JP2014211540A - Photosensitive resin structure, dry film, and flexible printed wiring board - Google Patents
Photosensitive resin structure, dry film, and flexible printed wiring board Download PDFInfo
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- 229920005989 resin Polymers 0.000 title claims abstract description 73
- 239000011347 resin Substances 0.000 title claims abstract description 73
- 239000012790 adhesive layer Substances 0.000 claims abstract description 35
- 239000011241 protective layer Substances 0.000 claims abstract description 34
- 238000011161 development Methods 0.000 claims abstract description 25
- 230000001681 protective effect Effects 0.000 claims abstract description 25
- 239000011342 resin composition Substances 0.000 claims description 52
- 238000000059 patterning Methods 0.000 claims description 6
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- 238000005476 soldering Methods 0.000 claims 1
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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 6
- 238000004519 manufacturing process Methods 0.000 description 6
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- 238000009413 insulation Methods 0.000 description 4
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- 238000003854 Surface Print Methods 0.000 description 3
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- 238000004080 punching Methods 0.000 description 3
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- 239000002253 acid Substances 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 2
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- 230000001678 irradiating effect Effects 0.000 description 2
- 229910001507 metal halide Inorganic materials 0.000 description 2
- 150000005309 metal halides Chemical class 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 238000007639 printing Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- KCTAWXVAICEBSD-UHFFFAOYSA-N prop-2-enoyloxy prop-2-eneperoxoate Chemical compound C=CC(=O)OOOC(=O)C=C KCTAWXVAICEBSD-UHFFFAOYSA-N 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- WBODDOZXDKQEFS-UHFFFAOYSA-N 1,2,3,4-tetramethyl-5-phenylbenzene Chemical group CC1=C(C)C(C)=CC(C=2C=CC=CC=2)=C1C WBODDOZXDKQEFS-UHFFFAOYSA-N 0.000 description 1
- GJZFGDYLJLCGHT-UHFFFAOYSA-N 1,2-diethylthioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=C(CC)C(CC)=CC=C3SC2=C1 GJZFGDYLJLCGHT-UHFFFAOYSA-N 0.000 description 1
- 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 1
- RIAHASMJDOMQER-UHFFFAOYSA-N 5-ethyl-2-methyl-1h-imidazole Chemical compound CCC1=CN=C(C)N1 RIAHASMJDOMQER-UHFFFAOYSA-N 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- MPIAGWXWVAHQBB-UHFFFAOYSA-N [3-prop-2-enoyloxy-2-[[3-prop-2-enoyloxy-2,2-bis(prop-2-enoyloxymethyl)propoxy]methyl]-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(COC(=O)C=C)(COC(=O)C=C)COCC(COC(=O)C=C)(COC(=O)C=C)COC(=O)C=C MPIAGWXWVAHQBB-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000004841 bisphenol A epoxy resin Substances 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000013039 cover film Substances 0.000 description 1
- 229930003836 cresol Natural products 0.000 description 1
- -1 diazonaphthoquinone compound Chemical class 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 238000003384 imaging method Methods 0.000 description 1
- 229920003986 novolac Polymers 0.000 description 1
- 239000004843 novolac epoxy resin Substances 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 230000000644 propagated effect Effects 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 230000007261 regionalization Effects 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 239000001488 sodium phosphate Substances 0.000 description 1
- 229910000162 sodium phosphate Inorganic materials 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
Images
Classifications
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/03—Use of materials for the substrate
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/22—Secondary treatment of printed circuits
- H05K3/28—Applying non-metallic protective coatings
Landscapes
- Engineering & Computer Science (AREA)
- Non-Metallic Protective Coatings For Printed Circuits (AREA)
- Materials For Photolithography (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Manufacturing & Machinery (AREA)
- Architecture (AREA)
- Structural Engineering (AREA)
Abstract
Description
本発明は、感光性樹脂構造体並びにそれを用いたドライフィルム及びフレキシブルプリント配線板に関し、詳しくは、フレキシブルプリント配線板上において微細なパターン形成が可能な感光性樹脂構造体、及びその硬化物を保護膜、例えば、カバーレイまたはソルダーレジストとして有するフレキシブルプリント配線板に関する。 The present invention relates to a photosensitive resin structure, a dry film using the same, and a flexible printed wiring board, and more specifically, a photosensitive resin structure capable of forming a fine pattern on a flexible printed wiring board, and a cured product thereof. The present invention relates to a flexible printed wiring board having a protective film, for example, a coverlay or a solder resist.
従来、フレキシブルプリント配線板の保護膜として、ポリイミドなどのフィルムに熱硬化型接着剤を塗布してなる非感光性樹脂構造体が用いられてきた。かかる非感光性樹脂構造体をパターン加工してフレキシブルプリント配線板上に形成する方法としては、従来、パンチングによる孔空け加工後、フレキシブルプリント配線板上に熱圧着する手法がとられてきた。あるいは、溶剤可溶性の熱硬化型樹脂組成物をフレキシブルプリント配線板上に直接パターン印刷し、熱硬化してパターンを形成する手法もとられてきた。特に、ポリイミドフィルムは、柔軟性を有しつつ、耐熱性、機械的特性、電気的特性に優れていることからフレキシブルプリント配線板に対する好適材料として使用されてきた（例えば、特許文献１参照）。 Conventionally, a non-photosensitive resin structure obtained by applying a thermosetting adhesive to a film such as polyimide has been used as a protective film for a flexible printed wiring board. As a method for forming such a non-photosensitive resin structure on a flexible printed wiring board by patterning, conventionally, a method of thermocompression bonding on the flexible printed wiring board after punching by punching has been used. Alternatively, a method has been used in which a solvent-soluble thermosetting resin composition is directly pattern-printed on a flexible printed wiring board and thermally cured to form a pattern. In particular, a polyimide film has been used as a suitable material for a flexible printed wiring board because it has flexibility and is excellent in heat resistance, mechanical properties, and electrical properties (see, for example, Patent Document 1).
しかしながら、上述の従来の手法ではパターン端部が塗布時や熱圧着時の樹脂の滲み出しによって形状が崩れるため、配線の微細化やフレキシブルプリント配線板に搭載されるチップ部品の小型化などで要求される微細パターンの形成は困難であった。 However, in the conventional method described above, the shape of the pattern edge part collapses due to resin oozing at the time of application or thermocompression bonding, so it is required for miniaturization of wiring and miniaturization of chip parts mounted on flexible printed wiring boards. It was difficult to form a fine pattern.
一方、微細加工が可能な回路永久保護膜として知られている感光性ソルダーレジストをフレキシブルプリント配線板のカバーレイとして適用することも考えられる。しかしながら、フレキシブルプリント配線板における感光性ソルダーレジストは柔軟性を付与するために低架橋密度化やエラストマー成分の添加が必要となり、これにより電気信頼性や屈曲性が低下し、これらの信頼性が熱硬化型保護膜に比べて劣ることになる。
そこで本発明の目的は、フレキシブルプリント配線板上において微細なパターン形成が可能で、絶縁性、屈曲性に優れる感光性樹脂構造体、及びその硬化物を保護膜、例えば、カバーレイまたはソルダーレジストとして有するフレキシブルプリント配線板を提供することにある。
On the other hand, it is also conceivable to apply a photosensitive solder resist known as a circuit permanent protective film capable of fine processing as a coverlay of a flexible printed wiring board. However, photosensitive solder resists in flexible printed wiring boards require low crosslink density and addition of elastomer components to give flexibility, which reduces electrical reliability and flexibility, and these reliability is It is inferior to the curable protective film.
Therefore, an object of the present invention is to form a photosensitive resin structure that is capable of forming a fine pattern on a flexible printed wiring board and is excellent in insulation and flexibility, and a cured product thereof as a protective film, for example, a coverlay or a solder resist. It is in providing the flexible printed wiring board which has.
本発明者らは、前記課題を解決するために鋭意検討した結果、フレキシブルプリント配線板の保護膜が、複数の現像性樹脂層を積層した感光性樹脂構造体から得られる構成とすることにより前記目的を達成し得ることを見出し、本発明を完成するに至った。 As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that the protective film of the flexible printed wiring board is obtained from a photosensitive resin structure in which a plurality of developable resin layers are laminated. The inventors have found that the object can be achieved and have completed the present invention.
すなわち、本発明の感光性樹脂構造体は、現像性接着層（Ａ）と、該現像性接着層（Ａ）を介してフレキシブルプリント配線板に積層される現像性保護層（Ｂ）と、を有する感光性樹脂構造体であって、少なくとも前記現像性保護層（Ｂ）は、光照射によりパターニングが可能であり、かつ、前記現像性接着層（Ａ）と前記現像性保護層（Ｂ）は、現像によりパターンを一括して形成することが可能であることを特徴とするものである。 That is, the photosensitive resin structure of the present invention comprises a developable adhesive layer (A) and a developable protective layer (B) laminated on the flexible printed wiring board via the developable adhesive layer (A). A photosensitive resin structure having at least the developable protective layer (B) can be patterned by light irradiation, and the developable adhesive layer (A) and the developable protective layer (B) are The pattern can be collectively formed by development.
特に、前記現像性接着層（Ａ）と前記現像性保護層（Ｂ）が共に、光照射によりパターニングが可能であることが好ましい。 In particular, it is preferable that both the developable adhesive layer (A) and the developable protective layer (B) can be patterned by light irradiation.
また、本発明の感光性樹脂構造体においては、前記現像性接着層（Ａ）が、前記現像性保護層（Ｂ）よりも厚いことが好ましい。 Moreover, in the photosensitive resin structure of this invention, it is preferable that the said developable contact bonding layer (A) is thicker than the said developable protective layer (B).
さらに、本発明の感光性樹脂構造体は、フレキシブルプリント配線板の屈曲部及び非屈曲部のうちの少なくともいずれか一方に用いることができ、また、フレキシブルプリント配線板のカバーレイ及びソルダーレジストのうちの少なくともいずれか一方を形成するために用いることができる。 Furthermore, the photosensitive resin structure of the present invention can be used for at least one of a bent portion and a non-bent portion of the flexible printed wiring board, and among the cover lay and the solder resist of the flexible printed wiring board. Can be used to form at least one of the following.
本発明のドライフィルムは、前記感光性樹脂構造体の少なくとも片面が、フィルムで支持又は保護されていることを特徴とするものである。 The dry film of the present invention is characterized in that at least one surface of the photosensitive resin structure is supported or protected by a film.
また、本発明のフレキシブルプリント配線板は、フレキシブルプリント配線板上に形成された前記感光性樹脂構造体を光照射によりパターニングし、現像によりパターンを一括して形成してなる保護膜を有することを特徴とするものである。 In addition, the flexible printed wiring board of the present invention has a protective film formed by patterning the photosensitive resin structure formed on the flexible printed wiring board by light irradiation and forming the pattern collectively by development. It is a feature.
好ましくは、前記現像性接着層（Ａ）は、フレキシブルプリント配線板上に、感光性又は非感光性の樹脂組成物（Ａ１）を塗布して形成される。 Preferably, the developable adhesive layer (A) is formed by applying a photosensitive or non-photosensitive resin composition (A1) on a flexible printed wiring board.
本発明によれば、フレキシブルプリント配線板上において微細なパターン形成が可能で、絶縁性、屈曲性に優れる感光性樹脂構造体、及びその硬化物を保護膜、例えば、カバーレイおよびソルダーレジストとして有するプリント配線板を提供することができる。 According to the present invention, it is possible to form a fine pattern on a flexible printed wiring board, and have a photosensitive resin structure excellent in insulation and flexibility, and a cured product thereof as a protective film, for example, a coverlay and a solder resist. A printed wiring board can be provided.
以下、本発明の実施の形態について、詳細に説明する。
（感光性樹脂構造体）
本発明の感光性樹脂構造体は、フレキシブルプリント配線板上に積層可能で、かつ、フレキシブルプリント配線板上で光照射によりパターニングが可能であり、現像によりパターンを一括して形成することが可能なものである。ここで、パターンは、パターン状の硬化物、すなわち、保護膜を意味する。
従来、パンチング加工されたカバーレイに接着剤を塗布した後、フレキシブルプリント配線板上にカバーレイを圧着していたが、本発明では、フレキシブルプリント配線板上に現像性接着層（Ａ）と現像性保護層（Ｂ）を積層した後、光照射及び現像により一括してパターンを形成することが可能である。
Hereinafter, embodiments of the present invention will be described in detail.
(Photosensitive resin structure)
The photosensitive resin structure of the present invention can be laminated on a flexible printed wiring board, and can be patterned by light irradiation on the flexible printed wiring board, and a pattern can be collectively formed by development. Is. Here, the pattern means a patterned cured product, that is, a protective film.
Conventionally, after an adhesive is applied to a punched coverlay, the coverlay is pressure-bonded on the flexible printed wiring board. In the present invention, the developing adhesive layer (A) and the development are applied on the flexible printed wiring board. After laminating the protective layer (B), it is possible to form a pattern all at once by light irradiation and development.
図１に、本発明の一実施の形態に係る感光性樹脂構造体を示す。
図示する構造体１は、フレキシブル基板２に銅回路３が形成されたフレキシブルプリント配線板上に、現像性接着層（Ａ）と現像性保護層（Ｂ）とを順に有し、少なくとも現像性保護層（Ｂ）が光照射によりパターニングが可能であり、かつ、現像性接着層（Ａ）と現像性保護層（Ｂ）とが現像によりパターンを一括形成することが可能なものである。ここで、パターニングとは、光照射された部分が、現像不可能状態から現像可能状態に変化すること（ポジ型）、又は、現像可能状態から現像不可能状態に変化すること（ネガ型）を言う。また、パターンの形成とは、光照射部分が現像されて未照射部分がパターン状に残ること（ポジ型）、又は、未照射部分が現像されて光照射部分がパターン状に残ること（ネガ型）を言う。
FIG. 1 shows a photosensitive resin structure according to an embodiment of the present invention.
The structure 1 shown in the figure has a developable adhesive layer (A) and a developable protective layer (B) in this order on a flexible printed wiring board in which a
特に、本発明の感光性樹脂構造体の現像性接着層（Ａ）と現像性保護層（Ｂ）とが共に光照射によりパターニングが可能である場合、微細なパターンを形成できるため好ましい。 In particular, when both the developable adhesive layer (A) and the developable protective layer (B) of the photosensitive resin structure of the present invention can be patterned by light irradiation, it is preferable because a fine pattern can be formed.
現像性接着層（Ａ）は、感光性または非感光性の樹脂組成物（Ａ１）により形成され、現像性保護層（Ｂ）は、樹脂組成物（Ａ１）と異なる感光性樹脂組成物（Ｂ１）により形成されている。
感光性又は非感光性の樹脂組成物（Ａ１）は、主に、保護膜に屈曲性を付与し得る材料から適宜選定される。微細なパターンの形成のためには、樹脂組成物（Ａ１）は感光性であることが好ましい。
一方、感光性樹脂組成物（Ｂ１）は、主に、絶縁性を付与し得る材料から適宜選定される。
The developable adhesive layer (A) is formed of a photosensitive or non-photosensitive resin composition (A1), and the developable protective layer (B) is a photosensitive resin composition (B1) different from the resin composition (A1). ).
The photosensitive or non-photosensitive resin composition (A1) is appropriately selected mainly from materials that can impart flexibility to the protective film. In order to form a fine pattern, the resin composition (A1) is preferably photosensitive.
On the other hand, the photosensitive resin composition (B1) is appropriately selected mainly from materials that can impart insulating properties.
本発明においては、現像性接着層（Ａ）は、保護膜の銅回路への追従性と屈曲性の観点より現像性保護層（Ｂ）よりも厚い方が好ましい。また、本発明の感光性樹脂構造体は、フレキシブルプリント配線板の屈曲部及び非屈曲部のうちの少なくともいずれか一方に用いることができ、具体的には、フレキシブルプリント配線板のカバーレイ及びソルダーレジストのうちの少なくともいずれか一方を形成するために用いることができる。非屈曲部としては、チップ実装部などが挙げられる。 In the present invention, the developing adhesive layer (A) is preferably thicker than the developing protective layer (B) from the viewpoint of followability of the protective film to the copper circuit and flexibility. The photosensitive resin structure of the present invention can be used for at least one of a bent portion and a non-bent portion of a flexible printed wiring board. Specifically, the cover lay and the solder of the flexible printed wiring board are used. It can be used to form at least one of the resists. Examples of the non-bent part include a chip mounting part.
現像方法としては、アルカリ水溶液を用いる現像（以下、アルカリ現像ともいう。）でも有機溶剤を用いる現像でもよいが、アルカリ現像が好ましい。
現像性接着層（Ａ）及び現像性保護層（Ｂ）に用いることができる感光性樹脂組成物（Ａ１）及び（Ｂ１）は、ポジ型でもネガ型でもよい。
ポジ型感光性組成物としては、光照射前後の極性変化により、光照射部（露光部ともいう。）が現像液により溶解するものであれば、公知慣用のものを用いることができる。例えば、ジアゾナフトキノン化合物とアルカリ可溶性樹脂を含有する組成物が挙げられる。
The development method may be development using an aqueous alkali solution (hereinafter also referred to as alkali development) or development using an organic solvent, but alkali development is preferred.
The photosensitive resin compositions (A1) and (B1) that can be used for the developable adhesive layer (A) and the developable protective layer (B) may be positive or negative.
As the positive photosensitive composition, a publicly known and conventional one can be used as long as the light irradiation part (also referred to as an exposure part) is dissolved by the developer due to the change in polarity before and after the light irradiation. For example, a composition containing a diazonaphthoquinone compound and an alkali-soluble resin can be mentioned.
ネガ型感光性組成物としては、光照射部が現像液に対して、難溶となるものであれば公知慣用のものを利用できる。例えば、光酸発生剤とアルカリ可溶性樹脂を含有する組成物、光塩基発生剤とアルカリ可溶性樹脂を含有する組成物、光重合開始剤とアルカリ可溶性樹脂を含有する組成物などが挙げられる。 As the negative photosensitive composition, a publicly known and conventional one can be used as long as the light irradiation part is hardly soluble in the developer. Examples thereof include a composition containing a photoacid generator and an alkali-soluble resin, a composition containing a photobase generator and an alkali-soluble resin, and a composition containing a photopolymerization initiator and an alkali-soluble resin.
感光性樹脂組成物（Ａ１）と（Ｂ１）の組み合わせとしては、ポジ型感光性樹脂組成物（Ａ１）とポジ型感光性樹脂組成物（Ｂ１）、ネガ型感光性樹脂組成物（Ａ１）とネガ型感光性樹脂組成物（Ｂ１）の組み合わせであればいずれでもよい。
例えば、光塩基発生剤を含有する組成物（Ａ１）と光塩基発生剤を含有する組成物（Ｂ１）、
光塩基発生剤を含有する組成物（Ａ１）と光重合開始剤を含有する組成物（Ｂ１）、
光重合開始剤を含有する組成物（Ａ１）と光塩基発生剤を含有する組成物（Ｂ１）、
光重合開始剤を含有する組成物（Ａ１）と光重合開始剤を含有する組成物（Ｂ１）、
の組合せ等が挙げられ、組み合わせは、実施形態に応じて選択できる。
As a combination of the photosensitive resin compositions (A1) and (B1), the positive photosensitive resin composition (A1), the positive photosensitive resin composition (B1), and the negative photosensitive resin composition (A1) Any combination of negative photosensitive resin composition (B1) may be used.
For example, a composition (A1) containing a photobase generator and a composition (B1) containing a photobase generator,
A composition (A1) containing a photobase generator and a composition (B1) containing a photopolymerization initiator,
A composition (A1) containing a photopolymerization initiator and a composition (B1) containing a photobase generator,
A composition (A1) containing a photopolymerization initiator and a composition (B1) containing a photopolymerization initiator,
The combination can be selected according to the embodiment.
本発明の感光性樹脂構造体は、フレキシブルプリント配線板の用途であるため、硬化時のゆがみ、反りを小さくすることができるものが好ましい。従って、上記光塩基発生剤を含有する組成物が好ましく、そのような組成物としては、例えば、光塩基発生剤と熱硬化性樹脂を含有し、付加反応により硬化する組成物も含まれる。 Since the photosensitive resin structure of the present invention is an application of a flexible printed wiring board, it is preferable to be able to reduce distortion and warpage during curing. Accordingly, a composition containing the photobase generator is preferred, and examples of such a composition include a composition containing a photobase generator and a thermosetting resin and cured by an addition reaction.
また、感光性樹脂組成物（Ａ１）及び感光性樹脂組成物（Ｂ１）のいずれか一方のみが、光酸発生剤、光塩基発生剤、又は光重合開始剤を有し、他方が、光酸発生剤、光塩基発生剤、及び光重合開始剤のいずれも含有しない構成でもよい。この場合、一方の感光性樹脂組成物に含まれる光酸発生剤、光塩基発生剤、又は光重合開始剤が、他方の感光性樹脂組成物を硬化すればよい。 Further, only one of the photosensitive resin composition (A1) and the photosensitive resin composition (B1) has a photoacid generator, a photobase generator, or a photopolymerization initiator, and the other has a photoacid generator. The structure which does not contain any of a generator, a photobase generator, and a photoinitiator may be sufficient. In this case, the photoacid generator, photobase generator, or photopolymerization initiator contained in one photosensitive resin composition may cure the other photosensitive resin composition.
また、本発明では、非感光性樹脂組成物（Ａ１）とポジ型感光性樹脂組成物（Ｂ１）との組み合わせでもよく、非感光性樹脂組成物（Ａ１）とネガ型感光性樹脂組成物（Ｂ１）との組み合わせでもよい。また、ポジ型感光性樹脂組成物（Ａ１）と非感光性樹脂組成物（Ｂ１）との組み合わせでもよく、ネガ型感光性樹脂組成物（Ａ１）と非感光性樹脂組成物（Ｂ１）との組み合わせでもよい。非感光性樹脂組成物（Ａ１）としては、熱硬化性樹脂を含有する組成物が挙げられる。 Moreover, in this invention, the combination of a non-photosensitive resin composition (A1) and a positive photosensitive resin composition (B1) may be sufficient, and a non-photosensitive resin composition (A1) and a negative photosensitive resin composition ( A combination with B1) may also be used. Moreover, the combination of positive photosensitive resin composition (A1) and non-photosensitive resin composition (B1) may be sufficient, and negative photosensitive resin composition (A1) and non-photosensitive resin composition (B1) A combination may be used. Examples of the non-photosensitive resin composition (A1) include a composition containing a thermosetting resin.
本発明の積層構造体の全膜厚は、１００μｍ以下が好ましく、４〜８０μｍの範囲がより好ましい。例えば積層構造体が２層である場合、現像性接着層（Ａ）は、例えば、３〜６０μｍであるがこれに限られない。このような厚みとすることにより、現像性接着層（Ａ）が回路に隙間なく密着できる。一方、現像性保護層（Ｂ）は、例えば、１〜２０μｍの厚さとすればよい。 The total film thickness of the laminated structure of the present invention is preferably 100 μm or less, and more preferably in the range of 4 to 80 μm. For example, when the laminated structure has two layers, the developable adhesive layer (A) is, for example, 3 to 60 μm, but is not limited thereto. By setting it as such thickness, a developable contact bonding layer (A) can closely_contact | adhere to a circuit without a gap. On the other hand, the developable protective layer (B) may have a thickness of 1 to 20 μm, for example.
図２は、図１に示すフレキシブルプリント配線板上の感光性樹脂構造体１を光照射した後、アルカリ現像液にて現像処理を施してパターン形成した状態を示す断面である。 FIG. 2 is a cross-sectional view showing a state in which a pattern is formed by irradiating the photosensitive resin structure 1 on the flexible printed wiring board shown in FIG.
（ドライフィルム）
本発明のドライフィルムは、前記感光性樹脂構造体の少なくとも片面が、フィルムで支持又は保護されている。
(Dry film)
In the dry film of the present invention, at least one surface of the photosensitive resin structure is supported or protected by the film.
ドライフィルムの製造は、例えば、感光性樹脂組成物（Ｂ１）を有機溶剤で希釈して適切な粘度に調整し、コンマコーター等でキャリアフィルム上に均一な厚さに塗布する。その塗布層を乾燥し、キャリアフィルム上に現像性保護層（Ｂ）を形成する。同様にして、該現像性保護層（Ｂ）上に、感光性又は非感光性の樹脂組成物（Ａ１）により現像性接着層（Ａ）を形成し、本発明のドライフィルムを得ることができる。
キャリアフィルムとしては、プラスチックフィルムが用いられる。キャリアフィルムの厚さについては特に制限はないが、一般に、１０〜１５０μｍの範囲で適宜選択される。 キャリアフィルム上に感光性樹脂構造体を形成した後、さらに、感光性樹脂構造体の表面に剥離可能なカバーフィルムを積層してもよい。
For production of the dry film, for example, the photosensitive resin composition (B1) is diluted with an organic solvent to adjust to an appropriate viscosity, and is applied to the carrier film with a uniform thickness using a comma coater or the like. The coating layer is dried to form a developable protective layer (B) on the carrier film. Similarly, a developable adhesive layer (A) can be formed on the developable protective layer (B) with a photosensitive or non-photosensitive resin composition (A1) to obtain the dry film of the present invention. .
A plastic film is used as the carrier film. Although there is no restriction | limiting in particular about the thickness of a carrier film, Generally, it selects suitably in the range of 10-150 micrometers. After forming the photosensitive resin structure on the carrier film, a peelable cover film may be further laminated on the surface of the photosensitive resin structure.
（フレキシブルプリント配線板）
本発明のフレキシブルプリント配線板は、本発明の感光性樹脂構造体をフレキシブルプリント配線板上で光照射によりパターニングし、現像液にて一括してパターンを形成してなる保護膜を有する。保護膜は、カバーレイ及びソルダーレジストのうちの少なくともいずれか一方であることが好ましい。
＜感光性樹脂構造体の製造方法＞
フレキシブルプリント配線板上に、現像性接着層（Ａ）と現像性保護層（Ｂ）を形成する方法としては、本発明のドライフィルムを用いるラミネート法でも、樹脂組成物（Ａ１）、（Ｂ１）をそのまま使用する塗布法でもよい。ラミネート法では、ラミネーター等により現像性接着層（Ａ）が、フレキシブルプリント配線板の屈曲部及び非屈曲部のうちの少なくともいずれか一方と接触するようにフレキシブルプリント配線板上にドライフィルムを貼り合わせる。
(Flexible printed wiring board)
The flexible printed wiring board of the present invention has a protective film formed by patterning the photosensitive resin structure of the present invention on the flexible printed wiring board by light irradiation and forming the pattern in a lump with a developer. The protective film is preferably at least one of a coverlay and a solder resist.
<Method for producing photosensitive resin structure>
As a method of forming the developable adhesive layer (A) and the developable protective layer (B) on the flexible printed wiring board, the resin compositions (A1) and (B1) can be formed by the laminating method using the dry film of the present invention. The coating method may be used as it is. In the laminating method, a dry film is pasted onto the flexible printed wiring board by a laminator or the like so that the developable adhesive layer (A) is in contact with at least one of the bent portion and the non-bent portion of the flexible printed wiring board. .
塗布法としては、スクリーン印刷などにより、フレキシブルプリント配線板上に感光性又は非感光性の樹脂組成物（Ａ１）と感光性樹脂組成物（Ｂ１）をそれぞれ順に塗布及び乾燥して現像性接着層（Ａ）と現像性保護層（Ｂ）を形成する。 As a coating method, a photosensitive adhesive composition or a non-photosensitive resin composition (A1) and a photosensitive resin composition (B1) are sequentially applied and dried on a flexible printed wiring board by screen printing or the like, and then a developing adhesive layer. (A) and a developable protective layer (B) are formed.
なお、フレキシブルプリント配線板に樹脂組成物（Ａ１）を塗布、乾燥して現像性接着層（Ａ）を形成し、その現像性接着層（Ａ）上に、感光性樹脂組成物（Ｂ１）からなるフィルムをラミネートして現像性保護層（Ｂ）を形成する方法でもよい。
逆に、樹脂組成物（Ａ１）からなるフィルムをフレキシブルプリント配線板にラミネートすることにより現像性接着層（Ａ）を形成し、その現像性接着層（Ａ）上に、感光性樹脂組成物（Ｂ１）を塗布、乾燥することにより現像性保護層（Ｂ）を形成してもよい。
The resin composition (A1) is applied to a flexible printed wiring board and dried to form a developable adhesive layer (A). On the developable adhesive layer (A), the photosensitive resin composition (B1) is used. The film which laminates may be formed and the method of forming a developable protective layer (B) may be used.
Conversely, a developable adhesive layer (A) is formed by laminating a film made of the resin composition (A1) on a flexible printed wiring board, and a photosensitive resin composition (A) is formed on the developable adhesive layer (A). The developable protective layer (B) may be formed by applying and drying B1).
＜光重合開始剤を含有するネガ型感光性樹脂構造体を用いたフレキシブルプリント配線板の製造方法＞
光重合開始剤を含有するネガ型積層樹脂構造体の場合、樹脂組成物（Ａ１）及び樹脂組成物（Ｂ１）のうちの少なくともいずれか一方が光重合開始剤を含有していればよい。
この場合、フレキシブルプリント配線板上に上記ラミネート法などにより、現像性接着層（Ａ）及び現像性保護層（Ｂ）を有する感光性樹脂構造体を形成する。その後、接触式又は非接触方式により、ネガ型感光性樹脂構造体に対して、パターン状に光を照射し、未照射部を現像して、ネガ型のパターンの保護膜を得る。さらに熱硬化性成分を含有している組成物の場合、例えば約１４０〜１８０℃の温度に加熱して熱硬化させることにより、耐熱性、耐薬品性、耐吸湿性、密着性、電気特性などの諸特性に優れた保護膜を形成することができる。
ネガ型感光性樹脂構造体が光重合開始剤を含有するため、ラジカル重合により光照射部が硬化する。
<The manufacturing method of the flexible printed wiring board using the negative photosensitive resin structure containing a photoinitiator>
In the case of a negative laminated resin structure containing a photopolymerization initiator, it suffices that at least one of the resin composition (A1) and the resin composition (B1) contains a photopolymerization initiator.
In this case, a photosensitive resin structure having a developable adhesive layer (A) and a developable protective layer (B) is formed on the flexible printed wiring board by the laminating method or the like. Thereafter, the negative photosensitive resin structure is irradiated with light in a pattern by a contact method or a non-contact method, and an unirradiated portion is developed to obtain a protective film having a negative pattern. Further, in the case of a composition containing a thermosetting component, for example, by heating to a temperature of about 140 to 180 ° C. and thermosetting, heat resistance, chemical resistance, moisture absorption resistance, adhesion, electrical characteristics, etc. A protective film having excellent characteristics can be formed.
Since the negative photosensitive resin structure contains a photopolymerization initiator, the light irradiation part is cured by radical polymerization.
＜光塩基発生剤を含むネガ型感光性樹脂構造体を用いたフレキシブルプリント配線板の製造方法＞
光塩基発生剤を含有するネガ型積層樹脂構造体の場合も、樹脂組成物（Ａ１）及び樹脂組成物（Ｂ１）のうちの少なくともいずれか一方が光塩基発生剤を含有していればよい。この場合も、まずは、上記ラミネート方法等により、フレキシブルプリント配線板上に現像性接着層（Ａ）及び現像性保護層（Ｂ）を有するネガ型感光性樹脂構造体を形成する。その後、ネガ型感光性樹脂構造体に対して、パターン状に光を照射することにより、光塩基発生剤から塩基を発生させて光照射部を硬化する。その後、現像により未照射部を除去してネガ型のパターンの保護膜を得る。なお、光照射後、現像性接着層（Ａ）及び現像性保護層（Ｂ）を加熱することが好ましい。
光照射により、光照射部で塩基が発生し、その塩基により、光塩基発生剤が不安定化し、さらに塩基が発生すると考えられる。このように塩基が化学的に増殖することにより、光照射部が深部まで十分硬化する。
<The manufacturing method of the flexible printed wiring board using the negative photosensitive resin structure containing a photobase generator>
Also in the case of a negative laminated resin structure containing a photobase generator, at least one of the resin composition (A1) and the resin composition (B1) only needs to contain a photobase generator. Also in this case, first, a negative photosensitive resin structure having a developable adhesive layer (A) and a developable protective layer (B) is formed on the flexible printed wiring board by the laminating method or the like. Thereafter, the negative photosensitive resin structure is irradiated with light in a pattern, thereby generating a base from the photobase generator and curing the light irradiation portion. Thereafter, the unirradiated portion is removed by development to obtain a protective film having a negative pattern. In addition, it is preferable to heat a developable contact bonding layer (A) and a developable protective layer (B) after light irradiation.
It is considered that a base is generated in the light irradiation part by light irradiation, the photobase generator is destabilized by the base, and further a base is generated. In this way, the base is chemically propagated, so that the light irradiation part is sufficiently cured to the deep part.
なお、現像後に、さらに、保護膜の絶縁信頼性を向上させるために紫外線を照射してもよい。また、現像後に、さらに、熱硬化（ポストキュア）工程を含んでもよく、現像後に紫外線照射と熱硬化をともに行ってもよい。熱硬化工程における加熱温度は、例えば、１６０℃以上である。 Note that after the development, ultraviolet rays may be further irradiated to improve the insulation reliability of the protective film. Further, after development, a heat curing (post-cure) step may be further included, and both ultraviolet irradiation and heat curing may be performed after development. The heating temperature in the thermosetting process is, for example, 160 ° C. or higher.
＜光酸発生剤を含有するネガ型感光性樹脂構造体を用いたフレキシブルプリント配線板の製造方法＞
光酸発生剤を含有するネガ型積層樹脂構造体の場合も、樹脂組成物（Ａ１）及び樹脂組成物（Ｂ１）のうちの少なくともいずれか一方が光酸発生剤を含有していればよい。この場合も、光塩基発生剤を含有する場合と同様に、上記ラミネート法等により、フレキシブルプリント配線板上に現像性接着層（Ａ）及び現像性保護層（Ｂ）を有するネガ型感光性樹脂構造体を形成する。その後、ネガ型感光性樹脂構造体に対して、パターン状に光を照射することにより、光酸発生剤から酸を発生させて、光照射部を硬化する。その後、上記同様の現像方法より、ネガ型のパターンの保護膜を得る。
<The manufacturing method of the flexible printed wiring board using the negative photosensitive resin structure containing a photo-acid generator>
Also in the case of a negative laminated resin structure containing a photoacid generator, it suffices that at least one of the resin composition (A1) and the resin composition (B1) contains a photoacid generator. In this case, as in the case of containing a photobase generator, a negative photosensitive resin having a developable adhesive layer (A) and a developable protective layer (B) on the flexible printed wiring board by the laminating method or the like. Form a structure. Thereafter, the negative photosensitive resin structure is irradiated with light in a pattern, thereby generating an acid from the photoacid generator and curing the light irradiation portion. Thereafter, a protective film having a negative pattern is obtained by the same developing method as described above.
＜ポジ型感光性樹脂構造体を用いたフレキシブルプリント配線板の製造方法＞
ポジ型積層樹脂構造体の場合も、樹脂組成物（Ａ１）及び樹脂組成物（Ｂ１）のうちの少なくともいずれか一方がポジ型組成物であればよい。この場合も、上記ラミネート法等により、フレキシブルプリント配線板上に現像性接着層（Ａ）及び現像性保護層（Ｂ）を有するポジ型感光性樹脂構造体を形成する。
そして、ポジ型感光性樹脂構造体に、パターン状に光を照射することにより、極性を変化させる。その後、光照射部を現像して、ポジ型のパターンの保護膜を得る。
<Method for producing flexible printed wiring board using positive photosensitive resin structure>
Also in the case of a positive type laminated resin structure, at least one of the resin composition (A1) and the resin composition (B1) may be a positive type composition. Also in this case, a positive photosensitive resin structure having a developable adhesive layer (A) and a developable protective layer (B) is formed on the flexible printed wiring board by the laminating method or the like.
Then, the polarity is changed by irradiating the positive photosensitive resin structure with light in a pattern. Thereafter, the light irradiation part is developed to obtain a protective film having a positive pattern.
上記光照射に用いられる露光機としては、高圧水銀灯ランプ、超高圧水銀灯ランプ、メタルハライドランプ、水銀ショートアークランプ等を搭載し、３５０〜４５０ｎｍの範囲で紫外線を照射する装置であればよく、さらに、直接描画装置（例えばコンピューターからのＣＡＤデータにより直接レーザーで画像を描くレーザーダイレクトイメージング装置）も用いることができる。
直描機のレーザー光源としては、最大波長が３５０〜４５０ｎｍの範囲にあるレーザー光を用いていればガスレーザー、固体レーザーどちらでもよい。画像形成のための露光量は膜厚等によって異なるが、一般には２０〜１５００ｍＪ／ｃｍ２の範囲内とすることができる。
As an exposure machine used for the light irradiation, a high-pressure mercury lamp lamp, an ultra-high pressure mercury lamp lamp, a metal halide lamp, a mercury short arc lamp, etc. are mounted, and any apparatus that irradiates ultraviolet rays in the range of 350 to 450 nm may be used. A direct drawing apparatus (for example, a laser direct imaging apparatus that directly draws an image with a laser using CAD data from a computer) can also be used.
As a laser light source of the direct drawing machine, either a gas laser or a solid laser may be used as long as laser light having a maximum wavelength in the range of 350 to 450 nm is used. The exposure amount for image formation varies depending on the film thickness and the like, but can generally be within a range of 20 to 1500 mJ / cm 2 .
前記現像方法としては、ディッピング法、シャワー法、スプレー法、ブラシ法等によることができ、現像液としては、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。 The developing method can be a dipping method, a shower method, a spray method, a brush method or the like, and as a developer, potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, sodium silicate, Alkaline aqueous solutions such as ammonia and amines can be used.
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はない。なお、「ｕｍ」は、マイクロメートルを意味する。 EXAMPLES The present invention will be specifically described below with reference to examples and comparative examples, but the present invention is not limited to the following examples. “Um” means micrometer.
（実施例１，２、比較例１，２）
下記表１に示す種々の成分を同表１に示す割合（質量部）にて配合し、攪拌機にて予備混合した後、３本ロールミルで混練し、感光性樹脂組成物を調製した。
(Examples 1 and 2, Comparative Examples 1 and 2)
Various components shown in Table 1 below were blended in the proportions (parts by mass) shown in Table 1, premixed with a stirrer, and then kneaded with a three-roll mill to prepare a photosensitive resin composition.
＊２：ジペンタエリスリトール ヘキサアクリレート（日本化薬社製）
＊３：ビスフェノールＡ型ノボラックエポキシ樹脂（ＤＩＣ社製）
＊４：テトラメチルビフェニル型エポキシ樹脂(三菱化学社製)
＊５：アミノアルキルフェノン光重合開始剤（ＢＡＳＦジャパン社製）
＊６：ジエチルチオキサントン増感剤（日本化薬社製）
＊７：硫酸バリウム（堺化学工業社製）
＊８：ポリイミドフィルム（東レ・デュポン社製）
＊９：カルボキシル基含有ビスフェノールＦ型エポキシアクリレート（日本化薬社製）
＊１０：トリメチロールプロパンＥＯ変性トリアクリレート(東亞合成社製)
＊１１：ビスフェノールＡ型エポキシ樹脂(分子量：１６００）(三菱化学社製)
＊１２：ビスフェノールＡ型エポキシ樹脂(分子量：９００）(三菱化学社製)
＊１３：ビスフェノールＡ型エポキシ樹脂(分子量：５００）(三菱化学社製)
＊１４：エチルメチルイミダゾール（四国化成工業社製）
* 2: Dipentaerythritol hexaacrylate (Nippon Kayaku Co., Ltd.)
* 3: Bisphenol A type novolac epoxy resin (DIC)
* 4: Tetramethylbiphenyl type epoxy resin (Mitsubishi Chemical Corporation)
* 5: Aminoalkylphenone photopolymerization initiator (BASF Japan)
* 6: Diethylthioxanthone sensitizer (Nippon Kayaku Co., Ltd.)
* 7: Barium sulfate (manufactured by Sakai Chemical Industry Co., Ltd.)
* 8: Polyimide film (Toray DuPont)
* 9: Carboxyl group-containing bisphenol F type epoxy acrylate (manufactured by Nippon Kayaku Co., Ltd.)
* 10: Trimethylolpropane EO-modified triacrylate (manufactured by Toagosei Co., Ltd.)
* 11: Bisphenol A epoxy resin (molecular weight: 1600) (Mitsubishi Chemical Corporation)
* 12: Bisphenol A type epoxy resin (molecular weight: 900) (Mitsubishi Chemical Corporation)
* 13: Bisphenol A type epoxy resin (molecular weight: 500) (Mitsubishi Chemical Corporation)
* 14: Ethylmethylimidazole (manufactured by Shikoku Chemicals)
（実施例１）
実施例１についてはラミネート法を用いた。実施例１では、キャリアフィルムにＢ層用の感光性樹脂組成物を塗布、乾燥して、現像性保護層を形成した後、その表面に、Ａ層用の感光性樹脂組成物を塗布、乾燥してドライフィルムを得た。そのドライフィルムを１２０℃でフレキシブルプリント配線板に圧着して、感光性樹脂構造体を形成した。膜厚を表１に示す。
（実施例２）
実施例２については全面印刷法を用い、Ａ層用の感光性樹脂組成物をフレキシブルプリント配線板上に塗布、乾燥した後、その表面にＢ層用の感光性樹脂組成物を塗布、乾燥し、感光性樹脂構造体を形成した。各膜厚を表１に示す。
（比較例１）
比較例１については全面印刷法を用い、Ｂ層用の感光性樹脂組成物をフレキシブルプリント配線板上に塗布、乾燥して、Ｂ層のみのフレキシブルプリント配線板を得た。膜厚を表１に示す。
（比較例２）
比較例２については全面印刷法を用い、Ａ層用の感光性樹脂組成物をフレキシブルプリント配線板上に塗布、乾燥して、Ａ層のみのフレキシブルプリント配線板を得た。膜厚を表１に示す。
（比較例３）
比較例３についてはラミネート法を用いた。比較例３では、パンチング加工により、５ｍｍ×５ｍｍの開口パターンを形成したポリイミドフィルムに、Ａ層用の樹脂を塗布、乾燥した後、１２０℃でフレキシブルプリント配線板に圧着した。これにより、パターンを有するフレキシブルプリント配線板を得た。その膜厚を表１に示す。
（比較例４）
比較例４ではパターン印刷法を用い、Ｂ層用の樹脂を開口５ｍｍ×５ｍｍのパターン印刷によりフレキシブルプリント配線板上に塗布、乾燥し、Ｂ層のみのパターンを有するフレキシブルプリント配線板を得た。膜厚を表１に示す。
Example 1
For Example 1, the laminating method was used. In Example 1, the photosensitive resin composition for layer B was applied to a carrier film and dried to form a developable protective layer, and then the photosensitive resin composition for layer A was applied to the surface and dried. A dry film was obtained. The dry film was pressure-bonded to a flexible printed wiring board at 120 ° C. to form a photosensitive resin structure. Table 1 shows the film thickness.
(Example 2)
About Example 2, the whole surface printing method was used, and after applying and drying the photosensitive resin composition for A layer on a flexible printed wiring board, the photosensitive resin composition for B layer was apply | coated and dried on the surface. A photosensitive resin structure was formed. Each film thickness is shown in Table 1.
(Comparative Example 1)
About the comparative example 1, the whole surface printing method was used, the photosensitive resin composition for B layers was apply | coated and dried on the flexible printed wiring board, and the flexible printed wiring board only of B layer was obtained. Table 1 shows the film thickness.
(Comparative Example 2)
For Comparative Example 2, the entire surface printing method was used, and the photosensitive resin composition for the A layer was applied onto the flexible printed wiring board and dried to obtain a flexible printed wiring board having only the A layer. Table 1 shows the film thickness.
(Comparative Example 3)
For Comparative Example 3, the laminating method was used. In Comparative Example 3, a layer A resin was applied to a polyimide film having a 5 mm × 5 mm opening pattern formed by punching, dried, and then pressure-bonded to a flexible printed wiring board at 120 ° C. Thereby, the flexible printed wiring board which has a pattern was obtained. The film thickness is shown in Table 1.
(Comparative Example 4)
In Comparative Example 4, a pattern printing method was used, and a B-layer resin was applied onto a flexible printed wiring board by pattern printing with an opening of 5 mm × 5 mm and dried to obtain a flexible printed wiring board having a pattern of only the B layer. Table 1 shows the film thickness.
＜アルカリ現像性試験＞
実施例１，２及び比較例１，２の感光性樹脂構造体については、メタルハライドランプ搭載の露光装置（HMW-680−GW20）を用いてネガマスクを介して露光量５００mJ/cm２で光照射し、現像（３０℃、０．２ＭＰａ、１質量％炭酸ナトリウム水溶液）を行い、アルカリ現像の可否を調べた。
<Alkali developability test>
The photosensitive resin structures of Examples 1 and 2 and Comparative Examples 1 and 2 were irradiated with light at an exposure amount of 500 mJ / cm 2 through a negative mask using an exposure apparatus (HMW-680-GW20) equipped with a metal halide lamp. Then, development (30 ° C., 0.2 MPa, 1 mass% sodium carbonate aqueous solution) was carried out to examine whether alkali development was possible.
＜屈曲性試験＞
実施例１，２の感光性樹脂構造体及び比較例１，２の樹脂層については、上記アルカリ現像性試験と同様に、光照射及び現像により、開口部（５×５ｍｍ）を有するパターンを形成した。
実施例１，２及び比較例１〜４のパターンを有するフレキシブルプリント配線板を、１８０°折り曲げた。割れが発生しない場合を良好とし、割れが発生しなかった場合を不良とした。
<Flexibility test>
For the photosensitive resin structures of Examples 1 and 2 and the resin layers of Comparative Examples 1 and 2, a pattern having an opening (5 × 5 mm) was formed by light irradiation and development as in the alkali developability test. did.
The flexible printed wiring boards having the patterns of Examples 1 and 2 and Comparative Examples 1 to 4 were bent 180 °. The case where no crack occurred was considered good, and the case where no crack occurred was regarded as defective.
＜電気特性試験＞
クシ型電極（ライン／スペース＝１００ｕｍ／１００ｕｍ）が形成されたフレキシブルプリント配線板に、上記アルカリ現像性試験と同様に、光照射及び現像により、実施例１、２及び比較例１〜４のパターンを形成し、評価基板を作成した。この評価基板を、１３０℃、湿度８５％の雰囲気下の高温高湿槽に入れ、電圧５０Ｖを荷電し、１０００時間、槽内ＨＡＳＴ試験を行った。ショートしなかった場合を良好とし、ショートした場合を不良とした。
<Electrical characteristics test>
Patterns of Examples 1 and 2 and Comparative Examples 1 to 4 were applied to a flexible printed wiring board on which comb-shaped electrodes (line / space = 100 μm / 100 μm) were formed by light irradiation and development in the same manner as the alkali developability test. To form an evaluation substrate. This evaluation board | substrate was put into the high-temperature, high-humidity tank of the atmosphere of 130 degreeC and humidity 85%, the voltage 50V was charged, and the in-chamber HAST test was done for 1000 hours. A case where no short circuit occurred was considered good, and a case where a short circuit occurred was regarded as defective.
＜開口部滲み試験＞
実施例１，２の感光性樹脂構造体及び比較例１，２の樹脂層については、上記アルカリ現像性試験と同様に、光照射及び現像により、開口部（５×５ｍｍ）を有するパターンを形成した。
実施例１，２及び比較例１〜４のパターンについて、開口部（５×５ｍｍ）内側への滲み出しの有無を評価した。前記各評価試験の結果を表２に示す。
<Opening bleeding test>
For the photosensitive resin structures of Examples 1 and 2 and the resin layers of Comparative Examples 1 and 2, a pattern having an opening (5 × 5 mm) was formed by light irradiation and development as in the alkali developability test. did.
About the pattern of Examples 1, 2 and Comparative Examples 1-4, the presence or absence of the oozing to an opening part (5x5 mm) inner side was evaluated. Table 2 shows the results of the evaluation tests.
上記表２に示す結果から、実施例１および２の感光性樹脂構造体は、フレキシブルプリント配線板上において現像による微細なパターンの形成が可能であることがわかった。また、実施例１，２の保護膜は、屈曲性及び電気絶縁性にも優れていることがわかった。
これに対し、比較例１の保護膜では、屈曲性が得られず、比較例２の保護膜では、絶縁性が不十分であった。一方、比較例３，４の保護膜は、いずれもフレキシブルプリント配線板上において、開口部への滲み出しが生じ、微細なパターンを形成するには適していないことが分かった。
From the results shown in Table 2 above, it was found that the photosensitive resin structures of Examples 1 and 2 can form a fine pattern by development on a flexible printed wiring board. Moreover, it turned out that the protective film of Example 1, 2 is excellent also in flexibility and electrical insulation.
On the other hand, the protective film of Comparative Example 1 did not provide flexibility, and the protective film of Comparative Example 2 had insufficient insulation. On the other hand, it was found that the protective films of Comparative Examples 3 and 4 were not suitable for forming a fine pattern because bleeding to the opening occurred on the flexible printed wiring board.
１ 感光性樹脂構造体
２ フレキシブル基材
３ 銅回路
Ａ 現像性接着層
Ｂ 現像性保護層
DESCRIPTION OF SYMBOLS 1 Photosensitive resin structure 2
Claims (8)
該現像性接着層（Ａ）を介してフレキシブルプリント配線板に積層される現像性保護層（Ｂ）と、を有する感光性樹脂構造体であって、
少なくとも前記現像性保護層（Ｂ）は、光照射によりパターニングが可能であり、かつ、前記現像性接着層（Ａ）と前記現像性保護層（Ｂ）は、現像によりパターンを一括して形成することが可能であることを特徴とする感光性樹脂構造体。 A developable adhesive layer (A);
A developable protective layer (B) laminated on the flexible printed wiring board via the developable adhesive layer (A), and a photosensitive resin structure comprising:
At least the developable protective layer (B) can be patterned by light irradiation, and the developable adhesive layer (A) and the developable protective layer (B) collectively form a pattern by development. A photosensitive resin structure characterized in that
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| JP2013087826A JP5847754B2 (en) | 2013-04-18 | 2013-04-18 | Photosensitive resin structure, dry film, and flexible printed wiring board |
| KR1020157028866A KR102229343B1 (en) | 2013-04-18 | 2014-04-17 | Laminate structure, flexible printed wiring board and method for manufacturing same |
| PCT/JP2014/060986 WO2014171525A1 (en) | 2013-04-18 | 2014-04-17 | Laminate structure, flexible printed wiring board and method for manufacturing same |
| CN201480021937.5A CN105164585B (en) | 2013-04-18 | 2014-04-17 | Laminated structure, flexible printed circuit board, and method for manufacturing same |
| TW103114237A TWI614571B (en) | 2013-04-18 | 2014-04-18 | Laminated structure, flexible printed wiring board and method of manufacturing same |
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| WO2017022547A1 (en) * | 2015-08-05 | 2017-02-09 | 太陽インキ製造株式会社 | Laminated structure, dry film and flexible printed wiring board |
| WO2023190811A1 (en) * | 2022-03-31 | 2023-10-05 | 株式会社レゾナック | Photosensitive multilayer resin film, printed wiring board, semiconductor package, and printed wiring board manufacturing method |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2017022547A1 (en) * | 2015-08-05 | 2017-02-09 | 太陽インキ製造株式会社 | Laminated structure, dry film and flexible printed wiring board |
| KR20180037219A (en) * | 2015-08-05 | 2018-04-11 | 다이요 잉키 세이조 가부시키가이샤 | A laminated structure, a dry film, and a flexible printed wiring board |
| JPWO2017022547A1 (en) * | 2015-08-05 | 2018-05-31 | 太陽インキ製造株式会社 | Laminated structure, dry film and flexible printed wiring board |
| KR102562958B1 (en) * | 2015-08-05 | 2023-08-04 | 다이요 홀딩스 가부시키가이샤 | Laminated structures, dry films and flexible printed wiring boards |
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| WO2023190811A1 (en) * | 2022-03-31 | 2023-10-05 | 株式会社レゾナック | Photosensitive multilayer resin film, printed wiring board, semiconductor package, and printed wiring board manufacturing method |
| WO2023188296A1 (en) * | 2022-03-31 | 2023-10-05 | 株式会社レゾナック | Photosensitive multilayer resin film, printed wiring board, semiconductor package and method for producing printed wiring board |
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