TWI743196B - Positive photosensitive resin composition, dry film, cured product, printed wiring board and semiconductor element - Google Patents

Positive photosensitive resin composition, dry film, cured product, printed wiring board and semiconductor element Download PDF

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TWI743196B
TWI743196B TW106131345A TW106131345A TWI743196B TW I743196 B TWI743196 B TW I743196B TW 106131345 A TW106131345 A TW 106131345A TW 106131345 A TW106131345 A TW 106131345A TW I743196 B TWI743196 B TW I743196B
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resin composition
photosensitive resin
silane coupling
positive photosensitive
coupling agent
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TW201827488A (en
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秋元真
許成強
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日商太陽控股股份有限公司
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    • 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
    • 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
    • G03F7/022—Quinonediazides
    • G03F7/023—Macromolecular quinonediazides; Macromolecular additives, e.g. binders
    • 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
    • G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
    • 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
    • G03F7/075—Silicon-containing compounds
    • 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
    • G03F7/16—Coating processes; Apparatus therefor
    • G03F7/168—Finishing the coated layer, e.g. drying, baking, soaking
    • 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
    • H05K1/0313—Organic insulating material
    • 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

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  • General Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Engineering & Computer Science (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials For Photolithography (AREA)
  • Non-Metallic Protective Coatings For Printed Circuits (AREA)

Abstract

提供殘膜率優良之正型感光性樹脂組成物、具有由該組成物所得到之樹脂層的乾膜、該組成物或該乾膜之樹脂層的硬化物、具有該硬化物之印刷配線板及具有該硬化物之半導體元件。一種正型感光性樹脂組成物等，其係含有(A)聚苯并噁唑前驅物、(B)光酸產生劑、(C)三聚氰胺系交聯劑及(D)矽烷偶合劑之正型感光性樹脂組成物，其特徵為前述(D)矽烷偶合劑，包含由具有芳基胺基之矽烷偶合劑及具有二個以上之三烷氧基矽烷基的矽烷偶合劑中選出之至少1種。Provides a positive photosensitive resin composition with an excellent residual film rate, a dry film having a resin layer obtained from the composition, a cured product of the composition or the resin layer of the dry film, and a printed wiring board having the cured product And a semiconductor device with the hardened product. A positive photosensitive resin composition, etc., which is a positive type containing (A) polybenzoxazole precursor, (B) photoacid generator, (C) melamine-based crosslinking agent, and (D) silane coupling agent A photosensitive resin composition characterized by the aforementioned (D) silane coupling agent comprising at least one selected from a silane coupling agent having an arylamine group and a silane coupling agent having two or more trialkoxysilyl groups .

Description

正型感光性樹脂組成物、乾膜、硬化物、印刷配線板及半導體元件Positive photosensitive resin composition, dry film, cured product, printed wiring board and semiconductor element

[0001] 本發明係關於正型感光性樹脂組成物、乾膜、硬化物、印刷配線板及半導體元件。[0001] The present invention relates to a positive photosensitive resin composition, a dry film, a cured product, a printed wiring board, and a semiconductor element.

[0002] 作為能夠以鹼水溶液顯像之正型感光性樹脂組成物，係使用摻合有聚苯并噁唑(PBO)前驅物與萘醌二疊氮化合物等之光酸產生劑的組成物。使如此之組成物熱硬化所得到的聚苯并噁唑硬化物，由於耐熱性及電絕緣性優良，故對於電材料之表面保護膜或層間絕緣膜，例如對於半導體元件之塗覆膜，或可撓印刷配線板材料、耐熱絕緣性層間材之應用係有所進展。 　　[0003] 為了使含有如上述之聚苯并噁唑前驅物的正型感光性樹脂組成物熱硬化，必須於高溫處理，但為了亦可使用於缺乏耐熱性的材料，又，由於環境面、成本面、安全面之要求，故要求減低處理溫度。作為如此的手段，以往已知有摻合交聯劑(例如專利文獻1、2)。 [先前技術文獻] [專利文獻] 　　[0004] 　　[專利文獻1]日本特開2009-265520號公報 　　[專利文獻2]日本特開2011-053458號公報[0002] As a positive photosensitive resin composition that can be developed with an aqueous alkali solution, a composition incorporating a photoacid generator such as a polybenzoxazole (PBO) precursor and a naphthoquinonediazide compound is used . The cured polybenzoxazole obtained by thermally curing such a composition is excellent in heat resistance and electrical insulation, so it is used for surface protection films or interlayer insulating films of electrical materials, such as coating films for semiconductor devices, or The application of flexible printed wiring board materials and heat-resistant insulating interlayer materials has progressed. [0003] In order to thermally harden the positive photosensitive resin composition containing the polybenzoxazole precursor as described above, it must be treated at a high temperature, but in order to also be used in materials that lack heat resistance, and due to environmental factors, Because of the cost and safety requirements, it is required to reduce the processing temperature. As such a means, it has been conventionally known to blend a crosslinking agent (for example, Patent Documents 1 and 2). [Prior Art Document] [Patent Document] 　　[0004] 　　[Patent Document 1] Japanese Patent Application Publication No. 2009-265520 　　[Patent Document 2] Japanese Patent Application Publication No. 2011-053458

[發明所欲解決之課題] 　　[0005] 但是，摻合交聯劑時，係有鹼顯像後之未曝光部的殘膜率降低的問題。 　　[0006] 因而本發明之目的，係提供殘膜率優良之正型感光性樹脂組成物、具有由該組成物所得到之樹脂層的乾膜、該組成物或該乾膜之樹脂層的硬化物、具有該硬化物之印刷配線板及具有該硬化物之半導體元件。 [用以解決課題之手段] 　　[0007] 本發明者等鑑於上述而戮力探討的結果，發現藉由使用特定之交聯劑與矽烷偶合劑，可解決上述課題，而完成本發明。 　　[0008] 亦即，本發明之正型感光性樹脂組成物，係含有(A)聚苯并噁唑前驅物、(B)光酸產生劑、(C)三聚氰胺系交聯劑及(D)矽烷偶合劑之正型感光性樹脂組成物，其特徵為前述(D)矽烷偶合劑，包含由具有芳基胺基之矽烷偶合劑及具有二個以上之三烷氧基矽烷基的矽烷偶合劑中選出之至少1種。 　　[0009] 本發明之正型感光性樹脂組成物，較佳為前述(D)矽烷偶合劑，包含具有芳基胺基之矽烷偶合劑。 　　[0010] 本發明之乾膜，其特徵為具有將前述感光性樹脂組成物塗佈於薄膜並乾燥而得到之樹脂層。 　　[0011] 本發明之硬化物，其特徵為使前述感光性樹脂組成物或前述乾膜之樹脂層硬化而得到。 　　[0012] 本發明之印刷配線板，其特徵為具有前述硬化物。 　　[0013] 本發明之半導體元件，其特徵為具有前述硬化物。 [發明之效果] 　　[0014] 依照本發明，可提供殘膜率優良之正型感光性樹脂組成物、具有由該組成物所得到之樹脂層的乾膜、該組成物或該乾膜之樹脂層的硬化物、具有該硬化物之印刷配線板及具有該硬化物之半導體元件。[Problem to be Solved by the Invention] 　　 [0005] However, when a crosslinking agent is blended, there is a problem that the residual film rate of the unexposed portion after alkali development decreases. [0006] Therefore, the object of the present invention is to provide a positive photosensitive resin composition having an excellent residual film rate, a dry film having a resin layer obtained from the composition, and curing of the composition or the resin layer of the dry film Object, a printed wiring board having the hardened object, and a semiconductor element having the hardened object. [Means for Solving the Problem] 　　[0007] In view of the above-mentioned results, the inventors have found that the above-mentioned problems can be solved by using a specific crosslinking agent and a silane coupling agent to complete the present invention. [0008] That is, the positive photosensitive resin composition of the present invention contains (A) a polybenzoxazole precursor, (B) a photoacid generator, (C) a melamine-based crosslinking agent, and (D) A positive photosensitive resin composition of a silane coupling agent, characterized in that the aforementioned (D) silane coupling agent comprises a silane coupling agent having an arylamine group and a silane coupling agent having two or more trialkoxysilyl groups At least one selected from among them.　　[0009] The positive photosensitive resin composition of the present invention is preferably the aforementioned (D) silane coupling agent, which includes a silane coupling agent having an arylamino group.　　[0010] The dry film of the present invention is characterized by having a resin layer obtained by applying the photosensitive resin composition to a film and drying it.　　[0011] The cured product of the present invention is characterized by being obtained by curing the photosensitive resin composition or the resin layer of the dry film.　　[0012] The printed wiring board of the present invention is characterized by having the aforementioned cured product.　　[0013] The semiconductor device of the present invention is characterized by having the aforementioned cured product. [Effects of the invention] 　　[0014] According to the present invention, it is possible to provide a positive photosensitive resin composition having an excellent residual film rate, a dry film having a resin layer obtained from the composition, the composition or the resin of the dry film The cured product of the layer, the printed wiring board with the cured product, and the semiconductor element with the cured product.

[0016] 以下，詳述本發明之正型感光性樹脂組成物所含有之成分。 　　[0017] [(A)聚苯并噁唑前驅物] 　　本發明之正型感光性樹脂組成物，含有(A)聚苯并噁唑前驅物。合成(A)聚苯并噁唑前驅物之方法並無特殊限定，以公知方法合成即可。例如，可使作為胺成分之二羥基二胺類與作為酸成分之二羧酸二氯化物等的二羧酸之二鹵化物反應而得到。 　　[0018] (A)聚苯并噁唑前驅物，較佳為具有下述重複構造之聚羥基醯胺酸。

Figure 02_image001
(式中，X表示4價有機基，Y表示2價有機基。n為1以上之整數、較佳為10~50、更佳為20~40)。 　　[0019] 以上述合成方法合成(A)聚苯并噁唑前驅物時，前述通式(1)中，X為前述二羥基二胺類之殘基，Y為前述二羧酸之殘基。 　　[0020] 前述二羥基二胺類，可列舉3,3’-二胺基-4,4’-二羥基聯苯、4,4’-二胺基-3,3’-二羥基聯苯、雙(3-胺基-4-羥基苯基)丙烷、雙(4-胺基-3-羥基苯基)丙烷、雙(3-胺基-4-羥基苯基)碸、雙(4-胺基-3-羥基苯基)碸、2,2-雙(3-胺基-4-羥基苯基)-1,1,1,3,3,3-六氟丙烷、2,2-雙(4-胺基-3-羥基苯基)-1,1,1,3,3,3-六氟丙烷等。其中尤以2,2-雙(3-胺基-4-羥基苯基)-1,1,1,3,3,3-六氟丙烷為佳。 　　[0021] 前述二羧酸可列舉間苯二甲酸、對苯二甲酸、5-tert-丁基間苯二甲酸、5-溴間苯二甲酸、5-氟間苯二甲酸、5-氯間苯二甲酸、2,6-萘二羧酸、4,4’-二羧基聯苯、4,4’-二羧基二苯基醚、4,4’-二羧基四苯基矽烷、雙(4-羧基苯基)碸、2,2-雙(p-羧基苯基)丙烷、2,2-雙(4-羧基苯基)-1,1,1,3,3,3-六氟丙烷等之具有芳香環之二羧酸；草酸、丙二酸、琥珀酸、1,2-環丁烷二羧酸、1,4-環己烷二羧酸、1,3-環戊烷二羧酸等之脂肪族系二羧酸。其中尤以4,4’-二羧基二苯基醚為佳。 　　[0022] 前述通式(1)中，X所表示之4價有機基係脂肪族基亦可芳香族基亦可，較佳為芳香族基，更佳為2個羥基與2個胺基係以鄰位而位於芳香環上。前述4價芳香族基之碳原子數，較佳為6~30、更佳為6~24。前述4價芳香族基之具體例子可列舉下述基，但不限定於此等，只要依用途選擇聚苯并噁唑前驅物中可含有的公知之芳香族基即可。 　　[0023]
Figure 02_image003
[0024] 前述4價芳香族基，於前述芳香族基當中，尤以下述基為佳。
Figure 02_image005
[0025] 前述通式(1)中，Y所表示之2價有機基係脂肪族基亦可芳香族基亦可，較佳為芳香族基，更佳為於芳香環上與前述通式(1)中之羰基鍵結。前述2價芳香族基之碳原子數，較佳為6~30、更佳為6~24。前述2價芳香族基之具體例子可列舉下述基，但不限定於此等，只要依用途來選擇聚苯并噁唑前驅物中所含有的公知之芳香族基即可。 　　[0026]
Figure 02_image007
(式中，A表示選自由單鍵、-CH2 -、-O-、-CO-、-S-、 -SO2 -、-NHCO-、-C(CF3 )2 -、-C(CH3 )2 -所成之群的2價基)。 　　[0027] 前述2價有機基，於前述芳香族基當中，尤以下述基為佳。
Figure 02_image009
[0028] (A)聚苯并噁唑前驅物，亦可含有2種以上之上述聚羥基醯胺酸的重複構造。又，亦可含有上述聚羥基醯胺酸的重複構造以外之構造，例如可含有聚醯胺酸之重複構造。 　　[0029] (A)聚苯并噁唑前驅物之數平均分子量(Mn)較佳為5,000~100,000、更佳為8,000~50,000。此處數平均分子量，係以(GPC)測定，以標準聚苯乙烯所換算之數值。又，(A)聚苯并噁唑前驅物之重量平均分子量(Mw)較佳為10,000~200,000、更佳為16,000~100,000。此處重量平均分子量，係以(GPC)測定，以標準聚苯乙烯所換算之數值。Mw/Mn較佳為1~5、更佳為1~3。 　　[0030] (A)聚苯并噁唑前驅物，可1種單獨使用、亦可組合2種以上使用。(A)聚苯并噁唑前驅物之摻合量，以組成物固體成分總量為基準較佳為60~90質量%。 　　[0031] [(B)光酸產生劑] 　　(B)光酸產生劑可列舉萘醌二疊氮化合物、二芳基鋶鹽、三芳基鋶鹽、二烷基苯甲醯甲基鋶鹽、二芳基錪鹽、芳基重氮鎓鹽、芳香族四羧酸酯、芳香族磺酸酯、硝基苄基酯、芳香族N-氧基醯亞胺磺酸酯、芳香族磺醯胺、苯醌重氮磺酸酯等。(B)光酸產生劑較佳為溶解抑制劑。其中尤以萘醌二疊氮化合物為佳。 　　[0032] 萘醌二疊氮化合物，具體而言例如可使用參(4-羥基苯基)-1-乙基-4-異丙基苯之萘醌二疊氮加成物(例如三寶化學研究所公司製之TS533、TS567、TS583、TS593)或四羥基二苯甲酮之萘醌二疊氮加成物(例如三寶化學研究所公司製之BS550、BS570、BS599)等。 　　[0033] (B)光酸產生劑可1種單獨使用、亦可組合2種以上使用。(B)光酸產生劑之摻合量，以組成物固體成分總量為基準，較佳為3~20質量%。 　　[0034] [(C)三聚氰胺系交聯劑] 　　(C)三聚氰胺系交聯劑，只要為具有三聚氰胺構造之交聯劑則無特殊限定，較佳為下述通式(2)表示之三聚氰胺系交聯劑。
Figure 02_image011
(式中，R21A 、R22A 、R23A 、R24A 、R25A 及R26A 較佳分別獨立地為碳數1~3之伸烷基。R21B 、R22B 、R23B 、R24B 、R25B 及R26B 較佳分別獨立地為氫原子或碳數1~3之烷基)。 　　[0035] 上述通式(2)中，R21A 、R22A 、R23A 、R24A 、R25A 及R26A 更佳分別為亞甲基。又，R21B 、R22B 、R23B 、R24B 、R25B 及R26B 更佳分別獨立地為甲基或氫原子。 　　[0036] (C)三聚氰胺系交聯劑可1種單獨使用、亦可組合2種以上使用。(C)三聚氰胺系交聯劑之摻合量，以組成物固體成分總量為基準，較佳為1~15質量%。若為1~15質量%，可提高未曝光部之殘膜率，且可防止曝光部之顯像殘留。 　　[0037] 本發明之正型感光性樹脂組成物，較佳含有(C)三聚氰胺系交聯劑以外之其他交聯劑，較佳為含有以下之交聯劑2、交聯劑5及交聯劑6的至少任一種。藉由含有(C)三聚氰胺系交聯劑，與交聯劑2、交聯劑5及交聯劑6的至少任一種，可得到溶解促進效果，顯像性成為良好。 　　[0038]
Figure 02_image013
Figure 02_image015
[0039] (C)三聚氰胺系交聯劑以外之其他交聯劑的摻合量，以組成物固體成分總量為基準，較佳為1~15質量%。特別地，交聯劑2、交聯劑5及交聯劑6之合計摻合量，以組成物固體成分總量為基準，較佳為1~15質量%。 　　[0040] [(D)矽烷偶合劑] 　　本發明之正型感光性樹脂組成物，(D)矽烷偶合劑，包含由具有芳基胺基之矽烷偶合劑及具有二個以上之三烷氧基矽烷基的矽烷偶合劑中選出之至少1種。 　　[0041] 前述芳基胺基之芳基，可列舉苯基、甲苯基、二甲苯基等之芳香族烴基；萘基、蒽基、菲基等之縮合多環芳香族基；噻吩基、吲哚基等之芳香族雜環基。 　　[0042] 前述具有芳基胺基之矽烷偶合劑，較佳為具有下述通式(3)表示之基的化合物。
Figure 02_image017
(式中，R31 ~R35 係分別獨立地表示氫原子或有機基)。 　　[0043] 前述通式(3)中，R31 ~R35 較佳為氫原子。 　　[0044] 前述具有芳基胺基之矽烷偶合劑，較佳為矽原子與芳基胺基，以碳數1~10之有機基，較佳為以碳數1~10之伸烷基鍵結。 　　[0045] 前述具有芳基胺基之矽烷偶合劑之具體例子較佳為下述化合物。
Figure 02_image019
[0046] 前述具有二個以上之三烷氧基矽烷基的矽烷偶合劑所具有之三烷氧基矽烷基可各自相同亦可相異，又，此等基所具有之烷氧基可各自相同亦可相異。烷氧基可列舉甲氧基、乙氧基、丙氧基、丁氧基等，其中尤以甲氧基、乙氧基為佳。 　　[0047] 前述具有二個以上之三烷氧基矽烷基的矽烷偶合劑，較佳為至少二個矽原子，係以碳數1~10之有機基，較佳係以碳數1~10之伸烷基鍵結。 　　[0048] 前述具有二個以上之三烷氧基矽烷基的矽烷偶合劑之具體例子較佳為下述化合物。
Figure 02_image021
[0049] (D)矽烷偶合劑，由於解像性優良，較佳為具有芳基胺基之矽烷偶合劑。 　　[0050] (D)矽烷偶合劑可1種單獨使用、亦可組合2種以上使用。(D)矽烷偶合劑之摻合量，以組成物固體成分總量為基準，較佳為1~15質量%。若為1~15質量%，可防止曝光部之顯像殘留。 　　[0051] 本發明之正型感光性樹脂組成物，於不損及本發明之效果的範圍內，亦可含有其他矽烷偶合劑。 　　[0052] 以下說明可摻合於本發明之正型感光性樹脂組成物中的其他成分。 　　[0053] (t-丁基兒茶酚) 　　本發明之正型感光性樹脂組成物，較佳為含有t-丁基兒茶酚。藉由含有t-丁基兒茶酚，顯像殘渣(浮渣)少，顯像性優良。 　　[0054] t-丁基兒茶酚之摻合量，以組成物固體成分總量為基準，較佳為0.1~2質量%。 　　[0055] 本發明之正型感光性樹脂組成物中可摻合溶劑。溶劑只要係會溶解(A)聚苯并噁唑前驅物、(B)光酸產生劑、(C)三聚氰胺系交聯劑、(D)矽烷偶合劑及其他添加劑者則無特殊限定。可列舉N,N’-二甲基甲醯胺、N-甲基吡咯啶酮、N-乙基-2-吡咯啶酮、N,N’-二甲基乙醯胺、二乙二醇二甲基醚、環戊酮、γ-丁內酯、α-乙醯基-γ-丁內酯、四甲基尿素、1,3-二甲基-2-咪唑啉酮(1,3-dimethyl-2-imidazolinone)、N-環己基-2-吡咯啶酮、二甲基亞碸、六甲基磷醯胺、吡啶、γ-丁內酯、二乙二醇單甲基醚作為一例。此等可單獨使用、亦可混合二種以上使用。所使用的溶劑之量，可依塗佈膜厚或黏度，相對於(A)聚苯并噁唑前驅物100質量份而言，以50~9000質量份之範圍使用。 　　[0056] 本發明之正型感光性樹脂組成物中，為了進一步提高光感度，亦可摻合公知之增感劑。 　　[0057] 又，本發明之正型感光性樹脂組成物中，為了提高與基材之接著性，亦可添加公知之接著助劑。 　　[0058] 為了對本發明之正型感光性樹脂組成物賦予加工特性或各種功能性，其他亦可摻合各種有機或無機之低分子或高分子化合物。例如可使用界面活性劑、調平劑、可塑劑、微粒子等。微粒子係包含聚苯乙烯、聚四氟乙烯等之有機微粒子；膠體二氧化矽、碳、層狀矽酸鹽等之無機微粒子。又，本發明之正型感光性樹脂組成物中亦可摻合各種著色劑及纖維等。 　　[0059] [乾膜] 　　本發明之乾膜，具有將本發明之正型感光性樹脂組成物塗佈後乾燥所得到之樹脂層。本發明之乾膜，係將樹脂層以鄰接於基材的方式層合來使用。 　　[0060] 可藉由刮刀塗佈器、唇模塗佈器、缺角輪塗佈器、薄膜塗佈器等之適當方法均勻塗佈本發明之正型感光性樹脂組成物於載體膜上並乾燥，形成前述樹脂層，較佳為於其上層合覆蓋膜藉以製造本發明之乾膜。覆蓋膜與載體膜可為相同之薄膜材料、亦可使用不同的薄膜。 　　[0061] 本發明之乾膜中，載體膜及覆蓋膜之薄膜材料，可使用作為乾膜所使用者而為人所知的任意物。 　　[0062] 就載體膜而言例如可使用2~150μm之厚度的聚對苯二甲酸乙二酯等之聚酯薄膜等之熱可塑性薄膜。 　　[0063] 就覆蓋膜而言，可使用聚乙烯薄膜、聚丙烯薄膜等，但與樹脂層之接著力小於載體膜者為佳。 　　[0064] 本發明之乾膜上的樹脂層之膜厚，較佳為100μm以下、更佳為5~50μm之範圍。 　　[0065] 使用本發明之正型感光性樹脂組成物，其硬化物之圖型膜，例如係如下述般製造。 　　[0066] 首先，步驟1，係將正型感光性樹脂組成物於基材上塗佈、乾燥，或者將樹脂層由乾膜轉印至基材上藉以得到塗膜。將正型感光性樹脂組成物塗佈於基材上之方法，可使用自以往起使用於感光性樹脂組成物之塗佈的方法，例如以旋轉塗佈器、棒塗佈器、刮刀塗佈器、淋幕塗佈器、網版印刷機等塗佈之方法；以噴霧塗佈器進行噴霧塗佈之方法；進而噴墨法等。塗膜之乾燥方法，可使用以風乾、烘箱或加熱板進行的加熱乾燥、真空乾燥等之方法。又，塗膜之乾燥，較期望於不會引起感光性樹脂組成物中之(A)聚苯并噁唑前驅物的閉環之條件下進行。具體而言，能夠以70~140℃、1~30分鐘的條件來進行自然乾燥、送風乾燥或者加熱乾燥。較佳為於加熱板上進行1~20分鐘乾燥。又，亦可進行真空乾燥，此時可於室溫下20分鐘~1小時之條件進行。 　　[0067] 基材並無特殊限制，可廣為應用矽晶圓等之半導體基材、配線基板、各種樹脂、金屬等。 　　[0068] 接著，步驟2，將上述塗膜透過具有圖型之光罩或者直接進行曝光。曝光光線係使用使(B)光酸產生劑活性化，而可產生酸之波長者。具體而言，曝光光線，較佳為最大波長350~410nm之範圍者。如上所述，適當使用增感劑時，可調整光感度。曝光裝置可使用接觸對準器(contact aligner)、鏡投射、步進器、雷射直接曝光裝置等。 　　[0069] 接著，可加熱，將未曝光部之(A)聚苯并噁唑前驅物的一部分閉環，作為步驟3。此處，閉環率為30%左右。加熱時間及加熱溫度，係依(A)聚苯并噁唑前驅物、塗佈膜厚、(B)光酸產生劑之種類而適當變更。 　　[0070] 接著，步驟4，將塗膜以顯像液處理。藉此，可將塗膜中之曝光部分去除，形成本發明之正型感光性樹脂組成物的圖型膜。 　　[0071] 顯像所使用之方法，可由以往已知之光阻的顯像方法，例如旋轉噴霧法、槳式法、伴隨超音波處理之浸漬法等當中選擇任意之方法。顯像液可列舉氫氧化鈉、碳酸鈉、矽酸鈉、氨水等之無機鹼類；乙胺、二乙胺、三乙胺、三乙醇胺等之有機胺類；氫氧化四甲基銨、氫氧化四丁基銨等之四級銨鹽類等之水溶液。又，亦可依需要，於此等中添加適當量之甲醇、乙醇、異丙醇等之水溶性有機溶劑或界面活性劑。之後，依需要以潤洗液洗淨塗膜而得到圖型膜。潤洗液可單獨或組合使用蒸餾水、甲醇、乙醇、異丙基醇等。又，亦可使用上述溶劑作為顯像液。 　　[0072] 之後，步驟5，將圖型膜加熱而得到硬化塗膜(硬化物)。此時，只要使(A)聚苯并噁唑前驅物閉環，而得到聚苯并噁唑即可。加熱溫度係適當設定為可硬化聚苯并噁唑之圖型膜。例如，於惰性氣體中，於150~350℃進行5~120分鐘左右的加熱。加熱溫度之更佳範圍係200~300℃。加熱係藉由使用例如加熱板、烘箱、可設定溫度程式之昇溫式烘箱來進行。此時之環境(氣體)可使用空氣，亦可使用氮、氬等之惰性氣體。 　　[0073] 本發明之正型感光性樹脂組成物之用途並無特殊限定，例如可列舉印刷油墨、接著劑、填充劑、電子材料、光電路零件、成形材料、阻劑材料、建築材料、3維造形、光學構件等使用樹脂材料之公知的各種領域/製品等。特別是可適合使用作為以聚苯并噁唑膜之耐熱性、尺寸安定性、絕緣性等之特性為有效的廣泛領域/製品，例如塗料或印刷油墨，或彩色濾光片、可撓顯示器用薄膜、半導體元件之被覆膜、電子零件、層間絕緣膜、防焊油墨等之印刷配線板之被覆膜、光電路、光電路零件、抗反射膜、全像術、光學構件或建築材料之形成材料。 　　[0074] 特別地，本發明之正型感光性樹脂組成物，主要作為圖型形成材料(阻劑)使用，藉此所形成之圖型膜，係作為由聚苯并噁唑所構成的永久膜，而發揮作為賦予耐熱性或絕緣性之成分的功能，適於形成例如彩色濾光片、可撓顯示器用薄膜、電子零件、半導體元件之被覆膜、層間絕緣膜、防焊油墨或覆蓋膜等之印刷配線板之被覆膜、焊壩(solder dam)、光電路、光電路零件、抗反射膜、其他光學構件或電子構件。 [實施例] 　　[0075] 以下，使用實施例更詳細說明本發明，但本發明不受下述實施例限定。再者，以下，記載為「份」及「%」者，只要無特別指明，均為質量基準。 　　[0076] (聚苯并噁唑(PBO)前驅物之合成) 　　於具備攪拌機、溫度計之0.5公升燒瓶中給入N-甲基吡咯啶酮212g，將雙(3-胺基-4-羥基醯胺苯基)六氟丙烷28.00g(76.5mmol)予以攪拌溶解。之後，將燒瓶浸於冰浴中，將燒瓶內保持於0~5℃，並且將4,4-二苯基醚二羧酸氯化物25.00g(83.2mmol)以固體形態每次5g地添加30分鐘，於冰浴中攪拌30分鐘。之後，於室溫繼續攪拌5小時。將經攪拌之溶液投入1L之離子交換水(比電阻值18.2MΩ･cm)中，回收析出物。之後，將所得之固體溶解於丙酮420mL，投入1L之離子交換水中。回收析出之固體後，減壓乾燥而得到具有羧基末端之下述重複構造的聚苯并噁唑(PBO)前驅物A1。聚苯并噁唑前驅物A1之數平均分子量(Mn)為12,900、重量平均分子量(Mw)為29,300、Mw/Mn為2.28。 　　[0077]
Figure 02_image023
[0078] (實施例1、2、比較例1~11) 　　對於上述合成之苯并噁唑前驅物100質量份，摻合重氮萘醌(DNQ)10質量份與下述表1記載之交聯劑5質量份、矽烷偶合劑5質量份後，添加N-甲基吡咯啶酮(NMP)使苯并噁唑前驅物成為30質量%，作為塗漆，使用旋轉塗佈器塗佈於矽基板上。以加熱板於120℃乾燥3分鐘，得到感光性樹脂組成物之乾燥塗膜。對所得之乾燥塗膜，使用高壓水銀燈，透過刻有圖型的遮罩照射200mJ/cm2 之泛光燈(broad light)。曝光後以2.38%氫氧化四甲基銨(TMAH)水溶液顯像60秒，以水潤洗，得到正型圖型膜。 　　[0079] 再者，下述表1中，三聚氰胺系交聯劑係使用交聯劑1(三和化學品公司製NIKALAC MW390)。又，具有芳基胺基之矽烷偶合劑及具有二個以上之三烷氧基矽烷基的矽烷偶合劑，係分別使用偶合劑1(信越聚矽氧公司製KBM-573)及2(信越聚矽氧公司製KBM-3066)。 　　[0080] (未曝光部殘膜率之評估) 　　於顯像後之圖型膜測定膜厚，藉由取與顯像前之膜厚的比，分別求得未曝光部殘膜率，以下述基準評估。 　　○：未曝光部殘膜率為75%以上 　　×：未曝光部殘膜率未達75% 　　[0081] (解像度之評估) 　　以電子顯微鏡(SEM“JSM-6010”)觀察顯像後之圖型膜，以無浮渣地可將曝光部圖型化之最少圖型的大小作為解像度(L(μm)/S(μm))。 　　[0082]
Figure 02_image025
[0083]
Figure 02_image027
Figure 02_image029
[0084]
Figure 02_image031
Figure 02_image033
[0085] 由表1所示結果，可知含有前述特定之交聯劑與矽烷偶合劑的本發明之正型感光性樹脂組成物，殘膜率優良。 　　[0086] (實施例3~6) 　　對於上述合成之苯并噁唑前驅物100質量份，摻合重氮萘醌(DNQ)10質量份與下述表2記載之各交聯劑5質量份、矽烷偶合劑5質量份、t-丁基兒茶酚0.5質量份後，添加N-甲基吡咯啶酮(NMP)使苯并噁唑前驅物成為30質量%，作為塗漆，使用旋轉塗佈器塗佈於矽基板上。以加熱板於120℃乾燥3分鐘，得到感光性樹脂組成物之乾燥塗膜。對所得之乾燥塗膜，使用高壓水銀燈，透過刻有圖型的遮罩照射200mJ/cm2 之泛光燈。曝光後以2.38%氫氧化四甲基銨(TMAH)水溶液顯像60秒，以水潤洗，得到正型圖型膜。 　　[0087] 再者，下述表2中，三聚氰胺系交聯劑係使用上述交聯劑1(三和化學品公司製NIKALAC MW390)。又，具有芳基胺基之矽烷偶合劑係使用上述偶合劑1(信越聚矽氧公司製KBM-573)。三聚氰胺系交聯劑以外之其他交聯劑係使用上述交聯劑2、5及6。 　　[0088] 下述表2中，以與上述相同之方法評估未曝光部殘膜率及解像度。 　　[0089] (浮渣之確認方法) 　　確認顯像後圖型之截面影像，以無圖型拖尾，整齊地無浮渣者為〇、以雖有圖型拖尾但可顯像至矽基板面者為△、以殘留有浮渣者為×。又，〇、△、×之評估例分別示於圖1~3。 　　[0090] 對於表1中之實施例1的感光性樹脂組成物亦同樣地進行評估，與實施例3~6一起將結果示於表2。 　　[0091]
Figure 02_image035
[0092] 　　t-丁基兒茶酚
Figure 02_image037
[0093] (實施例7、8、比較例12~25) 　　對於上述合成之苯并噁唑前驅物100質量份，摻合重氮萘醌(DNQ)10質量份與下述表3記載之交聯劑5質量份、矽烷偶合劑5質量份、t-丁基兒茶酚0.5質量份後，添加N-甲基吡咯啶酮(NMP)使苯并噁唑前驅物成為30質量%，作為塗漆，使用旋轉塗佈器塗佈於矽基板上。以加熱板於120℃乾燥3分鐘，得到感光性樹脂組成物之乾燥塗膜。對所得之乾燥塗膜，使用高壓水銀燈，透過刻有圖型的遮罩照射200mJ/cm2 之泛光燈。曝光後以2.38%氫氧化四甲基銨(TMAH)水溶液顯像60秒，以水潤洗，得到正型圖型膜。 　　[0094] 再者，下述表3中，三聚氰胺系交聯劑係使用上述交聯劑1(三和化學品公司製NIKALAC MW390)。又，具有芳基胺基之矽烷偶合劑及具有二個以上之三烷氧基矽烷基的矽烷偶合劑係分別使用上述偶合劑1(信越聚矽氧公司製KBM-573)及2(信越聚矽氧公司製KBM-3066)。 　　[0095] 下述表3中，以與上述相同之方法評估未曝光部殘膜率、解像度及浮渣。 　　[0096]
Figure 02_image039
[0097]
Figure 02_image041
Figure 02_image043
[0098] 由表2、3所示之結果，亦可知含有前述之特定交聯劑與矽烷偶合劑的本發明之正型感光性樹脂組成物，殘膜率優良。又，可知藉由於本發明之正型感光性樹脂組成物中摻合t-丁基兒茶酚，而顯像殘渣少，顯像性更優良。進一步地，可知藉由於本發明之正型感光性樹脂組成物中摻合其他交聯劑，顯像性更優良。[0016] Hereinafter, the components contained in the positive photosensitive resin composition of the present invention will be described in detail. [0017] [(A) Polybenzoxazole precursor] The positive photosensitive resin composition of the present invention contains (A) a polybenzoxazole precursor. The method for synthesizing the polybenzoxazole precursor (A) is not particularly limited, and it can be synthesized by a known method. For example, it can be obtained by reacting dihydroxydiamines as an amine component with dicarboxylic acid dihalides such as dicarboxylic acid dichloride as an acid component. [0018] (A) The polybenzoxazole precursor is preferably a polyhydroxyalamic acid having the following repeating structure.
Figure 02_image001
(In the formula, X represents a tetravalent organic group, and Y represents a divalent organic group. n is an integer of 1 or more, preferably 10 to 50, more preferably 20 to 40). [0019] When the (A) polybenzoxazole precursor is synthesized by the above-mentioned synthesis method, in the aforementioned general formula (1), X is the residue of the aforementioned dihydroxydiamine, and Y is the residue of the aforementioned dicarboxylic acid. [0020] The aforementioned dihydroxydiamines include 3,3'-diamino-4,4'-dihydroxybiphenyl, 4,4'-diamino-3,3'-dihydroxybiphenyl, Bis(3-amino-4-hydroxyphenyl)propane, bis(4-amino-3-hydroxyphenyl)propane, bis(3-amino-4-hydroxyphenyl) bis(4-amine) 3-hydroxyphenyl) sulfide, 2,2-bis(3-amino-4-hydroxyphenyl)-1,1,1,3,3,3-hexafluoropropane, 2,2-bis( 4-amino-3-hydroxyphenyl)-1,1,1,3,3,3-hexafluoropropane and the like. Among them, 2,2-bis(3-amino-4-hydroxyphenyl)-1,1,1,3,3,3-hexafluoropropane is particularly preferred. [0021] The aforementioned dicarboxylic acids include isophthalic acid, terephthalic acid, 5-tert-butyl isophthalic acid, 5-bromoisophthalic acid, 5-fluoroisophthalic acid, 5-chloroisophthalic acid, Phthalic acid, 2,6-naphthalenedicarboxylic acid, 4,4'-dicarboxybiphenyl, 4,4'-dicarboxydiphenyl ether, 4,4'-dicarboxytetraphenylsilane, bis(4 -Carboxyphenyl) sulfide, 2,2-bis(p-carboxyphenyl)propane, 2,2-bis(4-carboxyphenyl)-1,1,1,3,3,3-hexafluoropropane, etc. The dicarboxylic acid with aromatic ring; oxalic acid, malonic acid, succinic acid, 1,2-cyclobutane dicarboxylic acid, 1,4-cyclohexane dicarboxylic acid, 1,3-cyclopentane dicarboxylic acid The aliphatic dicarboxylic acid and so on. Among them, 4,4'-dicarboxydiphenyl ether is particularly preferred. [0022] In the aforementioned general formula (1), the tetravalent organic aliphatic group represented by X may also be an aromatic group, preferably an aromatic group, more preferably 2 hydroxyl groups and 2 amino groups. It is located on the aromatic ring in the ortho position. The number of carbon atoms of the aforementioned tetravalent aromatic group is preferably 6-30, more preferably 6-24. Specific examples of the aforementioned tetravalent aromatic group include the following groups, but are not limited to these groups, as long as the known aromatic group that can be contained in the polybenzoxazole precursor is selected according to the application. [0023]
Figure 02_image003
[0024] Among the aforementioned tetravalent aromatic groups, among the aforementioned aromatic groups, the following groups are particularly preferred.
Figure 02_image005
[0025] In the aforementioned general formula (1), the divalent organic aliphatic group represented by Y may also be an aromatic group, preferably an aromatic group, and more preferably on the aromatic ring and the aforementioned general formula ( 1) The carbonyl group is bonded. The number of carbon atoms of the aforementioned divalent aromatic group is preferably 6-30, more preferably 6-24. Specific examples of the aforementioned divalent aromatic group include the following groups, but are not limited to these groups, as long as the known aromatic group contained in the polybenzoxazole precursor is selected according to the application. [0026]
Figure 02_image007
(In the formula, A represents a single bond, -CH 2 -, -O-, -CO-, -S-, -SO 2 -, -NHCO-, -C(CF 3 ) 2 -, -C(CH 3 ) 2 -The divalent base of the group formed). [0027] Among the aforementioned divalent organic groups, among the aforementioned aromatic groups, the following groups are particularly preferred.
Figure 02_image009
[0028] (A) The polybenzoxazole precursor may also contain two or more repetitive structures of the above-mentioned polyhydroxy amide acid. In addition, structures other than the repeating structure of the above-mentioned polyhydroxyamic acid may be included, for example, the repeating structure of polyhydroxyamic acid may be included. [0029] (A) The number average molecular weight (Mn) of the polybenzoxazole precursor is preferably 5,000 to 100,000, more preferably 8,000 to 50,000. The number average molecular weight here is a value measured by (GPC) and converted to standard polystyrene. In addition, the weight average molecular weight (Mw) of the (A) polybenzoxazole precursor is preferably 10,000 to 200,000, more preferably 16,000 to 100,000. Here, the weight average molecular weight is measured by (GPC), and is a value converted from standard polystyrene. Mw/Mn is preferably 1-5, more preferably 1-3. [0030] (A) The polybenzoxazole precursor can be used alone or in combination of two or more. (A) The blending amount of the polybenzoxazole precursor is preferably 60 to 90% by mass based on the total solid content of the composition. [(B) Photoacid generator] (B) Photoacid generators include naphthoquinonediazide compounds, diarylsulfonates, triarylsulfonates, dialkylbenzylmethylsulfonates, Diaryl iodonium salt, aryl diazonium salt, aromatic tetracarboxylic acid ester, aromatic sulfonic acid ester, nitrobenzyl ester, aromatic N-oxylimidate sulfonate, aromatic sulfonamide , Benzoquinone diazosulfonate, etc. (B) The photoacid generator is preferably a dissolution inhibitor. Among them, naphthoquinone diazide compounds are particularly preferred. [0032] The naphthoquinone diazide compound, specifically, for example, the naphthoquinone diazide adduct of (4-hydroxyphenyl)-1-ethyl-4-isopropylbenzene (for example, Sambo Chemical Research TS533, TS567, TS583, TS593 manufactured by the company or naphthoquinone diazide adduct of tetrahydroxybenzophenone (for example BS550, BS570, BS599 manufactured by Sanbao Chemical Research Institute), etc. [0033] (B) The photoacid generator may be used singly or in combination of two or more kinds. (B) The blending amount of the photoacid generator is preferably 3-20% by mass based on the total solid content of the composition. [(C) Melamine-based crosslinking agent] (C) The melamine-based crosslinking agent is not particularly limited as long as it is a crosslinking agent having a melamine structure, and is preferably a melamine-based crosslinking agent represented by the following general formula (2) Crosslinking agent.
Figure 02_image011
(In the formula, R 21A , R 22A , R 23A , R 24A , R 25A and R 26A are each independently an alkylene having 1 to 3 carbon atoms. R 21B , R 22B , R 23B , R 24B , R Preferably, 25B and R 26B are each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms). [0035] In the above general formula (2), R 21A , R 22A , R 23A , R 24A , R 25A and R 26A are more preferably methylene groups. Furthermore, R 21B , R 22B , R 23B , R 24B , R 25B and R 26B are more preferably each independently a methyl group or a hydrogen atom. [0036] (C) The melamine-based crosslinking agent may be used alone or in combination of two or more kinds. (C) The blending amount of the melamine-based crosslinking agent is preferably 1 to 15% by mass based on the total solid content of the composition. If it is 1~15% by mass, the residual film rate in the unexposed area can be increased, and the image remaining in the exposed area can be prevented. [0037] The positive photosensitive resin composition of the present invention preferably contains (C) a crosslinking agent other than the melamine-based crosslinking agent, and preferably contains the following crosslinking agent 2, crosslinking agent 5, and crosslinking At least any one of Agent 6. By containing (C) a melamine-based crosslinking agent and at least any one of the crosslinking agent 2, the crosslinking agent 5, and the crosslinking agent 6, the dissolution promotion effect can be obtained, and the developability becomes good. [0038]
Figure 02_image013
Figure 02_image015
[0039] (C) The blending amount of other crosslinking agents other than the melamine-based crosslinking agent, based on the total solid content of the composition, is preferably 1 to 15% by mass. In particular, the total blending amount of the crosslinking agent 2, the crosslinking agent 5, and the crosslinking agent 6 is preferably 1 to 15% by mass based on the total solid content of the composition. [0040] [(D) Silane coupling agent] The positive photosensitive resin composition of the present invention, (D) the silane coupling agent, comprises a silane coupling agent having an arylamine group and a trialkoxy group having two or more At least one selected from the silane coupling agent of the silyl group. [0041] The aryl group of the aforementioned arylamino group includes aromatic hydrocarbon groups such as phenyl, tolyl, and xylyl; condensed polycyclic aromatic groups such as naphthyl, anthryl, and phenanthryl; thienyl, indyl, etc. Aromatic heterocyclic groups such as dolyl. [0042] The aforementioned silane coupling agent having an arylamine group is preferably a compound having a group represented by the following general formula (3).
Figure 02_image017
(In the formula, R 31 to R 35 each independently represent a hydrogen atom or an organic group). [0043] In the aforementioned general formula (3), R 31 to R 35 are preferably hydrogen atoms. [0044] The aforementioned silane coupling agent with an arylamino group is preferably a silicon atom and an arylamino group, and is bonded to an organic group with 1 to 10 carbon atoms, preferably an alkylene with 1 to 10 carbon atoms. . [0045] Specific examples of the aforementioned silane coupling agent having an arylamino group are preferably the following compounds.
Figure 02_image019
[0046] The trialkoxysilyl groups of the aforementioned silane coupling agent having two or more trialkoxysilyl groups may be the same or different, and the alkoxy groups of these groups may be the same. It can also be different. Examples of the alkoxy group include methoxy, ethoxy, propoxy, butoxy, etc. Among them, methoxy and ethoxy are particularly preferred. [0047] The aforementioned silane coupling agent having two or more trialkoxysilyl groups, preferably at least two silicon atoms, is an organic group with 1 to 10 carbons, preferably with 1 to 10 carbons. Alkylene bonding. [0048] Specific examples of the aforementioned silane coupling agent having two or more trialkoxysilyl groups are preferably the following compounds.
Figure 02_image021
[0049] (D) The silane coupling agent is preferably a silane coupling agent having an arylamine group due to its excellent resolution. [0050] (D) The silane coupling agent may be used singly or in combination of two or more. (D) The blending amount of the silane coupling agent is based on the total solid content of the composition, and is preferably 1 to 15% by mass. If it is 1~15% by mass, it can prevent the residual image of the exposed part. [0051] The positive photosensitive resin composition of the present invention may contain other silane coupling agents within a range that does not impair the effects of the present invention. [0052] The following describes other components that can be blended into the positive photosensitive resin composition of the present invention. [0053] (t-Butylcatechol) The positive photosensitive resin composition of the present invention preferably contains t-butylcatechol. By containing t-butylcatechol, there is less developing residue (scum) and excellent developability. [0054] The blending amount of t-butylcatechol is based on the total solid content of the composition, and is preferably 0.1 to 2% by mass. [0055] The positive photosensitive resin composition of the present invention may be blended with a solvent. The solvent is not particularly limited as long as it can dissolve (A) polybenzoxazole precursor, (B) photoacid generator, (C) melamine-based crosslinking agent, (D) silane coupling agent and other additives. Can enumerate N,N'-dimethylformamide, N-methylpyrrolidone, N-ethyl-2-pyrrolidone, N,N'-dimethylacetamide, diethylene glycol two Methyl ether, cyclopentanone, γ-butyrolactone, α-acetyl-γ-butyrolactone, tetramethylurea, 1,3-dimethyl-2-imidazolinone (1,3-dimethyl -2-imidazolinone), N-cyclohexyl-2-pyrrolidone, dimethyl sulfoxide, hexamethylphosphoramide, pyridine, γ-butyrolactone, and diethylene glycol monomethyl ether are examples. These can be used alone or in combination of two or more kinds. The amount of the solvent used can be used in the range of 50 to 9000 parts by mass relative to 100 parts by mass of the (A) polybenzoxazole precursor according to the thickness or viscosity of the coating film. [0056] In the positive photosensitive resin composition of the present invention, in order to further improve the photosensitivity, a known sensitizer may be blended. [0057] In addition, in the positive photosensitive resin composition of the present invention, in order to improve the adhesion to the substrate, a known adhesion auxiliary agent may be added. [0058] In order to impart processing characteristics or various functionalities to the positive photosensitive resin composition of the present invention, various organic or inorganic low-molecular or high-molecular compounds may also be blended. For example, surfactants, leveling agents, plasticizers, fine particles, etc. can be used. Microparticles include organic microparticles such as polystyrene and polytetrafluoroethylene; inorganic microparticles such as colloidal silica, carbon, and layered silicate. In addition, various coloring agents, fibers, etc. may be blended in the positive photosensitive resin composition of the present invention. [Dry Film] The dry film of the present invention has a resin layer obtained by coating the positive photosensitive resin composition of the present invention and drying it. The dry film of the present invention is used by laminating a resin layer adjacent to the substrate. [0060] The positive photosensitive resin composition of the present invention can be uniformly coated on the carrier film by an appropriate method such as a knife coater, a lip die coater, a chipped wheel coater, a film coater, etc. It is dried to form the aforementioned resin layer, and it is preferable to laminate a cover film thereon to manufacture the dry film of the present invention. The cover film and the carrier film can be the same film material, or different films can be used. [0061] In the dry film of the present invention, the carrier film and the film material of the cover film can be any thing known as the user of the dry film. [0062] For the carrier film, for example, a thermoplastic film such as a polyester film such as polyethylene terephthalate having a thickness of 2 to 150 μm can be used. [0063] As for the cover film, a polyethylene film, a polypropylene film, etc. can be used, but the adhesion to the resin layer is smaller than that of the carrier film. [0064] The thickness of the resin layer on the dry film of the present invention is preferably 100 μm or less, more preferably in the range of 5-50 μm. [0065] Using the positive photosensitive resin composition of the present invention, the patterned film of the cured product is produced as follows, for example. [0066] First, in step 1, the positive photosensitive resin composition is coated on the substrate and dried, or the resin layer is transferred from a dry film to the substrate to obtain a coating film. The method of coating the positive photosensitive resin composition on the substrate can be the method used for the coating of the photosensitive resin composition from the past, such as spin coater, bar coater, knife coating Coating methods such as spray coating machine, curtain coater, screen printing machine, etc.; spray coating method with spray coater; and inkjet method, etc. The drying method of the coating film can be air drying, heating drying in an oven or hot plate, vacuum drying, etc. In addition, it is more desirable to perform drying of the coating film under conditions that do not cause ring closure of the (A) polybenzoxazole precursor in the photosensitive resin composition. Specifically, it is possible to perform natural drying, air blowing drying, or heat drying under the conditions of 70 to 140°C for 1 to 30 minutes. Preferably, it is dried on a hot plate for 1 to 20 minutes. In addition, vacuum drying can also be carried out. In this case, it can be carried out at room temperature for 20 minutes to 1 hour. [0067] The substrate is not particularly limited, and semiconductor substrates such as silicon wafers, wiring substrates, various resins, metals, etc. can be widely used. [0068] Next, in step 2, the above-mentioned coating film is passed through a patterned photomask or directly exposed. The exposure light uses a wavelength that activates the (B) photoacid generator and can generate acid. Specifically, the exposure light preferably has a maximum wavelength in the range of 350 to 410 nm. As described above, when a sensitizer is appropriately used, the light sensitivity can be adjusted. The exposure device may use a contact aligner, mirror projection, stepper, laser direct exposure device, etc. [0069] Next, heating may be performed to close a part of the (A) polybenzoxazole precursor in the unexposed part, as step 3. Here, the closed loop rate is about 30%. The heating time and heating temperature are appropriately changed according to (A) polybenzoxazole precursor, coating film thickness, and (B) type of photoacid generator. [0070] Next, in step 4, the coating film is treated with a developing solution. Thereby, the exposed part of the coating film can be removed, and the patterned film of the positive photosensitive resin composition of the present invention can be formed. [0071] The method used for the imaging can be selected from the conventionally known photoresist imaging methods, such as the rotary spray method, the paddle method, the dipping method with ultrasonic treatment, and the like. The developing solution can include inorganic bases such as sodium hydroxide, sodium carbonate, sodium silicate, and ammonia; organic amines such as ethylamine, diethylamine, triethylamine, triethanolamine, etc.; tetramethylammonium hydroxide, hydrogen Aqueous solutions of quaternary ammonium salts such as tetrabutylammonium oxide. In addition, water-soluble organic solvents or surfactants such as methanol, ethanol, isopropanol, etc. may be added in appropriate amounts as needed. After that, as needed, the coating film is washed with a dampening solution to obtain a patterned film. The rinsing liquid can be used alone or in combination with distilled water, methanol, ethanol, isopropyl alcohol, etc. In addition, the above-mentioned solvents can also be used as a developing solution. [0072] Then, in step 5, the patterned film is heated to obtain a cured coating film (cured product). In this case, it is only necessary to close the ring of (A) the polybenzoxazole precursor to obtain polybenzoxazole. The heating temperature is appropriately set to a patterned film of curable polybenzoxazole. For example, in an inert gas, heating is performed at 150 to 350°C for about 5 to 120 minutes. The better range of heating temperature is 200~300℃. The heating is carried out by using, for example, a hot plate, an oven, and a temperature-rising oven that can be set to a temperature program. At this time, the environment (gas) can be air, or inert gas such as nitrogen and argon. [0073] The use of the positive photosensitive resin composition of the present invention is not particularly limited, and examples include printing inks, adhesives, fillers, electronic materials, optical circuit parts, molding materials, resist materials, building materials, etc. Various well-known fields/products, etc. using resin materials for dimensional molding and optical components. In particular, it can be suitably used as a wide range of products/products where the heat resistance, dimensional stability, and insulation properties of the polybenzoxazole film are effective, such as paints or printing inks, or color filters, flexible displays. Films, coating films for semiconductor components, electronic parts, interlayer insulating films, solder resist inks, etc., for printed wiring boards, optical circuits, optical circuit parts, anti-reflective films, holograms, optical components, or building materials Forming materials. [0074] In particular, the positive photosensitive resin composition of the present invention is mainly used as a pattern forming material (resist), and the pattern film formed by this is used as a permanent film made of polybenzoxazole. Film, which functions as a component that imparts heat resistance or insulation, and is suitable for forming, for example, color filters, flexible display films, electronic parts, coating films for semiconductor devices, interlayer insulating films, solder masks, or coatings Film and other printed wiring board coating film, solder dam (solder dam), optical circuit, optical circuit parts, anti-reflection film, other optical components or electronic components. [Examples] [0075] Hereinafter, the present invention will be explained in more detail using examples, but the present invention is not limited by the following examples. In addition, the following descriptions of "parts" and "%" are quality standards unless otherwise specified. [0076] (Synthesis of Polybenzoxazole (PBO) Precursor) Into a 0.5 liter flask equipped with a stirrer and a thermometer, 212 g of N-methylpyrrolidone was added, and the bis(3-amino-4-hydroxyl Aminophenyl) hexafluoropropane 28.00 g (76.5 mmol) was stirred and dissolved. After that, the flask was immersed in an ice bath, the inside of the flask was kept at 0~5°C, and 25.00 g (83.2 mmol) of 4,4-diphenyl ether dicarboxylic acid chloride was added in a solid form of 30 at a time of 5 g. Minutes, stirring in an ice bath for 30 minutes. After that, stirring was continued for 5 hours at room temperature. Put the stirred solution into 1L of ion exchange water (specific resistance value 18.2MΩ･cm), and recover the precipitate. After that, the obtained solid was dissolved in 420 mL of acetone and poured into 1 L of ion exchange water. After recovering the precipitated solid, it was dried under reduced pressure to obtain a polybenzoxazole (PBO) precursor A1 having the following repeating structure with a carboxyl terminal. The polybenzoxazole precursor A1 has a number average molecular weight (Mn) of 12,900, a weight average molecular weight (Mw) of 29,300, and Mw/Mn of 2.28. [0077]
Figure 02_image023
[0078] (Examples 1, 2, Comparative Examples 1 to 11) For 100 parts by mass of the benzoxazole precursor synthesized above, 10 parts by mass of naphthoquinone diazonium (DNQ) were blended with the following table 1 After 5 parts by mass of the coupling agent and 5 parts by mass of the silane coupling agent, N-methylpyrrolidone (NMP) is added to make the benzoxazole precursor 30% by mass. As a paint, a spin coater is used to coat the silicon On the substrate. It was dried on a hot plate at 120°C for 3 minutes to obtain a dry coating film of the photosensitive resin composition. For the resulting dry coating film, a high-pressure mercury lamp was used to illuminate a 200mJ/cm 2 broad light through a mask engraved with a pattern. After exposure, it was developed with a 2.38% tetramethylammonium hydroxide (TMAH) aqueous solution for 60 seconds and rinsed with water to obtain a positive pattern film. [0079] In addition, in the following Table 1, the melamine-based crosslinking agent used crosslinking agent 1 (NIKALAC MW390 manufactured by Sanwa Chemical Co., Ltd.). In addition, the silane coupling agent having an arylamine group and the silane coupling agent having two or more trialkoxysilyl groups are respectively using coupling agents 1 (KBM-573 manufactured by Shin-Etsu Polysiloxane Co., Ltd.) and 2 (Shin-Etsu Polysiloxane Co., Ltd.). KBM-3066 manufactured by Silicon Oxygen Corporation). (Evaluation of residual film rate in unexposed area) The film thickness of the pattern film after development was measured, and the film thickness in the unexposed area was determined by the ratio of the film thickness before development, as follows Benchmark assessment. ○: The residual film rate in the unexposed area is 75% or more. ×: The residual film rate in the unexposed area is less than 75%. For the film, the minimum pattern size that can pattern the exposed part without scum is the resolution (L(μm)/S(μm)). [0082]
Figure 02_image025
[0083]
Figure 02_image027
Figure 02_image029
[0084]
Figure 02_image031
Figure 02_image033
[0085] From the results shown in Table 1, it can be seen that the positive photosensitive resin composition of the present invention containing the aforementioned specific crosslinking agent and silane coupling agent has an excellent residual film rate. [0086] (Examples 3 to 6) For 100 parts by mass of the benzoxazole precursor synthesized above, 10 parts by mass of naphthoquinone diazide (DNQ) and 5 parts by mass of each crosslinking agent described in Table 2 below were blended , After 5 parts by mass of silane coupling agent and 0.5 parts by mass of t-butylcatechol, add N-methylpyrrolidone (NMP) to make the benzoxazole precursor 30% by mass. Use spin coating as a paint The cloth is coated on the silicon substrate. It was dried on a hot plate at 120°C for 3 minutes to obtain a dry coating film of the photosensitive resin composition. For the resulting dry coating film, use a high-pressure mercury lamp to illuminate a 200mJ/cm 2 floodlight through a mask engraved with a pattern. After exposure, it was developed with a 2.38% tetramethylammonium hydroxide (TMAH) aqueous solution for 60 seconds and rinsed with water to obtain a positive pattern film. [0087] In addition, in the following Table 2, the above-mentioned crosslinking agent 1 (NIKALAC MW390 manufactured by Sanwa Chemical Co., Ltd.) was used for the melamine-based crosslinking agent system. In addition, the above-mentioned coupling agent 1 (KBM-573 manufactured by Shin-Etsu Polysiloxane Co., Ltd.) was used as the silane coupling agent having an arylamine group. The above-mentioned cross-linking agents 2, 5, and 6 are used as other cross-linking agents other than the melamine-based cross-linking agent. [0088] In Table 2 below, the residual film rate and resolution of the unexposed area were evaluated by the same method as described above. [0089] (Method for confirming scum) After confirming the cross-sectional image of the pattern after development, the pattern is tailed with no pattern, and if there is no scum neatly, it is 0. Although there is pattern trailing, it can be imaged to the silicon substrate. The face is △, and the residue with scum is ×. In addition, evaluation examples of ○, △, and × are shown in Figs. 1 to 3, respectively. [0090] The photosensitive resin composition of Example 1 in Table 1 was also evaluated in the same manner, and the results are shown in Table 2 together with Examples 3 to 6. [0091]
Figure 02_image035
[0092] t-Butylcatechol
Figure 02_image037
[0093] (Examples 7, 8, Comparative Examples 12 to 25) For 100 parts by mass of the benzoxazole precursor synthesized above, 10 parts by mass of naphthoquinone diazide (DNQ) were blended with the following table 3 After 5 parts by mass of the coupling agent, 5 parts by mass of the silane coupling agent, and 0.5 parts by mass of t-butylcatechol, N-methylpyrrolidone (NMP) was added to make the benzoxazole precursor 30% by mass as a coating The lacquer is applied on the silicon substrate using a spin coater. It was dried on a hot plate at 120°C for 3 minutes to obtain a dry coating film of the photosensitive resin composition. For the resulting dry coating film, use a high-pressure mercury lamp to illuminate a 200mJ/cm 2 floodlight through a mask engraved with a pattern. After exposure, it was developed with a 2.38% tetramethylammonium hydroxide (TMAH) aqueous solution for 60 seconds and rinsed with water to obtain a positive pattern film. [0094] In addition, in the following Table 3, the above-mentioned crosslinking agent 1 (NIKALAC MW390 manufactured by Sanwa Chemical Co., Ltd.) was used for the melamine-based crosslinking agent system. In addition, the silane coupling agent having an arylamine group and the silane coupling agent having two or more trialkoxysilyl groups use the aforementioned coupling agents 1 (KBM-573 manufactured by Shin-Etsu Polysiloxane Co., Ltd.) and 2 (Shin-Etsu Polysiloxane Co., Ltd.), respectively. KBM-3066 manufactured by Silicon Oxygen Corporation). [0095] In the following Table 3, the unexposed area residual film rate, resolution, and scum were evaluated by the same method as described above. [0096]
Figure 02_image039
[0097]
Figure 02_image041
Figure 02_image043
[0098] From the results shown in Tables 2 and 3, it can also be seen that the positive photosensitive resin composition of the present invention containing the aforementioned specific crosslinking agent and silane coupling agent has an excellent residual film rate. In addition, it can be seen that since t-butylcatechol is blended into the positive photosensitive resin composition of the present invention, there is less development residue and better developability. Furthermore, it can be seen that by blending other crosslinking agents into the positive photosensitive resin composition of the present invention, the developability is more excellent.

[0015] 　　[圖1]顯示實施例中之浮渣之確認方法的評估〇之評估例的照片圖。 　　[圖2]顯示實施例中之浮渣之確認方法的評估△之評估例的照片圖。 　　[圖3]顯示實施例中之浮渣之確認方法的評估×之評估例的照片圖。[0015] 　　 [FIG. 1] A photograph showing an evaluation example of the evaluation of the method for confirming scum in the examples.　　 [Fig. 2] A photograph showing an evaluation example of the evaluation △ of the method for confirming scum in the examples.　　 [Fig. 3] A photograph showing an evaluation example of the evaluation of the method for confirming scum in the example ×.

Claims (6)

一種正型感光性樹脂組成物，其係含有(A)聚苯并噁唑前驅物、(B)光酸產生劑、(C)三聚氰胺系交聯劑及(D)矽烷偶合劑之正型感光性樹脂組成物，其特徵為前述正型感光性樹脂組成物，進一步含有t-丁基兒茶酚，作為浮渣去除劑，前述(D)矽烷偶合劑，包含由具有芳基胺基之矽烷偶合劑及具有二個以上之三烷氧基矽烷基的矽烷偶合劑中選出之至少1種。 A positive photosensitive resin composition containing (A) polybenzoxazole precursor, (B) photoacid generator, (C) melamine-based crosslinking agent and (D) silane coupling agent A resin composition characterized by the aforementioned positive photosensitive resin composition, further containing t-butylcatechol as a scum remover, and the aforementioned (D) silane coupling agent comprising a silane coupling agent having an arylamino group. At least one selected from coupling agents and silane coupling agents having two or more trialkoxysilyl groups. 如請求項1之正型感光性樹脂組成物，其中前述(D)矽烷偶合劑，包含具有芳基胺基之矽烷偶合劑。 The positive photosensitive resin composition of claim 1, wherein the aforementioned (D) silane coupling agent includes a silane coupling agent having an arylamine group. 一種乾膜，其特徵為具有將如請求項1之正型感光性樹脂組成物塗佈於薄膜並乾燥而得到之樹脂層。 A dry film characterized by having a resin layer obtained by coating and drying the positive photosensitive resin composition of claim 1 on a film. 一種硬化物，其特徵為使如請求項1或2之正型感光性樹脂組成物或如請求項3之乾膜之樹脂層硬化而得到。 A cured product characterized by curing the positive photosensitive resin composition of claim 1 or 2 or the resin layer of the dry film of claim 3. 一種印刷配線板，其特徵為具有如請求項4之硬化 物。 A printed wiring board characterized by hardening as in claim 4 Things. 一種半導體元件，其特徵為具有如請求項4之硬化物。 A semiconductor element characterized by having a hardened object as claimed in claim 4.
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Families Citing this family (2)

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JP2018097210A (en) * 2016-12-14 2018-06-21 日立化成デュポンマイクロシステムズ株式会社 Positive photosensitive resin composition, production method of cured pattern, cured product, interlayer insulating film, cover coat layer, surface protection film, and electronic component
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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TW201533524A (en) * 2014-02-28 2015-09-01 Jsr Corp Method for forming insulating film and device using insulating film
TW201600564A (en) * 2014-06-27 2016-01-01 Fujifilm Corp Thermosetting resin composition, cured film, manufacturing method for cured film, and semiconductor device

Family Cites Families (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TW594287B (en) * 2002-12-17 2004-06-21 Ind Tech Res Inst Transflective display with different pre-tilt angle structures and its manufacturing method
KR20070114267A (en) * 2005-03-25 2007-11-30 후지필름 일렉트로닉 머티리얼스 유.에스.에이., 아이엔씨. Pretreatment compositions
WO2007122929A1 (en) * 2006-03-30 2007-11-01 Jsr Corporation Radiation-sensitive insulating resin composition
KR101175080B1 (en) 2007-12-26 2012-10-26 아사히 가세이 이-매터리얼즈 가부시키가이샤 Precursor for heat-resistant resin and photosensitive resin composition containing the same
KR100914064B1 (en) * 2008-03-19 2009-08-28 제일모직주식회사 Positive type photosensitive resin composition
JP5169446B2 (en) 2008-04-28 2013-03-27 日立化成デュポンマイクロシステムズ株式会社 Photosensitive resin composition, polybenzoxazole film using the resin composition, method for producing patterned cured film, and electronic component
CN102016718B (en) * 2008-05-07 2013-10-16 住友电木株式会社 Positive-type photosensitive resin composition, cured film, protective film, insulating film, and semiconductor device and display device each comprising the cured film
CN102076740B (en) * 2008-07-03 2013-08-21 旭化成电子材料株式会社 Heat-resistant resin precursor and photosensitive resin composition comprising the same
WO2010113813A1 (en) 2009-03-31 2010-10-07 大日本印刷株式会社 Base-generating agent, photosensitive resin composition, patterning material comprising the photosensitive resin composition, patterning method and article using the photosensitive resin composition
JP2011053458A (en) 2009-09-02 2011-03-17 Hitachi Chemical Dupont Microsystems Ltd Photosensitive resin composition, method of manufacturing pattern-cured film using the same, and electronic component
WO2011135887A1 (en) * 2010-04-28 2011-11-03 旭化成イーマテリアルズ株式会社 Photosensitive resin composition
TWI430024B (en) * 2010-08-05 2014-03-11 Asahi Kasei E Materials Corp A photosensitive resin composition, a method for manufacturing a hardened bump pattern, and a semiconductor device

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TW201533524A (en) * 2014-02-28 2015-09-01 Jsr Corp Method for forming insulating film and device using insulating film
TW201600564A (en) * 2014-06-27 2016-01-01 Fujifilm Corp Thermosetting resin composition, cured film, manufacturing method for cured film, and semiconductor device

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