JP2008019336A - Photocurable and thermosetting one-pack type solder resist composition and printed wiring board using the same - Google Patents
Photocurable and thermosetting one-pack type solder resist composition and printed wiring board using the same Download PDFInfo
- Publication number
- JP2008019336A JP2008019336A JP2006191949A JP2006191949A JP2008019336A JP 2008019336 A JP2008019336 A JP 2008019336A JP 2006191949 A JP2006191949 A JP 2006191949A JP 2006191949 A JP2006191949 A JP 2006191949A JP 2008019336 A JP2008019336 A JP 2008019336A
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- Prior art keywords
- solder resist
- resist composition
- acid
- compound
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- Prior art date
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- Granted
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- 229910000679 solder Inorganic materials 0.000 title claims abstract description 57
- 239000000203 mixture Substances 0.000 title claims abstract description 50
- 229920001187 thermosetting polymer Polymers 0.000 title claims abstract description 15
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- 239000011347 resin Substances 0.000 claims abstract description 37
- -1 organic acid salt Chemical class 0.000 claims abstract description 35
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 31
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- 244000028419 Styrax benzoin Species 0.000 description 3
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- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 3
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- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 150000007964 xanthones Chemical class 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
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Abstract
Description
本発明は、プリント配線板の製造に有用なアルカリ現像可能な光硬化性・熱硬化性の一液型ソルダーレジスト組成物及びそれを用いたプリント配線板に関するものであり、さらに詳しくは、耐熱性、密着性、無電解金めっき耐性、電気特性の塗膜特性に優れ、かつ指触乾燥性、作業性に優れるアルカリ現像可能な光硬化性・熱硬化性の一液型ソルダーレジスト組成物及びそれを用いたプリント配線板に関する。 The present invention relates to a photocurable / thermosetting one-component solder resist composition useful for the production of printed wiring boards and a printed wiring board using the same, and more particularly, heat resistance , Photocurable / thermosetting one-component solder resist composition with excellent adhesiveness, electroless gold plating resistance, electrical coating properties, dry touch, and workability The present invention relates to a printed wiring board using the above.
現在、プリント配線板の製造に用いられるソルダーレジストは、高精度、高密度化の観点から、露光後、現像することにより画像形成し、加熱硬化して塗膜を形成する液状アルカリ現像型ソルダーレジストが使用されている。このような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としては、例えば、ノボラック型エポキシ化合物と不飽和モノカルボン酸との反応生成物に、飽和又は不飽和多塩基酸無水物を付加した活性エネルギー線硬化性樹脂、光重合開始剤、希釈剤、及びエポキシ化合物からなる二液型の液状ソルダーレジスト組成物が提案されている（例えば、特許文献１参照）。 Currently, the solder resist used in the production of printed wiring boards is a liquid alkaline development type solder resist that forms an image by developing after exposure and heat-cures to form a coating film from the viewpoint of high accuracy and high density. Is used. As an alkali development type solder resist using such a dilute alkaline aqueous solution, for example, an active energy obtained by adding a saturated or unsaturated polybasic acid anhydride to a reaction product of a novolak type epoxy compound and an unsaturated monocarboxylic acid. A two-component liquid solder resist composition composed of a linear curable resin, a photopolymerization initiator, a diluent, and an epoxy compound has been proposed (see, for example, Patent Document 1).
しかしながら、このような液状のアルカリ現像型ソルダーレジストのほとんどが、ノボラック型エポキシ化合物と不飽和モノカルボン酸の反応生成物に、多塩基酸無水物を付加した活性エネルギー線硬化性樹脂、光重合開始剤などからなる主剤と、希釈剤やエポキシ化合物などからなる硬化剤で構成される二液型のソルダーレジストであり、主剤と硬化剤をよく混合してから使用しなければならない。また、混合後のポットライフは２４時間以内と短く、さらに、乾燥工程と現像工程の間にも主剤の活性エネルギー線硬化性樹脂に含まれるカルボキシル基と硬化剤中のエポキシ化合物のエポキシ基が徐々に反応するため現像不良（熱かぶり）を起こすなど、作業上の問題点がある。 However, most of these liquid alkali development type solder resists are active energy ray-curable resins obtained by adding a polybasic acid anhydride to the reaction product of a novolak epoxy compound and an unsaturated monocarboxylic acid, and photopolymerization is initiated. It is a two-pack type solder resist composed of a main agent composed of an agent and a curing agent composed of a diluent, an epoxy compound, etc., and must be used after thoroughly mixing the main agent and the curing agent. Further, the pot life after mixing is as short as 24 hours or less, and further, the carboxyl group contained in the active energy ray-curable resin as the main agent and the epoxy group of the epoxy compound in the curing agent are gradually added between the drying step and the developing step. There is a problem in work, such as causing poor development (hot fogging).
このような課題に対して、例えば、１分子内に少なくとも１つ以上の遊離のカルボキシル基を有し、あるいはさらに１つ以上の光反応性不飽和基を有する室温で固形状の高分子化合物もしくはオリゴマー、希釈剤、光重合開始剤、メラミン又はその誘導体、あるいは更に２，４，６−トリスメルカプト−Ｓ−トリアジンを含む一液型のソルダーレジストが提案されている（例えば特許文献２参照）。しかしながらこの一液型ソルダーレジストは、作業性は優れるものの、耐熱性、無電解金めっき耐性が二液型の液状ソルダーレジストに比べ不安定であり、実用化されるに至っていない。 For such a problem, for example, at least one free carboxyl group in one molecule, or at least one photoreactive unsaturated group at room temperature, a solid polymer compound or A one-component solder resist containing an oligomer, a diluent, a photopolymerization initiator, melamine or a derivative thereof, or 2,4,6-trismercapto-S-triazine has been proposed (see, for example, Patent Document 2). However, although this one-pack type solder resist is excellent in workability, the heat resistance and electroless gold plating resistance are unstable as compared with the two-pack type liquid solder resist and have not yet been put into practical use.
また、このようなアルカリ現像型のソルダーレジストは、生産性の向上から高感度化や自動露光機に対応可能な指触性が求められている。一般的に、高感度化するためには、低分子量の光重合性モノマーを増量することが必要であるが、このような低分子量の光重合性モノマーを増量すると、指触乾燥性が著しく低下するという問題があった。
従って、本発明は、上記従来技術が抱える問題を解決する為になされたものであり、その主な目的は、一液型組成物として使用可能な保存安定性を有すると共に、ソルダーレジストとして十分満足できる耐熱性、密着性、無電解金めっき耐性、電気特性等の塗膜特性を有し、かつ指触乾燥性に優れ、高感度化も可能なアルカリ現像可能な光硬化・熱硬化性の一液型のソルダーレジスト組成物と、それを用いたドライフィルム、及びプリント配線板を提供することにある。 Therefore, the present invention has been made to solve the above-described problems of the prior art, and its main purpose is to have storage stability that can be used as a one-part composition and to be sufficiently satisfactory as a solder resist. One of the photocuring and thermosetting properties that can be developed with alkali that has heat resistance, adhesion, electroless gold plating resistance, electrical characteristics and other coating properties, excellent dryness to touch, and high sensitivity. It is an object to provide a liquid solder resist composition, a dry film using the same, and a printed wiring board.
前記目的を達成するべく鋭意研究を重ねた結果、本発明の第一の態様は、（Ａ）不飽和カルボン酸（ａ）と、前記不飽和カルボン酸以外の一分子中にエチレン性不飽和基を有する化合物（ｂ）とからなる共重合物に、一分子中に環状エーテル基とエチレン性不飽和脂基を併せ持つ化合物（ｃ）を付加して得られ、かつ軟化点が１３０〜２００℃であるカルボキシル基含有感光性樹脂、
（Ｂ）希釈剤、
（Ｃ）光重合開始剤、
（Ｄ）メラミン又はその有機酸塩、
及び（Ｅ）無機フィラーを含むことを特徴とするアルカリ現像可能な光硬化性・熱硬化性の一液型ソルダーレジスト組成物が提供される。
また、他の提供形態として、上記ソルダーレジスト組成物を、キャリアフィルムに塗布、乾燥して得られる光硬化性・熱硬化性のドライフィルムが提供される。
さらに、回路形成されたプリント配線板表面に、一液型ソルダーレジスト組成物、又はドライフィルムを用いて、ソルダーレジスト層が形成されていることを特徴とするプリント配線板が提供される。
As a result of intensive studies to achieve the above object, the first aspect of the present invention is that (A) an unsaturated carboxylic acid (a) and an ethylenically unsaturated group in one molecule other than the unsaturated carboxylic acid. It is obtained by adding a compound (c) having both a cyclic ether group and an ethylenically unsaturated fatty group in one molecule to a copolymer comprising a compound (b) having a softening point of 130 to 200 ° C. A certain carboxyl group-containing photosensitive resin,
(B) Diluent,
(C) a photopolymerization initiator,
(D) melamine or an organic acid salt thereof,
And (E) a photocurable / thermosetting one-component solder resist composition capable of alkali development, comprising an inorganic filler.
As another form of provision, there is provided a photocurable / thermosetting dry film obtained by applying the solder resist composition to a carrier film and drying.
Furthermore, a printed wiring board is provided in which a solder resist layer is formed on the surface of a printed wiring board on which a circuit is formed using a one-pack type solder resist composition or a dry film.
本発明のアルカリ現像可能な光硬化・熱硬化性のソルダーレジスト組成物は、一液型組成物として使用可能な保存安定性を有し、プリント配線板に塗布、乾燥後の乾燥管理幅も長く、さらにソルダーレジストとして十分満足できる耐熱性、密着性、無電解金めっき耐性、電気特性等の塗膜特性を有する事から、信頼性の高いプリント配線板を低価格で提供することも可能となる。また、このような保存安定性を有することから、ドライフィルムとしての保存安定性にも優れ、低温保管の必要性が無くなり、低コスト化が可能となる。
更に、指触乾燥性にも優れることから、自動露光機への対応も可能である。このような指触乾燥性を有していることから、光重合性モノマーの増量も可能であることから、高感度化も容易となる。
The photocurable / thermosetting solder resist composition capable of alkali development of the present invention has storage stability that can be used as a one-part composition, and has a long drying control width after being applied to a printed wiring board and dried. Furthermore, since it has coating properties such as heat resistance, adhesion, electroless gold plating resistance, and electrical properties that can be satisfactorily satisfied as a solder resist, it is also possible to provide highly reliable printed wiring boards at a low price. . In addition, since it has such storage stability, it is excellent in storage stability as a dry film, eliminates the need for low-temperature storage, and enables cost reduction.
Furthermore, since it is excellent in dryness to touch, it can be applied to an automatic exposure machine. Since it has such a touch-drying property, it is possible to increase the amount of the photopolymerizable monomer, so that it is easy to increase the sensitivity.
本発明のアルカリ現像可能な光硬化・熱硬化性の一液型ソルダーレジスト組成物の基本的態様は、（Ａ）不飽和カルボン酸（ａ）と、前記不飽和カルボン酸以外の一分子中にエチレン性不飽和基を有する化合物（ｂ）とからなる共重合物に、一分子中に環状エーテル基とエチレン性不飽和脂基を併せ持つ化合物（ｃ）を付加して得られ、かつ軟化点が１３０〜２００℃であるカルボキシル基含有感光性樹脂、
（Ｂ）希釈剤、
（Ｃ）光重合開始剤、
（Ｄ）メラミン又はその有機酸塩、
及び（Ｅ）無機フィラーを含むソルダーレジスト組成物が、一液型組成物として使用可能な保存安定性を有し、かつソルダーレジストとして満足できる耐熱性、密着性、無電解金めっき耐性、電気特性の塗膜特性に優れ、かつ指触乾燥性に優れることを見出し、本発明を完成するに至ったものである。
The basic aspect of the alkali-developable photocurable / thermosetting one-component solder resist composition of the present invention is (A) an unsaturated carboxylic acid (a) and a molecule other than the unsaturated carboxylic acid. It is obtained by adding a compound (c) having both a cyclic ether group and an ethylenically unsaturated fatty group in one molecule to a copolymer comprising the compound (b) having an ethylenically unsaturated group, and has a softening point. A carboxyl group-containing photosensitive resin having a temperature of 130 to 200 ° C .;
(B) Diluent,
(C) a photopolymerization initiator,
(D) melamine or an organic acid salt thereof,
And (E) a solder resist composition containing an inorganic filler has storage stability that can be used as a one-part composition, and is satisfactory as a solder resist, heat resistance, adhesion, electroless gold plating resistance, electrical properties It has been found that the coating film characteristics are excellent and the dryness to touch is excellent, and the present invention has been completed.
即ち、本発明のアルカリ現像可能な光硬化・熱硬化性の一液型ソルダーレジスト組成物は、第一の特徴は、不飽和カルボン酸（ａ）と、前記不飽和カルボン酸以外の一分子中にエチレン性不飽和基を有する化合物（ｂ）とからなる共重合物に、一分子中に環状エーテル基とエチレン性不飽和脂基を併せ持つ化合物（ｃ）を付加して得られ、かつ軟化点が１３０〜２００℃であるカルボキシル基含有感光性樹脂を用いた点にあり、このことにより、指触乾燥性に優れ、造膜性に優れた塗膜を得ることが可能となる。さらに、本発明の一液型ソルダーレジスト組成物は、従来品に使用されているエポキシ樹脂等の熱硬化成分の代わりに、メラミン又はその有機酸塩を前記カルボキシル基含有感光性樹脂と併用することにより、耐熱性、無電解金めっき耐性が著しく向上することを見出し、本発明の一液型ソルダーレジスト組成物を完成するに至った。
このようなメラミン又はその有機酸塩は、カルボキシル基含有感光性樹脂（Ａ）のエチレン性不飽和基と、メラミン又はその有機酸塩の活性水素が、加熱硬化中に一部付加反応し分子鎖に取り込まれ、銅箔へのキレート効果と防錆効果により、塗膜と銅箔の密着性を向上させるものと考えられる。
尚、本明細書において、軟化点とは、熱機械分析装置（ＴＭＡ）を用いて、５℃／分の昇温速度で昇温し、１ｇの荷重を架けた針入ブローブの位置変化量から求めた。
（但し、熱重合による軟化点の上昇を考慮し、測定樹脂に、約１，０００ｐｐｍの熱重合禁止剤を加えて測定した。）
That is, the alkali-developable photocurable / thermosetting one-component solder resist composition of the present invention is characterized in that the first feature is in the unsaturated carboxylic acid (a) and one molecule other than the unsaturated carboxylic acid. Obtained by adding a compound (c) having both a cyclic ether group and an ethylenically unsaturated fatty group in one molecule to a copolymer comprising the compound (b) having an ethylenically unsaturated group at the same time, and a softening point. Is a point in which a carboxyl group-containing photosensitive resin having a temperature of 130 to 200 ° C. is used, and this makes it possible to obtain a coating film excellent in dryness to touch and excellent in film forming property. Furthermore, in the one-component solder resist composition of the present invention, melamine or an organic acid salt thereof is used in combination with the carboxyl group-containing photosensitive resin instead of a thermosetting component such as an epoxy resin used in conventional products. As a result, it was found that the heat resistance and electroless gold plating resistance were remarkably improved, and the one-pack type solder resist composition of the present invention was completed.
Such a melamine or an organic acid salt thereof has a molecular chain in which the ethylenically unsaturated group of the carboxyl group-containing photosensitive resin (A) and the active hydrogen of the melamine or the organic acid salt thereof partially undergo an addition reaction during heat curing. It is considered that the adhesion between the coating film and the copper foil is improved by the chelating effect and the antirust effect on the copper foil.
In this specification, the softening point is determined from the amount of change in the position of the needle-inserted probe with a temperature of 5 ° C./min and a load of 1 g using a thermomechanical analyzer (TMA). Asked.
(However, in consideration of an increase in the softening point due to thermal polymerization, the measurement resin was measured by adding about 1,000 ppm of a thermal polymerization inhibitor.)
以下、本発明の光硬化性・熱硬化性の一液型ソルダーレジスト組成物の各構成成分について、詳しく説明する。
まず、本発明に用いられるカルボキシル基含有感光性樹脂（Ａ）は、不飽和カルボン酸（ａ）と、前記不飽和カルボン酸以外の一分子中にエチレン性不飽和基を有する化合物（ｂ）とからなる共重合物に、一分子中に環状エーテル基とエチレン性不飽和脂基を併せ持つ化合物（ｃ）を付加して得られ、かつ軟化点が１３０〜２００℃となる樹脂である。
カルボキシル基含有感光性樹脂（Ａ）の軟化点は、１３０〜２００℃、好ましくは１３５〜１８０℃、より好ましくは、１４０〜１８０℃である。軟化点が、上記範囲より低い場合、十分な指触乾燥性が得られなくなり、好ましくない。一方、上記範囲より、軟化点が高い場合、アルカリ現像性が低下するので、好ましくない。
尚、軟化点が２００℃を超える樹脂、例えば、Ｎ−フェニルマレイミドとメタクリル酸の共重合樹脂に、グリシジルメタクリレートを付加したような樹脂の場合、上記熱機械分析装置では、熱重合による軟化点上昇で正確な値は、測定できないため、近似的に、重合性の無いブチルグリシジルエーテルを付加した樹脂で、軟化点を推測した。（これらは、現像性が得られなかった。）
Hereinafter, each component of the photocurable / thermosetting one-component solder resist composition of the present invention will be described in detail.
First, the carboxyl group-containing photosensitive resin (A) used in the present invention includes an unsaturated carboxylic acid (a) and a compound (b) having an ethylenically unsaturated group in one molecule other than the unsaturated carboxylic acid. It is a resin obtained by adding a compound (c) having both a cyclic ether group and an ethylenically unsaturated fatty group in one molecule to a copolymer comprising the above, and having a softening point of 130 to 200 ° C.
The softening point of the carboxyl group-containing photosensitive resin (A) is 130 to 200 ° C, preferably 135 to 180 ° C, and more preferably 140 to 180 ° C. When the softening point is lower than the above range, it is not preferable because sufficient dryness to the touch cannot be obtained. On the other hand, when the softening point is higher than the above range, alkali developability is lowered, which is not preferable.
In the case of a resin having a softening point exceeding 200 ° C., for example, a resin in which glycidyl methacrylate is added to a copolymer resin of N-phenylmaleimide and methacrylic acid, the above thermomechanical analyzer increases the softening point due to thermal polymerization. Since an accurate value cannot be measured, the softening point was estimated with a resin to which butyl glycidyl ether having no polymerizable property was added. (These were not developable.)
このようなカルボキシル基含有感光性樹脂（Ａ）の重量平均分子量は、８，０００〜７０，０００、より好ましくは１０，０００〜５０，０００であることが好ましい。重量平均分子量が、８，０００未満の場合、十分な造膜性が得られず、好ましくない。一方、重量平均分子量が、７０，０００を超えた場合、カルボキシル基含有感光性樹脂の有機溶剤への溶解性が低下したり、現像性が低下するので、好ましくない。
また、上記カルボキシル基含有感光性樹脂（Ａ）の酸価は、３０〜１５０ｍｇＫＯＨ／ｇ、より好ましくは酸価５０〜１４０ｍｇＫＯＨ／ｇである。酸価が、３０ｍｇＫＯＨ／ｇ未満の場合、アルカリ水溶液に対する溶解性が悪くなり、現像が困難となるので好ましくない。一方、酸価が１５０ｍｇＫＯＨ／ｇより超えた場合、耐現像性が低下するので、好ましくない。
Such a carboxyl group-containing photosensitive resin (A) has a weight average molecular weight of 8,000 to 70,000, more preferably 10,000 to 50,000. When the weight average molecular weight is less than 8,000, sufficient film forming property cannot be obtained, which is not preferable. On the other hand, when the weight average molecular weight exceeds 70,000, the solubility of the carboxyl group-containing photosensitive resin in an organic solvent is lowered or the developability is lowered.
Moreover, the acid value of the said carboxyl group-containing photosensitive resin (A) is 30-150 mgKOH / g, More preferably, the acid value is 50-140 mgKOH / g. When the acid value is less than 30 mgKOH / g, the solubility in an alkaline aqueous solution is deteriorated and development is difficult, which is not preferable. On the other hand, when the acid value exceeds 150 mgKOH / g, the development resistance is lowered, which is not preferable.
上記カルボキシル基含有感光性樹脂（Ａ）の合成に用いられる不飽和カルボン酸（ａ）としては、アクリル酸、メタクリル酸、β−カルボキシルエチル（メタ）アクリレートなどの不飽和モノカルボン酸や、マレイン酸、フマル酸、イタコン酸、シトラコン酸などの不飽和二塩基酸、さらに、２−ヒドロキシエチル（メタ）アクリレート、２−ヒドロキシプロピル（メタ）アクリレート、ヒドロキシブチル（メタ）アクリレート等のヒドロキシル基含有の（メタ）アクリレートと、二塩基酸無水物の付加物などがある。前記二塩基酸無水物としては、無水フタル酸、メチルテトラヒドロ無水フタル酸、テトラヒドロ無水フタル酸、ヘキサヒドロ無水フタル酸、メチルヘキサヒドロ無水フタル酸、無水コハク酸、無水マレイン酸、無水イタコン酸、無水ナジック酸などが挙げられる。これらの中で、感光性、保存安定性の面から、アクリル酸又はメタクリル酸が特に好ましい。これら不飽和カルボン酸（ａ）は、単独又は２種類以上を混合して用いてもよい。
なお、本明細書において（メタ)アクリレートとは、アクリレート及びメタクリレート
を総称するものであり、他の類似の表現についても同様である。
As unsaturated carboxylic acid (a) used for the synthesis | combination of the said carboxyl group-containing photosensitive resin (A), unsaturated monocarboxylic acid, such as acrylic acid, methacrylic acid, (beta) -carboxylethyl (meth) acrylate, and maleic acid , Unsaturated dibasic acids such as fumaric acid, itaconic acid, citraconic acid, and hydroxyl group-containing (such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate) There are adducts of (meth) acrylate and dibasic acid anhydride. Examples of the dibasic acid anhydride include phthalic anhydride, methyltetrahydrophthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, succinic anhydride, maleic anhydride, itaconic anhydride, and nadic anhydride. An acid etc. are mentioned. Among these, acrylic acid or methacrylic acid is particularly preferable from the viewpoint of photosensitivity and storage stability. These unsaturated carboxylic acids (a) may be used alone or in admixture of two or more.
In this specification, (meth) acrylate is a general term for acrylate and methacrylate, and the same applies to other similar expressions.
本発明カルボキシル基含有感光性樹脂（Ａ）の合成に用いられる不飽和カルボン酸以外の一分子中にエチレン性不飽和基を有する化合物（ｂ）としては、スチレン、α−メチルスチレン、酢酸ビニル、安息香酸ビニルなどのビニル化合物；メチル（メタ）アクリレート、エチル（メタ）アクリレート、ラウリル（メタ）アクリレート、イソプロピル（メタ）アクリレート、ｔ−ブチル（メタ）アクリレート、２−エチルヘキシル（メタ）アクリレート、ラウリル（メタ）アクリレート、イソボルニル（メタ）アクリレート、ベンジル（メタ）アクリレート、フェニル（メタ）アクリレート、２−ヒドロキシエチル（メタ）アクリレート、２−ヒドロキシプロピル（メタ）アクリレート、４−ヒドロキシブチル（メタ）アクリレート、フェニルグリシジルエーテル（メタ）アクリレートなどの（メタ）アクリル酸エステル類などが挙げられる。 As the compound (b) having an ethylenically unsaturated group in one molecule other than the unsaturated carboxylic acid used for the synthesis of the carboxyl group-containing photosensitive resin (A) of the present invention, styrene, α-methylstyrene, vinyl acetate, Vinyl compounds such as vinyl benzoate; methyl (meth) acrylate, ethyl (meth) acrylate, lauryl (meth) acrylate, isopropyl (meth) acrylate, t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl ( (Meth) acrylate, isobornyl (meth) acrylate, benzyl (meth) acrylate, phenyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, phenyl (Meth) acrylic acid esters such as glycidyl ether (meth) acrylate.
本発明カルボキシル基含有感光性樹脂（Ａ）の合成に用いられる一分子中に環状エーテル基とエチレン性不飽和脂基を併せ持つ化合物（ｃ）としては、グリシジル（メタ）アクリレート、メチルグリシジル（メタ）アクリレート、３，４−エポキシシクロヘキシルメチル（メタ）アクリレート、３，４−エポキシシクロヘキシルエチル（メタ）アクリレート、３，４−エポキシシクロヘキシルブチル（メタ）アクリレート、３，４−エポキシシクロヘキシルメチルアミノアクリレート、（３−エチル−３−オキセタニル）メチル（メタ）アクリレート、（３−メチル−３−オキセタニル）メチル（メタ）アクリレート、３−オキセタニルメチル（メタ）アクリレート等が挙げられる。これらの中で特に３，４−エポキシシクロヘキシルメチル（メタ）アクリレートが好ましい。 As the compound (c) having both a cyclic ether group and an ethylenically unsaturated fatty group in one molecule used for the synthesis of the carboxyl group-containing photosensitive resin (A) of the present invention, glycidyl (meth) acrylate, methyl glycidyl (meth) Acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, 3,4-epoxycyclohexylethyl (meth) acrylate, 3,4-epoxycyclohexylbutyl (meth) acrylate, 3,4-epoxycyclohexylmethylamino acrylate, (3 -Ethyl-3-oxetanyl) methyl (meth) acrylate, (3-methyl-3-oxetanyl) methyl (meth) acrylate, 3-oxetanylmethyl (meth) acrylate and the like. Among these, 3,4-epoxycyclohexylmethyl (meth) acrylate is particularly preferable.
本発明に用いられる希釈剤（Ｂ）は、インキ組成物の粘度を調整して作業性を向上させるとともに、架橋密度を上げたり、密着性などを向上するために用いられ、光重合性モノマーなどの反応性希釈剤（Ｂ−１）や公知慣用の有機溶剤（Ｂ−２）が使用できる。
反応性希釈剤（Ｂ−１）としては、２−エチルヘキシル（メタ）アクリレート、シクロヘキシル（メタ）アクリレート等のアルキル（メタ）アクリレート類；２−ヒドロキシエチル（メタ）アクリレート、２−ヒドロキシプロピル（メタ）アクリレート等のヒドロキシアルキル（メタ）アクリレート類；エチレングリコール、プロピレングリコール、ジエチレングリコール、ジプロピレングリコール等のアルキレンオキシド誘導体のモノ又はジ（メタ）アクリレート類；ヘキサンジオール、トリシクロデカンジメタノール、トリメチロールプロパン、ペンタエリスリトール、ジトリメチロールプロパン、ジペンタエリスリトール、トリスヒドロキシエチルイソシアヌレート等の多価アルコール又はこれらのエチレンオキシド或いはプロピレンオキシド付加物の多価（メタ）アクリレート類；フェノキシエチル（メタ）アクリレート、ビスフェノールＡのポリエトキシジ（メタ）アクリレート等のフェノール類のエチレンオキシドあるいはプロピレンオキシド付加物の（メタ）アクリレート類；グリセリンジグリシジルエーテル、トリメチロールプロパントリグリシジルエーテル、トリグリシジルイソシアヌレートなどのグリジジルエーテルの（メタ）アクリレート類；及びメラミン（メタ）アクリレート等を挙げることができる。
これらは、単独または２種以上組み合わせて使用でき、密着性の点で親水性基含有の（メタ）アクリレート類が、また光硬化性の点で多官能性の（メタ）アクリレート類が好ましい。これらの光重合モノマーの配合量は、カルボキシル基含有感光性樹脂（Ａ）１００質量部に対して２０〜１２０質量部、より好ましく２０〜１００質量部であることが望ましい。２０質量部未満では、光反応性が悪く、１２０質量部より多い場合は、指触乾燥性が悪くなるので好ましくない。
The diluent (B) used in the present invention is used to adjust the viscosity of the ink composition to improve workability, and to increase the crosslink density or improve adhesion, such as a photopolymerizable monomer. The reactive diluent (B-1) or a known and commonly used organic solvent (B-2) can be used.
Examples of the reactive diluent (B-1) include alkyl (meth) acrylates such as 2-ethylhexyl (meth) acrylate and cyclohexyl (meth) acrylate; 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) Hydroxyalkyl (meth) acrylates such as acrylate; mono- or di (meth) acrylates of alkylene oxide derivatives such as ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol; hexanediol, tricyclodecane dimethanol, trimethylolpropane, Polyhydric alcohols such as pentaerythritol, ditrimethylolpropane, dipentaerythritol, trishydroxyethyl isocyanurate, or their ethylene oxide or propylene Polyhydric (meth) acrylates of xoxide adducts; (meth) acrylates of ethylene oxide or propylene oxide adducts of phenols such as phenoxyethyl (meth) acrylate and polyethoxydi (meth) acrylate of bisphenol A; glycerin diglycidyl ether, And (meth) acrylates of glycidyl ethers such as trimethylolpropane triglycidyl ether and triglycidyl isocyanurate; and melamine (meth) acrylate.
These can be used alone or in combination of two or more, and (meth) acrylates containing a hydrophilic group are preferable in terms of adhesion, and polyfunctional (meth) acrylates are preferable in terms of photocurability. The blending amount of these photopolymerization monomers is preferably 20 to 120 parts by mass, more preferably 20 to 100 parts by mass with respect to 100 parts by mass of the carboxyl group-containing photosensitive resin (A). If it is less than 20 parts by mass, the photoreactivity is poor, and if it is more than 120 parts by mass, the dryness to touch becomes poor, which is not preferable.
前記有機溶剤（Ｂ−２）としては、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、公知慣用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組み合わせて用いることができる。
このような有機溶剤の配合量は、コーティング方法や使用する有機溶剤の沸点により異なり、特に制限されるものでは無いが、高沸点の有機溶剤が多量に含まれる場合、指触乾燥性が低下したり、コーティング後、仮乾燥するまでに、ダレ等を発生するので好ましくない。
Examples of the organic solvent (B-2) include ketones such as methyl ethyl ketone and cyclohexanone; aromatic hydrocarbons such as toluene, xylene, and tetramethylbenzene; cellosolve, methyl cellosolve, butyl cellosolve, carbitol, methylcarbitol, butylcarbi Toluene, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol diethyl ether, tripropylene glycol monomethyl ether and other glycol ethers; 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 Seteto, esters such as propylene carbonate; octane, aliphatic hydrocarbons decane; petroleum ether, petroleum naphtha, and petroleum solvents such as solvent naphtha, organic solvents conventionally known can be used. These organic solvents can be used alone or in combination of two or more.
The amount of such an organic solvent varies depending on the coating method and the boiling point of the organic solvent to be used, and is not particularly limited. However, when a high-boiling organic solvent is contained in a large amount, the dryness to touch decreases. Or sagging after the coating and before temporary drying.
本発明に用いられる光重合開始剤（Ｃ）としては、例えば、ベンゾイン、ベンゾインメチルエーテル、ベンゾインエチルエーテル、ベンゾインイソプロピルエーテル等のベンゾインとベンゾインアルキルエーテル類；アセトフェノン、２，２−ジメトキシ−２−フェニルアセトフェノン、２，２−ジエトキシ−２−フェニルアセトフェノン、２，２−ジエトキシ−２−フェニルアセトフェノン、１，１−ジクロロアセトフェノン等のアセトフェノン類；２−メチル−１−［４−（メチルチオ）フェニル］−２−モルフォリノプロパン−１−オン、２−ベンジル−２−ジメチルアミノ−１−（４−モルフォリノフェニル）−ブタノン−１等のアミノアセトフェノン類；２−メチルアントラキノン、２−エチルアントラキノン、２−ターシャリーブチルアントラキノン、１−クロロアントラキノン等のアントラキノン類；２，４−ジメチルチオキサントン、２，４−ジエチルチオキサントン、２−クロロチオキサントン、２，４−ジイソプロピルチオキサントン等のチオキサントン類；アセトフェノンジメチルケタール、ベンジルジメチルケタール等のケタール類；ベンゾフェノン等のベンゾフェノン類；又はキサントン類；（２，６−ジメトキシベンゾイル）−２，４，４−ペンチルホスフィンオキサイド、ビス（２，４，６−トリメチルベンゾイル）−フェニルフォスフィンオキサイド、２，４，６−トリメチルベンゾイルジフェニルフォスフィンオキサイド、エチル−２，４，６−トリメチルベンゾイルフェニルフォスフィネイト等のフォスフィンオキサイド類；各種パーオキサイド類、チタノセン系開始剤などが挙げられ、これらは、Ｎ，Ｎ−ジメチルアミノ安息香酸エチルエステル、Ｎ，Ｎ−ジメチルアミノ安息香酸イソアミルエステル、ペンチル−４−ジメチルアミノベンゾエート、トリエチルアミン、トリエタノールアミン等の三級アミン類のような光増感剤等と併用しても良い。これらの光重合開始剤は単独で又は２種以上を組み合わせて用いることができる。またこれらの光重合開始剤（Ｃ）の配合量は、カルボキシル基含有感光性樹脂（Ａ）１００質量部に対して１〜２５質量部、より好ましくは２〜２０質量部である。前記配合量が１質量部未満の場合、光硬化性が低下し、露光・現像後のパターン形成が困難になるので好ましくない。一方、２５質量部を超えた場合、厚膜硬化性が低下し、またコスト高の原因となるので好ましくない。 Examples of the photopolymerization initiator (C) used in the present invention include benzoin and benzoin alkyl ethers such as benzoin, benzoin methyl ether, benzoin ethyl ether, and benzoin isopropyl ether; acetophenone, 2,2-dimethoxy-2-phenyl Acetophenones such as acetophenone, 2,2-diethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone; 2-methyl-1- [4- (methylthio) phenyl]- Aminoacetophenones such as 2-morpholinopropan-1-one and 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1; 2-methylanthraquinone, 2-ethylanthraquinone, 2- Tertiary Anthraquinones such as tilanthraquinone and 1-chloroanthraquinone; Thioxanthones such as 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone and 2,4-diisopropylthioxanthone; Acetophenone dimethyl ketal, benzyldimethyl ketal, etc. Benzophenones such as benzophenone; or xanthones; (2,6-dimethoxybenzoyl) -2,4,4-pentylphosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, Phosphine oxides such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide and ethyl-2,4,6-trimethylbenzoylphenylphosphinate; various peroxides And N, N-dimethylaminobenzoic acid ethyl ester, N, N-dimethylaminobenzoic acid isoamyl ester, pentyl-4-dimethylaminobenzoate, triethylamine, triethanolamine, and the like. You may use together with photosensitizers, such as tertiary amines, such as. These photopolymerization initiators can be used alone or in combination of two or more. Moreover, the compounding quantity of these photoinitiators (C) is 1-25 mass parts with respect to 100 mass parts of carboxyl group-containing photosensitive resin (A), More preferably, it is 2-20 mass parts. When the amount is less than 1 part by mass, the photocurability is lowered, and pattern formation after exposure / development becomes difficult. On the other hand, when the amount exceeds 25 parts by mass, the thick film curability is lowered and the cost is increased.
メラミン又はその有機酸塩（Ｄ）としては、メラミン又は、メラミンと当モルの有機酸を反応させたものが使用できる。メラミンの有機酸塩はメラミンを沸騰水中に溶解し、水あるいはアルコール等の親水性溶剤に溶解した有機酸を添加し、析出した塩をろ過することで得られる。メラミン分子中の１個のアミノ基は、反応性が速いが他の２個の反応性は低い為、反応は化学量論的に進行し、メラミン分子中の１個のアミノ基に有機酸が１個付加したメラミン塩が生成する。有機酸としては、カルボキシル基含有化合物、酸性リン酸エステル化合物、スルホン酸含有化合物が考えられ、いずれも使用することができるが、カルボキシル基含有化合物がより好ましい。 As melamine or its organic acid salt (D), melamine or a product obtained by reacting melamine with an equimolar amount of organic acid can be used. The organic acid salt of melamine can be obtained by dissolving melamine in boiling water, adding an organic acid dissolved in water or a hydrophilic solvent such as alcohol, and filtering the deposited salt. One amino group in the melamine molecule is fast reactive but the other two are low in reactivity, so the reaction proceeds stoichiometrically, and an organic acid is attached to one amino group in the melamine molecule. One added melamine salt is formed. Examples of the organic acid include a carboxyl group-containing compound, an acidic phosphate ester compound, and a sulfonic acid-containing compound, and any of them can be used, but a carboxyl group-containing compound is more preferable.
前記カルボキシル基含有化合物としては、モノカルボン酸としては、蟻酸、酢酸、プロピオン酸、酪酸、乳酸、グリコール酸、アクリル酸、メタクリル酸などがあり、ジカルボン酸としては、シュウ酸、マロン酸、コハク酸、グルタル酸、アジピン酸、セバシン酸、マレイン酸、イタコン酸、フタル酸、ヘキサヒドロフタル酸、３−メチルヘキサヒドロフタル酸、４−メチルヘキサヒドロフタル酸、３−エチルヘキサヒドロフタル酸、４−エチルヘキサヒドロフタル酸、テトラヒドロフタル酸、３−メチルテトラヒドロフタル酸、４−メチルテトラヒドロフタル酸、３−エチルテトラヒドロフタル酸、４−エチルテトラヒドロフタル酸、クロトン酸があり、またトリカルボン酸としては、トリメリット酸などがある。これらのなかでも、特にジカルボン酸とメラミンの等モル反応により得られる塩が、これを添加するソルダーレジストの特性低下が少なく、好ましい。また、多塩基酸無水物を用いることもできる。一般に多塩基酸無水物は、例えば沸騰水中に溶解することにより容易に開環して対応するポリカルボン酸を生成する。
これらのメラミン又はその有機酸塩（Ｄ）の配合量は、カルボキシル基含有感光性樹脂（Ａ）１００質量部に対して１〜２５質量部、より好ましくは２〜２０質量部であることが望ましい。前記配合量が１質量部未満である場合、密着性、耐熱性が低下し、２５質量部を越えると光反応性が低下する。なおメラミンの有機酸塩を使用する場合は、通常メラミンを使用する場合の約１．５〜２倍が必要である
Examples of the carboxyl group-containing compound include formic acid, acetic acid, propionic acid, butyric acid, lactic acid, glycolic acid, acrylic acid, and methacrylic acid as monocarboxylic acids, and oxalic acid, malonic acid, and succinic acid as dicarboxylic acids. , Glutaric acid, adipic acid, sebacic acid, maleic acid, itaconic acid, phthalic acid, hexahydrophthalic acid, 3-methylhexahydrophthalic acid, 4-methylhexahydrophthalic acid, 3-ethylhexahydrophthalic acid, 4- There are ethylhexahydrophthalic acid, tetrahydrophthalic acid, 3-methyltetrahydrophthalic acid, 4-methyltetrahydrophthalic acid, 3-ethyltetrahydrophthalic acid, 4-ethyltetrahydrophthalic acid, and crotonic acid. There are merit acids. Among these, a salt obtained by an equimolar reaction of dicarboxylic acid and melamine is particularly preferable because there is little deterioration in the properties of the solder resist to which it is added. Polybasic acid anhydrides can also be used. In general, polybasic acid anhydrides are easily opened by, for example, dissolving in boiling water to produce the corresponding polycarboxylic acids.
The blending amount of these melamines or organic acid salts (D) thereof is desirably 1 to 25 parts by mass, more preferably 2 to 20 parts by mass with respect to 100 parts by mass of the carboxyl group-containing photosensitive resin (A). . When the blending amount is less than 1 part by mass, the adhesion and heat resistance are lowered, and when it exceeds 25 parts by mass, the photoreactivity is lowered. In addition, when using the organic acid salt of melamine, about 1.5 to 2 times the case of using melamine is necessary.
無機フィラー（Ｅ）としては、硫酸バリウム、チタン酸バリウム、酸化ケイ素紛、微粉状酸化ケイ素、無定形シリカ、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種以上を組み合わせて用いることができる。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する目的で用いられる。その配合量は、カルボキシル基含有感光性樹脂（Ａ）１００質量部に対して５０〜２５０質量部であることが望ましい。上記範囲より少ない場合、密着性、耐熱性の低下などを生じ、一方多い場合、塗膜強度の低下や感度低下などを生じ、いずれも好ましくない。 Known inorganic fillers (E) such as barium sulfate, barium titanate, silicon oxide powder, finely divided silicon oxide, amorphous silica, talc, clay, magnesium carbonate, calcium carbonate, aluminum oxide, aluminum hydroxide, mica, etc. These inorganic fillers 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. The blending amount is desirably 50 to 250 parts by mass with respect to 100 parts by mass of the carboxyl group-containing photosensitive resin (A). When the amount is less than the above range, adhesion and heat resistance are reduced. On the other hand, when the amount is more than the above range, the coating strength is lowered and the sensitivity is lowered.
さらに、必要に応じて、公知慣用の着色顔料、着色染料、熱重合禁止剤、増粘剤、消泡剤、レベリング剤、カップリング剤、難燃助剤等が使用できる。
また、本発明の一液型ソルダーレジスト組成物は、保存安定性に悪影響を及ぼさない範囲で、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、ビスフェノール型エポキシ樹脂、ビフェニール型エポキシ樹脂やトリグリシジルイソシアヌレート等の公知慣用のエポキシ樹脂を使用することができる。特に、ビキシレノール型エポキシ樹脂やトリグリシシルイソシアヌレートなどの有機溶剤に難溶性のエポキシ樹脂を少量添加することにより、密着性等を向上することができる。
Furthermore, if necessary, known and commonly used coloring pigments, coloring dyes, thermal polymerization inhibitors, thickeners, antifoaming agents, leveling agents, coupling agents, flame retardant aids and the like can be used.
In addition, the one-component solder resist composition of the present invention has a phenol novolac type epoxy resin, a cresol novolac type epoxy resin, a bisphenol type epoxy resin, a biphenyl type epoxy resin, and a triglycidyl isocyanate within a range that does not adversely affect storage stability. Known and commonly used epoxy resins such as nurate can be used. In particular, adhesion and the like can be improved by adding a small amount of a poorly soluble epoxy resin to an organic solvent such as a bixylenol type epoxy resin or triglycidyl isocyanurate.
なお、本発明の一液型ソルダーレジスト組成物は、液状、ペースト状またはドライフィルムの形態で提供することができる。ドライフィルムとして供給する場合は、例えばキャリアフィルム上にロールコーターやドクターバー、ワイヤーバー方式、スピンコート方式、ドクタープレート方式等により本発明のソルダーレジスト組成物を塗布した後、６０〜１００℃に設定した乾燥炉で乾燥し有機溶剤を除去することにより、また必要に応じて離型フィルムを貼りつけることにより得ることができる。この際キャリアフィルム上のレジストの膜厚は、５〜１５０μｍ好ましくは１０〜６０μｍに調整される。上記キャリアフィルムとしては、ポリエチレンテレフタレート、ポリプロピレン等のフィルムが好適に使用される。 The one-component solder resist composition of the present invention can be provided in the form of a liquid, a paste or a dry film. When supplying as a dry film, for example, after applying the solder resist composition of the present invention on a carrier film by a roll coater, a doctor bar, a wire bar method, a spin coating method, a doctor plate method, etc., the temperature is set to 60 to 100 ° C. It can be obtained by drying in a drying oven to remove the organic solvent and, if necessary, attaching a release film. At this time, the thickness of the resist on the carrier film is adjusted to 5 to 150 μm, preferably 10 to 60 μm. As the carrier film, a film of polyethylene terephthalate, polypropylene or the like is preferably used.
以上のような組成を有する本発明の一液型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、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７０〜９０℃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、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、さらに、加熱硬化させることにより、耐熱性、密着性、無電解金めっき耐性、電気特性等に優れたソルダーレジスト膜を有するプリント基板が形成される。 The one-component solder resist composition of the present invention having the above composition is diluted as necessary to adjust the viscosity to be suitable for the coating method, and this is screen-printed, for example, on a printed wiring board on which a circuit is formed. A tack-free coating film is formed by applying the organic solvent contained in the composition at a temperature of 70 to 90 ° C. it can. Then, it can be exposed selectively with active energy rays through a photomask, and the unexposed part can be developed with a dilute alkaline aqueous solution to form a resist pattern. Furthermore, by heat curing, heat resistance, adhesion, electroless gold plating A printed circuit board having a solder resist film having excellent resistance, electrical characteristics and the like is formed.
前記希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、露光す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を用いることができる。その他、レーザー光線なども活性光線として利用できる。 As the dilute alkaline aqueous solution, alkaline aqueous solutions such as potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, sodium silicate, ammonia, amines and the like can be used. As an irradiation light source for exposure, 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 can be used. In addition, a laser beam can also be used as an actinic beam.
以下に実施例及び比較例を示して本発明について具体的に説明するが、本発明が下記実施例に限定されるものでないことはもとよりである。なお、以下において「部」とあるのは、特に断りのない限り全て「質量部」を示す。 EXAMPLES Hereinafter, the present invention will be described in detail with reference to examples and comparative examples, but the present invention is not limited to the following examples. In the following description, “part” means “part by mass” unless otherwise specified.
合成例１
温度計、撹拌機、滴下ロート、及び還流冷却器を備えたフラスコに、溶媒としてジプロピレングリコールモノメチルエーテル７００．０ｇを１１０℃まで加熱し、メタクリル酸２７０．０ｇ、メタクリル酸メチル１５３．０ｇ、ジプロピレングリコールモノメチルエーテル２９４．０ｇ、及び重合触媒としてｔ−ブチルパーオキシ−２−エチルヘキサノエート（日本油脂社製 パーブチルＯ）１０．０ｇの混合物を３時間かけて滴下し、更に１１０℃，３時間攪拌し重合触媒を失活させて共重合樹脂溶液を得た。この樹脂溶液を冷却後、３，４−エポキシシクロヘキシルメチルアクリレート（ダイセル化学工業（株）製サイクロマーＡ４００）３９０．０ｇ、トリフェニルホスフィン５．０ｇ、ハイドロキノンモノメチルエーテル１．５ｇを加え、１００℃に昇温し、攪拌することによってエポキシの開環付加反応を行った。このようにして得られたカルボキシル基含有感光性樹脂は、重量平均分子量が２２，０００でかつ、不揮発分が４５ｗｔ％、固形分酸価が７０ｍｇＫＯＨ／ｇであった。以下、この反応溶液を、ワニスＡ−１と称す。
Synthesis example 1
In a flask equipped with a thermometer, stirrer, dropping funnel, and reflux condenser, 700.0 g of dipropylene glycol monomethyl ether as a solvent is heated to 110 ° C., and 270.0 g of methacrylic acid, 153.0 g of methyl methacrylate, A mixture of 294.0 g of propylene glycol monomethyl ether and 10.0 g of t-butylperoxy-2-ethylhexanoate (Nippon Yushi Co., Ltd., Perbutyl O) as a polymerization catalyst was added dropwise over 3 hours. The polymerization catalyst was deactivated by stirring for a time to obtain a copolymer resin solution. After cooling this resin solution, 390.0 g of 3,4-epoxycyclohexylmethyl acrylate (Daicel Chemical Industries, Ltd. Cyclomer A400), 5.0 g of triphenylphosphine, and 1.5 g of hydroquinone monomethyl ether were added, and the mixture was heated to 100 ° C. Epoxy ring-opening addition reaction was carried out by heating and stirring. The carboxyl group-containing photosensitive resin thus obtained had a weight average molecular weight of 22,000, a non-volatile content of 45 wt%, and a solid content acid value of 70 mg KOH / g. Hereinafter, this reaction solution is called varnish A-1.
合成例２
温度計、撹拌機、滴下ロート、及び還流冷却器を備えたフラスコに、溶媒としてジプロピレングリコールモノメチルエーテル５００．０ｇを１１０℃まで加熱し、メタクリル酸１６５．０ｇ、メタクリル酸メチル８１．６ｇ、ジプロピレングリコールモノメチルエーテル１２０．４ｇ、及び重合触媒としてｔ−ブチルパーオキシ−２−エチルヘキサノエート（日本油脂社製 パーブチルＯ）６．２ｇの混合物を３時間かけて滴下し、更に１１０℃，３時間攪拌し重合触媒を失活させて共重合樹脂溶液を得た。この樹脂溶液を冷却後、３，４−エポキシシクロヘキシルメチルアクリレート（ダイセル化学工業（株）製サイクロマーＡ４００）１６７．０ｇ、トリフェニルホスフィン４．０ｇ、ハイドロキノンモノメチルエーテル１．０ｇを加え、１００℃に昇温し、攪拌することによってエポキシの開環付加反応を行った。このようにして得られたカルボキシル基含有感光性樹脂は、重量平均分子量が２３，０００でかつ、不揮発分が４０ｗｔ％、固形物の酸価が１３５ｍｇＫＯＨ／ｇであった。以下、この反応溶液を、ワニスＡ−２と称す。
Synthesis example 2
In a flask equipped with a thermometer, a stirrer, a dropping funnel and a reflux condenser, 500.0 g of dipropylene glycol monomethyl ether as a solvent is heated to 110 ° C., and 165.0 g of methacrylic acid, 81.6 g of methyl methacrylate, A mixture of 120.4 g of propylene glycol monomethyl ether and 6.2 g of t-butyl peroxy-2-ethylhexanoate (Nippon Yushi Co., Ltd., perbutyl O) as a polymerization catalyst was added dropwise over 3 hours. The polymerization catalyst was deactivated by stirring for a time to obtain a copolymer resin solution. After cooling the resin solution, 167.0 g of 3,4-epoxycyclohexylmethyl acrylate (Cyclomer A400 manufactured by Daicel Chemical Industries, Ltd.), 4.0 g of triphenylphosphine, and 1.0 g of hydroquinone monomethyl ether were added, and the mixture was heated to 100 ° C. Epoxy ring-opening addition reaction was carried out by heating and stirring. The carboxyl group-containing photosensitive resin thus obtained had a weight average molecular weight of 23,000, a non-volatile content of 40 wt%, and a solid acid value of 135 mg KOH / g. Hereinafter, this reaction solution is called varnish A-2.
合成例３
温度計、撹拌機、滴下ロート、及び還流冷却器を備えたフラスコに、溶媒としてジプロピレングリコールモノメチルエーテル２００．０ｇを１１０℃まで加熱し、β−カルボキシルエチルアクリレート２９．６ｇ、メタクリル酸７０．８ｇ、メタクリル酸メチル１３９．５ｇ、ジプロピレングリコールモノメチルエーテル１２３．０ｇ、及び重合触媒としてｔ−ブチルパーオキシ−２−エチルヘキサノエート（日本油脂社製 パーブチルＯ）７．０ｇの混合物を３時間かけて滴下し、更に１１０℃，３時間攪拌し重合触媒を失活させて共重合樹脂溶液を得た。この樹脂溶液を冷却後、グリシジルメタクリレート１１０．５ｇ、トリフェニルホスフィン４．０ｇ、ハイドロキノンモノメチルエーテル１．０ｇを加え、１００℃に昇温し、攪拌することによってエポキシの開環付加反応を行った。このようにして得られたカルボキシル基含有感光性樹脂は、重量平均分子量が１５，０００でかつ、不揮発分が５２ｗｔ％、固形物の酸価が４０ｍｇＫＯＨ／ｇであった。以下、この反応溶液を、ワニスＡ−３と称す。
Synthesis example 3
In a flask equipped with a thermometer, a stirrer, a dropping funnel and a reflux condenser, 200.0 g of dipropylene glycol monomethyl ether as a solvent is heated to 110 ° C., 29.6 g of β-carboxyethyl acrylate, 70.8 g of methacrylic acid. , 139.5 g of methyl methacrylate, 123.0 g of dipropylene glycol monomethyl ether, and 7.0 g of t-butyl peroxy-2-ethylhexanoate (Perbutyl O manufactured by NOF Corporation) as a polymerization catalyst over 3 hours Then, the mixture was further stirred at 110 ° C. for 3 hours to deactivate the polymerization catalyst to obtain a copolymer resin solution. After cooling this resin solution, 110.5 g of glycidyl methacrylate, 4.0 g of triphenylphosphine and 1.0 g of hydroquinone monomethyl ether were added, and the temperature was raised to 100 ° C., followed by stirring to carry out an epoxy ring-opening addition reaction. The carboxyl group-containing photosensitive resin thus obtained had a weight average molecular weight of 15,000, a nonvolatile content of 52 wt%, and a solid acid value of 40 mgKOH / g. Hereinafter, this reaction solution is called varnish A-3.
比較合成例１
温度計、撹拌機、滴下ロート、及び還流冷却器を備えたフラスコに、溶媒としてジプロピレングリコールモノメチルエーテル４００．０ｇを１１０℃まで加熱し、メタクリル酸１７２．０ｇ、メタクリル酸メチル１００．０ｇ、メタクリル酸エチル１１４．０ｇ、ジプロピレングリコールモノメチルエーテル２４４．０ｇ、及び重合触媒としてｔ−ブチルパーオキシ−２−エチルヘキサノエート（日本油脂社製 パーブチルＯ）７．８ｇの混合物を３時間かけて滴下し、更に１１０℃，３時間攪拌し重合触媒を失活させて共重合樹脂溶液を得た。この樹脂溶液を冷却後、グリシジルメタクリレート１５８．０ｇ、トリフェニルホスフィン６．０ｇ、ハイドロキノンモノメチルエーテル１．５ｇを加え、１００℃に昇温し、攪拌することによってエポキシの開環付加反応を行った。このようにして得られたカルボキシル基含有感光性樹脂は、重量平均分子量が２９，０００でかつ、不揮発分が５０ｗｔ％、固形物の酸価が９１ｍｇＫＯＨ／ｇであった。以下、この反応溶液を、ワニスＲ−１と称す。
Comparative Synthesis Example 1
In a flask equipped with a thermometer, a stirrer, a dropping funnel, and a reflux condenser, 400.0 g of dipropylene glycol monomethyl ether as a solvent is heated to 110 ° C., and 172.0 g of methacrylic acid, 100.0 g of methyl methacrylate, methacrylic acid A mixture of 114.0 g of ethyl acid, 244.0 g of dipropylene glycol monomethyl ether, and 7.8 g of t-butyl peroxy-2-ethylhexanoate (Perbutyl O manufactured by NOF Corporation) was added dropwise over 3 hours as a polymerization catalyst. The mixture was further stirred at 110 ° C. for 3 hours to deactivate the polymerization catalyst to obtain a copolymer resin solution. After cooling this resin solution, 158.0 g of glycidyl methacrylate, 6.0 g of triphenylphosphine, and 1.5 g of hydroquinone monomethyl ether were added, and the mixture was heated to 100 ° C. and stirred to carry out an epoxy ring-opening addition reaction. The thus obtained carboxyl group-containing photosensitive resin had a weight average molecular weight of 29,000, a nonvolatile content of 50 wt%, and a solid acid value of 91 mgKOH / g. Hereinafter, this reaction solution is referred to as Varnish R-1.
（１）カルボキシル基含有感光性樹脂の軟化点測定
上記合成例１〜３、及び比較合成例１で得られた各ワニスに、軟化点測定時の熱重合を防止するために、重合禁止剤として、ｐ−メトキシフェノール（メトキノン）約１，０００ｐｐｍ添加した後、ガラス板に塗布し、８０℃で４時間乾燥した。乾燥後、ガラス板から剥がした塗膜を試験試料として、熱機械分析装置 ブルカー・エイエックスエス株式会社製のＴＭＳ４０００Ｓを用いて、以下の条件で、軟化点を測定した。その結果を、表２に示した。
ブローブ：針入ブローブ
荷重：１ｇ
昇温速度：１０℃／ｍｉｎ
測定範囲：３０〜２５０℃
(1) Measurement of softening point of carboxyl group-containing photosensitive resin In order to prevent thermal polymerization at the time of softening point measurement in each of the varnishes obtained in Synthesis Examples 1 to 3 and Comparative Synthesis Example 1, as a polymerization inhibitor After adding about 1,000 ppm of p-methoxyphenol (methoquinone), it was applied to a glass plate and dried at 80 ° C. for 4 hours. The softening point was measured on condition of the following conditions using TMS4000S made from a thermomechanical analyzer Bruker AXS Co., Ltd. using the coating film peeled off from the glass plate after drying as a test sample. The results are shown in Table 2.
Probe: Needle-in probe Probe Load: 1g
Temperature increase rate: 10 ° C / min
Measurement range: 30-250 ° C
実施例１〜４、及び比較例１〜３
前記合成例１〜３、及び比較合成例で得られた各ワニス（固形分が１００となるように配合）を用い、下記表１に示す配合割合で各成分を配合し、３本ロールミルを用いて混練し、アルカリ現像可能な光硬化性・熱硬化性の一液型ソルダーレジスト組成物を調製した。尚、印刷時、必要に応じて、有機溶剤で希釈した。
Examples 1-4 and Comparative Examples 1-3
Using each varnish obtained in Synthesis Examples 1 to 3 and Comparative Synthesis Example (mixed so that the solid content is 100), each component is blended in the blending ratio shown in Table 1 below, and a three roll mill is used. And kneaded to prepare a photocurable / thermosetting one-component solder resist composition capable of alkali development. In addition, it diluted with the organic solvent as needed at the time of printing.
上記実施例１〜４及び比較例１〜３の各一液型ソルダーレジスト組成物について、以下の各項目について試験を行い、評価した。各評価の結果を、表２に示した。尚、評価試験の方法は以下に示す。 About each one-pack type solder resist composition of the said Examples 1-4 and Comparative Examples 1-3, it tested about each following item and evaluated. The results of each evaluation are shown in Table 2. The evaluation test method is shown below.
（２）保存安定性
上記実施例１〜４及び比較例１〜３の各一液型ソルダーレジスト組成物を調整した後、２５℃での粘度の初期値を、ＥＨＤ型粘度計で測定（５ｒｐｍ値）し、その後、２０℃の恒温槽に６ヶ月間保管し、初期値と同様に粘度を測定した。その増粘率から、以下の判定基準で評価した。
○：増粘率が１２０％以内。
△：増粘率が１２０〜２００％以内。
×：ゲル化もしくは増粘率が２００％以上。
(2) Storage stability After adjusting the one-component solder resist compositions of Examples 1 to 4 and Comparative Examples 1 to 3, the initial value of viscosity at 25 ° C. was measured with an EHD viscometer (5 rpm Value) and then stored in a constant temperature bath at 20 ° C. for 6 months, and the viscosity was measured in the same manner as the initial value. From the viscosity increase rate, the following criteria were used for evaluation.
○: Thickening rate is within 120%.
(Triangle | delta): Thickening rate is 120 to 200% or less.
X: Gelation or thickening rate is 200% or more.
（３）現像性
上記実施例１〜４及び比較例１〜３で得られた各一液型ソルダーレジスト組成物を、それぞれ銅張り基板上にスクリーン印刷で全面塗布し、熱風循環式乾燥炉で、９０℃，６０分乾燥させ、スプレー圧０．２ＭＰaの１ｗｔ％Ｎａ２ＣＯ３水溶液で１分間現像し、その塗膜表面の現像性を、以下の基準で評価した。
○：塗膜が完全に除去され、残渣なし。
△：ほんの僅かにフィラー残りあり、
×：塗膜の残渣あり
(3) Developability Each one-component solder resist composition obtained in Examples 1 to 4 and Comparative Examples 1 to 3 was applied on the entire surface of a copper-clad substrate by screen printing, and then heated in a hot air circulation drying oven. The film was dried at 90 ° C. for 60 minutes, developed with a 1 wt% Na 2 CO 3 aqueous solution with a spray pressure of 0.2 MPa for 1 minute, and the developability of the coating film surface was evaluated according to the following criteria.
○: The coating film is completely removed and there is no residue.
Δ: Slightly filler remaining,
X: Residual film residue
（４）感度
上記実施例１〜４及び比較例１〜３で得られた一液型ソルダーレジスト組成物を、ガラスエポキシ基板にスクリーン印刷でそれぞれ全面塗布し、熱風循環式乾燥炉で８０℃，３０分乾燥した。これらの基板に、コダックＮｏ．２のステップタブレットを当て、２００ｍＪ／ｃｍ２で露光し、スプレー圧０．２ＭＰaの１ｗｔ％Ｎａ２ＣＯ３水溶液で、１分間現像し、塗膜が完全に残っている段数を評価した。
(4) Sensitivity The one-pack type solder resist compositions obtained in Examples 1 to 4 and Comparative Examples 1 to 3 were each applied to the entire surface of a glass epoxy substrate by screen printing, and then heated at 80 ° C. in a hot air circulation drying oven. Dry for 30 minutes. On these substrates, Kodak No. 2 step tablets were applied, exposed at 200 mJ / cm 2 , developed with a 1 wt% Na 2 CO 3 aqueous solution with a spray pressure of 0.2 MPa for 1 minute, and the number of steps where the coating film remained completely was evaluated.
（５）タック性
上記実施例１〜４及び比較例１〜３得られた一液型ソルダーレジスト組成物を、回路形成されたプリント配線板にスクリーン印刷でそれぞれ全面塗布し、熱風循環式乾燥炉で８０℃，３０分乾燥した。この評価基板に、ネガパターンを当て、真空下で接触露光した。その後、常圧に戻し、ネガパターンを剥がす時の付着性を、以下の基準で評価した。
○：貼り付き無し。
△：若干、貼り付き有り。
×：貼り付き有り。
(5) Tackiness The one-pack type solder resist compositions obtained in Examples 1 to 4 and Comparative Examples 1 to 3 were each applied to the printed circuit board on which the circuit was formed by screen printing, respectively, and a hot-air circulating drying oven And dried at 80 ° C. for 30 minutes. A negative pattern was applied to the evaluation substrate, and contact exposure was performed under vacuum. Then, it returned to normal pressure and evaluated the adhesiveness at the time of peeling a negative pattern on the following references | standards.
○: No sticking.
Δ: Slightly attached.
X: There is sticking.
（６）はんだ耐熱性
上記実施例１〜７及び比較例１〜４で得られた一液型ソルダーレジスト組成物を、回路形成されたプリント配線板にスクリーン印刷でそれぞれ全面塗布し、熱風循環式乾燥炉で８０℃，３０分乾燥した。これらの基板にソルダーレジストパターンが描かれたネガフィルムを当て、露光量３００ｍＪ／ｃｍ２の露光条件で露光し、スプレー圧０．２ＭＰaの１ｗｔ％Ｎａ２ＣＯ３水溶液で１分間現像し、ソルダーレジストパターンを形成した。この基板を、１５０℃で６０分熱硬化し、評価基板を作製した。
この評価基板に、ロジン系フラックスを塗布して、予め２６０℃に設定したはんだ槽に３０秒間浸漬し、イソプロピルアルコールでフラックスを洗浄した後、セロハン粘着テープによるピールテストを行い、レジスト層の膨れ・剥がれ・変色について、以下の基準で評価した。
○： 全く変化が認められないもの
△： ほんの僅か変色等の変化があるもの
×： レジスト層の膨れ、剥がれがあるもの
(6) Solder heat resistance The one-pack type solder resist compositions obtained in Examples 1 to 7 and Comparative Examples 1 to 4 were each applied to the printed circuit board on which the circuit was formed by screen printing. It was dried at 80 ° C. for 30 minutes in a drying furnace. A negative film on which a solder resist pattern is drawn is applied to these substrates, exposed under an exposure condition of an exposure amount of 300 mJ / cm 2 , and developed with a 1 wt% Na 2 CO 3 aqueous solution with a spray pressure of 0.2 MPa for 1 minute. A pattern was formed. This substrate was thermally cured at 150 ° C. for 60 minutes to produce an evaluation substrate.
A rosin-based flux is applied to this evaluation substrate, immersed in a solder bath set at 260 ° C. in advance for 30 seconds, the flux is washed with isopropyl alcohol, a peel test is performed with a cellophane adhesive tape, and the resist layer is swollen. The peeling and discoloration were evaluated according to the following criteria.
○: No change at all △: Slight change in color, etc. ×: Resist layer swelling or peeling
（７）無電解金めっき耐性
上記（６）と同様にして評価基板を作製した。この評価基板を、市販の無電解ニッケルめっき液と無電解金めっき液を用いて、ニッケル５μｍ、金０．０３μｍとなるような条件で無電解金めっきを行なった。このめっき後の評価基板について、セロハン粘着テープによるピールテストを行い、レジスト層の剥がれ、めっきのしみ込みについて、以下の基準で評価した。
○： 全く変化が認められないもの
△ ： ほんの僅かに剥がれ、しみ込みがあるもの
× ： 塗膜に剥がれがあるもの
(7) Resistance to electroless gold plating An evaluation substrate was prepared in the same manner as in (6) above. This evaluation substrate was subjected to electroless gold plating using commercially available electroless nickel plating solution and electroless gold plating solution under the conditions of nickel 5 μm and gold 0.03 μm. About the evaluation board | substrate after this plating, the peel test by a cellophane adhesive tape was performed, and the following references | standards evaluated the peeling of the resist layer and the penetration of plating.
○: No change at all △: Slightly peeled off, with smudges ×: Painted film with peeling
（８）電気絶縁性
ＩＰＣ Ｂ−２５テストパターンのクシ型電極Ｂクーポンを用い、上記（６）と同様の条件で評価基板を作製し、このクシ型電極にＤＣ１００Ｖのバイアス電圧を印加し、８５℃、８５％Ｒ．Ｈ．の恒温恒湿槽にて１，０００時間後の絶縁抵抗値を測定した。
(8) Electrical Insulation An evaluation board was prepared under the same conditions as in (6) above using a comb-type electrode B coupon with an IPC B-25 test pattern, and a bias voltage of DC 100 V was applied to the comb-type electrode, and 85 ° C, 85% R.V. H. The insulation resistance value after 1,000 hours was measured in a constant temperature and humidity chamber.
表２に示す結果から明らかなように、本発明にかかる実施例１〜４の一液型ソルダーレジスト組成物は、保存安定性に優れ、感度も高く、またタック性にも優れている。また、ソルダーレジストとして必要なはんだ耐熱性、無電解金めっき耐性、電気絶縁性も、満足する特性を有している。
一方、カルボキシル基含有感光性樹脂の軟化点９５℃である比較例１は、タック性に劣っている。また、このタック性を改良するために、反応性希釈剤を減らした比較例２は、感度が大幅に低下した。
また、従来の二液型ソルダーレジストと同様に、カルボキシル基１当量に対して、約１．１当量のエポキシ樹脂を配合した比較例３は、耐熱性等には、優れているが、一液型ソルダーレジスト組成物としての保存安定性には、著しく劣っていた。
As is apparent from the results shown in Table 2, the one-component solder resist compositions of Examples 1 to 4 according to the present invention are excellent in storage stability, high in sensitivity, and excellent in tackiness. Moreover, the solder heat resistance, the electroless gold plating resistance, and the electrical insulation necessary for the solder resist have satisfactory characteristics.
On the other hand, Comparative Example 1 in which the softening point of the carboxyl group-containing photosensitive resin is 95 ° C. is inferior in tackiness. In addition, in Comparative Example 2 in which the reactive diluent was reduced in order to improve the tackiness, the sensitivity was greatly lowered.
Moreover, like the conventional two-component solder resist, Comparative Example 3 in which about 1.1 equivalent of epoxy resin is blended with 1 equivalent of carboxyl group is excellent in heat resistance, etc. The storage stability as a type solder resist composition was remarkably inferior.
Claims (5)
（Ｂ）希釈剤、
（Ｃ）光重合開始剤、
（Ｄ）メラミン又はその有機酸塩、
及び（Ｅ）無機フィラーを含むことを特徴とするアルカリ現像可能な光硬化性・熱硬化性の一液型ソルダーレジスト組成物。 (A) a copolymer comprising an unsaturated carboxylic acid (a) and a compound (b) having an ethylenically unsaturated group in one molecule other than the unsaturated carboxylic acid, a cyclic ether group in one molecule; A carboxyl group-containing photosensitive resin obtained by adding the compound (c) having an ethylenically unsaturated fatty group and having a softening point of 130 to 200 ° C.,
(B) Diluent,
(C) a photopolymerization initiator,
(D) melamine or an organic acid salt thereof,
And (E) a photocurable / thermosetting one-component solder resist composition capable of alkali development, comprising an inorganic filler.
A solder resist layer is formed on the surface of the printed wiring board formed with a circuit using the one-component solder resist composition according to any one of claims 1 to 3 or the dry film according to claim 4. Printed wiring board characterized by being made.
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| JP5575436B2 (en) * | 2009-09-01 | 2014-08-20 | 太陽ホールディングス株式会社 | Alkali-developable photocurable resin composition, dry film and cured product thereof, and printed wiring board using them |
| WO2012132423A1 (en) * | 2011-03-31 | 2012-10-04 | 太陽ホールディングス株式会社 | Photocurable/thermosetting inkjet composition, and printed wiring board using same |
| JP5847814B2 (en) * | 2011-06-17 | 2016-01-27 | 太陽インキ製造株式会社 | Photo-curable thermosetting resin composition |
| JP6738335B2 (en) * | 2015-08-05 | 2020-08-12 | 太陽インキ製造株式会社 | Laminated structure, dry film and flexible printed wiring board |
| CN109810559B (en) * | 2019-02-28 | 2021-11-19 | 江苏艾森半导体材料股份有限公司 | High-dispersity matte solder resist ink |
| CN112159639B (en) * | 2020-11-09 | 2022-05-06 | 珠海市能动科技光学产业有限公司 | Modified high-molecular adhesive and dry film photoresist containing same |
| CN114395287A (en) * | 2021-12-30 | 2022-04-26 | 广州斯达利电子原料有限公司 | Solder resist ink, solder resist layer and Mini-LED printed circuit board |
| CN114262537A (en) * | 2021-12-30 | 2022-04-01 | 广州斯达利电子原料有限公司 | Solder resist ink, preparation method thereof, solder resist layer and Mini-LED printed circuit board |
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