JP2007322546A - Photosetting and thermosetting solder resist composition, and printed wiring board using the same - Google Patents
Photosetting and thermosetting solder resist composition, and printed wiring board using the same Download PDFInfo
- Publication number
- JP2007322546A JP2007322546A JP2006150452A JP2006150452A JP2007322546A JP 2007322546 A JP2007322546 A JP 2007322546A JP 2006150452 A JP2006150452 A JP 2006150452A JP 2006150452 A JP2006150452 A JP 2006150452A JP 2007322546 A JP2007322546 A JP 2007322546A
- Authority
- JP
- Japan
- Prior art keywords
- solder resist
- resist composition
- carboxyl group
- resin
- printed wiring
- 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
Links
- 229910000679 solder Inorganic materials 0.000 title claims abstract description 70
- 239000000203 mixture Substances 0.000 title claims abstract description 43
- 229920001187 thermosetting polymer Polymers 0.000 title claims abstract description 18
- 229920005989 resin Polymers 0.000 claims abstract description 49
- 239000011347 resin Substances 0.000 claims abstract description 49
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 34
- 125000003118 aryl group Chemical group 0.000 claims abstract description 28
- 150000001875 compounds Chemical class 0.000 claims abstract description 27
- 239000004593 Epoxy Substances 0.000 claims abstract description 18
- 239000003085 diluting agent Substances 0.000 claims abstract description 12
- 239000003999 initiator Substances 0.000 claims abstract description 10
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 46
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 18
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 17
- OUPZKGBUJRBPGC-UHFFFAOYSA-N 1,3,5-tris(oxiran-2-ylmethyl)-1,3,5-triazinane-2,4,6-trione Chemical compound O=C1N(CC2OC2)C(=O)N(CC2OC2)C(=O)N1CC1CO1 OUPZKGBUJRBPGC-UHFFFAOYSA-N 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 9
- 229920006026 co-polymeric resin Polymers 0.000 claims description 8
- 125000003700 epoxy group Chemical group 0.000 claims description 8
- 125000000466 oxiranyl group Chemical group 0.000 claims description 6
- JIHQDMXYYFUGFV-UHFFFAOYSA-N 1,3,5-triazine Chemical group C1=NC=NC=N1 JIHQDMXYYFUGFV-UHFFFAOYSA-N 0.000 claims description 4
- 229920006243 acrylic copolymer Polymers 0.000 claims description 4
- 239000004408 titanium dioxide Substances 0.000 abstract 1
- 229920000647 polyepoxide Polymers 0.000 description 28
- 239000003822 epoxy resin Substances 0.000 description 26
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 25
- -1 hydroxypropyl Chemical group 0.000 description 18
- 238000000576 coating method Methods 0.000 description 17
- 238000012360 testing method Methods 0.000 description 17
- 239000011248 coating agent Substances 0.000 description 15
- 239000000243 solution Substances 0.000 description 15
- 238000002845 discoloration Methods 0.000 description 10
- 238000001035 drying Methods 0.000 description 10
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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 9
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- 238000000034 method Methods 0.000 description 9
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- 230000015572 biosynthetic process Effects 0.000 description 8
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- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 6
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 239000002253 acid Substances 0.000 description 5
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- 238000011161 development Methods 0.000 description 5
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- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 4
- 229910052753 mercury Inorganic materials 0.000 description 4
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- 239000003208 petroleum Substances 0.000 description 4
- 238000000016 photochemical curing Methods 0.000 description 4
- 239000000377 silicon dioxide Substances 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 230000000007 visual effect Effects 0.000 description 4
- FPZWZCWUIYYYBU-UHFFFAOYSA-N 2-(2-ethoxyethoxy)ethyl acetate Chemical compound CCOCCOCCOC(C)=O FPZWZCWUIYYYBU-UHFFFAOYSA-N 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
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- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 238000010292 electrical insulation Methods 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- 235000019382 gum benzoic Nutrition 0.000 description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 150000007519 polyprotic acids Polymers 0.000 description 3
- 238000002310 reflectometry Methods 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 238000007650 screen-printing Methods 0.000 description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 description 3
- 239000010936 titanium Substances 0.000 description 3
- 229910052719 titanium Inorganic materials 0.000 description 3
- 239000002966 varnish Substances 0.000 description 3
- KMOUUZVZFBCRAM-OLQVQODUSA-N (3as,7ar)-3a,4,7,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1C=CC[C@@H]2C(=O)OC(=O)[C@@H]21 KMOUUZVZFBCRAM-OLQVQODUSA-N 0.000 description 2
- GIMQKKFOOYOQGB-UHFFFAOYSA-N 2,2-diethoxy-1,2-diphenylethanone Chemical compound C=1C=CC=CC=1C(OCC)(OCC)C(=O)C1=CC=CC=C1 GIMQKKFOOYOQGB-UHFFFAOYSA-N 0.000 description 2
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- YSUQLAYJZDEMOT-UHFFFAOYSA-N 2-(butoxymethyl)oxirane Chemical compound CCCCOCC1CO1 YSUQLAYJZDEMOT-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 2
- LWRBVKNFOYUCNP-UHFFFAOYSA-N 2-methyl-1-(4-methylsulfanylphenyl)-2-morpholin-4-ylpropan-1-one Chemical compound C1=CC(SC)=CC=C1C(=O)C(C)(C)N1CCOCC1 LWRBVKNFOYUCNP-UHFFFAOYSA-N 0.000 description 2
- NJWGQARXZDRHCD-UHFFFAOYSA-N 2-methylanthraquinone Chemical compound C1=CC=C2C(=O)C3=CC(C)=CC=C3C(=O)C2=C1 NJWGQARXZDRHCD-UHFFFAOYSA-N 0.000 description 2
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229930185605 Bisphenol Natural products 0.000 description 2
- 229920000298 Cellophane Polymers 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 2
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- 239000002202 Polyethylene glycol Substances 0.000 description 2
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- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 description 2
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- 239000002390 adhesive tape Substances 0.000 description 2
- 125000002723 alicyclic group Chemical group 0.000 description 2
- 239000012965 benzophenone Substances 0.000 description 2
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- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
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Landscapes
- Materials For Photolithography (AREA)
- Non-Metallic Protective Coatings For Printed Circuits (AREA)
Abstract
Description
本発明は、プリント配線板の永久マスクとしての使用に適し、露光後、アルカリ水溶液で現像することにより画像形成し、その後加熱硬化することにより、高反射率のソルダーレジスト膜を形成することができる光硬化性・熱硬化性ソルダーレジスト組成物、および回路形成されたプリント配線板表面に、該組成物を用いてソルダーレジストパターンを形成して得られるプリント配線板に関する。 The present invention is suitable for use as a permanent mask of a printed wiring board, and after exposure, an image can be formed by developing with an aqueous alkali solution, and then heat-cured to form a highly reflective solder resist film. The present invention relates to a photocurable / thermosetting solder resist composition and a printed wiring board obtained by forming a solder resist pattern on the surface of a printed wiring board on which a circuit is formed using the composition.
プリント配線板は、一般的に積層版に張り合わせた銅箔を、回路配線に従ってエッチングしたものであり、電子部品が所定の場所に配置され、はんだ付けが行われる。ソルダーレジスト膜は、このようなプリント配線板に電子部品をはんだ付けする際の回路の保護膜として使用されるものである。このソルダーレジスト膜は、はんだ付けの際に、はんだが不必要な部分に付着するのを防止すると共に、回路導体が空気に直接曝されて、酸素や湿分により腐食されるのを防止する。さらに、回路基板の永久保護膜としても機能する。そのため、密着性、電気絶縁性、はんだ耐熱性、耐溶剤性、耐薬品性などの諸特性が要求される。 A printed wiring board is generally obtained by etching a copper foil bonded to a laminated plate in accordance with circuit wiring, and electronic components are arranged at predetermined locations and soldered. The solder resist film is used as a protective film for a circuit when an electronic component is soldered to such a printed wiring board. This solder resist film prevents solder from adhering to unnecessary portions during soldering, and prevents the circuit conductor from being directly exposed to air and being corroded by oxygen or moisture. Furthermore, it functions as a permanent protective film for the circuit board. Therefore, various properties such as adhesion, electrical insulation, solder heat resistance, solvent resistance, and chemical resistance are required.
また、プリント配線板は、高密度化実現のため微細化（ファイン化）、多層化およびワンボード化の一途をたどっており、実装方式も、表面実装技術（ＳＭＴ）へと推移している。そのため、ソルダーレジスト膜も、ファイン化、高解像性、高精度、高信頼性の要求が高まっている。 In addition, printed wiring boards have been increasingly miniaturized (finer), multilayered, and one-boarded to achieve higher density, and the mounting method has also shifted to surface mounting technology (SMT). Therefore, the demand for finer, high resolution, high accuracy, and high reliability of the solder resist film is also increasing.
このようなソルダーレジストのパターンを形成する技術として、微細なパターンを正確に形成できるフォトレジスト法が、特に環境面の配慮等から、アルカリ現像型の液状フォトレジスト法が主流となっている。 As a technique for forming such a solder resist pattern, an alkali development type liquid photoresist method is mainly used as a photoresist method capable of accurately forming a fine pattern, particularly in consideration of the environment.
例えば、特許文献１および特許文献２には、ノボラック型エポキシ樹脂に不飽和モノカルボン酸を反応させ、さらに多塩基酸無水物を付加させた反応生成物をベースポリマーとするアルカリ水溶液で現像可能な液状レジストインキ組成物が開示されている。 For example, in Patent Document 1 and Patent Document 2, development is possible with an aqueous alkali solution using a reaction product obtained by reacting a novolak epoxy resin with an unsaturated monocarboxylic acid and further adding a polybasic acid anhydride as a base polymer. A liquid resist ink composition is disclosed.
一方で、近年、携帯端末、パソコン、テレビ等の液晶ディスプレイのバックライト、また照明器具の光源など、低電力で発光する発光ダイオード（ＬＥＤ）を、ソルダーレジスト膜が被覆形成されたプリント配線板に直接実装する用途が増えてきている。 On the other hand, in recent years, light-emitting diodes (LEDs) that emit light at low power, such as backlights for liquid crystal displays in portable terminals, personal computers, televisions, etc., and light sources for lighting fixtures, have been applied to printed wiring boards coated with solder resist films. Applications for direct mounting are increasing.
そこで、ＬＥＤの光を効率よく利用するために、高反射率のソルダーレジスト膜を有するプリント配線板が求められている。
本発明の目的は、ＬＥＤの光を効率よく利用することができる、高反射率のソルダーレジスト膜を有するプリント配線板、および高反射率のソルダーレジスト膜を形成できる白色の光硬化性・熱硬化性ソルダーレジスト組成物を提供することにある。本発明のより具体的な目的は、現像型ソルダーレジストに要求されるコーティング性、光硬化性、現像性、はんだ耐熱性、密着性、電気絶縁性等の特性を有し、経時による反射率の低下および劣化による着色を抑えた高反射率のソルダーレジスト膜を形成することができ、ＬＥＤをプリント配線板に実装した際に全体として照度を上げることができる白色の光硬化性・熱硬化性ソルダーレジスト組成物を提供することにある。 An object of the present invention is to provide a printed wiring board having a high-reflectance solder resist film that can efficiently use the light of the LED, and a white photo-curing / thermosetting capable of forming a high-reflectance solder resist film. An object of the present invention is to provide a conductive solder resist composition. A more specific object of the present invention is to provide coating solder, photocurability, developability, solder heat resistance, adhesion, electrical insulation, and other properties required for development-type solder resists, and reflectivity over time. A white photo-curing / thermosetting solder that can form a high-reflectance solder resist film that suppresses coloring due to degradation and deterioration, and can increase the overall illuminance when the LED is mounted on a printed wiring board It is to provide a resist composition.
本発明者等は鋭意研究した結果、芳香環を有さないカルボキシル基含有樹脂と白色顔料としてルチル型酸化チタンを使用することにより、樹脂の芳香環および酸化チタンの光活性に起因する、光による樹脂の劣化（黄変）を抑えることができ、高反射率を長期間に渡って達成することができることを見出した。 As a result of diligent research, the present inventors have used a carboxyl group-containing resin having no aromatic ring and a rutile-type titanium oxide as a white pigment, resulting in light caused by light activity of the aromatic ring of the resin and titanium oxide. It has been found that the deterioration (yellowing) of the resin can be suppressed and a high reflectance can be achieved over a long period of time.
すなわち、本発明の第１の側面によれば、（Ａ）芳香環を有さないカルボキシル基含有樹脂、（Ｂ）光重合開始剤、（Ｃ）エポキシ化合物、（Ｄ）ルチル型酸化チタン、および（Ｅ）希釈剤を含むことを特徴とする白色の光硬化性・熱硬化性ソルダーレジスト組成物が提供される。 That is, according to the first aspect of the present invention, (A) a carboxyl group-containing resin having no aromatic ring, (B) a photopolymerization initiator, (C) an epoxy compound, (D) a rutile-type titanium oxide, and (E) A white photo-curing / thermosetting solder resist composition characterized by containing a diluent is provided.
また、本発明の他の側面によれば、回路形成されたプリント配線板表面に、第１の側面による白色の光硬化性・熱硬化性ソルダーレジスト組成物を用いてソルダーレジスト膜を形成して得られるプリント配線板が提供される。 According to another aspect of the present invention, a solder resist film is formed on the surface of a printed wiring board on which a circuit is formed using the white photocurable / thermosetting solder resist composition according to the first aspect. The resulting printed wiring board is provided.
本発明によれば、現像型ソルダーレジストとして要求されるコーティング性、光硬化性、現像性、はんだ耐熱性、密着性、電気絶縁性等の特性を有し、経時による反射率の低下および劣化による着色を抑えた高反射率のソルダーレジスト膜を形成することができ、ＬＥＤをプリント配線板に実装した際に全体として照度を上げることができる。 According to the present invention, it has characteristics such as coating properties, photocurability, developability, solder heat resistance, adhesion, and electrical insulation required as a development type solder resist, and it is caused by a decrease and deterioration of reflectance over time. It is possible to form a solder resist film having a high reflectance that suppresses coloring, and the illuminance can be increased as a whole when the LED is mounted on a printed wiring board.
以下、本発明をさらに詳しく説明する。 Hereinafter, the present invention will be described in more detail.
本発明の白色のソルダーレジスト組成物は、（Ａ）芳香環を有さないカルボキシル基含有樹脂、（Ｂ）光重合開始剤、（Ｃ）エポキシ化合物、（Ｄ）ルチル型酸化チタン、および（Ｅ）希釈剤を含む。 The white solder resist composition of the present invention comprises (A) a carboxyl group-containing resin having no aromatic ring, (B) a photopolymerization initiator, (C) an epoxy compound, (D) a rutile-type titanium oxide, and (E ) Contains diluent.
芳香環を有さないカルボキシル基含有樹脂（Ａ）としては、芳香環を持たないカルボキシル基を有する樹脂であれば、それ自体に感光性の不飽和二重結合を１個以上有する感光性のカルボキシル基含有樹脂、および感光性の不飽和二重結合を有さないカルボキシル基含有樹脂のいずれも使用可能であり、特定のものに限定されるものではない。特に以下に列挙する樹脂の中で芳香環を有さないもの（オリゴマーまたはポリマーのいずれでもよい）を好適に使用することができる。すなわち、
（１）不飽和カルボン酸と不飽和二重結合を有する化合物の共重合によって得られるカルボキシル基含有樹脂、
（２）カルボキシル基含有（メタ）アクリル系共重合樹脂に、１分子中にオキシラン環とエチレン性不飽和基を有する化合物との反応により得られる感光性のカルボキシル基含有樹脂、
（３）１分子中にそれぞれ１個のエポキシ基と不飽和二重結合を有する化合物と、不飽和二重結合を有する化合物の共重合体に、不飽和モノカルボン酸を反応させ、生成した第２級の水酸基に飽和または不飽和多塩基酸無水物を反応させて得られる感光性のカルボキシル基含有樹脂、
（４）水酸基含有ポリマーに、飽和または不飽和多塩基酸無水物を反応させた後、生成したカルボン酸に、１分子中にそれぞれ１個のエポキシ基と不飽和二重結合を有する化合物を反応させて得られる感光性の水酸基およびカルボキシル基含有樹脂
である。
As the carboxyl group-containing resin (A) not having an aromatic ring, a photosensitive carboxyl having at least one photosensitive unsaturated double bond in itself is a resin having a carboxyl group not having an aromatic ring. Either a group-containing resin or a carboxyl group-containing resin having no photosensitive unsaturated double bond can be used, and is not limited to a specific one. In particular, among the resins listed below, those having no aromatic ring (any of oligomers or polymers) can be preferably used. That is,
(1) a carboxyl group-containing resin obtained by copolymerization of an unsaturated carboxylic acid and a compound having an unsaturated double bond,
(2) a photosensitive carboxyl group-containing resin obtained by reacting a carboxyl group-containing (meth) acrylic copolymer resin with a compound having an oxirane ring and an ethylenically unsaturated group in one molecule;
(3) A compound formed by reacting an unsaturated monocarboxylic acid with a copolymer of a compound having one epoxy group and an unsaturated double bond in each molecule and a compound having an unsaturated double bond. A photosensitive carboxyl group-containing resin obtained by reacting a secondary hydroxyl group with a saturated or unsaturated polybasic acid anhydride,
(4) After reacting a hydroxyl group-containing polymer with a saturated or unsaturated polybasic acid anhydride, the resulting carboxylic acid is reacted with a compound having one epoxy group and an unsaturated double bond in each molecule. A photosensitive hydroxyl group- and carboxyl group-containing resin.
これらの中でも、上記（２）の感光性のカルボキシル基含有樹脂である、（ａ）カルボキシル基含有（メタ）アクリル系共重合樹脂と、（ｂ）１分子中にオキシラン環とエチレン性不飽和基を有する化合物との反応により得られるカルボキシル基を有する共重合系樹脂が好ましい。 Among these, (a) the carboxyl group-containing (meth) acrylic copolymer resin (2), which is the photosensitive carboxyl group-containing resin of (2), and (b) an oxirane ring and an ethylenically unsaturated group in one molecule. A copolymer resin having a carboxyl group obtained by a reaction with a compound having an aromatic group is preferred.
（ａ）のカルボキシル基含有（メタ）アクリル系共重合樹脂は、（メタ）アクリル酸エステルと、１分子中に１個の不飽和基と少なくとも１個のカルボキシル基を有する化合物とを共重合させて得られる。共重合樹脂（ａ）を構成する（メタ）アクリル酸エステルとしては、メチル（メタ）アクリレート、エチル（メタ）アクリレート、プロピル（メタ）アクリレート、ブチル（メタ）アクリレート、ペンチル（メタ）アクリレート、ヘキシル（メタ）アクリレート等の（メタ）アクリル酸アルキルエステル類、２−ヒドロキシエチル（メタ）アクリレート、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、カプロラクトン変性２−ヒドロキシエチル（メタ）アクリレート等の水酸基含有（メタ）アクリル酸エステル類、メトキシジエチレングリコール（メタ）アクリレート、エトキシジエチレングリコール（メタ）アクリレート、イソオクチルオキシジエチレングリコール（メタ）アクリレート、フェノキシトリエチレングリコール（メタ）アクリレート、メトキシトリエチレングリコール（メタ）アクリレート、メトキシポリエチレングリコール（メタ）アクリレート等のグリコール変性（メタ）アクリレート類などが挙げられる。これらは単独で用いても、２種以上を混合して用いてもよい。なお、本明細書中において、（メタ）アクリレートとは、アクリレートおよびメタアクリレートを総称する用語であり、他の類似の表現についても同様である。 The carboxyl group-containing (meth) acrylic copolymer resin (a) is obtained by copolymerizing a (meth) acrylic acid ester and a compound having one unsaturated group and at least one carboxyl group in one molecule. Obtained. Examples of the (meth) acrylic acid ester constituting the copolymer resin (a) include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, pentyl (meth) acrylate, hexyl ( Hydroxyl groups such as (meth) acrylic acid alkyl esters such as (meth) acrylate, 2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, caprolactone-modified 2-hydroxyethyl (meth) acrylate Containing (meth) acrylic acid esters, methoxydiethylene glycol (meth) acrylate, ethoxydiethylene glycol (meth) acrylate, isooctyloxydiethylene glycol (meth) acrylate, phenoxy Triethylene glycol (meth) acrylate, methoxy triethylene glycol (meth) acrylate, glycol-modified (meth) acrylates such as methoxy polyethylene glycol (meth) acrylate. These may be used alone or in combination of two or more. In addition, in this specification, (meth) acrylate is a term that collectively refers to acrylate and methacrylate, and the same applies to other similar expressions.
また、１分子中に１個の不飽和基と少なくとも１個のカルボキシル基を有する化合物としては、アクリル酸、メタクリル酸、不飽和基とカルボン酸の間が鎖延長された変性不飽和モノカルボン酸、例えばβ−カルボキシエチル（メタ）アクリレート、２−アクリロイルオキシエチルコハク酸、２−アクリロイルオキシエチルヘキサヒドロフタル酸、ラクトン変性等によりエステル結合を有する不飽和モノカルボン酸、エーテル結合を有する変性不飽和モノカルボン酸、さらにはマレイン酸等のカルボキシル基を分子中に２個以上含むものなどが挙げられる。これらは単独で用いても、２種以上を混合して用いてもよい。 In addition, examples of the compound having one unsaturated group and at least one carboxyl group in one molecule include acrylic acid, methacrylic acid, and a modified unsaturated monocarboxylic acid in which a chain is extended between the unsaturated group and the carboxylic acid. For example, β-carboxyethyl (meth) acrylate, 2-acryloyloxyethyl succinic acid, 2-acryloyloxyethyl hexahydrophthalic acid, unsaturated monocarboxylic acid having an ester bond due to lactone modification, etc., modified unsaturated having an ether bond Examples thereof include monocarboxylic acids, and those containing two or more carboxyl groups in the molecule, such as maleic acid. These may be used alone or in combination of two or more.
（ｂ）１分子中にオキシラン環とエチレン性不飽和基を有する化合物としては、１分子中にエチレン性不飽和基とオキシラン環を有する化合物であればよく、例えば、グリシジル（メタ）アクリレート、α−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等を挙げることができる。中でも、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。これら（ｂ）１分子中にオキシラン環とエチレン性不飽和基を有する化合物は、単独で用いても２種以上を混合して用いてもよい。 (B) The compound having an oxirane ring and an ethylenically unsaturated group in one molecule may be a compound having an ethylenically unsaturated group and an oxirane ring in one molecule. For example, glycidyl (meth) acrylate, α -Methyl glycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, 3,4-epoxycyclohexylethyl (meth) acrylate, 3,4-epoxycyclohexylbutyl (meth) acrylate, 3,4-epoxycyclohexyl Examples include methylamino acrylate. Among these, 3,4-epoxycyclohexylmethyl (meth) acrylate is preferable. These (b) compounds having an oxirane ring and an ethylenically unsaturated group in one molecule may be used alone or in admixture of two or more.
芳香環を有さないカルボキシル基含有樹脂（Ａ）は、その酸価が５０〜２００ｍｇＫＯＨ／ｇの範囲にあることが必要である。酸価が５０ｍｇＫＯＨ／ｇ未満の場合には、弱アルカリ水溶液での未露光部分の除去が難しい。２００ｍｇＫＯＨ／ｇを超えると、硬化被膜の耐水性、電気特性が劣るなどの問題がある。また、カルボキシル基含有樹脂（Ａ）の重量平均分子量は、５，０００〜１００，０００の範囲にあることが好ましい。重量平均分子量が５０００未満であると指触乾燥性が著しく劣る傾向がある。また、重量平均分子量が１００，０００を超えると現像性、貯蔵安定性が著しく悪化する問題を生じるために好ましくない。 The carboxyl group-containing resin (A) not having an aromatic ring needs to have an acid value in the range of 50 to 200 mgKOH / g. When the acid value is less than 50 mgKOH / g, it is difficult to remove the unexposed portion with a weak alkaline aqueous solution. When it exceeds 200 mgKOH / g, there are problems such as poor water resistance and electrical properties of the cured coating. Moreover, it is preferable that the weight average molecular weight of carboxyl group-containing resin (A) exists in the range of 5,000-100,000. When the weight average molecular weight is less than 5000, the dryness to touch tends to be extremely poor. On the other hand, if the weight average molecular weight exceeds 100,000, it is not preferable because developability and storage stability are remarkably deteriorated.
本発明に用いられる光重合開始剤（Ｂ）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、２−（ジメチルアミノ）−２−［（４−メチルフェニル）メチル］−１−［４−（４−モルフォリニル）フェニル］−１−ブタノン等のアミノアルキルフェノン類；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。 Examples of the photopolymerization initiator (B) 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]- 2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1,2- (dimethylamino) -2-[(4-methylphenyl) methyl ] -1- [4- (4-morpholinyl) Nyl] -1-butanone and other aminoalkylphenones; 2-methylanthraquinone, 2-ethylanthraquinone, 2-tertiarybutylanthraquinone, 1-chloroanthraquinone and other anthraquinones; 2,4-dimethylthioxanthone, 2,4- Thioxanthones such as diethylthioxanthone, 2-chlorothioxanthone, 2,4-diisopropylthioxanthone; ketals such as acetophenone dimethyl ketal and benzyldimethyl ketal; benzophenones such as benzophenone; or xanthones; (2,6-dimethoxybenzoyl)- 2,4,4-pentylphosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine Phosphine oxides such as oxide, ethyl-2,4,6-trimethylbenzoylphenyl phosphinate; various peroxides, titanocene-based initiators, etc., which are N, N-dimethylaminobenzoic acid ethyl ester N, N-dimethylaminobenzoic acid isoamyl ester, pentyl-4-dimethylaminobenzoate, triethylamine, triethanolamine, and other photosensitizers such as triethanolamine may be used in combination. These photopolymerization initiators can be used alone or in combination of two or more.
光重合開始剤（Ｂ）の配合量は、芳香環を有さないカルボキシル基含有樹脂（Ａ）１００質量部に対して好ましくは１〜３０質量部、より好ましくは２〜２５質量部である。光重合開始剤（Ｂ）の配合量が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、３０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。 The blending amount of the photopolymerization initiator (B) is preferably 1 to 30 parts by mass, more preferably 2 to 25 parts by mass with respect to 100 parts by mass of the carboxyl group-containing resin (A) having no aromatic ring. When the blending amount of the photopolymerization initiator (B) 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 30 parts by mass, the thick film curability is lowered and the cost is increased.
次に、エポキシ化合物（Ｃ）としては、公知慣用の各種エポキシ樹脂、例えばビスフェノールＳ型エポキシ樹脂、ジグリシジルフタレート樹脂、トリグリシジルイソシアヌレート（例えば日産化学（株）製のＴＥＰＩＣ−Ｈ（Ｓ−トリアジン環骨格面に対し３個のエポキシ基が同一方向に結合した構造をもつβ体）や、ＴＥＰＩＣ（β体と、Ｓ−トリアジン環骨格面に対し１個のエポキシ基が他の２個のエポキシ基と異なる方向に結合した構造をもつα体との混合物）等）などの複素環式エポキシ樹脂、ビキシレノール型エポキシ樹脂、ビフェノール型エポキシ樹脂、テトラグリシジルキシレノイルエタン樹脂などの希釈剤に難溶性のエポキシ樹脂や、ビスフェノールＡ型エポキシ樹脂、水添ビスフェノールＡ型エポキシ樹脂、ビスフェノールＦ型樹脂、臭素化ビスフェノールＡ型エポキシ樹脂、フェノールノボラック型またはクレゾールノボラック型エポキシ樹脂、脂環式エポキシ樹脂、ビスフェノールＡのノボラック型エポキシ樹脂、キレート型エポキシ樹脂、グリオキザール型エポキシ樹脂、アミノ基含有エポキシ樹脂、ゴム変性エポキシ樹脂、ジシクロペンタジエンフェノリック型エポキシ樹脂、シリコーン変性エポキシ樹脂、ε−カプロラクトン変性エポキシ樹脂などの希釈剤に可溶性のエポキシ樹脂などが挙げられる。これらのエポキシ樹脂は、単独でまたは２種以上を組み合わせて用いることができる。 Next, as the epoxy compound (C), various known and commonly used epoxy resins such as bisphenol S type epoxy resin, diglycidyl phthalate resin, triglycidyl isocyanurate (for example, TEPIC-H (S-triazine manufactured by Nissan Chemical Co., Ltd.) Β-epoxies having a structure in which three epoxy groups are bonded in the same direction to the ring skeleton plane, and TEPIC (beta isomer, one epoxy group for the S-triazine ring skeleton plane and the other two epoxies) Difficult to use diluents such as heterocyclic epoxy resins, bixylenol type epoxy resins, biphenol type epoxy resins, tetraglycidyl xylenoyl ethane resins, etc.) Soluble epoxy resin, bisphenol A type epoxy resin, hydrogenated bisphenol A type epoxy resin, bisphenol Type resin, brominated bisphenol A type epoxy resin, phenol novolak type or cresol novolak type epoxy resin, alicyclic epoxy resin, bisphenol A novolak type epoxy resin, chelate type epoxy resin, glyoxal type epoxy resin, amino group-containing epoxy resin And epoxy resins that are soluble in diluents such as rubber-modified epoxy resins, dicyclopentadiene phenolic epoxy resins, silicone-modified epoxy resins, and ε-caprolactone-modified epoxy resins. These epoxy resins can be used alone or in combination of two or more.
上記した中でも、芳香環を有さないエポキシ化合物を用いることがより好ましい。中でも、Ｓ−トリアジン骨格面に対して同一方向にエポキシ基が結合した構造をもつβ体のトリグリシジルイソシアヌレートを５０重量％以上含有するトリグリシジルイソシアヌレート（例えば、日産化学（株）製ＴＥＰＩＣ−Ｈ）が特に好ましい。β体のトリグリシジルイソシアヌレートを５０重量％以上含有するトリグリシジルイソシアヌレートは、光硬化によるソルダーレジスト膜のパターニングの段階まで透明であり、その後熱硬化する際に白濁する傾向がある。従って、得られるソルダーレジスト膜の白色度をさらに高め、高反射率のものとすることができる。 Among the above, it is more preferable to use an epoxy compound having no aromatic ring. Among them, triglycidyl isocyanurate containing 50 wt% or more of β-form triglycidyl isocyanurate having a structure in which an epoxy group is bonded in the same direction with respect to the S-triazine skeleton surface (for example, TEPIC manufactured by Nissan Chemical Co., Ltd.) H) is particularly preferred. Triglycidyl isocyanurate containing 50% by weight or more of β-form triglycidyl isocyanurate is transparent up to the step of patterning the solder resist film by photocuring, and tends to become cloudy when thermally cured thereafter. Therefore, it is possible to further increase the whiteness of the obtained solder resist film and to have a high reflectance.
エポキシ化合物（Ｃ）の配合量は、芳香環を有さないカルボキシ基含有樹脂（Ａ）１００質量部に対して好ましくは５〜７０質量部、より好ましくは５〜６０質量部である。エポキシ化合物（Ｃ）の配合量が７０質量部を超えると、現像液での未露光部分の溶解性が低下し、現像残りが発生しやすくなり、実用上使用することが難しい。一方、５質量部未満であると、カルボキシル基含有樹脂（Ａ）のカルボキシル基が未反応の状態で残存するため、硬化塗膜の電気特性、はんだ耐熱性、耐薬品性が充分に得られ難くなる傾向がある。 The compounding amount of the epoxy compound (C) is preferably 5 to 70 parts by mass, more preferably 5 to 60 parts by mass with respect to 100 parts by mass of the carboxy group-containing resin (A) having no aromatic ring. When the compounding quantity of an epoxy compound (C) exceeds 70 mass parts, the solubility of the unexposed part in a developing solution will fall, it will become easy to generate | occur | produce the image development residue, and it is difficult to use it practically. On the other hand, if the amount is less than 5 parts by mass, the carboxyl group of the carboxyl group-containing resin (A) remains in an unreacted state, and thus it is difficult to sufficiently obtain the electrical properties, solder heat resistance, and chemical resistance of the cured coating film. Tend to be.
カルボキシル基共重合系樹脂（Ａ）のカルボキシル基と、エポキシ化合物（Ｃ）のエポキシ基とは、開環重合により反応するが、希釈剤（Ｅ）や組成物中の他の物質に易溶性エポキシ樹脂を用いた場合、乾燥時の熱により架橋が進みやすい。そのため、架橋反応を抑制して乾燥時間を長くとりたい場合には、難溶性のエポキシ樹脂単独で、または易溶性のエポキシ樹脂と共に用いることが望ましい。 The carboxyl group of the carboxyl group copolymer resin (A) and the epoxy group of the epoxy compound (C) react by ring-opening polymerization, but are readily soluble in the diluent (E) and other substances in the composition. When a resin is used, crosslinking is likely to proceed due to heat during drying. Therefore, when it is desired to suppress the crosslinking reaction and increase the drying time, it is desirable to use the hardly soluble epoxy resin alone or together with the easily soluble epoxy resin.
本発明では、白色顔料として、ルチル型酸化チタン（Ｄ）を用いることを特徴としている。アナターゼ型酸化チタンは、ルチル型と比較して白色度が高いためによく使用される。しかしながら、アナターゼ型酸化チタンは、光触媒活性を有するために、ソルダーレジスト組成物中の樹脂の変色を引き起こすことがある。これに対し、ルチル型酸化チタンは、白色度はアナターゼ型と比較して若干劣るものの、光活性を殆ど有さないために、安定したソルダーレジスト膜を得ることができる。ルチル型酸化チタン（Ｄ）としては、公知のルチル型のものを使用することができる。具体的には、富士チタン工業（株）製ＴＲ−６００、ＴＲ−７００、ＴＲ−７５０、ＴＲ−８４０、石原産業（株）製Ｒ−５５０、Ｒ−５８０、Ｒ−６３０、Ｒ−８２０、ＣＲ−５０、ＣＲ−６０、ＣＲ−９０、チタン工業（株）製ＫＲ−２７０、ＫＲ−３１０、ＫＲ−３８０等を使用することができる。 In the present invention, rutile type titanium oxide (D) is used as a white pigment. Anatase-type titanium oxide is often used because of its high whiteness compared to the rutile type. However, since anatase-type titanium oxide has photocatalytic activity, it may cause discoloration of the resin in the solder resist composition. In contrast, rutile titanium oxide has a slightly lower whiteness than the anatase type, but has almost no photoactivity, so that a stable solder resist film can be obtained. As a rutile type titanium oxide (D), a well-known rutile type thing can be used. Specifically, TR-600, TR-700, TR-750, TR-840 manufactured by Fuji Titanium Industry Co., Ltd., R-550, R-580, R-630, R-820 manufactured by Ishihara Sangyo Co., Ltd., CR-50, CR-60, CR-90, KR-270, KR-310, KR-380, etc. manufactured by Titanium Industry Co., Ltd. can be used.
ルチル型酸化チタン（Ｄ）の配合量は、芳香環を有さないカルボキシ基含有樹脂（Ａ）１００質量部に対して、好ましくは５０〜３００質量部、より好ましくは６０〜２６０質量部である。配合量が３００質量部を超えると、光硬化性が低下し、硬化深度が低くなり好ましくない。一方、５０質量部未満であると、隠ぺい力が小さく、高反射率のソルダーレジスト膜を得ることができない。 The compounding amount of the rutile type titanium oxide (D) is preferably 50 to 300 parts by mass, more preferably 60 to 260 parts by mass with respect to 100 parts by mass of the carboxy group-containing resin (A) having no aromatic ring. . If the blending amount exceeds 300 parts by mass, the photocurability is lowered and the curing depth is lowered, which is not preferable. On the other hand, if it is less than 50 parts by mass, the hiding power is small, and a solder resist film having a high reflectance cannot be obtained.
また、本発明では、シリカ粒子（Ｆ）を併用すると、より深い硬化深度を有するソルダーレジスト組成物を得ることができる。これは、シリカの屈折率がカルボキシル基含有樹脂（Ａ）と比較的近いためと考えられる。 Moreover, in this invention, when a silica particle (F) is used together, the soldering resist composition which has a deeper hardening depth can be obtained. This is considered because the refractive index of silica is relatively close to the carboxyl group-containing resin (A).
このようなシリカ粒子（Ｆ）としては、公知のものを使用することができる。例えば、球状シリカ（アドマテックス社製アドマファインＳＯ−Ｅ１、ＳＯ−Ｅ２、ＳＯ−Ｅ５等）、微粉状酸化ケイ素、無定形シリカ、結晶性シリカ、溶融シリカ等を挙げることができる。これらシリカ粒子は、単独でまたは２種以上を組み合わせて用いることができる。シリカ粒子（Ｆ）の配合量は、芳香環を有さないカルボキシ基含有樹脂（Ａ）１００質量部に対して、好ましくは５０〜２００質量部である。 Known silica particles (F) can be used. For example, spherical silica (Admafine SO-E1, SO-E2, SO-E5, etc. manufactured by Admatechs), finely divided silicon oxide, amorphous silica, crystalline silica, fused silica and the like can be mentioned. These silica particles can be used alone or in combination of two or more. The compounding amount of the silica particles (F) is preferably 50 to 200 parts by mass with respect to 100 parts by mass of the carboxy group-containing resin (A) having no aromatic ring.
本発明で使用される希釈剤（Ｅ）としては、光重合性モノマー及び／又は有機溶剤が挙げられる。光重合性モノマーとしては、２−ヒドロキシエチルアクリレート、２−ヒドロキシブチルアクリレートなど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、メトキシテトラエチレングリコール、ポリエチレングリコール、プロピレングリコールなどのグリコール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、Ｎ−メチロールアクリルアミドなど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などのアミノアルキルアクリレート類；ヘキサンジオール、トリメチロールプロパン、ペンタエリスリトール、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などの多価アルコール又はこれらのエチレンオキサイドもしくはプロピレンオキサイド付加物の多価アクリレート類；フェノキシアクリレート、ビスフェノールＡジアクリレート及び、これらのフェノール類のエチレンオキサイドあるいはプロピレンオキサイド付加物などのアクリレート類；グル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などのグリシジルエーテルのアクリレート類；メラミンアクリレート；及び／又は上記アクリレート類に対応するメタクリレート類等を挙げることができる。 As a diluent (E) used by this invention, a photopolymerizable monomer and / or an organic solvent are mentioned. As photopolymerizable monomers, hydroxyalkyl acrylates such as 2-hydroxyethyl acrylate and 2-hydroxybutyl acrylate; mono- or diacrylates of glycols such as ethylene glycol, methoxytetraethylene glycol, polyethylene glycol, propylene glycol; N, Acrylamides such as N-dimethylacrylamide and N-methylolacrylamide; aminoalkyl acrylates such as N, N-dimethylaminoethyl acrylate; hexanediol, trimethylolpropane, pentaerythritol, dipentaerythritol, tris-hydroxyethyl isocyanurate, etc. Polyhydric alcohols or polyhydric acrylates of these ethylene oxide or propylene oxide adducts Acrylates such as phenoxy acrylate, bisphenol A diacrylate and ethylene oxide or propylene oxide adducts of these phenols; acrylates of glycidyl ethers such as glycerin diglycidyl ether, trimethylolpropane triglycidyl ether; melamine acrylate; And / or methacrylates corresponding to the above acrylates.
一方、有機溶剤としては、メチルエチルケトン、シクロヘキサノンなどのケトン類；トルエン、キシレン、テトラメチルベンゼンなどの芳香族炭化水素類；メチルセロソルブ、エチルセロソルブ、ブチルセロソルブ、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、ジエチレングリコールモノエチルエーテル、ジプロプレングリコールモノエチルエーテル、トリエチレングリコールモノエチルエーテルなどのグリコールエーテル類；酢酸エチル、酢酸ブチル、セロソルブアセテート、ジエチレングリコールモノエチルエーテルアセテート及び上記グリコールエーテル類のエステル化物などのエステル類；エタノール、プロパノール、エチレングリコール、プロピレングリコールなどのアルコール類；オクタン、デカンなどの脂肪族炭化水素類；石油エーテル、石油ナフサ、水添石油ナフサ、ソルベントナフサなどの石油系溶剤等を挙げることができる。 On the other hand, as organic solvents, ketones such as methyl ethyl ketone and cyclohexanone; aromatic hydrocarbons such as toluene, xylene, and tetramethylbenzene; methyl cellosolve, ethyl cellosolve, butyl cellosolve, methyl carbitol, butyl carbitol, propylene glycol monomethyl ether , Glycol ethers such as diethylene glycol monoethyl ether, dipropylene glycol monoethyl ether, triethylene glycol monoethyl ether; esters such as ethyl acetate, butyl acetate, cellosolve acetate, diethylene glycol monoethyl ether acetate and esterified products of the above glycol ethers Alcohols such as ethanol, propanol, ethylene glycol, propylene glycol; Mention may be made of petroleum ether, petroleum naphtha, hydrogenated petroleum naphtha, a petroleum solvent or the like, such as solvent naphtha; Tan, aliphatic hydrocarbons such as decane.
上記のような希釈剤（Ｅ）は、単独で又は２種以上の混合物として用いることができる。芳香環を有さないカルボキシル基含有樹脂（Ａ）１００質量部に対して、２０〜３００質量部の希釈剤（Ｅ）を用いることが好ましい。前記希釈剤の使用目的は、光重合性モノマーは、塗布しやすい状態にするだけでなく、活性エネルギー線硬化性樹脂を希釈し、光重合性を増強するものであり、一方、有機溶剤は、乾燥させることにより造膜せしめたるためである。従って、用いる希釈剤に応じて、フォトマスクを塗膜に接触させる接触方式あるいは非接触方式のいずれかの露光方式が用いられる。 The diluent (E) as described above can be used alone or as a mixture of two or more. It is preferable to use 20 to 300 parts by mass of the diluent (E) with respect to 100 parts by mass of the carboxyl group-containing resin (A) having no aromatic ring. The purpose of use of the diluent is not only to make the photopolymerizable monomer easy to apply, but also to dilute the active energy ray curable resin to enhance photopolymerization, while the organic solvent is This is because the film is formed by drying. Therefore, either a contact method or a non-contact exposure method in which the photomask is brought into contact with the coating film is used depending on the diluent used.
さらに、必要に応じて、硬化促進剤、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。 Furthermore, a curing accelerator, a thermal polymerization inhibitor, a thickener, an antifoaming agent, a leveling agent, a coupling agent, a flame retardant aid and the like can be used as necessary.
本発明の白色の光硬化性・熱硬化性ソルダーレジスト組成物は、液状、ペースト状の形態で提供することができる。 The white photocurable / thermosetting solder resist composition of the present invention can be provided in a liquid or paste form.
本発明の白色の光硬化性・熱硬化性ソルダーレジスト組成物を、必要に応じて希釈して塗布方法に適した粘度に調整する。これを、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することにより、本発明のプリント配線板を得ることができる。ここで用いられる希アルカリ水溶液としては、０．５〜５重量％の炭酸ナトリウム水溶液が一般的であるが、他のアルカリ使用液を使用することも可能である。他の希アルカリ水溶液としては、例えば、水酸化カリウム、水酸化ナトリウム、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、アミン類等のアルカリ水溶液を挙げることができる。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。 The white photocurable / thermosetting solder resist composition of the present invention is diluted as necessary to adjust the viscosity to be suitable for the coating method. This is applied to a printed wiring board on which a circuit is formed by a method such as a screen printing method, a curtain coating method, a spray coating method, or a roll coating method, and an organic solvent contained in the composition at a temperature of 70 to 90 ° C., for example. A tack-free coating film can be formed by evaporating and drying. Then, the printed wiring board of this invention can be obtained by exposing with an active energy ray selectively through a photomask, developing an unexposed part with dilute alkaline aqueous solution, and forming a resist pattern. The dilute alkaline aqueous solution used here is generally 0.5 to 5% by weight aqueous sodium carbonate solution, but other alkaline use liquids can also be used. Examples of other dilute alkaline aqueous solutions include alkaline aqueous solutions such as potassium hydroxide, sodium hydroxide, potassium carbonate, sodium phosphate, sodium silicate, ammonia, and amines. 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.
このようにして得られたソルダーレジスト膜の耐熱性を向上させるために、１００〜２００℃の熱、紫外線または遠赤外線により、ソルダーレジスト膜を二次硬化させることが望ましい。 In order to improve the heat resistance of the solder resist film thus obtained, it is desirable to secondarily cure the solder resist film with heat of 100 to 200 ° C., ultraviolet rays or far infrared rays.
本発明の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膜は、高反射率を有すること、また、密着性、耐熱性、耐溶剤性並びに電気特性等のソルダーレジストに要求される諸特性を満たすことがわかった。本発明により形成されたソルダーレジストは、加速劣化試験後も高い反射率を保つ。 The solder resist film formed using the solder resist composition of the present invention has high reflectivity, and various properties required for the solder resist such as adhesion, heat resistance, solvent resistance and electrical properties. I found it to satisfy. The solder resist formed by the present invention maintains a high reflectance even after an accelerated deterioration test.
以下、本発明を実施例により説明するが、本発明はこれに限定されるものではない。 EXAMPLES Hereinafter, although an Example demonstrates this invention, this invention is not limited to this.
（Ａ）芳香環を有さないカルボキシル基含有樹脂の合成
合成例１
攪拌機、温度計、還流冷却器、滴下ロートおよび窒素導入管を備えた２リットルセパラブルフラスコに、溶媒としてジエチレングリコールジメチルエーテル９００ｇ、および重合開始剤としてｔ−ブチルパーオキシ２−エチルヘキサノエート（日本油脂（株）製パーブチルＯ）２１．４ｇを加えて９０℃に加熱した。加熱後、ここに、メタクリル酸３０９．９ｇ、メタクリル酸メチル１１６．４ｇ、およびラクトン変性２−ヒドロキシエチルメタクリレート（ダイセル化学工業（株）製プラクセルＦＭ１）１０９．８ｇを、重合開始剤であるビス（４−ｔ−ブチルシクロヘキシル）パーオキシジカーボネート（日本油脂（株）製パーロイルＴＣＰ）２１．４ｇと共に３時間かけて滴下して加え、さらに６時間熟成することにより、カルボキシル基含有共重合樹脂を得た。なお、反応は、窒素雰囲気下で行った。
(A) Synthesis of carboxyl group-containing resin having no aromatic ring Synthesis Example 1
In a 2 liter separable flask equipped with a stirrer, thermometer, reflux condenser, dropping funnel and nitrogen introducing tube, 900 g of diethylene glycol dimethyl ether as a solvent and t-butylperoxy 2-ethylhexanoate (Nippon Yushi) as a polymerization initiator 21.4 g of Perbutyl O manufactured by Co., Ltd. was added and heated to 90 ° C. After heating, 309.9 g of methacrylic acid, 116.4 g of methyl methacrylate, and 109.8 g of lactone-modified 2-hydroxyethyl methacrylate (Daicel Chemical Industries, Ltd., Plaxel FM1) were added to the bis ( 4-t-butylcyclohexyl) peroxydicarbonate (Perroyl TCP manufactured by Nippon Oil & Fats Co., Ltd.) was added dropwise over 3 hours, and further aged for 6 hours to obtain a carboxyl group-containing copolymer resin. It was. The reaction was performed under a nitrogen atmosphere.
次に、得られたカルボキシル基含有共重合樹脂に、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（株）製サイクロマーＡ２００）３６３．９ｇ、開環触媒としてジメチルベンジルアミン３．６ｇ、重合抑制剤としてハイドロキノンモノメチルエーテル１．８０ｇを加え、１００℃に加熱し、攪拌することによりエポキシの開環付加反応を行った。１６時間後、固形分の酸価が１０８．９ｍｇＫＯＨ／ｇ、重量平均分子量が２５，０００の、芳香環を有さないカルボキシル基含有樹脂を５３．８重量％（不揮発分）含む溶液を得た。以下、この反応溶液をＡ−１ワニスと呼ぶ。 Next, 363.9 g of 3,4-epoxycyclohexylmethyl acrylate (Daicel Chemical Co., Ltd. Cyclomer A200), 3.6 g of dimethylbenzylamine as a ring-opening catalyst, polymerization inhibition were added to the obtained carboxyl group-containing copolymer resin. As an agent, 1.80 g of hydroquinone monomethyl ether was added, heated to 100 ° C., and stirred to carry out an epoxy ring-opening addition reaction. After 16 hours, a solution containing 53.8% by weight (nonvolatile content) of a carboxyl group-containing resin having no aromatic ring and having an acid value of solids of 108.9 mgKOH / g and a weight average molecular weight of 25,000 was obtained. . Hereinafter, this reaction solution is referred to as A-1 varnish.
合成例２
温度計、攪拌機、滴下ロート、および還流冷却器を備えたフラスコに、溶媒としてジエチレングリコールモノエチルエーテルアセテート、触媒としてアゾビスイソブチロニトリルを入れ、窒素雰囲気下、８０℃に加熱し、メタアクリル酸とメチルメタアクリレートを０．４０：０．６０のモル比で混合したモノマーを約２時間かけて滴下した。さらに１時間攪拌した後、温度を１１５℃にまで上げ、失活させて樹脂溶液を得た。
Synthesis example 2
A flask equipped with a thermometer, stirrer, dropping funnel, and reflux condenser is charged with diethylene glycol monoethyl ether acetate as a solvent and azobisisobutyronitrile as a catalyst, heated to 80 ° C. in a nitrogen atmosphere, and methacrylic acid. And methyl methacrylate mixed at a molar ratio of 0.40: 0.60 was added dropwise over about 2 hours. After further stirring for 1 hour, the temperature was raised to 115 ° C. and deactivated to obtain a resin solution.
この樹脂溶液を冷却後、触媒として臭化テトラブチルアンモニウムを用い、９５〜１０５℃で３０時間の条件で、ブチルグリシジルエーテルを０．４０のモル比で、得られた樹脂のカルボキシル基の等量と付加反応させ、冷却した。 After cooling the resin solution, tetrabutylammonium bromide was used as a catalyst, and butyl glycidyl ether was equivalence of butyl glycidyl ether at a molar ratio of 0.40 under the conditions of 95 to 105 ° C. for 30 hours. And the reaction was cooled.
さらに得られた樹脂のＯＨ基に対して、９５〜１０５℃で８時間の条件で、無水テトラヒドロフタル酸を０．２６のモル比で付加反応させた。冷却後取り出して、固形分の酸価が７８．１ｍｇＫＯＨ／ｇ、重量平均分子量が３５，０００の芳香環を有さないカルボキシル基含有樹脂を５０質量％（不揮発分）含む溶液を得た。以下、この反応溶液をＡ−２ワニスと呼ぶ。 Furthermore, tetrahydrophthalic anhydride was subjected to addition reaction at a molar ratio of 0.26 under the condition of 95 to 105 ° C. for 8 hours with respect to the OH group of the obtained resin. The solution was taken out after cooling to obtain a solution containing 50% by mass (nonvolatile content) of a carboxyl group-containing resin having no aromatic ring having a solid content acid value of 78.1 mgKOH / g and a weight average molecular weight of 35,000. Hereinafter, this reaction solution is called A-2 varnish.
（Ｒ）芳香環を有するカルボキシル基含有樹脂の合成
比較合成例１
温度計、攪拌器、滴下ロート、および還流冷却器を備えたフラスコに、クレゾールノボラック型エポキシ樹脂（大日本インキ化学工業社製エピクロンＮ−６８０、エポキシ当量＝２１０）２１０ｇと、溶媒としてのカルビトールアセテート９６．４ｇとを加え、加熱溶解させた。続いて、重合禁止剤としてハイドロキノン０．１ｇ、反応触媒としてトリフェニルホスフィン２．０ｇを加えた。この混合物を９５〜１０５℃に加熱し、アクリル酸７２ｇを徐々に滴下し、酸価が３．０ｍｇＫＯＨ／ｇ以下となるまで、約１６時間反応させた。この反応生成物を、８０〜９０℃にまで冷却した後、テトラヒドロフタル酸無水物７６．１ｇを加え、赤外吸光分析により、酸無水物の吸収ピーク（１７８０ｃｍ−１）が無くなるまで、約６時間反応させた。この反応溶液に、出光石油化学社製の芳香族系溶剤イプゾール＃１５０を９６．４ｇ加え、希釈した後取り出した。このようにして得られたカルボキシル基含有の感光性ポリマー溶液は、不揮発分が６５重量％、固形物の酸価が７８ｍｇＫＯＨ／ｇであった。以下、この反応溶液をＲ−１ワニスと呼ぶ。
(R) Synthesis of carboxyl group-containing resin having aromatic ring Comparative synthesis example 1
In a flask equipped with a thermometer, a stirrer, a dropping funnel, and a reflux condenser, 210 g of cresol novolac type epoxy resin (Epicron N-680, Epoxy equivalent = 210, manufactured by Dainippon Ink & Chemicals, Inc.) and carbitol as a solvent 96.4 g of acetate was added and dissolved by heating. Subsequently, 0.1 g of hydroquinone as a polymerization inhibitor and 2.0 g of triphenylphosphine as a reaction catalyst were added. This mixture was heated to 95-105 ° C., 72 g of acrylic acid was gradually added dropwise, and the mixture was reacted for about 16 hours until the acid value became 3.0 mgKOH / g or less. The reaction product was cooled to 80 to 90 ° C., 76.1 g of tetrahydrophthalic anhydride was added, and about 6 until an absorption peak (1780 cm −1 ) of the acid anhydride disappeared by infrared absorption analysis. Reacted for hours. To this reaction solution, 96.4 g of aromatic solvent ipsol # 150 manufactured by Idemitsu Petrochemical Co., Ltd. was added, diluted and taken out. The thus obtained carboxyl group-containing photosensitive polymer solution had a nonvolatile content of 65% by weight and a solid acid value of 78 mgKOH / g. Hereinafter, this reaction solution is called R-1 varnish.
実施例１〜７、比較例１〜２
表１に従って各成分を配合・攪拌して３本ロールにて分散させてそれぞれソルダーレジスト組成物とした。表中の数字は、質量部を示す。
Each component was blended and stirred according to Table 1 and dispersed with a three roll to obtain a solder resist composition. The numbers in the table indicate parts by mass.
Ａ−１：カルボキシル基およびアクリロイル基含有共重合樹脂（合成例１）
Ａ−２：カルボキシル基含有共重合樹脂（合成例２）
Ｒ−１：カルボキシル基およびアクリロイル基含有樹脂（比較合成例１）
Ｒ８２０：石原産業社製ルチル型酸化チタン
ＫＡ−１５（富士）チタン製アナターゼ型酸化チタン
ＴＥＰＩＣ−Ｈ：日産化学（株）製β体トリグリシジルイソシアヌレート
ＴＥＰＩＣ−Ｓ：日産化学（株）製α体およびβ体混合トリグリシジルイソシアヌレート
２０２１Ｐ：ダイセル化学工業製 脂環式エポキシ樹脂
ＨＢＰＡ：丸善石油化学製 水添ビスフェノール型エポキシ樹脂 ＨＢＰＡ−ＤＧＥ
８２８：ジャパンエポキシレジン製 ビスフェノール型エポキシ樹脂
ＳＯ−Ｅ５：アドマテック製球状シリカ
開始剤：チバスペシャルティケミカルズ製 イルガキュア９０７
増感剤：日本化薬製 ＤＥＴＸ
モノマー：ジペンタエリスリトルヘキサアクリレート
ＫＳ−６６：信越シリコーン製シリコーンオイル
溶剤：カルビトールアセテート。
A-1: A carboxyl group- and acryloyl group-containing copolymer resin (Synthesis Example 1)
A-2: Copolymer resin containing carboxyl group (Synthesis Example 2)
R-1: Resin containing carboxyl group and acryloyl group (Comparative Synthesis Example 1)
R820: Ishihara Sangyo Co., Ltd. Rutile Titanium Oxide KA-15 (Fuji) Titanium Anatase Titanium Oxide TEPIC-H: Nissan Chemical Co., Ltd. β-body triglycidyl isocyanurate TEPIC-S: Nissan Chemical Co., Ltd. α body And β-form mixed triglycidyl isocyanurate 2021P: manufactured by Daicel Chemical Industries, alicyclic epoxy resin HBPA: manufactured by Maruzen Petrochemical Co., Ltd. Hydrogenated bisphenol type epoxy resin HBPA-DGE
828: Bisphenol epoxy resin SO-E5 made by Japan Epoxy Resin: Spherical silica initiator made by Admatech: Irgacure 907 made by Ciba Specialty Chemicals
Sensitizer: Nippon Kayaku DETX
Monomer: Dipentaeryth little hexaacrylate KS-66: Shin-Etsu silicone silicone oil Solvent: carbitol acetate
実施例２および実施例３の組成物を、１００ｍｍ×１５０ｍｍの大きさで１．０ｍｍの厚さのガラス板に、スクリーン印刷法により、膜厚が４０μｍとなるように１００メッシュポリエステルバイアス製の版を使用してベタパターンで印刷した。その後、８０℃で１０分間、熱風循環式乾燥炉で乾燥させた。これに、同条件を用いて組成物の印刷を再び行い、８０℃で２０分間、熱風循環式乾燥炉で乾燥させ、試験片とした。この試験片のガラス面側から、プリント配線板用露光機オーク製作所製ＨＭＷ−６８０ＧＷを用いて、３０ｍｍ角のネガパターンを残すように、３００ｍＪ／ｃｍ２の積算光量で紫外線露光し、３０℃１％の炭酸ナトリウム水溶液を現像液として、プリント配線板用現像機にて６０秒間現像し、続いて１５０℃で６０分間、熱風循環式乾燥炉で熱硬化を行った。ガラスの厚みとガラスを含めた塗膜の厚みをマイクロメーターで測定し、その差により残存している塗膜の膜厚をもとめたところ、実施例２においては３８μｍであり、実施例３においては４７μｍであった。 A plate made of 100 mesh polyester bias, using the composition of Example 2 and Example 3 on a glass plate having a size of 100 mm × 150 mm and a thickness of 1.0 mm by screen printing so that the film thickness becomes 40 μm. Was used to print a solid pattern. Then, it was dried in a hot air circulation type drying furnace at 80 ° C. for 10 minutes. The composition was again printed using the same conditions, and dried in a hot air circulation drying oven at 80 ° C. for 20 minutes to obtain a test piece. From the glass surface side of this test piece, UV exposure was performed with an integrated light amount of 300 mJ / cm 2 so as to leave a 30 mm square negative pattern using an HMW-680GW manufactured by Oak Manufacturing Co., Ltd. % Aqueous solution of sodium carbonate as a developing solution was developed for 60 seconds with a developing machine for printed wiring boards, and then thermally cured at 150 ° C. for 60 minutes in a hot-air circulating drying furnace. When the thickness of the glass and the thickness of the coating film including the glass were measured with a micrometer, and the film thickness of the remaining coating film was determined by the difference, it was 38 μm in Example 2, and in Example 3, It was 47 μm.
次いで、ソルダーレジスト組成物を用いて形成されるソルダーレジスト膜の諸性質を調べるために、以下のようにして試験し、評価を行った。 Subsequently, in order to investigate the various properties of the solder resist film formed using the solder resist composition, the test was conducted as follows.
（１）耐光性
各ソルダーレジスト組成物を、１００ｍｍ×１５０ｍｍの大きさで１．６ｍｍの厚さのＦＲ−４銅張り積層板にスクリーン印刷法にて、膜厚４０μｍとなるように１００メッシュポリエステルバイアス製の版を使用してベタパターンで印刷し、８０℃で３０分間に渡って熱風循環式乾燥炉にて乾燥させた。プリント配線板用露光機オーク製作所製ＨＭＷ−６８０ＧＷを用いて、３０ｍｍ角のネガパターンを残すように、５００ｍＪ／ｃｍ２の積算光量で、また実施例６に関しては１０００ｍＪ／ｃｍ２の積算光量で紫外線露光し、３０℃１％の炭酸ナトリウム水溶液を現像液として、プリント配線板用現像機にて６０秒間現像し、続いて１５０℃で６０分間、熱風循環式乾燥炉で熱硬化を行い、特性試験用の試験片を作製した。
(1) Light resistance Each solder resist composition was 100 mm × 150 mm in size and 1.6 mm thick FR-4 copper-clad laminate by screen printing, 100 mesh polyester to a film thickness of 40 μm. Printing was performed with a solid pattern using a bias plate and dried in a hot air circulation drying oven at 80 ° C. for 30 minutes. Using printed wiring board for an exposure apparatus Oak Seisakusho HMW-680GW, ultraviolet so as to leave a negative pattern of 30mm square, with integrated light quantity of 500 mJ / cm 2, also for Example 6 with the integrated light quantity of 1000 mJ / cm 2 Developed with a 1% sodium carbonate aqueous solution at 30 ° C. for 60 seconds in a developing machine for printed wiring boards, followed by heat curing at 150 ° C. for 60 minutes in a hot air circulating drying oven, and a property test Test specimens were prepared.
得られた試験片をミノルタ製色彩色差計ＣＲ−４００で測定した。その後ＵＶコンベア炉（出力１５０Ｗ／ｃｍ メタルハライドランプ コールドミラー）で５０Ｊ／ｃｍ２、１００Ｊ／ｃｍ２、１５０Ｊ／ｃｍ２の光を照射して加速劣化させた。結果を表２〜５に示す。
表２〜５において、ＹはＸＹＺ表色系の反射率を示し、Ｌ＊は、Ｌ＊ａ＊ｂ＊表色系の明度を表わす。ａ＊は赤方向、−ａ＊は緑方向、ｂ＊は黄方向、−ｂ＊は青方向を示し、ゼロに近いほど彩度がないことを示す。ΔＥ＊ａｂは、色の変化を示す。この値が小さいほど色の変化が小さいことを示す。目視評価項目については、二重丸は変色が感じられない、丸印は殆ど変色がない、三角印はやや変色がある、バツ印は明らかな変色があることを示す。 In Tables 2 to 5, Y represents the reflectance of the XYZ color system, and L * represents the lightness of the L * a * b * color system. a * indicates the red direction, -a * indicates the green direction, b * indicates the yellow direction, and -b * indicates the blue direction. The closer to zero, the lower the saturation. ΔE * ab indicates a change in color. A smaller value indicates a smaller color change. As for the visual evaluation items, the double circle shows no discoloration, the circle shows almost no discoloration, the triangle shows some discoloration, and the cross indicates clear discoloration.
表２〜５から明らかな通り、本発明の組成物を用いた実施例１〜７においては、加速劣化後も、反射率は低下せず、明度の変化も小さく、および色の変化であるΔＥ＊ａｂの値が小さいことがわかる。また、目視評価でも変色は全くないか、殆どない。なお、実施例７は、エポキシ化合物として、芳香環を有するものを用いている。実施例の中でも色の変化であるΔＥ＊ａｂ値が若干大きい傾向があり、このことからも、エポキシ化合物としては、芳香環を有さないものを用いることがより好ましいことがわかる。 As is apparent from Tables 2 to 5, in Examples 1 to 7 using the composition of the present invention, even after accelerated deterioration, the reflectance does not decrease, the change in brightness is small, and ΔE which is a change in color. * It can be seen that the value of ab is small. In addition, there is no or almost no discoloration by visual evaluation. In Example 7, an epoxy compound having an aromatic ring is used. Among the examples, the ΔE * ab value, which is a color change, tends to be slightly large. This also indicates that it is more preferable to use an epoxy compound having no aromatic ring.
比較例１は、カルボキシル基含有感光性樹脂として芳香環を有する従来の樹脂を用いたものである。表からわかるように、ソルダーレジスト組成物中に芳香環を有する組成物は、加速劣化後、反射率Ｙおよび明度Ｌ＊は共に大きく低下しており、および色の変化であるΔＥ＊ａｂの値も大きい。また、目視評価においても、変色が認められる。このことから、ソルダーレジスト組成物中の樹脂中に芳香環を有するものを用いると、ソルダーレジスト膜が光により劣化することがわかる。 Comparative Example 1 uses a conventional resin having an aromatic ring as a carboxyl group-containing photosensitive resin. As can be seen from the table, in the composition having an aromatic ring in the solder resist composition, after accelerated deterioration, both the reflectance Y and the lightness L * are greatly reduced, and the value of ΔE * ab which is a color change Is also big. Moreover, discoloration is recognized also in visual evaluation. From this, it is understood that when a resin having an aromatic ring is used in the resin in the solder resist composition, the solder resist film is deteriorated by light.
また、比較例２はルチル型酸化チタンに代えてアナターゼ型酸化チタンを含むものである。アナターゼ型酸化チタンは表からも明らかな通り、初期の反射率は高いが、加速劣化後に、反射率Ｙおよび明度Ｌ＊は共に大きく低下し、色の変化であるΔＥ＊ａｂ値も大きい。また、目視評価においても変色がみられる。このことから、アナターゼ型酸化チタンよりもルチル型酸化チタンのほうが、高反射率のソルダーレジスト組成物成分としては優れていることがわかった。 Comparative Example 2 contains anatase type titanium oxide instead of rutile type titanium oxide. As is apparent from the table, the anatase-type titanium oxide has a high initial reflectance, but after accelerated deterioration, both the reflectance Y and the lightness L * are greatly reduced, and the ΔE * ab value, which is a color change, is also large. Moreover, discoloration is seen also in visual evaluation. From this, it was found that rutile type titanium oxide is superior as a solder resist composition component having high reflectivity than anatase type titanium oxide.
（２）耐熱性
（１）と同様に作製した各試験片に、ロジン系フラックスを塗布して２６０℃のはんだ槽で１０秒間フローさせた。その後、プロピレングリコールモノメチルエーテルアセテートで洗浄し、乾燥させた後に、セロハン粘着テープによるピールテストを行い、塗膜の剥がれについて評価した。結果を表６に示す。ここで、丸印は、塗膜の剥がれがなかったこと、バツ印は、塗膜の剥がれがあったことを示す。
(2) Heat resistance A rosin flux was applied to each test piece prepared in the same manner as in (1) and allowed to flow in a solder bath at 260 ° C. for 10 seconds. Then, after washing with propylene glycol monomethyl ether acetate and drying, a peel test with a cellophane adhesive tape was performed to evaluate the peeling of the coating film. The results are shown in Table 6. Here, the circle mark indicates that the coating film has not been peeled off, and the cross mark indicates that the coating film has been peeled off.
（３）耐溶剤性
（１）と同様に作製した各試験片を、プロピレングリコールモノメチルエーテルアセテートに３０分間浸漬し、乾燥させた後に、セロハン粘着テープによるピールテストを行い、塗膜の剥がれと変色について評価した。結果を表６に併せて示す。ここで、丸印は、塗膜の剥がれや変色がなかったこと、バツ印は、塗膜の剥がれや変色があったことを示す。
(3) Solvent resistance Each test piece prepared in the same manner as in (1) was dipped in propylene glycol monomethyl ether acetate for 30 minutes and dried, and then a peel test with a cellophane adhesive tape was performed to peel and discolor the coating film. Was evaluated. The results are also shown in Table 6. Here, the circle mark indicates that there was no peeling or discoloration of the coating film, and the cross mark indicates that there was peeling or discoloration of the coating film.
（４）鉛筆硬度試験
（１）と同様に作製した各試験片に、芯の先が平らになるように研がれたＢから９Ｈの鉛筆を、約４５°の角度で押し付けて、塗膜の剥がれが生じない鉛筆の硬さを記録した。結果を、表６に併せて示す。
(4) Pencil hardness test A B to 9H pencil sharpened so that the tip of the core is flattened against each test piece prepared in the same manner as in (1) at an angle of about 45 ° to form a coating film The hardness of the pencil where no peeling occurred was recorded. The results are also shown in Table 6.
（５）絶縁抵抗試験
ＦＲ−４銅張り積層板の代わりにＩＰＣ Ｂ−２５テストパターンのクシ型電極Ｂクーポンを用いること以外は（１）と同様の条件で試験片を作製した。この試験片に、ＤＣ５００Ｖのバイアスを印加し、絶縁抵抗値を測定した。結果を、表６に併せて示す。
表６からも明らかなように、一般的に用いられるソルダーレジスト組成物を用いた比較例１および２と同様の結果が、本発明のソルダーレジスト組成物を用いた実施例１〜７においても得られた。従って、本発明のソルダーレジスト組成物により形成されるソルダーレジスト膜も、一般的に要求される諸特性を満たしていることがわかった。 As is apparent from Table 6, the same results as in Comparative Examples 1 and 2 using a commonly used solder resist composition were also obtained in Examples 1 to 7 using the solder resist composition of the present invention. It was. Accordingly, it has been found that the solder resist film formed by the solder resist composition of the present invention also satisfies various properties generally required.
以上詳述した通り、本発明によれば、高反射率の光硬化性・熱硬化性のソルダーレジスト組成物を得ることができる。本発明のソルダーレジスト組成物により形成されたソルダーレジスト膜は、光劣化を受けにくく長期間の使用に耐えるものである。 As described above in detail, according to the present invention, a photoreflective / thermosetting solder resist composition having a high reflectance can be obtained. The solder resist film formed from the solder resist composition of the present invention is resistant to photodegradation and can withstand long-term use.
Claims (6)
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
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| JP2006150452A JP4340272B2 (en) | 2006-05-30 | 2006-05-30 | Photocurable / thermosetting solder resist composition and printed wiring board using the same |
| CN2007101084057A CN101082773B (en) | 2006-05-30 | 2007-05-30 | Photo- and thermo-setting solder resist composition and printed wire board using same |
| CN201010143016XA CN101866108B (en) | 2006-05-30 | 2007-05-30 | Photosetting and thermosetting solder resist composition, and printed wiring board using the same |
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| JP2006150452A JP4340272B2 (en) | 2006-05-30 | 2006-05-30 | Photocurable / thermosetting solder resist composition and printed wiring board using the same |
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| JP4340272B2 JP4340272B2 (en) | 2009-10-07 |
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| CN (2) | CN101082773B (en) |
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Also Published As
| Publication number | Publication date |
|---|---|
| CN101082773A (en) | 2007-12-05 |
| CN101866108A (en) | 2010-10-20 |
| JP4340272B2 (en) | 2009-10-07 |
| CN101082773B (en) | 2010-08-11 |
| CN101866108B (en) | 2013-11-13 |
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