JP2008020632A - Photocurable/heat curable one-liquid type solder resist composition and printed wiring board using same - Google Patents
Photocurable/heat curable one-liquid type solder resist composition and printed wiring board using same Download PDFInfo
- Publication number
- JP2008020632A JP2008020632A JP2006191885A JP2006191885A JP2008020632A JP 2008020632 A JP2008020632 A JP 2008020632A JP 2006191885 A JP2006191885 A JP 2006191885A JP 2006191885 A JP2006191885 A JP 2006191885A JP 2008020632 A JP2008020632 A JP 2008020632A
- Authority
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- Prior art keywords
- acid
- solder resist
- group
- resist composition
- anhydride
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
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- 229910000679 solder Inorganic materials 0.000 title claims abstract description 54
- 239000000203 mixture Substances 0.000 title claims abstract description 43
- 239000007788 liquid Substances 0.000 title abstract description 7
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 58
- 229920005989 resin Polymers 0.000 claims abstract description 45
- 239000011347 resin Substances 0.000 claims abstract description 45
- -1 organic acid salt Chemical class 0.000 claims abstract description 40
- 239000002253 acid Substances 0.000 claims abstract description 35
- 229920000877 Melamine resin Polymers 0.000 claims abstract description 21
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000003085 diluting agent Substances 0.000 claims abstract description 11
- 239000003513 alkali Substances 0.000 claims abstract description 9
- 239000003999 initiator Substances 0.000 claims abstract description 8
- 239000011256 inorganic filler Substances 0.000 claims abstract description 7
- 229910003475 inorganic filler Inorganic materials 0.000 claims abstract description 7
- 150000001875 compounds Chemical class 0.000 claims description 27
- 150000008065 acid anhydrides Chemical class 0.000 claims description 20
- 238000006243 chemical reaction Methods 0.000 claims description 18
- 238000011161 development Methods 0.000 claims description 14
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 13
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 12
- 230000015572 biosynthetic process Effects 0.000 claims description 12
- 238000003786 synthesis reaction Methods 0.000 claims description 12
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 11
- 229920001187 thermosetting polymer Polymers 0.000 claims description 11
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 10
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- 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 claims description 5
- 229920006026 co-polymeric resin Polymers 0.000 claims description 5
- FALRKNHUBBKYCC-UHFFFAOYSA-N 2-(chloromethyl)pyridine-3-carbonitrile Chemical compound ClCC1=NC=CC=C1C#N FALRKNHUBBKYCC-UHFFFAOYSA-N 0.000 claims description 4
- MWSKJDNQKGCKPA-UHFFFAOYSA-N 6-methyl-3a,4,5,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1CC(C)=CC2C(=O)OC(=O)C12 MWSKJDNQKGCKPA-UHFFFAOYSA-N 0.000 claims description 4
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- 229940014800 succinic anhydride Drugs 0.000 claims description 4
- MUTGBJKUEZFXGO-OLQVQODUSA-N (3as,7ar)-3a,4,5,6,7,7a-hexahydro-2-benzofuran-1,3-dione Chemical compound C1CCC[C@@H]2C(=O)OC(=O)[C@@H]21 MUTGBJKUEZFXGO-OLQVQODUSA-N 0.000 claims description 3
- 150000004292 cyclic ethers Chemical group 0.000 claims description 3
- 239000003595 mist Substances 0.000 abstract description 13
- 238000007747 plating Methods 0.000 abstract description 13
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 abstract description 11
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- 239000010931 gold Substances 0.000 abstract description 11
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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
- 229910052757 nitrogen Inorganic materials 0.000 description 9
- 239000003795 chemical substances by application Substances 0.000 description 8
- 230000035945 sensitivity Effects 0.000 description 8
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 8
- 239000002966 varnish Substances 0.000 description 8
- 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 7
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- 238000010521 absorption reaction Methods 0.000 description 6
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- 239000000178 monomer Substances 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 238000007650 screen-printing Methods 0.000 description 5
- FPZWZCWUIYYYBU-UHFFFAOYSA-N 2-(2-ethoxyethoxy)ethyl acetate Chemical compound CCOCCOCCOC(C)=O FPZWZCWUIYYYBU-UHFFFAOYSA-N 0.000 description 4
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 4
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 238000009835 boiling Methods 0.000 description 4
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 4
- 238000001723 curing Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- NWVVVBRKAWDGAB-UHFFFAOYSA-N hydroquinone methyl ether Natural products COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 4
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 4
- 229910052753 mercury Inorganic materials 0.000 description 4
- 150000007524 organic acids Chemical class 0.000 description 4
- 150000007519 polyprotic acids Polymers 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- 229910052708 sodium Inorganic materials 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 239000007921 spray Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 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 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 3
- QCAHUFWKIQLBNB-UHFFFAOYSA-N 3-(3-methoxypropoxy)propan-1-ol Chemical compound COCCCOCCCO QCAHUFWKIQLBNB-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 244000028419 Styrax benzoin Species 0.000 description 3
- 235000000126 Styrax benzoin Nutrition 0.000 description 3
- 235000008411 Sumatra benzointree Nutrition 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
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- 229960002130 benzoin Drugs 0.000 description 3
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- 239000011889 copper foil Substances 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 3
- 235000019382 gum benzoic Nutrition 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 150000007974 melamines Chemical class 0.000 description 3
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- 238000012360 testing method Methods 0.000 description 3
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- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-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
- 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
- OFNISBHGPNMTMS-UHFFFAOYSA-N 3-methylideneoxolane-2,5-dione Chemical compound C=C1CC(=O)OC1=O OFNISBHGPNMTMS-UHFFFAOYSA-N 0.000 description 2
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- 238000013007 heat curing Methods 0.000 description 2
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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、電気特性等の塗膜特性に優れ、ミストの少ない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 and thermosetting one-pack solder resist composition with excellent coating properties such as adhesion, electroless gold plating resistance, electrical properties, etc., and low mist development, and printed wiring board using the same About.
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に優れ、ミストの少ない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-part solder resist composition with excellent heat resistance, adhesion, electroless gold plating resistance, electrical properties and other coating properties that can be developed with low mist and capable of alkali development. Another object of the present invention is to provide a dry film 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)1分子中にエチレン性不飽和基を2個以上有し、かつカルボキシル基を1個以上有し、そのカルボキシル基の酸強度pKaが、5.0以下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) one molecule has two or more ethylenically unsaturated groups and one or more carboxyl groups. A carboxyl group-containing photosensitive resin having a carboxyl group acid strength pKa of 5.0 or less,
(B) Diluent,
(C) a photopolymerization initiator,
A photocurable / thermosetting one-component solder resist composition capable of alkali development is provided, which comprises (D) melamine or an organic acid salt thereof and (E) 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、はんだ耐熱時等に発生するミストも少ないことから、生産設備や作業環境を汚染することが無いという効果もある。
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 there is little mist generated at the time of solder heat resistance, there is an effect that the production equipment and the working environment are not contaminated.
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)1分子中にエチレン性不飽和基を2個以上有し、かつカルボキシル基を1個以上有し、そのカルボキシル基の酸強度pKaが、5.0以下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、電気特性などの塗膜特性に優れていることを見出し、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) having two or more ethylenically unsaturated groups in one molecule and having a carboxyl group. A carboxyl group-containing photosensitive resin having at least one and having an acid strength pKa of the carboxyl group of 5.0 or less,
(B) Diluent,
(C) a photopolymerization initiator,
(D) Solder resist composition containing melamine or an organic acid salt thereof and (E) inorganic filler has storage stability that can be used as a one-part composition, and heat resistance and adhesion that can be satisfied as a solder resist The present invention has been completed by finding that it has excellent coating properties such as properties, electroless gold plating resistance and electrical properties.
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、1分子中にエチレン性不飽和基を2個以上有し、かつカルボキシル基を1個以上有し、そのカルボキシル基の酸強度pKaが、5.0以下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、このように、比較的活性の高いカルボキシル基を有していることにより、不飽和二重結合とマイケル付加反応したり、メラミン又はその有機酸塩とアミド化したり、さらには樹脂中や無機フィラー中の水酸基などとエステル化反応することにより、耐熱性に優れた硬化塗膜を提供できることを見出し、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。
また、本発明の第二の特徴である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、酸強度pKaとは、25℃の水溶液における酸解離定数であり、下記式1により求められる化合物特有の定数である。
pKa=−log10([H3O+][A−]/[HA]) … (式1)
式中、[HA]は酸の濃度、[H3O+]はオキソニウムイオン(水和した水素イオン)濃度、[A−]は酸の共役塩基(酸残基)の濃度、log10は常用対数を示す。
本発明では、ハメット指示薬を用いて、電位差滴定法により、測定した。
That is, the alkali-developable photocurable / thermosetting one-component solder resist composition of the present invention has the first feature that two or more ethylenically unsaturated groups are contained in one molecule, and a carboxyl group. The carboxyl group has an acid strength pKa of 5.0 or less, and thus has a carboxyl group having a relatively high activity. Excellent heat resistance due to Michael addition reaction with unsaturated double bond, amidation with melamine or its organic acid salt, and esterification reaction with hydroxyl group in resin or inorganic filler. The present inventors have found that a cured coating film can be provided, and have completed the one-component solder resist composition of the present invention.
Moreover, the melamine or its organic acid salt which is the second feature of the present invention is that the ethylenically unsaturated group of the carboxyl group-containing photosensitive resin (A) and the active hydrogen of the melamine or its organic acid salt are being heated and cured. It is considered that the adhesion between the coating film and the copper foil is improved due to a chelate effect and an antirust effect on the copper foil.
In this specification, the acid strength pKa is an acid dissociation constant in an aqueous solution at 25 ° C., and is a constant specific to a compound obtained by the following formula 1.
pKa = −log 10 ([H 3 O + ] [A − ] / [HA]) (Formula 1)
In the formula, [HA] is an acid concentration, [H 3 O + ] is an oxonium ion (hydrated hydrogen ion) concentration, [A − ] is an acid conjugate base (acid residue) concentration, and log 10 is The common logarithm is shown.
In the present invention, measurement was performed by potentiometric titration using a Hammett indicator.
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、1分子中にエチレン性不飽和基を2個以上有し、かつカルボキシル基を1個以上有し、そのカルボキシル基の酸強度pKaが、5.0以下であるカルボキシル基含有感光性樹脂であり、例えば、以下に列挙するようなカルボキシル基含有感光性樹脂が挙げられる。
(1)(a)1分子中に2個以上のエポキシ基を有する化合物に、(b)エチレン性不飽和基含有モノカルボン酸を反応させた後、生成した二級水酸基に、(c)反応後の酸強度pKaが5.0以下となる二塩基酸無水物を反応させて得られるカルボキシル基含有感光性樹脂(A−1)、
(2)pKaが5.0以下である(d)アクリル酸及び/又は(e)メタクリル酸と、(f)それ以外のエチレン性不飽和基を有する化合物から合成される共重合樹脂のカルボキシル基の一部に、(g)1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(h)を付加して得られるカルボキシル基含有感光性樹脂(A−2)、
(3)グリシジル(メタ)アクリレートや3,4−エポキシシクロヘキシルメチル(メタ)アクリレート等のエポキシ基と不飽和二重結合を有する化合物と、それ以外の不飽和二重結合を有する化合物との共重合体に、(メタ)アクリル酸などの不飽和カルボン酸を反応させ、生成した二級の水酸基に(c)反応後の酸強度pKaが5.0以下となる二塩基酸無水物を反応させて得られるカルボキシル基含有感光性樹脂、
(4)多官能エポキシ化合物と、(メタ)アクリル酸などの不飽和モノカルボン酸と、一分子中に少なくとも1個のアルコール性水酸基と、エポキシ基と反応するアルコール性水酸基以外の1個の反応性基を有する化合物(例えば、ジメチロールプロピオン酸など)との反応生成物に、(c)反応後の酸強度pKaが5.0以下となる二塩基酸無水物を反応させて得られるカルボキシル基含有感光性樹脂などが挙げられる。
これらの中で、(1)に記載したカルボキシル基含有感光性樹脂(A−1)、及び(2)に記載したカルボキシル基含有感光性樹脂(A−2)が、合成が容易であり、安定した特性を有する塗膜を提供できるので、好ましい。
なお、本明細書において、(メタ)アクリル酸とは、アクリル酸、メタクリル酸、及びそれらの混合物を総称する用語で、他の類似の表現についても同様である。
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 has two or more ethylenically unsaturated groups and one or more carboxyl groups in one molecule, and the acid strength of the carboxyl group. It is a carboxyl group-containing photosensitive resin having a pKa of 5.0 or less, and examples thereof include carboxyl group-containing photosensitive resins as listed below.
(1) (a) After reacting a compound having two or more epoxy groups in one molecule with (b) an ethylenically unsaturated group-containing monocarboxylic acid, the resulting secondary hydroxyl group is subjected to (c) reaction A carboxyl group-containing photosensitive resin (A-1) obtained by reacting a dibasic acid anhydride having a subsequent acid strength pKa of 5.0 or less,
(2) A carboxyl group of a copolymer resin synthesized from (d) acrylic acid and / or (e) methacrylic acid having a pKa of 5.0 or less and (f) any other compound having an ethylenically unsaturated group (G) a carboxyl group-containing photosensitive resin (A-2) obtained by adding (g) a compound (h) having both a cyclic ether group and an ethylenically unsaturated fatty group in one molecule,
(3) Copolymerization of a compound having an unsaturated double bond with an epoxy group such as glycidyl (meth) acrylate or 3,4-epoxycyclohexylmethyl (meth) acrylate, and a compound having an unsaturated double bond other than that An unsaturated carboxylic acid such as (meth) acrylic acid is reacted with the coalescence, and (c) a dibasic acid anhydride having an acid strength pKa after reaction of 5.0 or less is reacted with the generated secondary hydroxyl group. The resulting carboxyl group-containing photosensitive resin,
(4) One reaction other than a polyfunctional epoxy compound, an unsaturated monocarboxylic acid such as (meth) acrylic acid, at least one alcoholic hydroxyl group in one molecule, and an alcoholic hydroxyl group that reacts with an epoxy group (C) a carboxyl group obtained by reacting a reaction product with a compound having a functional group (for example, dimethylolpropionic acid) with a dibasic acid anhydride having an acid strength pKa after reaction of 5.0 or less. And a photosensitive resin.
Among these, the carboxyl group-containing photosensitive resin (A-1) described in (1) and the carboxyl group-containing photosensitive resin (A-2) described in (2) are easily synthesized and stable. It is preferable because a coating film having the above characteristics can be provided.
In addition, in this specification, (meth) acrylic acid is a term which generically refers to acrylic acid, methacrylic acid, and mixtures thereof, and the same applies to other similar expressions.
本発明の第一の特徴であるカルボキシル基含有感光性樹脂(A)のカルボキシル基の酸強度pKaは、5.0以下、好ましくは5.0〜2.0の範囲にあることが好ましい。
カルボキシル基の酸強度pKaが、5.0を超える場合、アクリレート化合物との付加反応やメラミン類とのアミド化反応、さらに水酸基とのエステル化反応が起こりにくくなり、十分な塗膜特性が得られなくなるので、好ましくない。さらに、このように架橋反応が起こらないことにより、はんだ付け時等に、ミスト(揮発成分)が発生したりするので好ましくない。一方、酸強度pKaが、1.0未満の場合、銅箔等の金属の腐食の原因となるので、好ましくない。
また、本発明のカルボキシル基含有感光性樹脂(A)の重量平均分子量は、4,000〜50,000、より好ましくは8,000〜30,000であることが好ましい。重量平均分子量が、4,000未満の場合、十分な指触乾燥性が得られず、好ましくない。一方、重量平均分子量が、50,000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。
さらに、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。
The acid strength pKa of the carboxyl group of the carboxyl group-containing photosensitive resin (A), which is the first feature of the present invention, is 5.0 or less, preferably 5.0 to 2.0.
When the acid strength pKa of the carboxyl group exceeds 5.0, an addition reaction with an acrylate compound, an amidation reaction with melamines, and an esterification reaction with a hydroxyl group are unlikely to occur, and sufficient coating film characteristics are obtained. Since it disappears, it is not preferable. Furthermore, since the crosslinking reaction does not occur in this way, mist (volatile component) is generated at the time of soldering or the like, which is not preferable. On the other hand, an acid strength pKa of less than 1.0 is not preferable because it causes corrosion of metals such as copper foil.
Moreover, it is preferable that the weight average molecular weights of the carboxyl group-containing photosensitive resin (A) of this invention are 4,000-50,000, More preferably, it is 8,000-30,000. When the weight average molecular weight is less than 4,000, sufficient dryness to the touch cannot be obtained, which is not preferable. On the other hand, when the weight average molecular weight exceeds 50,000, the solubility of the carboxyl group-containing photosensitive resin in an organic solvent is lowered or the developability is lowered, which is not preferable.
Furthermore, the acid value of the said carboxyl group-containing photosensitive resin (A) is 30-150 mgKOH / g, More preferably, it 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(1)に記載したカルボキシル基含有感光性樹脂(A−1)の合成に用いられる1分子中に2個以上のエポキシ基を有する化合物(以下、多官能エポキシ化合物と略す。)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A型エポキシ樹脂、ビスフェノールF型エポキシ樹脂、ビスフェノールS型エポキシ樹脂、臭素化ビスフェノールA型エポキシ樹脂、水添ビスフェノールA型エポキシ樹脂、ビフェノール型エポキシ樹脂、ビキシレノール型エポキシ樹脂、フェノールノボラック型エポキシ樹脂、クレゾールノボラック型エポキシ樹脂、臭素化フェノールノボラック型エポキシ樹脂、ビスフェノールAのノボラック型エポキシ樹脂などのグリシジルエーテル化合物;テレフタル酸ジグリシジルエステル、ヘキサヒドロフタル酸ジグリシジルエステル、ダイマー酸ジグリシジルエステルなどのグリシジルエステル化合物;トリグリシジルイソシアヌレート、N,N,N’,N’−テトラグリシジルメタキシレンジアミン、N,N,N’,N’−テトラグリシジルビスアミノメチルシクロヘキサン、N,N−ジグリシジルアニリンなどのグリシジルアミン化合物;グリシジル(メタ)アクリレートと、その他の重合性モノマーとの共重合樹脂などが挙げられる。これらの中で、フェノールノボラック型エポキシ樹脂、及びクレゾールノボラック型エポキシ樹脂が、高感度で耐熱性に優れる硬化塗膜を提供できることから、好ましい。さらに、軟化点が60℃以上のクレゾールノボラック型エポキシ樹脂が、指触乾燥性にも優れることから、より好ましい。
これらの多官能エポキシ化合物(a)は、単独で又は2種類以上を併用して用いることもできる。
As a compound (hereinafter abbreviated as a polyfunctional epoxy compound) having two or more epoxy groups in one molecule used for the synthesis of the carboxyl group-containing photosensitive resin (A-1) described in (1) above, Various commonly used epoxy resins such as bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, brominated bisphenol A type epoxy resin, hydrogenated bisphenol A type epoxy resin, biphenol type epoxy resin, bixylenol type Glycidyl ether compounds such as epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, brominated phenol novolac type epoxy resin, bisphenol A novolac type epoxy resin; terephthalic acid diglycidyl ester, hexahydroph Glycidyl ester compounds such as diglycidyl oxalate and diglycidyl dimer; triglycidyl isocyanurate, N, N, N ′, N′-tetraglycidyl metaxylenediamine, N, N, N ′, N′-tetraglycidyl Examples thereof include glycidylamine compounds such as bisaminomethylcyclohexane and N, N-diglycidylaniline; copolymer resins of glycidyl (meth) acrylate and other polymerizable monomers. Among these, a phenol novolac type epoxy resin and a cresol novolac type epoxy resin are preferable because they can provide a cured film having high sensitivity and excellent heat resistance. Furthermore, a cresol novolac type epoxy resin having a softening point of 60 ° C. or more is more preferable because it is excellent in dryness to touch.
These polyfunctional epoxy compounds (a) can be used alone or in combination of two or more.
前記カルボキシル基含有感光性樹脂(A−1)の合成に用いられるエチレン性不飽和基含有モノカルボン酸(b)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、又は、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。これらエチレン性不飽和基含有モノカルボン酸(b)は、単独又は2種類以上を併用して用いてもよい。 Examples of the ethylenically unsaturated group-containing monocarboxylic acid (b) used for the synthesis of the carboxyl group-containing photosensitive resin (A-1) include unsaturated acids such as acrylic acid, methacrylic acid, and β-carboxylethyl (meth) acrylate. Monocarboxylic acid, or adduct of 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, hydroxyl group-containing (meth) acrylate such as hydroxybutyl (meth) acrylate, and dibasic acid anhydride and so on. 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 ethylenically unsaturated group-containing monocarboxylic acids (b) may be used alone or in combination of two or more.
本発明カルボキシル基含有感光性樹脂(A−1)の合成に用いられる反応後の酸強度pKaが5.0以下となる二塩基酸無水物(c)、より好ましくは、反応後の酸強度pKaが、2.0〜5.0となる二塩基酸無水物としては、コハク酸無水物、シトラコン酸無水物、イタコン酸無水物、マレイン酸無水物、ヘキサヒドロフタル酸無水物、メチルヘキサヒドロフタル酸無水物、テトラヒドロフタル酸無水物、メチルテトラヒドロフタル酸無水物、トリアルキルテトラヒドロフタル酸無水物、エンドメチレンテトラヒドロフタル酸無水物、メチルエンドメチレンテトラヒドロフタル酸無水物などが挙げられる。
これらの中で、特に、ヘキサヒドロフタル酸無水物、メチルヘキサヒドロフタル酸無水物、テトラヒドロフタル酸無水物、メチルテトラヒドロフタル酸無水物、コハク酸無水物が、硬化物の特性面から、好ましい。これらの二塩基酸無水物(c)は、単独又は2種類以上を併用して用いてもよい。
また、これらの二塩基酸無水物(c)の付加量は、得られるカルボキシル基含有感光性樹脂(A−1)の酸価が、30〜150mgKOH/gとなる範囲であり、前記多官能エポキシ化合物(a)とエチレン性不飽和基含有モノカルボン酸(b)の反応により生成する水酸基1当量当たり、0.4〜0.9当量、好ましくは0.45〜0.7当量である。
The dibasic acid anhydride (c) used for the synthesis of the carboxyl group-containing photosensitive resin (A-1) of the present invention, wherein the acid strength pKa after reaction is 5.0 or less, more preferably acid strength pKa after reaction. However, the dibasic acid anhydrides of 2.0 to 5.0 include succinic acid anhydride, citraconic acid anhydride, itaconic acid anhydride, maleic acid anhydride, hexahydrophthalic acid anhydride, methylhexahydrophthalic acid. Examples of the acid anhydride include tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, trialkyltetrahydrophthalic anhydride, endomethylenetetrahydrophthalic anhydride, and methylendomethylenetetrahydrophthalic anhydride.
Among these, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, and succinic anhydride are particularly preferable from the viewpoint of the properties of the cured product. These dibasic acid anhydrides (c) may be used alone or in combination of two or more.
The addition amount of these dibasic acid anhydrides (c) is such that the acid value of the resulting carboxyl group-containing photosensitive resin (A-1) is in the range of 30 to 150 mgKOH / g, and the polyfunctional epoxy The amount is 0.4 to 0.9 equivalent, preferably 0.45 to 0.7 equivalent, per 1 equivalent of hydroxyl group formed by the reaction of the compound (a) and the ethylenically unsaturated group-containing monocarboxylic acid (b).
本発明のカルボキシル基含有感光性樹脂(A)の第ニの態様である前記(2)に記載したカルボキシル基含有感光性樹脂(A−2)は、pKaが5.0以下である(d)アクリル酸及び/又は(e)メタクリル酸と、(f)それ以外のエチレン性不飽和基を有する化合物から合成される共重合樹脂のカルボキシル基の一部に、(g)1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(h)を付加して得られるカルボキシル基含有感光性樹脂であり、好ましくは、酸価が30〜150mgKOH/gで、重量平均分子量が、8,000〜50,000である。 The carboxyl group-containing photosensitive resin (A-2) described in (2), which is the second aspect of the carboxyl group-containing photosensitive resin (A) of the present invention, has a pKa of 5.0 or less (d) (G) a part of the carboxyl group of a copolymer resin synthesized from acrylic acid and / or (e) methacrylic acid and (f) any other compound having an ethylenically unsaturated group; Carboxyl group-containing photosensitive resin obtained by adding a compound (h) having both a group and an ethylenically unsaturated fatty group, and preferably has an acid value of 30 to 150 mgKOH / g and a weight average molecular weight of 8,000. ~ 50,000.
上記カルボキシル基含有感光性樹脂(A−2)の合成に用いられるアクリル酸(d)、メタクリル酸(e)以外のエチレン性不飽和基を有する化合物(f)としては、例えば、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)アクリレートなどのアルキル(メタ)アクリレート化合物;シクロヘキシル(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)アクリレートなどのシクロ環又は芳香環含有(メタ)アクリレート化合物;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)アクリレートなどの水酸基含有(メタ)アクリレート化合物;N−フェニルマレイミドやN−シクロヘキシルマレイミドなどのマレイミド化合物;フェニルグリシジルエーテルなどのモノエポキシ化合物の(メタ)アクリル酸エステル類などが挙げられる。 Examples of the compound (f) having an ethylenically unsaturated group other than acrylic acid (d) and methacrylic acid (e) used for the synthesis of the carboxyl group-containing photosensitive resin (A-2) include styrene, α- Vinyl compounds such as methylstyrene, vinyl acetate, vinyl benzoate; methyl (meth) acrylate, ethyl (meth) acrylate, lauryl (meth) acrylate, isopropyl (meth) acrylate, t-butyl (meth) acrylate, 2-ethylhexyl ( Alkyl (meth) acrylate compounds such as meth) acrylate and lauryl (meth) acrylate; cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, benzyl (meth) acrylate, phenyl (meth) acrylate and other cyclo rings or aromatic rings ( Meta) Acry Hydroxyl group-containing (meth) acrylate compounds such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate and 4-hydroxybutyl (meth) acrylate; N-phenylmaleimide and N-cyclohexylmaleimide And (meth) acrylic acid esters of monoepoxy compounds such as phenyl glycidyl ether.
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(g)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 (g) 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、カルボン酸、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、電気特性面からカルボン酸が最も好ましい。 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. As the organic acid, a carboxylic acid, an acidic phosphoric acid ester compound, and a sulfonic acid-containing compound can be considered, and any of them can be used, but carboxylic acid is most preferable in terms of electrical characteristics.
前記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、メタクリル酸のモノカルボン酸や、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、クロトン酸などのジカルボン酸、さらに、トリメリット酸などのトリカルボン酸が使用できる。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 carboxylic acid include formic acid, acetic acid, propionic acid, butyric acid, lactic acid, glycolic acid, acrylic acid, methacrylic acid monocarboxylic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, sebacic acid, maleic acid Acid, itaconic acid, phthalic acid, hexahydrophthalic acid, 3-methylhexahydrophthalic acid, 4-methylhexahydrophthalic acid, 3-ethylhexahydrophthalic acid, 4-ethylhexahydrophthalic acid, tetrahydrophthalic acid, 3 -Dicarboxylic acids such as methyltetrahydrophthalic acid, 4-methyltetrahydrophthalic acid, 3-ethyltetrahydrophthalic acid, 4-ethyltetrahydrophthalic acid, and crotonic acid, and tricarboxylic acids such as trimellitic acid can be used. 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
攪拌機、温度計、環流冷却管、滴下ロート及び窒素導入管を備えた2リットルのセパラブルフラスコに、クレゾールノボラック型エポキシ樹脂(日本化薬(株)製、EOCN−104S、軟化点92℃、エポキシ当量=220g/当量)660g、カルビトールアセテート 310.0gを仕込み、90℃に加熱・攪拌し、溶解した。次に、一旦80℃まで冷却し、アクリル酸 216g、トリフェニルホスフィン 4.0g、メチルハイドロキノン1.3gを加えて、90〜100℃で12時間反応させ、酸価が0.2mgKOH/gの反応生成物を得た。これにテトラヒドロフタル酸無水物 273.6gを仕込み、90℃に加熱し、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8時間反応させた。この反応液に、出光石油化学社製の芳香族系溶剤イプゾール#150 310.0部を加え、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感光性樹脂ワニスは、不揮発分65%、固形物の酸価87.5mgKOH/gであった。以下、この反応溶液をA−1−1ワニスと称す。
Synthesis example 1
To a 2 liter separable flask equipped with a stirrer, thermometer, reflux condenser, dropping funnel and nitrogen introduction tube, a cresol novolac type epoxy resin (manufactured by Nippon Kayaku Co., Ltd., EOCN-104S, softening point 92 ° C., epoxy (Equivalent = 220 g / equivalent)) 660 g and carbitol acetate 310.0 g were charged, heated and stirred at 90 ° C., and dissolved. Next, it is once cooled to 80 ° C., 216 g of acrylic acid, 4.0 g of triphenylphosphine, and 1.3 g of methylhydroquinone are added and reacted at 90-100 ° C. for 12 hours, and the acid value is 0.2 mg KOH / g. The product was obtained. This was charged with 273.6 g of tetrahydrophthalic anhydride, heated to 90 ° C., and reacted for about 8 hours until the absorption peak (1780 cm −1 ) of the acid anhydride disappeared by infrared absorption analysis. To this reaction solution, 310.0 parts of Idemitsu Petrochemical's aromatic solvent ipsol # 150 was added, diluted, and taken out. The carboxyl group-containing photosensitive resin varnish thus obtained had a non-volatile content of 65% and a solid acid value of 87.5 mgKOH / g. Hereinafter, this reaction solution is referred to as A-1-1 varnish.
合成例2
攪拌機、温度計、環流冷却管、滴下ロート及び窒素導入管を備えた2リットルのセパラブルフラスコに、クレゾールノボラック型エポキシ樹脂(日本化薬(株)製、EOCN−104S、軟化点92℃、エポキシ当量=220g/当量)660g、カルビトールアセテート 284.3gを仕込み、90℃に加熱・攪拌し、溶解した。次に、一旦80℃まで冷却し、アクリル酸 216g、トリフェニルホスフィン 4.0g、メチルハイドロキノン1.3gを加えて、90〜100℃で12時間反応させ、酸価が0.2mgKOH/gの反応生成物を得た。これにコハク酸無水物 180.0gを仕込み、90℃に加熱し、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8時間反応させた。この反応液に、出光石油化学社製の芳香族系溶剤イプゾール#150 284.3部を加え、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感光性樹脂ワニスは、不揮発分65%、固形物の酸価95.5mgKOH/gであった。以下、この反応溶液をA−1−2ワニスと称す。
Synthesis example 2
To a 2 liter separable flask equipped with a stirrer, thermometer, reflux condenser, dropping funnel and nitrogen introduction tube, a cresol novolac type epoxy resin (manufactured by Nippon Kayaku Co., Ltd., EOCN-104S, softening point 92 ° C., epoxy (Equivalent = 220 g / equivalent) 660 g and carbitol acetate 284.3 g were charged, heated to 90 ° C. and stirred to dissolve. Next, it is once cooled to 80 ° C., 216 g of acrylic acid, 4.0 g of triphenylphosphine, and 1.3 g of methylhydroquinone are added and reacted at 90-100 ° C. for 12 hours, and the acid value is 0.2 mg KOH / g. The product was obtained. This was charged with 180.0 g of succinic anhydride, heated to 90 ° C., and reacted for about 8 hours until the absorption peak (1780 cm −1 ) of the acid anhydride disappeared by infrared absorption analysis. To this reaction liquid, 284.3 parts of aromatic solvent ipsol # 150 manufactured by Idemitsu Petrochemical Co., Ltd. was added, diluted, and taken out. The carboxyl group-containing photosensitive resin varnish thus obtained had a nonvolatile content of 65% and a solid acid value of 95.5 mgKOH / g. Hereinafter, this reaction solution is referred to as A-1-2 varnish.
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、A−2−1ワニスと称す。
Synthesis example 3
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 referred to as A-2-1 varnish.
比較合成例1
攪拌機、温度計、環流冷却管、滴下ロート及び窒素導入管を備えた2リットルのセパラブルフラスコに、クレゾールノボラック型エポキシ樹脂(日本化薬(株)製、EOCN−104S、軟化点92℃、エポキシ当量=220g/当量)660g、カルビトールアセテート 307.6gを仕込み、90℃に加熱・攪拌し、溶解した。次に、一旦80℃まで冷却し、アクリル酸 216g、トリフェニルホスフィン 4.0g、メチルハイドロキノン1.3gを加えて、90〜100℃で12時間反応させ、酸価が0.2mgKOH/gの反応生成物を得た。これにフタル酸無水物 266.4gを仕込み、90℃に加熱し、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8時間反応させた。この反応液に、出光石油化学社製の芳香族系溶剤イプゾール#150 307.6部を加え、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感光性樹脂ワニスは、不揮発分65%、固形物の酸価88.2mgKOH/gであった。以下、この反応溶液をR−1ワニスと称す。
Comparative Synthesis Example 1
To a 2 liter separable flask equipped with a stirrer, thermometer, reflux condenser, dropping funnel and nitrogen introduction tube, a cresol novolac type epoxy resin (manufactured by Nippon Kayaku Co., Ltd., EOCN-104S, softening point 92 ° C., epoxy (Equivalent = 220 g / equivalent)) 660 g and carbitol acetate 307.6 g were charged, heated and stirred at 90 ° C., and dissolved. Next, it is once cooled to 80 ° C., 216 g of acrylic acid, 4.0 g of triphenylphosphine, and 1.3 g of methylhydroquinone are added and reacted at 90-100 ° C. for 12 hours, and the acid value is 0.2 mg KOH / g. The product was obtained. This was charged with 266.4 g of phthalic anhydride, heated to 90 ° C., and reacted for about 8 hours until the absorption peak (1780 cm −1 ) of the acid anhydride disappeared by infrared absorption analysis. To this reaction solution, 307.6 parts of aromatic solvent ipsol # 150 manufactured by Idemitsu Petrochemical Co. was added, diluted, and taken out. The carboxyl group-containing photosensitive resin varnish thus obtained had a nonvolatile content of 65% and a solid acid value of 88.2 mgKOH / g. Hereinafter, this reaction solution is referred to as R-1 varnish.
実施例1〜3、及び比較例1、2
合成例1〜3、及び比較合成例1で得られた各ワニスを用い、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 to 3 and Comparative Examples 1 and 2
Using each varnish obtained in Synthesis Examples 1 to 3 and Comparative Synthesis Example 1, the components are blended in the blending ratios shown in Table 1 below, kneaded using a three-roll mill, and photocurable with alkali development. -A thermosetting one-component solder resist composition was prepared. In addition, it diluted with the organic solvent as needed at the time of printing.
上記実施例1〜3及び比較例1、2の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。評価の結果を下記表2に示す。尚評価試験の方法は以下に示す。 With respect to the one-component solder resist compositions of Examples 1 to 3 and Comparative Examples 1 and 2, the following items were tested and evaluated. The results of evaluation are shown in Table 2 below. The evaluation test method is shown below.
(1)保存安定性
上記実施例1〜3及び比較例1、2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。
○: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。
(1) Storage stability Each one-pack type solder resist composition obtained in Examples 1 to 3 and Comparative Examples 1 and 2 was applied on the entire surface of a copper-clad substrate by screen printing, and a hot-air circulating drying furnace. Then, it 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.
○: Thickening rate is within 120%.
(Triangle | delta): Thickening rate is 120 to 200% or less.
X: Gelation or thickening rate is 200% or more.
(2)現像性
上記実施例1〜3及び比較例1、2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
(2) Developability Each one-component solder resist composition obtained in Examples 1 to 3 and Comparative Examples 1 and 2 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
(3)感度
上記実施例1〜3及び比較例1、2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。
(3) Sensitivity The one-pack type solder resist compositions obtained in Examples 1 to 3 and Comparative Examples 1 and 2 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.
(4)タック性
上記実施例1〜3及び比較例1、2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。
(4) Tackiness The above-described one-part solder resist compositions obtained in Examples 1 to 3 and Comparative Examples 1 and 2 were each coated on the entire surface of a printed wiring board on which a circuit was formed by screen printing. 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.
(5)はんだ耐熱性
上記実施例1〜3及び比較例1、2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
(5) Solder heat resistance The one-pack type solder resist compositions obtained in Examples 1 to 3 and Comparative Examples 1 and 2 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
(6)無電解金めっき耐性
上記(5)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
(6) Resistance to electroless gold plating An evaluation substrate was produced in the same manner as in (5) 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
(7)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(5)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。
(7) Electrical Insulation An evaluation board is produced under the same conditions as in (5) above using a comb-type electrode B coupon with an IPC B-25 test pattern, and a bias voltage of DC 100 V is applied to the comb-type electrode. ° C, 85% R.V. H. The insulation resistance value after 1,000 hours was measured in a constant temperature and humidity chamber.
(8)ミストの発生量
上記(5)と同様にして評価基板を作製した。この評価基板を、10cm×10cm角に切断し、2Lの金属缶に入れ、さらに蓋の上部に水を入れたシャーレを乗せて、260℃のホットプレート上で30分間加熱した。このようにして、基板から出るミストを金属缶の蓋に付着させた。この操作を10回繰り返し、金属缶の蓋に付着したミストの量を、下記の基準で評価した。
○:金属缶の蓋に付着しているミストが無い。
△:金属缶の蓋に、微量のミストが付着している。
×:金属缶の蓋に、明らかに判るミストが付着している。
(8) Amount of mist generated An evaluation substrate was produced in the same manner as in (5) above. This evaluation substrate was cut into a 10 cm × 10 cm square, placed in a 2 L metal can, and a petri dish containing water was placed on the top of the lid, and heated on a hot plate at 260 ° C. for 30 minutes. In this way, the mist from the substrate was adhered to the lid of the metal can. This operation was repeated 10 times, and the amount of mist adhering to the lid of the metal can was evaluated according to the following criteria.
○: There is no mist adhering to the lid of the metal can.
Δ: A very small amount of mist is attached to the lid of the metal can.
X: Mist clearly recognized is attached to the lid of the metal can.
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1〜3の一液型ソルダーレジスト組成物は、保存安定性、感度、タック性に優れ、またミストの発生量も少ないことが判る。
一方、カルボキシル基の酸強度pKaが約5.4のフタル酸無水物を使用した比較例1、2は、ミストの発生量が多いことが判る。また、感度も低く、感度を実施例並に上げるため、反応性希釈剤の量を増やした比較例2は、タック性が著しく低下した。
As is clear from the results shown in Table 2, the one-component solder resist compositions of Examples 1 to 3 according to the present invention are excellent in storage stability, sensitivity, and tackiness, and have a small amount of mist generated. I understand.
On the other hand, it can be seen that Comparative Examples 1 and 2 using a phthalic anhydride having a carboxyl group acid strength pKa of about 5.4 generate a large amount of mist. Moreover, since the sensitivity was low and the sensitivity was increased to the same level as in the example, the tackiness was significantly reduced in Comparative Example 2 in which the amount of the reactive diluent was increased.
Claims (6)
(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 carboxyl group-containing photosensitive resin having two or more ethylenically unsaturated groups and one or more carboxyl groups in one molecule, and having an acid strength pKa of 5.0 or less. ,
(B) Diluent,
(C) a photopolymerization initiator,
A photocurable and thermosetting one-component solder resist composition capable of alkali development, comprising (D) melamine or an organic acid salt thereof and (E) an inorganic filler.
A solder resist film is formed by using the one-component solder resist composition according to any one of claims 1 to 4 or the dry film according to claim 5 on a printed wiring board surface on which a circuit is formed. Printed wiring board.
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JPWO2009119821A1 (en) * | 2008-03-28 | 2011-07-28 | 太陽ホールディングス株式会社 | Curable resin composition, cured product thereof, and printed wiring board |
JP5787516B2 (en) * | 2008-03-28 | 2015-09-30 | 太陽ホールディングス株式会社 | Curable resin composition, cured product thereof, and printed wiring board |
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WO2013129028A1 (en) | 2012-02-29 | 2013-09-06 | 凸版印刷株式会社 | Needle-like material and method for manufacturing needle-like material |
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CN101105629A (en) | 2008-01-16 |
JP5027458B2 (en) | 2012-09-19 |
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