigment such as black, for example, but could not simultaneously achieve the thinning of the solder resist layer and concealment of the circuit pattern. .
本発明は、前述したような問題を解消するためになされたものであり、その主たる目的は、形成されるソルダーレジスト層を薄膜化しても、電気絶縁性、耐熱性、密着性、耐薬品性、耐めっき性、硬度等のソルダーレジストに要求される諸特性を損なうことなく、その下に存在する回路パターンを隠蔽できる有色ソルダーレジスト組成物を提供することにある。
本発明の他の目的は、かかるソルダーレジスト組成物を用いて形成されたソルダーレジストを有し、該ソルダーレジストにより回路パターンが隠蔽されているプリント配線板を提供することにある。
The present invention has been made in order to solve the above-described problems, and its main purpose is to provide electrical insulation, heat resistance, adhesion, and chemical resistance even when the formed solder resist layer is thinned. Another object of the present invention is to provide a colored solder resist composition capable of concealing a circuit pattern existing thereunder without impairing various properties required for the solder resist such as plating resistance and hardness.
Another object of the present invention is to provide a printed wiring board having a solder resist formed using such a solder resist composition and having a circuit pattern concealed by the solder resist.
前記目的を達成するために、本発明によれば、光硬化性成分及び／又は熱硬化性成分を含有するソルダーレジスト組成物において、顔料として着色顔料と白顔料を組み合わせて含有することを特徴とするソルダーレジスト組成物が提供される。好適な態様においては、上記白顔料は酸化チタンである。
さらに本発明によれば、上記ソルダーレジスト組成物から形成されたソルダーレジストを有するプリント配線板が提供される。
In order to achieve the above object, according to the present invention, the solder resist composition containing a photocurable component and / or a thermosetting component contains a combination of a color pigment and a white pigment as a pigment. A solder resist composition is provided. In a preferred embodiment, the white pigment is titanium oxide.
Furthermore, according to this invention, the printed wiring board which has a soldering resist formed from the said soldering resist composition is provided.
本発明のソルダーレジスト組成物は、顔料として着色顔料と白顔料を組み合わせて含有しているため、形成されるソルダーレジスト層を薄膜化しても、電気絶縁性、耐熱性、密着性、耐薬品性、耐めっき性、硬度等のソルダーレジストに要求される諸特性を損なうことなく、回路パターンの隠蔽性に優れている。そのため、プリント配線板の重要な構成部分である回路パターンについて、第三者が模倣、盗用することを効果的に防止できる。 Since the solder resist composition of the present invention contains a combination of a color pigment and a white pigment as a pigment, even if the solder resist layer to be formed is made thin, electrical insulation, heat resistance, adhesion, chemical resistance It is excellent in circuit pattern concealing ability without impairing various properties required for solder resist such as plating resistance and hardness. Therefore, it is possible to effectively prevent a third party from imitating and stealing a circuit pattern that is an important component of the printed wiring board.
本発明者らは、ソルダーレジストによるプリント配線板の回路パターン隠蔽性について鋭意研究の結果、顔料として着色顔料と白顔料を組み合わせて含有している場合、ソルダーレジストに要求される諸特性を損なうことなく、ソルダーレジスト層を薄膜化しても回路パターンを有効に隠蔽できることを見出し、本発明を完成するに至ったものである。
本発明のソルダーレジスト組成物は、顔料（Ａ）として着色顔料（Ａ−１）と白顔料（Ａ−２）を組み合わせて含有している他は、他の光硬化性成分、熱硬化性成分等については従来のソルダーレジスト組成物をそのまま適用できる。
As a result of earnest research on the circuit pattern concealing property of a printed wiring board by a solder resist, the present inventors impair various properties required for a solder resist when a pigment contains a combination of a color pigment and a white pigment. However, the present inventors have found that the circuit pattern can be effectively concealed even if the solder resist layer is thinned, and the present invention has been completed.
The solder resist composition of the present invention contains, as a pigment (A), a combination of a color pigment (A-1) and a white pigment (A-2), other photocurable components and thermosetting components. For example, a conventional solder resist composition can be applied as it is.
着色顔料（Ａ−１）としては、カーボンブラック、ナフタレンブラック、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などの公知慣用の着色顔料を用いることができる。
一方、白顔料（Ａ−２）としては、酸化チタン、酸化亜鉛、塩基性炭酸塩、塩基性硫酸鉛、硫酸鉛、硫化亜鉛、酸化アンチモンなどの顔料を用いることができる。なかでも、着色力と無毒性という点から酸化チタンが好ましい。
As the color pigment (A-1), known and commonly used color pigments such as carbon black, naphthalene black, phthalocyanine blue, phthalocyanine green, iodin green, disazo yellow, crystal violet and the like can be used.
On the other hand, as the white pigment (A-2), pigments such as titanium oxide, zinc oxide, basic carbonate, basic lead sulfate, lead sulfate, zinc sulfide, and antimony oxide can be used. Of these, titanium oxide is preferable in terms of coloring power and nontoxicity.
これら着色顔料（Ａ−１）と白顔料（Ａ−２）の配合比率は、（Ａ−１）：（Ａ−２）＝１：１０〜１０：１の割合が好ましい。白顔料（Ａ−２）の配合比率が上記範囲よりも低い場合、回路パターンを有効に隠蔽できず、一方、上記範囲よりも高い場合、着色顔料による着色が薄くなるので好ましくない。
また、ソルダーレジスト組成物中のこれら着色顔料と白顔料の合計量は、組成物全体の０．５〜１０質量％、好ましくは１〜５質量％の範囲が好適である。着色顔料と白顔料の合計量が０．５質量％未満の場合、回路パターンの隠蔽性が悪く、一方、１０質量％を超えて多量に配合した場合、隠蔽性は１０質量％で既に最大限発揮された状態に達しており、それ以上の添加は経済的に無駄であるため、好ましくない。
本発明によれば、上記のように、より少ない顔料の配合量にて回路パターンを有効に隠蔽できる。従って、光特性に悪影響を及ぼすことなく、薄膜でも回路パターンを有効に隠蔽できる。
The blending ratio of the colored pigment (A-1) and the white pigment (A-2) is preferably (A-1) :( A-2) = 1: 10 to 10: 1. When the blending ratio of the white pigment (A-2) is lower than the above range, the circuit pattern cannot be effectively concealed. On the other hand, when it is higher than the above range, the coloring by the color pigment becomes thin, which is not preferable.
The total amount of these colored pigments and white pigments in the solder resist composition is 0.5 to 10% by mass, preferably 1 to 5% by mass of the entire composition. When the total amount of the colored pigment and the white pigment is less than 0.5% by mass, the concealing property of the circuit pattern is poor. Since it has reached the state where it has been exerted, addition beyond that is economically wasteful, which is not preferable.
According to the present invention, as described above, the circuit pattern can be effectively concealed with a smaller amount of pigment. Therefore, the circuit pattern can be effectively concealed even with a thin film without adversely affecting the optical characteristics.
熱硬化型のソルダーレジスト組成物は、必須成分として（Ｂ）分子中に２個以上の環状エーテル基を有する化合物と、その硬化剤としての（Ｃ）分子中にフェノール性水酸基、カルボキシル基等の環状エーテル基と反応し得る基を２個以上有する化合物を含有し、必要に応じて（Ｄ）硬化触媒を含有する。分子中に２個以上の環状エーテル基を有する化合物（Ｂ）としては、分子中に２個以上のエポキシ基を有する多官能エポキシ化合物（Ｂ−１）及び／又は分子中に２個以上のオキセタニル基を有する多官能オキセタン化合物（Ｂ−２）を好適に用いることができる。 The thermosetting solder resist composition comprises (B) a compound having two or more cyclic ether groups in the molecule as essential components, and (C) a phenolic hydroxyl group, a carboxyl group, etc. in the molecule as the curing agent. A compound having two or more groups capable of reacting with a cyclic ether group is contained, and (D) a curing catalyst is contained as necessary. The compound (B) having two or more cyclic ether groups in the molecule includes a polyfunctional epoxy compound (B-1) having two or more epoxy groups in the molecule and / or two or more oxetanyl groups in the molecule. A polyfunctional oxetane compound (B-2) having a group can be suitably used.
多官能エポキシ化合物（Ｂ−１）としては、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、水添ビスフェノールＡ型エポキシ樹脂、ノボラック型エポキシ樹脂、グリシジルアミン型エポキシ樹脂、ヒダントイン型エポキシ樹脂、脂環式エポキシ樹脂、ビキシレノール型もしくはビフェノール型エポキシ樹脂又はそれらの混合物、ビスフェノールＳ型エポキシ樹脂、トリグリシジルイソシアヌレートに代表される複素環式エポキシ樹脂などが挙げられるが、これらに限られるものではない。 Examples of the polyfunctional epoxy compound (B-1) include bisphenol A type epoxy resin, bisphenol F type epoxy resin, hydrogenated bisphenol A type epoxy resin, novolac type epoxy resin, glycidylamine type epoxy resin, hydantoin type epoxy resin, Examples include, but are not limited to, alicyclic epoxy resins, bixylenol type or biphenol type epoxy resins or mixtures thereof, bisphenol S type epoxy resins, heterocyclic epoxy resins represented by triglycidyl isocyanurate, and the like. Absent.
多官能オキセタン化合物（Ｂ−２）としては、例えば、キシリレンジオキセタン、ビフェニル型オキセタン、ノボラック型オキセタンなどが挙げられるが、これらに限られるものではない。
前記した分子中に２個以上の環状エーテル基を有する化合物（Ｂ）は、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。
Examples of the polyfunctional oxetane compound (B-2) include, but are not limited to, xylylene oxetane, biphenyl type oxetane, novolak type oxetane, and the like.
The compound (B) having two or more cyclic ether groups in the molecule can be used alone or in combination of two or more.
分子中に２個以上のフェノール性水酸基を有する多官能フェノール性水酸基含有化合物（Ｃ−１）としては、例えばフェノールノボラック、クレゾールノボラック、ビニルフェノールなどが挙げられる。 Examples of the polyfunctional phenolic hydroxyl group-containing compound (C-1) having two or more phenolic hydroxyl groups in the molecule include phenol novolac, cresol novolac, and vinylphenol.
分子中に２個以上のカルボキシル基を有する化合物（Ｃ−２）としては、例えば、ジョンクリル６７（ジョンソンポリマー社製）、ＣＩＣ酸（四国化成工業社製）などが挙げられる。 Examples of the compound (C-2) having two or more carboxyl groups in the molecule include Jonkrill 67 (manufactured by Johnson Polymer Co., Ltd.), CIC acid (manufactured by Shikoku Kasei Kogyo Co., Ltd.) and the like.
前記した分子中に２個以上の環状エーテル基を有する化合物（Ｂ）と分子中にフェノール性水酸基、カルボキシル基等の環状エーテル基と反応し得る基を２個以上有する化合物（Ｃ）との配合割合は、通常の割合でよいが、前記環状エーテル基を有する化合物（Ｂ）の環状エーテル基１当量に対し、フェノール性水酸基、カルボキシル基等の環状エーテル基と反応し得る基を２個以上有する化合物（Ｃ）の官能基が０．５〜２当量、好ましくは０．８〜１．２当量となる割合が望ましい。 Compounding of the compound (B) having two or more cyclic ether groups in the molecule and the compound (C) having two or more groups capable of reacting with a cyclic ether group such as a phenolic hydroxyl group or a carboxyl group in the molecule The ratio may be a normal ratio, but has at least two groups capable of reacting with a cyclic ether group such as a phenolic hydroxyl group and a carboxyl group with respect to 1 equivalent of the cyclic ether group of the compound (B) having a cyclic ether group. The ratio in which the functional group of the compound (C) is 0.5 to 2 equivalents, preferably 0.8 to 1.2 equivalents is desirable.
本発明のソルダーレジスト組成物は、その熱硬化特性を向上させるために硬化触媒（Ｄ）を含有することが好ましい。この硬化触媒としては、例えば、イミダゾール類、アミン類などが挙げられるが、これらに限られるものではなく、エポキシ樹脂やオキセタン化合物の硬化触媒、もしくはエポキシ基及び／又はオキセタニル基とカルボキシル基の反応を促進するものであればよく、単独で又は２種以上を混合して使用してもかまわない。
硬化触媒（Ｄ）の配合量は通常の量的割合で充分であり、例えば前記分子中に２個以上の環状エーテル基を有する化合物（Ｂ）１００質量部に対して０．１〜２０質量部、好ましくは０．５〜１５．０質量部の割合である。
The solder resist composition of the present invention preferably contains a curing catalyst (D) in order to improve its thermosetting characteristics. Examples of the curing catalyst include, but are not limited to, imidazoles and amines. The curing catalyst for epoxy resins and oxetane compounds, or the reaction of epoxy groups and / or oxetanyl groups with carboxyl groups. Any one may be used as long as it promotes, and it may be used alone or in admixture of two or more.
The amount of the curing catalyst (D) is sufficient in a normal quantitative ratio, for example, 0.1 to 20 parts by mass with respect to 100 parts by mass of the compound (B) having two or more cyclic ether groups in the molecule. The ratio is preferably 0.5 to 15.0 parts by mass.
一方、本発明の光硬化型のソルダーレジスト組成物は、少なくとも光硬化性成分（Ｅ）及び光重合開始剤（Ｆ）を含有する。光硬化性成分（Ｅ）としては、各種光重合性モノマー（Ｅ−１）や感光性プレポリマー（Ｅ−２）を用いることができる。
光重合性モノマー（Ｅ−１）の代表的なものとしては、２−ヒドロキシエチルアクリレート等のヒドロキシアルキルアクリレート類、エチレングリコール等のグリコール類のモノ又はジアクリレート類、Ｎ，Ｎ−ジメチルアクリルアミド等のアクリルアミド類、Ｎ，Ｎ−ジメチルアミノエチルアクリレート等のアミノアルキルアクリレート類、多価アルコールもしくはフェノール類又はそれらのエチレオキサイド付加物もしくはプロピレンオキサイド付加物などの多価アクリレート類、グリシジルエーテルのアクリレート類など、及び上記アクリレート類に対応する各メタクリレート類などが挙げられるが、これらに限定されるものではない。
On the other hand, the photocurable solder resist composition of the present invention contains at least a photocurable component (E) and a photopolymerization initiator (F). As the photocurable component (E), various photopolymerizable monomers (E-1) and photosensitive prepolymers (E-2) can be used.
Representative examples of the photopolymerizable monomer (E-1) include hydroxyalkyl acrylates such as 2-hydroxyethyl acrylate, mono- or diacrylates of glycols such as ethylene glycol, N, N-dimethylacrylamide, and the like. Acrylamides, aminoalkyl acrylates such as N, N-dimethylaminoethyl acrylate, polyhydric alcohols or phenols, polyhydric acrylates such as their ethylene oxide adducts or propylene oxide adducts, glycidyl ether acrylates, etc. And methacrylates corresponding to the acrylates, but are not limited thereto.
感光性プレポリマー（Ｅ−２）としては、従来知られている各種光硬化性樹脂を用いることができ、特定のものに限定されないが、アルカリ水溶液による現像が可能であり、しかも基板に対する密着性、耐熱性、耐薬品性、電気絶縁性、硬度等の皮膜特性に優れたレジスト皮膜が得られる点から、分子中にカルボキシル基と２個以上のエチレン性不飽和結合を併せ持つ感光性プレポリマー（オリゴマー又はポリマー）が好ましい。 As the photosensitive prepolymer (E-2), conventionally known various photocurable resins can be used, and the photosensitive prepolymer (E-2) is not limited to a specific one, but development with an alkaline aqueous solution is possible, and adhesion to a substrate is also possible. Photosensitive prepolymer having a carboxyl group and two or more ethylenically unsaturated bonds in the molecule from the point of obtaining a resist film with excellent film properties such as heat resistance, chemical resistance, electrical insulation and hardness. Oligomer or polymer) is preferred.
上記感光性プレポリマー（Ｅ−２）としては、例えば、
（１）１分子中に少なくとも２個のエポキシ基を有する多官能のエポキシ化合物のエポキシ基と不飽和モノカルボン酸のカルボキシル基をエステル化反応（全エステル化又は部分エステル化、好ましくは全エステル化）させ、生成した水酸基にさらに飽和又は不飽和の多塩基酸無水物を反応させて得られるカルボキシル基含有感光性樹脂、
（２）アルキル（メタ）アクリレートとグリシジル（メタ）アクリレートからなる共重合体に（メタ）アクリル酸を反応させた後、さらに飽和又は不飽和の多塩基酸無水物を反応させて得られるカルボキシル基含有感光性樹脂、
（３）ヒドロキシアルキル（メタ）アクリレートとアルキル（メタ）アクリレートとグリシジル（メタ）アクリレートとの共重合体に（メタ）アクリル酸を反応させた後、さらに飽和又は不飽和の多塩基酸無水物を反応させて得られるカルボキシル基含有感光性樹脂、
（４）アルキル（メタ）アクリレートと（メタ）アクリル酸との共重合体にグリシジル（メタ）アクリレートを部分的に反応させて得られるカルボキシル基含有感光性樹脂、
（５）１分子中に少なくとも２個のエポキシ基を有する多官能エポキシ化合物と、不飽和モノカルボン酸と、１分子中に少なくとも２個の水酸基と、エポキシ基と反応する水酸基以外の１個の他の反応性基を有する化合物との反応生成物に、飽和又は不飽和の多塩基酸無水物を反応させて得られるカルボキシル基含有感光性樹脂、
（６）無水マレイン酸等の不飽和多塩基酸無水物とスチレン等のビニル基を有する芳香族炭化水素との共重合体に、ヒドロキシアルキル（メタ）アクリレートを反応させて得られるカルボキシル基含有感光性樹脂、
（７）１分子中に少なくとも２個のオキセタン環を有する多官能オキセタン化合物に不飽和モノカルボン酸を反応させ、得られた変性オキセタン樹脂中の一級水酸基に対して飽和又は不飽和多塩基酸無水物を反応させて得られるカルボキシル基含有感光性樹脂、
（８）ノボラック型フェノール樹脂とアルキレンオキシドとの反応生成物に不飽和モノカルボン酸を反応させ、得られた反応生成物に飽和又は不飽和多塩基酸無水物を反応させて得られるカルボキシル基含有感光性樹脂や、
（９）１分子中に少なくとも２個のエポキシ基を有する多官能エポキシ化合物と、不飽和モノカルボン酸と、１分子中に少なくとも２個の水酸基と、エポキシ基と反応する水酸基以外の１個の他の反応性基を有する化合物との反応生成物に、飽和又は不飽和の多塩基酸無水物と不飽和基含有モノイソシアネートを反応させて得られる生成物等の不飽和基含有ポリカルボン酸ウレタン樹脂などを挙げることができる。
Examples of the photosensitive prepolymer (E-2) include:
(1) Esterification reaction (total esterification or partial esterification, preferably total esterification) of an epoxy group of a polyfunctional epoxy compound having at least two epoxy groups in one molecule and a carboxyl group of an unsaturated monocarboxylic acid Carboxyl group-containing photosensitive resin obtained by further reacting the generated hydroxyl group with a saturated or unsaturated polybasic acid anhydride,
(2) A carboxyl group obtained by reacting a copolymer composed of alkyl (meth) acrylate and glycidyl (meth) acrylate with (meth) acrylic acid and further reacting with a saturated or unsaturated polybasic acid anhydride. Containing photosensitive resin,
(3) After reacting a copolymer of hydroxyalkyl (meth) acrylate, alkyl (meth) acrylate and glycidyl (meth) acrylate with (meth) acrylic acid, a saturated or unsaturated polybasic acid anhydride is further added. Carboxyl group-containing photosensitive resin obtained by reaction,
(4) a carboxyl group-containing photosensitive resin obtained by partially reacting a copolymer of alkyl (meth) acrylate and (meth) acrylic acid with glycidyl (meth) acrylate,
(5) A polyfunctional epoxy compound having at least two epoxy groups in one molecule, an unsaturated monocarboxylic acid, at least two hydroxyl groups in one molecule, and one hydroxyl group that reacts with an epoxy group A carboxyl group-containing photosensitive resin obtained by reacting a reaction product with a compound having another reactive group with a saturated or unsaturated polybasic acid anhydride,
(6) Carboxyl group-containing photosensitivity obtained by reacting a hydroxyalkyl (meth) acrylate with a copolymer of an unsaturated polybasic acid anhydride such as maleic anhydride and an aromatic hydrocarbon having a vinyl group such as styrene. Resin,
(7) A polyfunctional oxetane compound having at least two oxetane rings in one molecule is reacted with an unsaturated monocarboxylic acid, and the resulting modified oxetane resin is saturated or unsaturated polybasic acid anhydride with respect to the primary hydroxyl group. Carboxyl group-containing photosensitive resin obtained by reacting a product,
(8) Carboxyl group-containing product obtained by reacting a reaction product of a novolak-type phenolic resin with an alkylene oxide with an unsaturated monocarboxylic acid and reacting the resulting reaction product with a saturated or unsaturated polybasic acid anhydride Photosensitive resin,
(9) A polyfunctional epoxy compound having at least two epoxy groups in one molecule, an unsaturated monocarboxylic acid, at least two hydroxyl groups in one molecule, and one hydroxyl group that reacts with an epoxy group Unsaturated group-containing polycarboxylic acid urethanes such as products obtained by reacting saturated or unsaturated polybasic acid anhydrides and unsaturated group-containing monoisocyanates with reaction products with compounds having other reactive groups Examples thereof include resins.
上記感光性プレポリマーがカルボキシル基を有する場合には、アルカリ現像が可能になるが、カルボキシル基を有さない場合には、有機溶剤により現像することになる。カルボキシル基を含有する感光性プレポリマーの酸価は、その種類によって好適な範囲は異なるが、一般に３０〜２００ｍｇＫＯＨ／ｇの範囲にあることが必要であり、好ましい範囲は４０〜１２０ｍｇＫＯＨ／ｇである。酸価が３０ｍｇＫＯＨ／ｇより小さい場合にはアルカリ水溶液への溶解性が悪くなり、逆に２００ｍｇＫＯＨ／ｇより大きすぎると、硬化膜の耐アルカリ性、電気特性等のレジストとしての特性を下げる要因となるので、いずれも好ましくない。 When the photosensitive prepolymer has a carboxyl group, alkali development is possible, but when the photosensitive prepolymer does not have a carboxyl group, development is performed with an organic solvent. The acid value of the photosensitive prepolymer containing a carboxyl group is preferably in the range of 30 to 200 mgKOH / g, although the preferred range varies depending on the type, and the preferred range is 40 to 120 mgKOH / g. . When the acid value is less than 30 mgKOH / g, the solubility in an alkaline aqueous solution is deteriorated. Conversely, when the acid value is more than 200 mgKOH / g, the resist properties such as alkali resistance and electrical properties of the cured film are lowered. Therefore, neither is preferable.
光重合開始剤（Ｆ）としては、例えば、ベンゾインとベンゾインアルキルエーテル類、アセトフェノン類、２−メチル−１−［４−（メチルチオ）フェニル］−２−モルホリノアミノプロパノン−１、２−ベンジル−２−ジメチルアミノ−１−（４−モルホリノフェニル）−ブタン−１−オン等のアミノアセトフェノン類、アントラキノン類、チオキサントン類、ケタール類、有機過酸化物、チオール化合物、ベンゾフェノン類又はキサントン類、オキシム化合物などが挙げられるが、特にこれらに限られるものではなく、紫外光もしくは可視光領域で光を吸収し、（メタ）アクリロイル基等の不飽和基をラジカル重合させるものであれば、光重合開始剤、光開始助剤に限らず、単独であるいは複数併用して使用できる。 Examples of the photopolymerization initiator (F) include benzoin and benzoin alkyl ethers, acetophenones, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinoaminopropanone-1, 2-benzyl- Aminoacetophenones such as 2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, anthraquinones, thioxanthones, ketals, organic peroxides, thiol compounds, benzophenones or xanthones, oxime compounds However, the photopolymerization initiator is not particularly limited as long as it absorbs light in the ultraviolet or visible light region and radically polymerizes an unsaturated group such as a (meth) acryloyl group. These are not limited to photoinitiating aids, and can be used alone or in combination.
前記光重合開始剤（光開始助剤を用いる場合にはそれらの合計量）の使用量は、前記光硬化性成分（Ｅ）１００質量部に対して０．１〜２５質量部、好ましくは０．５〜２０質量部の割合が望ましい。光重合開始剤の配合量が上記範囲よりも少ない場合、活性エネルギー線の照射を行っても硬化しないか、もしくは照射時間を増やす必要があり、適切な皮膜物性が得られ難くなる。一方、上記範囲よりも多量に光重合開始剤を添加すると、経済的に好ましくない。 The usage-amount of the said photoinitiator (The total amount when using a photoinitiator adjuvant) is 0.1-25 mass parts with respect to 100 mass parts of said photocurable components (E), Preferably it is 0. A ratio of 0.5 to 20 parts by mass is desirable. When the blending amount of the photopolymerization initiator is less than the above range, it is not cured even when active energy rays are irradiated, or it is necessary to increase the irradiation time, and it is difficult to obtain appropriate film properties. On the other hand, adding a photopolymerization initiator in a larger amount than the above range is not economically preferable.
本発明のソルダーレジスト組成物を光硬化・熱硬化型に組成する場合には、少なくとも前記光硬化性成分（Ｅ）、特にカルボキシル基を含有する感光性プレポリマー（Ｅ−２）、及び光重合開始剤（Ｆ）と共に、前記分子中に２個以上の環状エーテル基を有する化合物（Ｂ）を含有し、必要に応じて前記硬化触媒（Ｄ）を含有する。このような光硬化・熱硬化型のソルダーレジスト組成物の場合、分子中に２個以上の環状エーテル基を有する化合物（Ｂ）の配合割合は、前記光硬化性成分（Ｅ）１００質量部に対して１０質量部以上、１００質量部以下の割合で充分であり、好ましくは１５〜６０質量部の割合である。 When the solder resist composition of the present invention is formed into a photocurable / thermosetting type, at least the photocurable component (E), particularly a photosensitive prepolymer (E-2) containing a carboxyl group, and photopolymerization. The compound (B) which has a 2 or more cyclic ether group in the said molecule | numerator is contained with the initiator (F), and the said curing catalyst (D) is contained as needed. In the case of such a photocuring / thermosetting solder resist composition, the compounding ratio of the compound (B) having two or more cyclic ether groups in the molecule is 100 parts by mass of the photocurable component (E). On the other hand, a ratio of 10 parts by mass or more and 100 parts by mass or less is sufficient, and a ratio of 15 to 60 parts by mass is preferable.
本発明のソルダーレジスト組成物は、硬化性成分等を溶解し希釈せしめ、それによって液状として塗布し、次いで乾燥させることにより造膜せしめ、接触露光を可能とするため、有機溶剤を含有することができる。有機溶剤としては、例えば、ケトン類、芳香族炭化水素類、グリコールエーテル類、グリコールエーテルアセテート類、エステル類、アルコール類、石油系溶剤などが挙げられる。
有機溶剤の使用量は特定の割合に限定されるものではなく、選択する塗布方法に応じて適宜設定できる。
The solder resist composition of the present invention may contain an organic solvent in order to dissolve and dilute a curable component, etc., thereby applying as a liquid, and then forming a film by drying to allow contact exposure. it can. Examples of the organic solvent include ketones, aromatic hydrocarbons, glycol ethers, glycol ether acetates, esters, alcohols, petroleum solvents, and the like.
The usage-amount of an organic solvent is not limited to a specific ratio, It can set suitably according to the coating method to select.
本発明のソルダーレジスト組成物は、必要に応じて、硫酸バリウム、チタン酸バリウム、酸化ケイ素粉、微粉状酸化ケイ素、無定形シリカ、結晶性シリカ、溶融シリカ、球状シリカ、タルク、クレー、炭酸マグネシウム、炭酸カルシウム、酸化アルミニウム、水酸化アルミニウム、マイカ等の公知慣用の無機フィラーを単独で又は２種以上配合することができる。これらは塗膜の硬化収縮を抑制し、密着性、硬度などの特性を向上させる目的で用いられる。 The solder resist composition of the present invention can be used as necessary in barium sulfate, barium titanate, silicon oxide powder, finely divided silicon oxide, amorphous silica, crystalline silica, fused silica, spherical silica, talc, clay, magnesium carbonate. In addition, known inorganic fillers such as calcium carbonate, aluminum oxide, aluminum hydroxide and mica can be used alone or in combination of two or more. These are used for the purpose of suppressing curing shrinkage of the coating film and improving properties such as adhesion and hardness.
本発明のソルダーレジスト組成物は、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、ｔ−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、モンモリロナイトなどの公知慣用の増粘剤、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、アセトアセトキシエチルアクリレート、アクリロイルモルフォリン、テトラヒドロフルフリルアクリレート等の密着性付与剤、界面活性剤、光吸収剤、チキソ性付与剤などのような公知慣用の各種添加剤類を配合することができる。 If necessary, the solder resist composition of the present invention may be a known conventional thermal polymerization inhibitor such as hydroquinone, hydroquinone monomethyl ether, t-butylcatechol, pyrogallol, phenothiazine, or the like, or a known conventional polymer such as fine silica, organic bentonite, or montmorillonite. Thickener, silicone-based, fluorine-based, polymer-based antifoaming agent and / or leveling agent, imidazole-based, thiazole-based, triazole-based silane coupling agent, acetoacetoxyethyl acrylate, acryloylmorpholine, tetrahydro Various commonly known additives such as an adhesion-imparting agent such as furfuryl acrylate, a surfactant, a light absorber, and a thixotropic agent can be blended.
以上説明したような本発明のソルダーレジスト組成物は、必要に応じて希釈して塗布方法に適した粘度に調整し、これを例えば、熱硬化型のソルダーレジスト組成物の場合には、回路形成されたプリント配線板にスクリーン印刷等により所定のパターンに塗布し、加熱硬化することによってソルダーレジストパターンを形成することができる。
一方、光硬化型又は光硬化・熱硬化型のソルダーレジスト組成物の場合には、回路形成されたプリント配線板にスクリーン印刷法、カーテンコート法、スプレーコート法、ロールコート法等の方法により塗布し、例えば約６０〜１００℃の温度で組成物中に含まれる有機溶剤を揮発乾燥させることにより、タックフリーの塗膜を形成できる。その後、レーザー光等の活性エネルギー線をパターン通りに直接照射するか、またはパターンを形成したフォトマスクを通して選択的に活性エネルギー線により露光し、未露光部を希アルカリ水溶液により現像してレジストパターンを形成できる。さらに、光硬化・熱硬化型のソルダーレジスト組成物の場合には、加熱硬化のみ、または活性エネルギー線の照射後加熱硬化もしくは加熱硬化後活性エネルギー線の照射で最終硬化（本硬化）させることにより、密着性、はんだ耐熱性、耐吸湿性、ＰＣＴ耐性、無電解金めっき耐性、耐屈曲性、耐折性、柔軟性、反り、電気絶縁性に優れた硬化膜（硬化物）が形成される。
The solder resist composition of the present invention as described above is diluted as necessary to adjust the viscosity to be suitable for the coating method. For example, in the case of a thermosetting solder resist composition, circuit formation is performed. A solder resist pattern can be formed by applying a predetermined pattern on the printed wiring board by screen printing or the like, followed by heat curing.
On the other hand, in the case of a photo-curing type or photo-curing / thermo-curing type solder resist composition, it is applied to a printed wiring board formed with a circuit by a method such as a screen printing method, a curtain coating method, a spray coating method or a roll coating method. For example, a tack-free coating film can be formed by evaporating and drying an organic solvent contained in the composition at a temperature of about 60 to 100 ° C. Thereafter, active energy rays such as laser light are directly irradiated according to the pattern, or selectively exposed with active energy rays through a photomask on which the pattern is formed, and the unexposed portion is developed with a dilute alkaline aqueous solution to form a resist pattern. Can be formed. Furthermore, in the case of a photo-curing / thermosetting type solder resist composition, by final curing (main curing) only by heat curing, or by heat curing after irradiation with active energy rays or irradiation with active energy rays after heat curing. A cured film (cured product) excellent in adhesion, solder heat resistance, moisture absorption resistance, PCT resistance, electroless gold plating resistance, bending resistance, folding resistance, flexibility, warpage, and electrical insulation is formed. .
上記アルカリ水溶液としては、水酸化カリウム、水酸化ナトリウム、炭酸ナトリウム、炭酸カリウム、リン酸ナトリウム、ケイ酸ナトリウム、アンモニア、アミン類などのアルカリ水溶液が使用できる。
また、光硬化させるための照射光源としては、低圧水銀灯、中圧水銀灯、高圧水銀灯、超高圧水銀灯、キセノンランプ又はメタルハライドランプなどが適当である。その他、レーザー光線なども活性エネルギー線として利用できる。
As the alkaline aqueous solution, alkaline aqueous solutions such as potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, sodium silicate, ammonia and amines can be used.
As the irradiation light source for photocuring, a low-pressure mercury lamp, a medium-pressure mercury lamp, a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, a xenon lamp, a metal halide lamp, or the like is appropriate. In addition, laser beams and the like can also be used as active energy rays.
以下、実施例及び比較例を示して本発明についてより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、以下において特に断りのない限り、「部」は「質量部」を意味するものとする。 EXAMPLES Hereinafter, although an Example and a comparative example are shown and this invention is demonstrated more concretely, it cannot be overemphasized that this invention is not limited to the following Example. In the following description, “part” means “part by mass” unless otherwise specified.
実施例１
太陽インキ製造（株）製熱硬化ソルダーレジストインキＳ−５００（主剤Ｓ−５００Ｅ０１（ノボラック変性型エポキシ樹脂、クレゾールノボラック型エポキシ樹脂、フェノール樹脂を主成分とし、顔料としてのカーボンブラック、その他無機フィラー等の添加剤を含有）と硬化剤ＨＤ−５０（フェノール樹脂を主成分とし、硬化触媒としてイミダゾールを含有）の９：１混合品；カーボンブラック濃度１．２％）１００部に対し、酸化チタン３部を配合し、ディゾルバーにて充分攪拌し、３本ロールミルにて分散を３度繰り返し、熱硬化型のソルダーレジスト組成物を調製した。
Example 1
Taiyo Ink Manufacture Co., Ltd. Thermosetting Solder Resist Ink S-500 (Main Agent S-500E01 (Novolac Modified Epoxy Resin, Cresol Novolak Epoxy Resin, Phenol Resin Main Component, Carbon Black as Pigment, Other Inorganic Fillers, etc.) ) And curing agent HD-50 (phenol resin as a main component and imidazole as a curing catalyst) 9: 1 mixture; carbon black concentration 1.2%) 100 parts titanium oxide 3 Parts were mixed, sufficiently stirred with a dissolver, and dispersed three times with a three-roll mill to prepare a thermosetting solder resist composition.
実施例２
太陽インキ製造（株）製紫外線硬化ソルダーレジストインキＵＶＲ−１８２Ｅ（アクリレートモノマー含有ノボラック型アクリレート誘導体及びアクリレートモノマーを主成分とし、光重合開始剤、顔料としてカーボンブラック、その他無機フィラー等の添加剤を含有；カーボンブラック濃度０．７％）１００部に対し、酸化チタン１部を配合し、ディゾルバーにて充分攪拌し、３本ロールミルにて分散を３度繰り返し、光硬化型のソルダーレジスト組成物を調製した。
Example 2
UV curing solder resist ink UVR-182E (manufactured by Taiyo Ink Mfg. Co., Ltd.) (mainly composed of acrylate monomer-containing novolac acrylate derivative and acrylate monomer, photopolymerization initiator, pigment as carbon black, and other additives such as inorganic filler) ; Carbon black concentration 0.7%) 100 parts of titanium oxide is mixed with 1 part of titanium oxide, sufficiently stirred with a dissolver, and dispersed three times with a three roll mill to prepare a photocurable solder resist composition. did.
実施例３
太陽インキ製造（株）製現像型ソルダーレジストインキＰＳＲ（主剤ＰＳＲ−４０００ＥＧ２３（カルボキシル基含有ノボラック型アクリレート樹脂を主成分とし、光重合開始剤と、硬化触媒としてのジシアンジアミドと、着色顔料としてカーボンブラック、その他無機フィラー等の添加剤を含有）と硬化剤ＣＡ−４０Ｇ２３（ノボラック変性型エポキシ樹脂、イソシアヌル酸変性型エポキシ樹脂、アクリレートモノマーを主成分として含有）の７：３混合品；カーボンブラック濃度０．３％）１００部に対し、酸化チタン１部を配合し、ディゾルバーにて充分攪拌し、３本ロールミルにて分散を３度繰り返し、光硬化・熱硬化型型のソルダーレジスト組成物を調製した。
Example 3
Development type solder resist ink PSR (main component PSR-4000EG23 (mainly a carboxyl group-containing novolac acrylate resin, a photopolymerization initiator, dicyandiamide as a curing catalyst), carbon black as a coloring pigment, manufactured by Taiyo Ink Manufacturing Co., Ltd. 7: 3 mixed product of other additives such as inorganic filler) and curing agent CA-40G23 (containing novolac-modified epoxy resin, isocyanuric acid-modified epoxy resin and acrylate monomer as main components); 3%) 100 parts of titanium oxide was mixed with 1 part of titanium oxide, sufficiently stirred with a dissolver, and dispersed three times with a three-roll mill to prepare a photocuring / thermosetting type solder resist composition.
比較例１
実施例１において、酸化チタンを配合しなかった以外は実施例１と同様にして、熱硬化型のソルダーレジスト組成物を調製した。
Comparative Example 1
In Example 1, a thermosetting solder resist composition was prepared in the same manner as in Example 1 except that no titanium oxide was added.
比較例２
実施例２において、酸化チタンを配合しなかった以外は実施例２と同様にして、光硬化型のソルダーレジスト組成物を調製した。
Comparative Example 2
In Example 2, a photocurable solder resist composition was prepared in the same manner as in Example 2 except that no titanium oxide was added.
比較例３
実施例３において、酸化チタンを配合しなかった以外は実施例３と同様にして、光硬化・熱硬化型のソルダーレジスト組成物を調製した。
Comparative Example 3
In Example 3, a photocuring / thermosetting solder resist composition was prepared in the same manner as in Example 3 except that no titanium oxide was added.
比較例４
実施例１において、酸化チタン３部に代えてカーボンブラック３部を配合した以外は実施例１と同様にして、熱硬化型のソルダーレジスト組成物を調製した。
Comparative Example 4
In Example 1, a thermosetting solder resist composition was prepared in the same manner as in Example 1 except that 3 parts of carbon black was added instead of 3 parts of titanium oxide.
比較例５
実施例２において、酸化チタン１部に代えてカーボンブラック１部を配合した以外は実施例２と同様にして、光硬化型のソルダーレジスト組成物を調製した。
Comparative Example 5
In Example 2, a photocurable solder resist composition was prepared in the same manner as in Example 2 except that 1 part of carbon black was added instead of 1 part of titanium oxide.
比較例６
実施例３において、酸化チタン１部に代えてカーボンブラック１部を配合した以外は実施例３と同様にして、光硬化・熱硬化型のソルダーレジスト組成物を調製した。
前記各実施例及び各比較例で調製したソルダーレジスト組成物の組成を表１にまとめて示す。
Comparative Example 6
In Example 3, a photocuring / thermosetting solder resist composition was prepared in the same manner as in Example 3 except that 1 part of carbon black was added instead of 1 part of titanium oxide.
Table 1 summarizes the compositions of the solder resist compositions prepared in the above Examples and Comparative Examples.
試験例
前記各実施例及び各比較例で調製したソルダーレジスト組成物を、熱硬化型のソルダーレジスト組成物の場合には、ＦＲ−４基材上に回路パターンを作製した基板に１５０メッシュのポリエステル製版にてスクリーン印刷を行い、１５０℃で２０分間硬化させた。一方、光硬化型のソルダーレジスト組成物の場合には、ＦＲ−４基材上に回路パターンを作製した基板に１５０メッシュのポリエステル製版にてスクリーン印刷を行い、ＵＶ照射機で３５０ｎｍの波長にて積算光量１Ｊ／ｃｍ2のＵＶ光を照射して硬化させた。また、光硬化・熱硬化型のソルダーレジスト組成物の場合には、ＦＲ−４基材上に回路パターンを作製した基板に１００メッシュのポリエステル製版にてスクリーン印刷を行い、８０℃で３０分間乾燥させた。その後、露光機で３５０ｎｍの波長にて積算光量３００ｍＪ／ｃｍ2のＵＶ光を照射し、１％炭酸ソーダ水溶液にて現像後、１５０℃で６０分間硬化させた。
Test Example When the solder resist composition prepared in each of the above Examples and Comparative Examples is a thermosetting solder resist composition, a 150 mesh polyester is applied to a substrate on which a circuit pattern is formed on an FR-4 base material. Screen printing was performed by plate making and cured at 150 ° C. for 20 minutes. On the other hand, in the case of a photocurable solder resist composition, screen printing is performed on a substrate having a circuit pattern formed on an FR-4 base material using a 150 mesh polyester plate, and a UV irradiation machine is used at a wavelength of 350 nm. Curing was performed by irradiating UV light with an integrated light amount of 1 J / cm 2 . In the case of a photo-curing / thermosetting solder resist composition, screen printing is performed with a 100-mesh polyester plate on a substrate having a circuit pattern formed on an FR-4 base material, followed by drying at 80 ° C. for 30 minutes. I let you. Thereafter, UV light with an integrated light quantity of 300 mJ / cm 2 was irradiated at a wavelength of 350 nm with an exposure machine, developed with a 1% sodium carbonate aqueous solution, and cured at 150 ° C. for 60 minutes.
このようにして作製した基板について、以下のようにして回路パターンの隠蔽性について評価した。
隠蔽性の評価方法：
作製した基板をソルダーレジスト上から目視で観察し、回路バターンの見え方を以下の基準で評価した。
○：回路が見えない。
×：回路が見える。
結果を表２に示す。なお、表２には、形成されたソルダーレジストの膜厚も併せて示す。
The circuit pattern concealment was evaluated for the substrate thus fabricated as follows.
Concealment evaluation method:
The produced substrate was visually observed from above the solder resist, and the appearance of the circuit pattern was evaluated according to the following criteria.
○: The circuit is not visible.
X: The circuit is visible.
The results are shown in Table 2. Table 2 also shows the film thickness of the formed solder resist.
なお、本発明は、その具体的適用形態としてソルダーレジスト組成物について説明したが、本発明の顔料の組合せは、隠蔽性が要求される他の用途への適用も期待できる。
In addition, although this invention demonstrated the soldering resist composition as the specific application form, the combination of the pigment of this invention can anticipate the application to the other use as which hiding property is requested | required.
Claims (3)
The printed wiring board which has a soldering resist formed from the soldering resist composition of Claim 1.
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| JP2004129558A JP4700924B2 (en) | 2004-04-26 | 2004-04-26 | Solder resist composition and printed wiring board having solder resist formed therefrom |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2013105066A (en) * | 2011-11-15 | 2013-05-30 | Kaneka Corp | New production kit for photosensitive resin composition, and use of the same |
| JP2014098139A (en) * | 2012-10-19 | 2014-05-29 | Taiyo Ink Mfg Ltd | Curable resin composition, curable resin composition for forming solder resist, cured coating film, and printed wiring board |
| KR20140076483A (en) | 2012-12-11 | 2014-06-20 | 다이요 잉키 세이조 가부시키가이샤 | Photocurable resin composition, solder resist and printed wiring board |
| KR20150118033A (en) | 2014-04-11 | 2015-10-21 | 다이요 잉키 세이조 가부시키가이샤 | Photosensitive resin composition, dry film, cured product and printed wiring board |
| KR20160079681A (en) | 2014-12-26 | 2016-07-06 | 다이요 잉키 세이조 가부시키가이샤 | Curable resin composition, dry film, cured product, and printed wiring board |
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| JPH09138504A (en) * | 1995-11-15 | 1997-05-27 | Sanyo Chem Ind Ltd | Photosensitive resin composition |
| JP2001171272A (en) * | 1999-12-21 | 2001-06-26 | Dainippon Printing Co Ltd | Card |
| JP2004511636A (en) * | 2000-10-18 | 2004-04-15 | チバ スペシャルティ ケミカルズ ホールディング インコーポレーテッド | Low color dark curable composition |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JPS63299171A (en) * | 1987-05-28 | 1988-12-06 | Kyocera Corp | Photovoltaic device |
| JPH09138504A (en) * | 1995-11-15 | 1997-05-27 | Sanyo Chem Ind Ltd | Photosensitive resin composition |
| JP2001171272A (en) * | 1999-12-21 | 2001-06-26 | Dainippon Printing Co Ltd | Card |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2013105066A (en) * | 2011-11-15 | 2013-05-30 | Kaneka Corp | New production kit for photosensitive resin composition, and use of the same |
| JP2014098139A (en) * | 2012-10-19 | 2014-05-29 | Taiyo Ink Mfg Ltd | Curable resin composition, curable resin composition for forming solder resist, cured coating film, and printed wiring board |
| KR20140076483A (en) | 2012-12-11 | 2014-06-20 | 다이요 잉키 세이조 가부시키가이샤 | Photocurable resin composition, solder resist and printed wiring board |
| KR20150118033A (en) | 2014-04-11 | 2015-10-21 | 다이요 잉키 세이조 가부시키가이샤 | Photosensitive resin composition, dry film, cured product and printed wiring board |
| KR20160079681A (en) | 2014-12-26 | 2016-07-06 | 다이요 잉키 세이조 가부시키가이샤 | Curable resin composition, dry film, cured product, and printed wiring board |
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| JP4700924B2 (en) | 2011-06-15 |
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