TW201003309A - Light sensitive resin composition, cured matter and printed circuit substrate having solder mask layer formed with the cured matter - Google Patents

Light sensitive resin composition, cured matter and printed circuit substrate having solder mask layer formed with the cured matter Download PDF

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TW201003309A
TW201003309A TW098109741A TW98109741A TW201003309A TW 201003309 A TW201003309 A TW 201003309A TW 098109741 A TW098109741 A TW 098109741A TW 98109741 A TW98109741 A TW 98109741A TW 201003309 A TW201003309 A TW 201003309A
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Taiwan
Prior art keywords
resin composition
pigment
photosensitive resin
coloring agent
manufactured
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TW098109741A
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Chinese (zh)
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TWI522735B (en
Inventor
Yoko Shibasaki
Masao Arima
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Taiyo Ink Mfg Co Ltd
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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
    • G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
    • 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
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic 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
    • G03F7/004—Photosensitive materials
    • G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
    • G03F7/11—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having cover layers or intermediate layers, e.g. subbing layers
    • 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
    • G03F7/20—Exposure; Apparatus 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
    • G03F7/20—Exposure; Apparatus therefor
    • G03F7/2002—Exposure; Apparatus therefor with visible light or UV light, through an original having an opaque pattern on a transparent support, e.g. film printing, projection printing; by reflection of visible or UV light from an original such as a printed image
    • 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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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Engineering & Computer Science (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Architecture (AREA)
  • Structural Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Materials For Photolithography (AREA)
  • Non-Metallic Protective Coatings For Printed Circuits (AREA)

Abstract

The present invention provides a light sensitive resin composition having high coloring ability, excellent concealment, and may form a solder mask layer having high length-width ratio. The light sensitive resin composition is characterized by containing perylene series coloring agents and carboxylic acid resin.

Description

201003309 六、發明說明： 【發明所屬之技術領域】 本發明爲有關一種著色感光性樹脂組成物。更詳細言 之’本發明爲可提供一種具有可遮蔽電路不良外觀等之優 良隱蔽性，且具有高解析性之抗焊阻劑層的具有優良著色 力與解析性之感光性樹脂組成物。 【先前技術】 鹼顯影性感光性組成物被大量作爲印刷配線板用之抗 焊阻劑使用。抗焊阻劑爲具有保護印刷基板之電路等之目 的，但其著色力爲造成印刷配線板之外觀或電路之隱蔽性 產生極大影響之重要特性。 即，抗焊阻劑之著色力不充分時’將會汙染形成於印 刷配線板上之銅電路，或因極顯著之變色而造成印刷配線 板之良品率顯著降低。此外’近來於印刷配線板之後製程 C 之實裝步驟已形成自動化’而由機械進行對構件之裝設’ 故於辨識畫像之際將會產生不易辨識抗焊阻劑與銅電路等 不佳狀況。該現象於印刷配線板之最後檢查之A01 ( Automatic Optical Inspection)之際也會產生相同之問題 〇 目前市售之抗焊阻劑，雖依膜厚或基材之銅的前處理 而有所不同，但以CIE L*a*b*顯示系表示時，綠色之L*値 爲40至60、a*値爲-10至-28、b*値爲6至18’藍色之L*値 爲40至60、a*値爲-10至- 28、bM直爲-6至-18’特別是綠色 201003309 、藍色之L*値同時爲40〜50時，就AOI之觀點而言爲較佳 ，一般必須具有此程度之著色力。 又’光抗焊阻劑之感光特性，一般而百，市面上已有 售售膜厚約20 " m ’且具有30 // m至50 μ m左右解析性之阻 劑。但是，最近該些抗焊阻劑對於具有高電路厚度之印刷 基板並無法達到充分之硬化深度，故仍存在無法形成微小 線路之問題。一般而言，抗焊阻劑因塗佈於形成有電路之 基板上，故該阻劑之厚度與電路厚度具有對應性。例如， 電路厚度爲35/im時，將抗焊阻劑之厚度於電路上塗佈20 //m時，其於電路間可形成約30〜35//m，電路厚度爲70 時，爲約60〜70#πι。其中，即使電路厚度於35μιη之 基板上可形成5 0 // m之阻劑線路，但仍會存在於電路厚度 爲70 // m之基板上無法形成100 // m之影像等問題。 最近，使用於以高電壓驅動之構件之配線板以日漸高 電路厚度化、高密度化，而有要求可適應於該基板之高解 析性的抗焊阻劑。 但是，抗焊阻劑一般爲使用酞菁系之綠與藍及作爲輔 助使用的黃色之著色劑，但因該些著色劑無論任一者於紫 外線區域皆具有較大之吸收，故該添加量過多時，將會影 響紫外線之透過性而無法得到良好之解析性。因此，欲提 供一種可形成同時滿足良好之隱蔽性與高解析性之抗焊阻 劑層的感光性樹脂組成物仍存在實際困難性。 [專利文獻1 ]特開2 〇 〇 〇 - 7 9 7 4號公報，申請專利範圍 201003309 【發明內容】 本發明爲提供一種可形成具有高度著色力與優良隱蔽 性，且具有高長徑比之解析性的抗焊阻劑層之感光性樹脂 組成物爲目的。 本發明者等經過深入硏究結果，得知著色劑至少使用 茈系著色劑所得之感光性樹脂組成物時，可使以往抗焊阻 劑中有關解析性之上述問題得到解決，且可得到充分著色 力之效果，因而完成本發明。 即，本發明爲有關含有（A-1)茈系著色劑，及（B) 含羧酸之樹脂爲特徵之感光性樹脂組成物。 本發明之感光性樹脂組成物之一實施態樣爲，含有至 少爲茈系著色劑（A-1 )之染料者。 又，本發明之感光性樹脂組成物之一實施態樣爲，含 有至少爲茈系著色劑（A-1 )之顏料者。 又，本發明之感光性樹脂組成物之一實施態樣爲，其 色調爲綠色或檀色。 又，本發明之感光性樹脂組成物之一實施態樣爲，除 茈系著色劑（A-1 )以外，尙含有酞菁系著色劑（A-2 )及 /或其他之著色劑所得者。 又，本發明之感光性樹脂組成物之一實施態樣爲，鹼 顯影性光抗焊阻劑。 又，本發明中，其他之實施樣態爲，將上述感光性樹 脂組成物塗佈於負載薄膜上，經乾燥所得之乾薄膜。 又，本發明中，其他之實施樣態爲，使上述感光性樹 -7- 201003309 脂組成物或上述乾薄膜於形成電路之基板上硬化所得之硬 化物。 又’本發明中，其他之實施樣態爲，於形成電路之基 板上’具有由上述硬化物所得之抗焊阻劑層之印刷電路基 板。 本發明之兼具高度著色力且具有優良解析性之感光性 樹脂組成物，可提供同時滿足作爲邁向高電路厚度化、高 密度化之印刷配線板用的抗焊阻劑層所要求之具有高度解 析性與優良隱蔽性之抗焊阻劑層。 以下，將對本發明作詳細說明。 本發明之感光性樹脂組成物，其著色劑爲使用含有（ A-1)茈系著色劑爲第一之特徵，其一實施態樣中，可爲 尙含有酞菁系著色劑所得之該色調呈現綠色或橙色之感光 性樹脂組成物。如此，首先將對本發明之著色劑進行說明 (A-1 )茈系著色劑 本發明含有茈系著色劑（A-1 )之感光性樹脂組成物 ，對於以往著色系之光阻劑，特別是印刷配線板用之抗焊 阻劑可賦予其高解析性。其理由乃因爲以往使用之著色劑 爲酞菁綠、酞菁藍等酞菁系顏料與，蒽醌與異吲哚啉（ Isoindoline)系黃色顏料所得者。即，酞菁系於3 00nm至 400nm之間具有較大吸收，因黃色顏料系於具有相對局透 過性之長波長區域（ 380nm-450nm)具有較大之吸收，故 201003309 無法使光源產生之光線充分到達阻劑底部，而會造成 深度降低。 又’茈系著色劑與上述著色劑相比較時，其紫外 域之吸收較少’且具有充分之著色力，因而具有高解 ，故可提供抗焊阻劑等之阻劑材料兼具有必要之耐熱 電氣絕緣性之感光性樹脂組成物。 本發明中，著色劑可使用慣用公知之物質，其可 料、染料、色素中任一者皆可’或將2種以上混合使 可。尙、本發明中，顏料係指色彩索引（C.I.; Society of Dyers and Colourists公司發行）中，被分 顏料（Pigment )之化合物，染料爲被分類Solvent以 Sol vent以外）之化合物，或Lumogen (登錄商標）等 質。 茈系著色劑中，標示爲綠色、黃色、橙色、紅色 色、黒色等之物質，例如下所示般，標記有色彩索 C.I.; The Society of Dyers and Colourists 公司發行 號之物質。 -綠色：Solvent Green 5 -檀色:Solvent Orange 5 5 -糸工色：Solvent Red 1 3 5, 1 79; Pigment Red 123, 1 66, 1 78, 1 79, 1 90, 1 94，224; -紫色：Pigment Violet 29 -黒色:Pigment Black 31, 32 亦可使用上述以外之茈系著色劑，例如，已知不 硬化 線區 析力 性、 爲顏 用亦 The 類爲 外（ 之物 '紫 引（ )編 149, 具有 -9- 201003309 色彩索引編號之集光性螢光染料之BASF公司之Lumogen ( 登錄商標）F Yellow 083、Lumogen F Orange 240、 Lumogen F Red305、Lumogen F Green850等，其與其他之 茈系化合物相同般，於紫外線區域具有較少之吸收，且具 有高著色力，故亦可配合使用。 茈系著色劑之添加率，於考慮著色性與紫外線吸收量 時’以相對於後述（B )含羧酸之樹脂1 00質量份，較佳爲 使用0.0 1〜5.0質量份，更佳爲〇.〇5〜3.0質量份。 其中，作爲茈系著色劑較佳者爲Solvent Green 5、 Solvent Orange 55、Solvent Red 13 5 ' Solvent Redl79、 Lumogen (登錄商標）等之染料系，特佳爲Solvent Green 5。顏料系以Pigment Black31爲佳。 於不阻礙本發明之目的範圍内，茈系以外之其他之著 色劑（顏料、染料、色素中任一者皆可）可含有所需要之 份量，該些著色劑例如以下之例示。其中又以酞菁系著色 劑（A-2 )與茈系著色劑（A-1 )之混合爲佳。 (1 )藍色著色劑 藍色著色劑例如有酞菁系、蒽醌系著色劑，顏料系中 爲分類爲顏料（Pigment)之化合物，具體而言，例如下 述內容般，附有色彩索引（C.I. ; The Society 〇f Dye^ and Colourists公司發行）編號之化合物等。201003309 VI. Description of the Invention: [Technical Field of the Invention] The present invention relates to a colored photosensitive resin composition. More specifically, the present invention provides a photosensitive resin composition having excellent color strength and resolution, which has excellent receptivity to mask a poor appearance of a circuit and the like, and has a high-resistance solder resist layer. [Prior Art] The alkali-developable photosensitive composition is used in a large amount as a solder resist for a printed wiring board. The solder resist is intended to have a circuit for protecting a printed substrate, etc., but its coloring power is an important characteristic that greatly affects the appearance of the printed wiring board or the concealability of the circuit. That is, when the coloring power of the solder resist is insufficient, the copper circuit formed on the printed wiring board is contaminated, or the yield of the printed wiring board is remarkably lowered due to extremely remarkable discoloration. In addition, the installation steps of the process C after the recent printing of the wiring board have been automated, and the components are mounted by the machine. Therefore, when the image is recognized, it is difficult to identify the solder resist and the copper circuit. . This phenomenon also causes the same problem at the time of A01 (Automatic Optical Inspection), which is the last inspection of printed wiring boards. The currently available solder resists vary depending on the film thickness or the pretreatment of the copper of the substrate. However, when expressed in CIE L*a*b* display, the green L*値 is 40 to 60, the a*値 is -10 to -28, and the b*値 is 6 to 18' blue L*値40 to 60, a*値 is -10 to -28, bM is directly -6 to -18', especially green 201003309, blue L*値 is 40~50, which is better from the viewpoint of AOI It is generally necessary to have this degree of color power. Further, the photosensitive characteristics of the photoresist are generally one hundred, and a film having a thickness of about 20 " m ' and having a resolution of about 30 // m to 50 μm is commercially available. However, recently, these solder resists have not been able to achieve a sufficient hardening depth for a printed substrate having a high circuit thickness, so that there is still a problem that a minute line cannot be formed. In general, since the solder resist is applied to the substrate on which the circuit is formed, the thickness of the resist corresponds to the thickness of the circuit. For example, when the thickness of the circuit is 35/im, when the thickness of the solder resist is 20 / m on the circuit, it can be formed between the circuits by about 30 to 35 / / m, and when the thickness of the circuit is 70, 60~70#πι. Among them, even if a circuit having a circuit thickness of 35 μm can form a resist line of 50 // m, there is still a problem that an image of 100 // m cannot be formed on a substrate having a circuit thickness of 70 // m. Recently, a wiring board for a member driven by a high voltage has been increasingly thickened and densified, and there is a need for a solder resist which can be adapted to the high resolution of the substrate. However, the solder resist is generally a green coloring agent using phthalocyanine green and blue, and is used as an auxiliary coloring agent. However, since any of these coloring agents has a large absorption in the ultraviolet region, the amount of the additive is increased. When it is too much, it will affect the transparency of ultraviolet rays and will not provide good resolution. Therefore, there is still practical difficulty in providing a photosensitive resin composition which can form a solder resist layer which satisfies both good concealability and high resolution. [Patent Document 1] Japanese Laid-Open Patent Publication No. Hei No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. The photosensitive resin composition of the analytical solder resist layer is for the purpose. As a result of intensive investigation, the present inventors have found that when the coloring agent is at least a photosensitive resin composition obtained by using an anthraquinone coloring agent, the above problems relating to analyzability in the conventional solder resist can be solved and can be sufficiently obtained. The effect of the coloring power thus completes the present invention. That is, the present invention relates to a photosensitive resin composition characterized by containing (A-1) an anthraquinone-based coloring agent and (B) a carboxylic acid-containing resin. One embodiment of the photosensitive resin composition of the present invention is a dye containing at least an anthraquinone coloring agent (A-1). Further, in one embodiment of the photosensitive resin composition of the present invention, the pigment containing at least the anthraquinone coloring agent (A-1) is contained. Further, in one embodiment of the photosensitive resin composition of the present invention, the color tone is green or sandal. Further, in one embodiment of the photosensitive resin composition of the present invention, in addition to the anthraquinone-based coloring agent (A-1), the phthalocyanine-based coloring agent (A-2) and/or other coloring agent are obtained. . Further, one embodiment of the photosensitive resin composition of the present invention is an alkali developable photoresist. Further, in the present invention, the other embodiment is a dry film obtained by applying the photosensitive resin composition onto a supported film and drying it. Further, in the present invention, in another embodiment, the photosensitive resin -7-201003309 fat composition or the dry film is cured on the substrate on which the circuit is formed. Further, in the present invention, the other embodiment is a printed circuit board having a solder resist layer obtained from the cured product on a substrate on which a circuit is formed. The photosensitive resin composition having a high coloring power and excellent resolvability of the present invention can provide a solder resist layer which is required for a printed wiring board which is high in thickness and high in density. Highly analytical and excellent concealed solder resist layer. Hereinafter, the present invention will be described in detail. In the photosensitive resin composition of the present invention, the coloring agent is characterized in that the (A-1) anthraquinone-based coloring agent is used as the first component, and in one embodiment, the coloring matter obtained by the cerium-containing phthalocyanine-based coloring agent may be used. A green or orange photosensitive resin composition is present. Thus, the coloring agent of the present invention will be described first. (A-1) Anthraquinone coloring agent The photosensitive resin composition containing the anthraquinone coloring agent (A-1) of the present invention is particularly useful for a conventional coloring photoresist. A solder resist for a printed wiring board can impart high resolution. The reason for this is that conventionally used coloring agents are phthalocyanine-based pigments such as phthalocyanine green and phthalocyanine blue, and yttrium and Isoindoline-based yellow pigments. That is, the phthalocyanine system has a large absorption between 300 nm and 400 nm, and since the yellow pigment has a large absorption in a long wavelength region (380 nm to 450 nm) having a relatively local permeability, 201003309 cannot produce light rays from a light source. Fully reach the bottom of the resist and cause a reduction in depth. Moreover, when the bismuth coloring agent is compared with the above coloring agent, its absorption in the ultraviolet region is less, and it has sufficient coloring power, so that it has a high solution, so that a resist material such as a solder resist can be provided and necessary. A photosensitive resin composition having heat-resistant electrical insulation properties. In the present invention, a conventionally known substance can be used as the coloring agent, and any of the materials, dyes and pigments can be used in combination or in combination of two or more kinds. In the present invention, the term "pigment" refers to a compound which is classified as a pigment in a color index (CI; issued by Society of Dyers and Colourists), a dye is classified as Solvent (other than Sol vent), or Lumogen (login Trademark) is equal. Among the lanthanide coloring agents, those indicated as green, yellow, orange, red, and ochre, such as those shown below, are labeled with the color code C.I.; The Society of Dyers and Colourists. - Green: Solvent Green 5 - Tan: Solvent Orange 5 5 - Completion: Solvent Red 1 3 5, 1 79; Pigment Red 123, 1 66, 1 78, 1 79, 1 90, 1 94,224; Purple: Pigment Violet 29 - Twilight: Pigment Black 31, 32 It is also possible to use a tanning colorant other than the above, for example, it is known that it does not harden the line area, and it is also used for the purpose. ( ) 149, Lumogen (registered trademark) F Yellow 083, Lumogen F Orange 240, Lumogen F Red305, Lumogen F Green850, etc. of BASF Corporation with -9-201003309 color index number. The bismuth-based compound has the same absorption in the ultraviolet region and has high coloring power, so it can also be used in combination. The addition ratio of the lanthanoid coloring agent is considered in the case of considering the coloring property and the ultraviolet absorbing amount. (B) 100 parts by mass of the carboxylic acid-containing resin, preferably 0.01 to 5.0 parts by mass, more preferably 5 to 3.0 parts by mass. Among them, preferred as the anthraquinone coloring agent is Solvent Green 5 , Solvent Orange 55, Solvent Red 13 5 ' Solvent Redl79 A dye system such as Lumogen (registered trademark) is particularly preferred as Solvent Green 5. The pigment is preferably Pigment Black 31. Other coloring agents other than lanthanum (pigment, dye, pigment) are not inhibited from the object of the present invention. Any of these may be contained in an amount of a coloring agent, for example, exemplified below, wherein a mixture of a phthalocyanine coloring agent (A-2) and an anthraquinone coloring agent (A-1) is preferred. (1) Blue coloring agent The blue coloring agent is, for example, a phthalocyanine-based or an anthraquinone-based coloring agent, and a pigment is classified into a pigment (Pigment), and specifically, for example, the following is accompanied by a color index. (CI; The Society 〇f Dye^ and Colourists issued) No. of compounds.

Pigment Blue 15 ' Pigment Blue 15:1 > Pigment Blue 15:2 ' Pigment Blue 15:3 ' Pigment Blue 15:4 > Pigment -10- 201003309Pigment Blue 15 ' Pigment Blue 15:1 > Pigment Blue 15:2 ' Pigment Blue 15:3 ' Pigment Blue 15:4 > Pigment -10- 201003309

Blue 15:6、Pigment Blue 16、Pigment Blue 60。 染料系例如可使用Blue 15:6, Pigment Blue 16, Pigment Blue 60. Dye systems can be used, for example

Solvent Blue 35 、Solvent Blue 45、Solvent Blue 63 、Solvent Blue 68、Solvent Blue 70 、Solvent Blue 83、Solvent Blue 35, Solvent Blue 45, Solvent Blue 63, Solvent Blue 68, Solvent Blue 70, Solvent Blue 83,

Solvent Blue 87 、 Solvent Blue 94 、 Solvent Blue 97 、 Solvent Blue 101、Solvent Blue 104、Solvent Blue 122、 Solvent Blue 136、Solvent Blue 67、Solvent Blue 70等。 上述以外亦可使用被金屬取代或無取代之酞菁系著色劑。 (2 )綠色著色劑 綠色著色劑’同樣的具有酞菁系、蒽醌系，具體而言 ，其可使用 Pigment Green 7、Pigment Green 36、Solvent Green 3、Solvent Green 20' Solvent Green 28等。上述以 外’亦可使用金屬取代或無取代之酞菁系著色劑。 (3 )黃色著色劑 黃色著色劑具有蒽醌系、異吲哚啉酮系、縮合偶氮系 、苯倂咪唑酮（Benzimidazolone)系、單偶氮系、雙偶氮 系等，其具體之例示係如以下所列舉之內容。 (蒽醌系）Solvent Blue 87, Solvent Blue 94, Solvent Blue 97, Solvent Blue 101, Solvent Blue 104, Solvent Blue 122, Solvent Blue 136, Solvent Blue 67, Solvent Blue 70, etc. A phthalocyanine coloring agent substituted with or without a metal may be used in addition to the above. (2) Green colorant The green colorant 'is similarly to the phthalocyanine system or the oxime system. Specifically, Pigment Green 7, Pigment Green 36, Solvent Green 3, Solvent Green 20' Solvent Green 28 and the like can be used. A phthalocyanine-based coloring agent which is substituted with or substituted with a metal may also be used. (3) Yellow colorant The yellow colorant has an anthraquinone, an isoindolinone type, a condensed azo type, a Benzimidazolone type, a monoazo type, a bisazo type, etc., and a specific example thereof It is as listed below. (蒽醌系)

Solvent Yellow 163、Pigment Yellow 24、PigmentSolvent Yellow 163, Pigment Yellow 24, Pigment

Yellow 108 ' Pigment Yell〇w 193 , Pigment Yellow 147 ' -11 - 201003309Yellow 108 ' Pigment Yell〇w 193 , Pigment Yellow 147 ' -11 - 201003309

Pigment Yellow 199、Pigment Yellow 202 ； (異吲哚啉酮系）Pigment Yellow 199, Pigment Yellow 202; (isoporphyrinone)

Pigment Yellow 1 10、Pigment Yellow 109、Pigment Yellow 139、Pigment Yellow 179、Pigment Yellow 185 ; (縮合偶氮系）Pigment Yellow 1 10, Pigment Yellow 109, Pigment Yellow 139, Pigment Yellow 179, Pigment Yellow 185; (condensed azo)

Pigment Yellow 93、Pigment Yellow 94、Pigment Yellow 95、Pigment Yellow 128、Pigment Yellow 155、 Pigment Yellow 166、Pigment Yellow 18 0； (苯倂咪唑酮系）Pigment Yellow 93, Pigment Yellow 94, Pigment Yellow 95, Pigment Yellow 128, Pigment Yellow 155, Pigment Yellow 166, Pigment Yellow 18 0; (Benzimidazolone)

Pigment Yellow 120 ' Pigment Yellow 151 ' Pigment Yellow 154、Pigment Yellow 156、Pigment Yellow 175、 Pigment Yellow 181 ； (單偶氮系）Pigment Yellow 120 ' Pigment Yellow 151 ' Pigment Yellow 154, Pigment Yellow 156, Pigment Yellow 175, Pigment Yellow 181 ; (monoazo)

Pigment Yellowl, 2, 3, 4, 5, 6, 9, 10, 12, 61, 62, 62:1，65，73，74, 75, 97，100, i〇4，105，111，116，167, 168， 169， 182, 183； (雙偶氮系）Pigment Yellowl, 2, 3, 4, 5, 6, 9, 10, 12, 61, 62, 62:1,65,73,74, 75, 97,100, i〇4,105,111,116,167 , 168, 169, 182, 183; (double azo)

Pigment Yellowl2, 13，1 4, 1 6, 1 7, 5 5, 63，81，8 3, 8 7, 126，127，1 52, 1 70，172，174，176，188，198。 -12- 201003309 (4 )紅色著色劑 紅色著色劑，例如單偶氮系、雙偶氮系、單偶氮色澱 系、苯倂咪唑酮系、二酮吡咯倂吡略系、縮合偶氮系、蒽 醌系、喹吖酮系等’具體而言，例如以下所例示之內容。 (單偶氮系）Pigment Yellowl 2, 13, 1 4, 1 6, 1 7, 5 5, 63, 81, 8 3, 8 7, 126, 127, 1 52, 1 70, 172, 174, 176, 188, 198. -12- 201003309 (4) Red coloring agent red coloring agent, for example, monoazo, azo, monoazo, phthalimidazole, diketopyrrole, condensed azo Specifically, the oxime system, the quinacridone system, etc., for example, are exemplified below. (monoazo)

Pigment Red 1，2，3，4，5，6，8, 9, 12，14，15，16，17, 21，22, 2 3，31，32, 112，114，146，147，151，170，184，187, 188，193，2 1 0, 245, 2 53，25 8，266，267，268, 269 ; (雙偶氮系）Pigment Red 1,2,3,4,5,6,8, 9, 12,14,15,16,17, 21,22, 2 3,31,32,112,114,146,147,151,170 ,184,187, 188,193,2 1 0, 245, 2 53,25 8,266,267,268, 269 ; (bisazo)

Pigment Red 3 7, 3 8，41 ; (單偶氮色澱系）Pigment Red 3 7, 3 8,41 ; (monoazo lake system)

Pigment Red 48:1, 48:2, 4 8:3, 48:4，49:1, 49:2, 50:1, 52:1, 52:2, 53:1, 53:2, 57:1, 58:4, 63:1, 63:2, 64:1, 68 ； (苯倂咪唑酮系）Pigment Red 48:1, 48:2, 4 8:3, 48:4, 49:1, 49:2, 50:1, 52:1, 52:2, 53:1, 53:2, 57:1 , 58:4, 63:1, 63:2, 64:1, 68 ; (benzoimidazole)

Pigment Red 171、Pigment Red 17 5、Pigment Red 176、Pigment Red 185、Pigment Red 208 ； (二酮吡咯倂吡咯系）Pigment Red 171, Pigment Red 17 5, Pigment Red 176, Pigment Red 185, Pigment Red 208; (diketopyrrolepyrrole)

Pigment Red 254、Pigment Red 255、Pigment Red -13- 201003309 264、Pigment Red 270、Pigment Red 272 ； (縮合偶氮系）Pigment Red 254, Pigment Red 255, Pigment Red -13- 201003309 264, Pigment Red 270, Pigment Red 272; (condensed azo)

Pigment Red 220、Pigment Red 144、Pigment Red 166、Pigment Red 214、Pigment Red 220、Pigment Red 221、Pigment Red 242 ； (蒽醌系）Pigment Red 220, Pigment Red 144, Pigment Red 166, Pigment Red 214, Pigment Red 220, Pigment Red 221, Pigment Red 242;

Pigment Red 168、Pigment Red 177、Pigment Red 216、Solvent Red 149、Solvent Red 150、Solvent Red 52 、Solvent Red 207 ； (喹吖酮系）Pigment Red 168, Pigment Red 177, Pigment Red 216, Solvent Red 149, Solvent Red 150, Solvent Red 52, Solvent Red 207; (quinacridone)

Pigment Red 122、Pigment Red 202、Pigment Red 206、Pigment Red 207、Pigment Red 209 o 就調整其他色調爲目的時，可添加紫、橙、褐色、黒 等之著色劑。 具體之例示如，Pigment Violet 19、23、32、36、38 、42、Solvent Violet 13、36、C.I.顏料橙 1、C.I.顏料橙 5 、C.I.顏料橙13、C.I.顏料橙14、C.I.顏料橙16、C.I.顏料 橙17、C.I_顏料橙24、C.I.顏料橙34、C.I.顏料橙36、C.I. 顏料橙3 8、C . I.顏料橙4 0、C . I.顏料橙4 3、C . I.顏料橙4 6、 C.I.顔料橙49、C.I.顏料橙51、C.I.顏料橙61、C.I.顏料橙 63、C.I.顏料橙64、C.I.顏料橙71、C.I.顏料橙73、C.I.顏 -14- 201003309 料褐23、C.I.顏料褐25; C.I.顏料黑1、C.I.顏料黑7等。 本發明中’著色劑之添加率，可配合所得之感光性樹 脂組成物或其硬化被膜所形成之抗焊阻劑層所需要之色調 ’具體而言’需添加至可呈現的綠色或橙色之充分比例。 本發明中’感光性樹脂組成物或其硬化被膜所呈現之 綠色與橙色，係指由觀察者經由肉眼觀察時，具有可被辨 識出綠色與橙色程度之色調之意。具體而言，係指經由 JISZ872 1規定之方法測定、顯示該感光性樹脂組成物與其 硬化被膜之外觀色調時，屬於孟塞爾色相環（Munsell color hue ring )色相環（財團法人 日本色彩硏究所監修 新基本色表系列2 孟塞爾系統 日本色硏事業股份有限 公司發行；參考圖1 )上，10Y至10BG (綠色）、10R至 10 YR (橙色）之色相範圍，更佳爲彩度爲2以上、未達16 ，亮度爲2以上、未達9，更佳爲彩度爲3以上、未達15, 亮度爲3以上、未達9未満之綠色系、橙色系等可呈現彩色 L 之內容。 茈系著色劑（A -1 )與其他之著色劑之添加比例’因 受到所使用之著色劑的種類或其他之添加劑等的種類所影 響，故無法統一規範，但可予以適當設定，例如，與酞菁 系著色劑（A-2)之添加比，就質量比而言’以茈系著色 劑（A-1 ):酞菁系著色劑（A-2 ) = 1 : 0〜1 : 20之比例 添加爲佳。 其次，將對本發明之感光性樹脂組成物之著色劑以外 的各構成成份進行詳細說明。 -15- 201003309 本發明之感光性樹脂組成物可使用如下述內容般之材 料。 (B)含羧酸之樹脂 本發明之組成物中，就賦予鹼顯影性等目的時，可使 用分子中具有羧基之含羧酸之樹脂（B)，其可使用以往 公知之各種樹脂化合物。特別是，分子中具有乙烯性不飽 和雙鍵之含羧酸感光性樹脂（B ’），就光硬化性或耐顯影 性等觀點而言爲更佳。又，該不飽和雙鍵以由丙烯酸或甲 基丙烯酸或其衍生物所產生者爲佳。 含羧酸之樹脂（B )之具體例，以以下所列舉之化合 物爲佳。 (1) (甲基）丙烯酸與含不飽和基之物經共聚合所 得之含羧酸之樹脂。 (2) 二異氰酸酯與含羧酸之二醇（dialcohol)化合 物及二醇（diol )化合物之聚加成反應所得之含羧酸脂胺 基甲酸酯樹脂。 (3) 二異氰酸酯與2官能環氧（甲基）丙烯酸酯或其 部份酸酐改質物及含羧酸之二醇化合物及二醇化合物之聚 加成反應所得之感光性含羧酸之胺基甲酸酯樹脂。 (4) 前述（2)或（3)之樹脂的合成中，於分子内 加入1個之羥基與1個以上之具有（甲基）丙烯酸基之化合 物所得之末端（甲基）丙烯酸化之含羧酸之胺基甲酸酯樹 脂。 -16- 201003309 (5) 目(j述（2)或（3)之樹脂的合成中，於分子内 加入1個之異氰酸醋基與1個以上之具有（甲基）丙嫌酸基 之化合物所得之末端（甲基）丙烯酸化之含羧酸之胺基甲 酸酯樹脂。 (6) 2官能與多官能（固形）環氧樹脂與（甲基）丙 烯酸反應，於側鏈所存在之羥基附加二質子酸酐所得感光 性含羧酸之樹脂。 (7 ) 2官能（固形）環氧樹脂之羥基再經表氯醇（ epichlorohydrin )環氧化所得之多官能環氧樹脂再與（甲 基）丙烯酸反應，所生成之羥基再加成二質子酸酐所得之 感光性含羧酸之樹脂。 (8) 2官能環氧丙烷樹脂與二羧酸反應，所生成之1 級之羥基再加成二元酸酐所得之含羧酸之聚酯樹脂。 (9) 上述樹脂再加成1分子内具有 1個之環氧基與1 個以上之（甲基）丙烯酸基之化合物所得之感光性含羧酸 之樹脂。 又，本說明書中，（甲基）丙烯酸酯係爲丙烯酸酯、 甲基丙烯酸酯及該些混合物之統稱用語，其他之類似表現 亦爲相同之內容。 上述含羧酸之樹脂（B)，因於骨架·聚合物之側鏈 上具有多數游離之羧基，故可經由稀鹼水溶液顯影。 又，上述含羧酸之樹脂（B )之酸價以40〜200 mgKOH/g之範圍爲佳，更佳爲45〜120 mgK〇H/g之範圍 。含羧酸之樹脂的酸價未達40 mgK〇H/ g時’則造成驗顯 -17- 201003309 影之困難性，又，超過200 mgKOH/ g時，因顯影液會促 進曝光部之溶解，故超過必要以上之線路狹窄化，或可能 會造成無法區別曝光部與未曝光部而同時被顯影液溶解剝 離，無法形成正常之阻劑圖型之描繪等，而爲不佳。 又，上述含羧酸之樹脂（B)之重量平均分子量，依 樹脂骨架而有所不同，一般爲約2,000〜150,000，更佳爲 5,000〜100, 〇〇〇之範圍爲佳。重量平均分子量未達2, 〇〇〇時 ’因去黏著（tackfree )性能劣化，故會造成曝光後之塗 膜的耐濕性惡化，顯影時產生膜削減，解析度大幅劣化等 情形。又，重量平均分子量超過1 5 0,0 0 0時，造成顯影性 顯著惡化，貯藏安定性劣化等情形。 該些含羧酸之樹脂（B)之添加率，於全組成物中， 較佳爲2 0〜6 0質量％，更佳爲3 0〜5 0質量％。少於上述範 圍之情形，因塗膜強度會有降低情形而爲不佳。又，多於 上述範圍時，因黏性過高，故會有塗佈性等降低之情形， 而爲不佳。 該些含羧酸之樹脂並不限於上述用途皆可使用，其可 使用1種或將多數混合使用亦可。 (c)光聚合引發劑 本發明之感光性樹脂組成物，爲含有光聚合引發劑（ C)所得者。 光聚合引發劑（C )，以使用由肟酯系光聚合引發劑 、α-胺基乙醯苯系光聚合引發劑，及醯基膦氧化物系光 -18- 201003309 聚合引發劑所成群中所選出之1種以上之光聚合引發劑爲 佳。 肟酯系光聚合引發劑，就市售品例如汽巴.特用化學 公司製之 CGI-325 、 IRGACURE OXE01 ' IRGACURE OXE02等，ADEKA公司製N-1919等。該些肟酯系光聚合引 發劑，可單獨或將2種以上組合使用皆可。 α -胺基乙醯苯系光聚合引發劑例如，2-甲基-1-〔 4-(甲基硫）苯基〕-2 -嗎啉代丙酮-1、2 -苄基-2 -二甲基胺 基-1 - ( 4 -嗎啉代苯基）-丁烷-1 -酮、2 -(二甲基胺基）-2 -〔（4-甲基苯基）甲基〕-l-〔 4-(4-嗎啉基）苯基〕-1-丁 酮、N，N-二甲基胺基乙醯苯等。市售品例如汽巴·特用化 學公 司製之 IRGACURE907 、 IRGACURE369 、 IRGACURE379 等。 醯基膦氧化物系光聚合引發劑，例如2,4,6 -三甲基苯 醯二苯基膦氧化物、雙（2,4,6-三甲基苯醯）-苯基膦氧化 物、雙（2,6-二甲氧基苯醯）-2，4,4-三甲基-戊基膦氧化物 等。市售品例如BASF公司製之RUSIRIN TPO (商品名）、 汽巴•特用化學公司製之IRGACURE819等。 該些光聚合引發劑（C)之添加率，相對於前述含羧 酸之樹脂（B) 100質量份，較佳爲〇.〇1〜30質量份，更佳 爲0.5〜15質量份之範圍。未達o.oi質量份時，於銅上之光 硬化性不足，會造成塗膜剝離，耐藥品性等塗膜特性降低 等’而爲不佳。又’超過3 0質量份時，將因光聚合引發劑 (C)之抗焊阻劑塗膜表面具有劇烈之光吸收，故會有深 -19- 201003309 部硬化性降低之傾向，而爲不佳。 又，膀酯系光聚合引發劑之情形，其添加率’相封於 前述含羧酸之樹脂（B) 100質量份，較佳爲〇·01〜20質量 份，更佳爲0.01〜5質量份之範圍爲佳。 又本發明之感光性樹脂組成物中，可使用上述化合物 以外之光聚合引發劑，或光引發輔劑及增感劑’例如’苯 偶因化合物、乙醯苯化合物、蒽醌化合物、噻噸酮（ thioxanthone )化合物、縮酮化合物、二苯甲酮化合物、 咕噸酮（t h i ο X a n t h ο n e )化合物、與3級胺化合物等。 苯偶因化合物之具體例’例如，苯偶因、苯偶因甲基 醚、苯偶因乙基醚、苯偶因異丙基醚。 乙醯苯化合物之具體例’例如，乙醯苯、2，2_二甲氧 基-2-苯基乙醯苯、2,2-二乙氧基-2_苯基乙醯苯、丨丨-二氯 基乙醯苯。 蒽醌化合物之具體例’例如，2 -甲基惠_、2 -乙基蒽 醌、2-t-丁基蒽醌、1-氯基蒽醌。 噻噸酮化合物之具體例，例如，2，4 -二甲基噻噸酮、 2,4 -二乙基噻噸酮、2-氯基噻噸酮、2,4_二異丙基噻噸酮 〇 縮酮化合物之具體例，例如，乙醯苯二甲基縮酮、苄 基二甲基縮酮。 二苯甲酮化合物之具體例’例如，二苯甲酮、4 _苯醢 二苯基硫醚、4 -苯醯·4’-甲基二苯基硫醚、4_苯醯_4’_乙基 二苯基硫醚、4-苯醯-4’-丙基二苯基硫醚。 -20- 201003309 3級胺化合物之具體例，例如，乙醇胺化合物、具有 二烷基胺基苯構造之化合物、例如，4,4’-二甲基胺基二苯 甲酮（日本曹達公司製NISOKIYUAMABP(商品名））、 4,4’-二乙基胺基二苯甲酮（保土之谷化學公司製EAB )等 之二烷基胺基二苯甲酮、7-(二乙基胺基）-4-甲基- 2H-1-苯倂吡喃-2-酮（7-(二乙基胺基）-4-甲基薰草素）等之 含有二烷基胺基之薰草素化合物、4-二甲基胺基安息香酸 乙酯（日本化藥公司製KAYAKIYU EPA) 、2-二甲基胺基 安息香酸乙醋（國際微胃生物科技公司製Quantacure DMB) 、4-二甲基胺基安息香酸（η-丁氧基）乙基（國際微生物 科技公司製Quantacure ΒΕΑ) 、p-二甲基胺基安息香酸異 戊乙基酯（日本化藥公司製KAYAKIYU DMBI ) 、4-二甲 基胺基安息香酸2_乙基己醋（Van Dyk公司製Esolc)1 507) 、4,4，-二乙基胺基二苯甲酮（保土之谷化學公司製EAB) 〇 上述內容之中’以使用噻噸酮化合物與3級胺化合物 爲佳。含有噻噸酮化合物時’就深部硬化性等觀點而言爲 較佳，其中又以2，4 -二甲基噻噸酮、2,4 -二乙基噻噸酮、 2 -氯基噻噸酮、2，4_二異丙基噻噸酮等之噻噸酮化合物爲 佳。 該些噻噸酮化合物之添加率，相對於上述含羧酸之樹 脂（B ) 100質量份’較佳爲20質量份以下，更佳爲1〇質量 份以下。噻噸酮化合物之添加率過多時，會造成厚膜硬化 性降低，其因會造成成本升高，故亦爲不佳。 -21 - 201003309 3級胺化合物，以具有二烷基胺基苯構造之化合物爲 佳，其中又以，二烷基胺基二苯甲酮化合物，最大吸收波 長爲350〜41〇nm之含有二烷基胺基之薰草素化合物爲最佳 。二烷基胺基二苯甲酮化合物，例如4,4’-二乙基胺基二苯 甲酮以其毒性亦較低，而爲較佳。最大吸收波長爲3 5 0〜 410 nm之含有二烷基胺基之薰草素化合物，因其最大吸收 波長爲紫外線區域，故其著色較少，而形成具有無色透明 之感光性組成物，其於使用著色劑時，可反應著色劑本體 之顏色，而可提供著色抗焊阻劑膜。特別是，7 -(二乙基 胺基）-4-甲基-2H-1-苯倂吡喃-2-酮相對於波長400〜 410nm之雷射光顯示出優良之增感效果而爲較佳。 該些3級胺化合物之添加率，相對於前述含羧酸之樹 脂（B) 100質量份，較佳爲0.1〜20質量份，更佳爲0.1〜 1 〇質量份之比例。3級胺化合物之添加率未達0.1質量份時 ，會有未能得到充分之增感效果的傾向。超過20質量份時 ，將因3級胺化合物而會於乾燥抗焊阻劑塗膜之表面形成 劇烈之光吸收，而會有深部硬化性降低之傾向。 該些光聚合引發劑、光引發輔劑與增感劑，可單獨使 用或使用2種類以上之混合物。 (D )分子中具有2個以上之乙烯性不飽和基之化合物 本發明之感光性樹脂組成物’爲含有分子中具有2個 以上之乙烯性不飽和基之化合物（D )所得者。 分子中具有2個以上之乙烯性不飽和基之化合物（D ) -22- 201003309 爲，經由活性能量線照射結果，形成光硬化’可幫助前述 含羧酸之樹脂（B )形成對鹼水溶液不溶化’或不溶化之 化合物。該些化合物，例如乙二醇、甲氧基四乙二醇、聚 乙二醇、丙二醇等之甘醇的二丙烯酸酯類；己烷二醇、三 羥甲基丙烷、季戊四醇、二季戊四醇、三-羥基乙基三聚 異氰酸酯等多元醇或該些之乙烯氧化物加成物或丙烯氧化 物加成物等多元丙烯酸酯類；苯氧基丙烯酸酯 '雙酚A二 丙烯酸酯，及該些之酚類的乙烯氧化物加成物或丙烯氧化 物加成物等之多元丙烯酸酯類；丙三醇二縮水甘油醚、丙 三醇三縮水甘油醚、三羥甲基丙烷三縮水甘油醚、三縮水 甘油三聚異氰酸酯等之縮水甘油醚等多元丙烯酸酯類；及 三聚氰胺丙烯酸酯，及/或對應於上述丙烯酸酯之各甲基 丙烯酸酯類等。 此外，例如甲酚酚醛清漆型環氧樹脂等之多官能環氧 樹脂，與丙烯酸反應所得之環氧丙烯酸酯樹脂，或，再於 該些環氧丙稀酸酯樹脂之經基上，與季戊四醇三丙嫌酸酯 等之羥基丙烯酸酯與異佛爾酮二異氰酸酯等之二異氰酸酯 之半胺基甲酸酯化合物反應所得之環氧胺基甲酸酯丙烯酸 酯化合物等。該些環氧丙烯酸酯系樹脂，不會造成指觸乾 燥性降低，而可提高光硬化性。 該些分子中具有2個以上之乙烯性不飽和基之化合物 (D)的添加率，相對於前述（B)含羧酸之樹脂1〇〇質量 份，較佳爲5〜100質量份，更佳爲！〜70質量份之比例。 前述添加率未達5質量份時’其光硬化性會降低，且經由 -23- 201003309 活性能量線照射後之驗顯影，亦不容易形成圖型，而爲不 佳。又’超過1 〇〇質量份時’因會降低對鹼水溶液之溶解 性，而使塗膜脆化，故亦爲不佳。 (E )熱硬化性成份 本發明之感光性樹脂組成物中，爲賦予其耐熱性，可 添加（E )熱硬化性成份。特佳者爲分子中具有2個以上之 環狀醚基及/或環狀硫醚基（以下，簡稱爲環狀（硫）醚 基）之熱硬化性成份（E )。 該些分子中具有2個以上之環狀（硫）醚基之熱硬化 性成份（F) ’以分子中具有3、4或5員環之環狀醚基，或 環狀硫醚基中任一者或具有2個以上2種類之基的化合物爲 佳，例如’分子内具有至少2個以上之環氧基的化合物， 即，多官能環氧化合物（E-1)，分子内至少具有2個以上 之環氧丙烷基之化合物，即，多官能環氧丙烷化合物（E -2)、分子内具有2個以上之環狀硫醚基之化合物，即，環 氧硫化合物（episulfide) ( E-3)等。 前述多官能環氧化合物（E-1)，例如，日本環氧樹 脂公司製之 Epikote828、Epikote834、EpikotelOOl 、 Epikotel004，大日本油墨化學工業公司製之Epiclon840、 Epiclon850、Epiclonl050、Epiclon2055，東都化成公司製 之 EpotootoYD-011、YD-013、YD-127、YD-128，道化學 公司製之 D. E. R. 317、D. E. R. 331、D. E. R. 661、D. E· R. 664、 汽巴 •特用化學公司之Araldite607 1 、 -24- 201003309Pigment Red 122, Pigment Red 202, Pigment Red 206, Pigment Red 207, Pigment Red 209 o For the purpose of adjusting other color tones, a coloring agent such as purple, orange, brown, or enamel may be added. Specific examples are, for example, Pigment Violet 19, 23, 32, 36, 38, 42, Solvent Violet 13, 36, CI Pigment Orange 1, CI Pigment Orange 5, CI Pigment Orange 13, CI Pigment Orange 14, CI Pigment Orange 16, CI Pigment Orange 17, C.I_Pigment Orange 24, CI Pigment Orange 34, CI Pigment Orange 36, CI Pigment Orange 3 8, C. I. Pigment Orange 4 0, C. I. Pigment Orange 4 3, C. I .Pigment Orange 4 6 , CI Pigment Orange 49, CI Pigment Orange 51, CI Pigment Orange 61, CI Pigment Orange 63, CI Pigment Orange 64, CI Pigment Orange 71, CI Pigment Orange 73, CI Yan-14-201003309 Brown 23 , CI Pigment Brown 25; CI Pigment Black 1, CI Pigment Black 7, etc. In the present invention, the addition ratio of the coloring agent can be added to the green or orange color which can be exhibited by the color tone required for the resistive resist layer formed by the obtained photosensitive resin composition or the cured film thereof. Full proportion. In the present invention, the green color and the orange color appearing in the photosensitive resin composition or the cured film thereof mean that the color of the green and orange colors can be recognized by the observer when observed by the naked eye. Specifically, when measuring the color tone of the photosensitive resin composition and the cured film thereof by the method specified in JIS Z872 1, it belongs to the Munsell color hue ring hue circle (Japanese color research) The new basic color table series 2 is supervised by Munsell Systems Japan Colors Co., Ltd.; refer to Figure 1), the range of hue of 10Y to 10BG (green), 10R to 10 YR (orange), more preferably chroma 2 or more, less than 16, brightness 2 or more, less than 9, more preferably 3 or more, less than 15, brightness of 3 or more, less than 9 green, orange, etc. The content. The addition ratio of the anthraquinone coloring agent (A-1) to other coloring agents is affected by the type of the coloring agent to be used or the type of other additives, and thus cannot be uniformly standardized, but can be appropriately set, for example, In comparison with the addition ratio of the phthalocyanine coloring agent (A-2), in terms of the mass ratio, the coloring agent (A-1): phthalocyanine coloring agent (A-2) = 1 : 0 to 1: 20 The ratio is added as well. Next, each constituent component other than the coloring agent of the photosensitive resin composition of the present invention will be described in detail. -15- 201003309 A photosensitive resin composition of the present invention can be used as described below. (B) carboxylic acid-containing resin In the composition of the present invention, when a purpose such as alkali developability is imparted, a carboxylic acid-containing resin (B) having a carboxyl group in a molecule can be used, and various conventionally known resin compounds can be used. In particular, the carboxylic acid-containing photosensitive resin (B') having an ethylenic unsaturated double bond in the molecule is more preferable from the viewpoints of photocurability and development resistance. Further, the unsaturated double bond is preferably produced from acrylic acid or methacrylic acid or a derivative thereof. Specific examples of the carboxylic acid-containing resin (B) are preferably the compounds listed below. (1) A carboxylic acid-containing resin obtained by copolymerizing (meth)acrylic acid with an unsaturated group-containing material. (2) A carboxylic acid ester-containing urethane resin obtained by a polyaddition reaction of a diisocyanate with a carboxylic acid-containing dialcohol compound and a diol compound. (3) a photosensitive carboxylic acid-containing amine group obtained by a polyaddition reaction of a diisocyanate with a bifunctional epoxy (meth) acrylate or a partial acid anhydride modified product thereof, a carboxylic acid-containing diol compound and a diol compound Formate resin. (4) In the synthesis of the resin of the above (2) or (3), a terminal (meth)acrylated product obtained by adding one hydroxyl group to one or more compounds having a (meth)acryl group in the molecule A carboxylic acid urethane resin. -16- 201003309 (5) In the synthesis of the resin of (2) or (3), one isocyanate group and one or more (meth)acrylic acid groups are added to the molecule. a terminal (meth)acrylated carboxylic acid-containing urethane resin obtained from the compound. (6) A bifunctional and polyfunctional (solid) epoxy resin reacts with (meth)acrylic acid in the side chain a photosensitive carboxylic acid-containing resin obtained by adding a di-proton anhydride to a hydroxyl group. (7) A polyfunctional epoxy resin obtained by epoxidation of a hydroxyl group of a 2-functional (solid) epoxy resin with epichlorohydrin and (methyl) a photosensitive carboxylic acid-containing resin obtained by reacting an acrylic acid with a hydroxyl group formed by adding a diproton anhydride. (8) A 2-functional propylene oxide resin is reacted with a dicarboxylic acid, and a hydroxyl group of the first-stage hydroxy group is further added thereto. A carboxylic acid-containing polyester resin obtained by the carboxylic acid anhydride. (9) A photosensitive carboxylic acid obtained by further adding a compound having one epoxy group and one or more (meth)acrylic groups in one molecule. Further, in the present specification, the (meth) acrylate is acrylic acid. The esters, methacrylates, and the likes of these mixtures are the same. The above-mentioned carboxylic acid-containing resin (B) has a large number of free carboxyl groups in the side chain of the skeleton/polymer. Therefore, the acid value of the carboxylic acid-containing resin (B) is preferably in the range of 40 to 200 mgKOH/g, more preferably in the range of 45 to 120 mgK〇H/g. When the acid value of the acid resin is less than 40 mgK〇H/g, it will cause difficulty in the detection of -17-201003309. Moreover, when it exceeds 200 mgKOH/g, the developer will promote the dissolution of the exposed portion, so it exceeds If the above-mentioned route is narrowed, the exposed portion and the unexposed portion may not be distinguished, and the developer may be dissolved and peeled off at the same time, and the formation of a normal resist pattern may not be formed, which is not preferable. The weight average molecular weight of the resin (B) varies depending on the resin skeleton, and is generally about 2,000 to 150,000, more preferably 5,000 to 100, and the range of ruthenium is preferred. The weight average molecular weight is less than 2, 〇〇〇 When 'dackfree' performance is degraded, The moisture resistance of the coating film after the exposure is deteriorated, and the film is reduced during the development, and the resolution is largely deteriorated. When the weight average molecular weight exceeds 150,000, the developability is remarkably deteriorated, and the storage stability is improved. In the case of deterioration, etc., the addition ratio of the carboxylic acid-containing resin (B) is preferably from 20 to 60% by mass, more preferably from 30 to 50% by mass, based on the total composition. In the case where the coating film strength is lowered, it is not preferable. When the amount is more than the above range, the viscosity is too high, so that the coating property or the like is lowered, which is not preferable. These carboxylic acid-containing resins are not limited to the above-mentioned uses, and they may be used singly or in combination of a plurality of them. (c) Photopolymerization initiator The photosensitive resin composition of the present invention is obtained by containing a photopolymerization initiator (C). The photopolymerization initiator (C) is grouped using a phthalone-based photopolymerization initiator, an α-aminoethyl benzene-based photopolymerization initiator, and a mercaptophosphine oxide-based light-18-201003309 polymerization initiator. One or more photopolymerization initiators selected from the above are preferred. The oxime ester-based photopolymerization initiator is commercially available as CGI-325, IRGACURE OXE01 'IRGACURE OXE02, manufactured by Ciba Specialty Chemicals Co., Ltd., N-1919 manufactured by ADEKA Co., Ltd., and the like. These oxime ester-based photopolymerization initiators may be used alone or in combination of two or more. α-Aminoethyl benzene-based photopolymerization initiator, for example, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinoacetone-1,2-benzyl-2 -di Methylamino-1-(4-morpholinophenyl)-butane-1-one, 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-l -[4-(4-morpholinyl)phenyl]-1-butanone, N,N-dimethylaminoethyl benzene, and the like. Commercial products such as IRGACURE 907, IRGACURE 369, IRGACURE 379, etc. manufactured by Ciba Specialty Chemicals Co., Ltd., etc. Mercaptophosphine oxide photopolymerization initiator, for example, 2,4,6-trimethylphenylhydrazine diphenylphosphine oxide, bis(2,4,6-trimethylphenylhydrazine)-phenylphosphine oxide , bis(2,6-dimethoxybenzoquinone)-2,4,4-trimethyl-pentylphosphine oxide, and the like. Commercially available products are, for example, RUSIRIN TPO (trade name) manufactured by BASF Corporation, and IRGACURE 819 manufactured by Ciba Specialty Chemicals Co., Ltd., and the like. The addition ratio of the photopolymerization initiator (C) is preferably from 1 to 30 parts by mass, more preferably from 0.5 to 15 parts by mass, per 100 parts by mass of the carboxylic acid-containing resin (B). . When the mass fraction of o. oi is not obtained, the light hardening property on the copper is insufficient, and the coating film is peeled off, and the coating property such as chemical resistance is lowered, which is not preferable. In addition, when the amount exceeds 30 parts by mass, the surface of the anti-solder resist coating film of the photopolymerization initiator (C) has a strong light absorption, so that the deep -19-201003309 portion has a tendency to decrease in hardenability, and is not good. Further, in the case of a urethane-based photopolymerization initiator, the addition ratio is preferably 100 parts by mass of the carboxylic acid-containing resin (B), preferably 0.001 to 20 parts by mass, more preferably 0.01 to 5 parts by mass. The range is best. Further, in the photosensitive resin composition of the present invention, a photopolymerization initiator other than the above compounds, or a photoinitiator adjuvant and a sensitizer such as a benzoin compound, an acetophenone compound, an anthraquinone compound, and a thioxanthene can be used. A thioxanthone compound, a ketal compound, a benzophenone compound, a thi ox X anth ο ne compound, a tertiary amine compound, and the like. Specific examples of the benzoin compound are, for example, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether. Specific examples of the acetophenone compound are, for example, acetophenone, 2,2-dimethoxy-2-phenylethyl benzene, 2,2-diethoxy-2-phenyl phenyl benzene, hydrazine - Dichloroethyl benzene. Specific examples of the hydrazine compound 'e.g., 2-methyl oxime, 2-ethyl hydrazine, 2-t-butyl hydrazine, 1-chloro hydrazine. Specific examples of the thioxanthone compound, for example, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-diisopropylthioxanthene Specific examples of the ketoxime ketone compound are, for example, acetophenone ketal and benzyl dimethyl ketal. Specific examples of the benzophenone compound 'for example, benzophenone, 4-phenylindole diphenyl sulfide, 4-benzoquinone 4'-methyldiphenyl sulfide, 4_benzoquinone_4'_ Ethyl diphenyl sulfide, 4-phenylhydrazine-4'-propyl diphenyl sulfide. -20- 201003309 Specific examples of the tertiary amine compound, for example, an ethanolamine compound, a compound having a dialkylaminobenzene structure, for example, 4,4'-dimethylaminobenzophenone (NISOKIYUAMABP, manufactured by Nippon Soda Co., Ltd.) (trade name)), 4,4'-diethylaminobenzophenone (EAB manufactured by Hodogaya Chemical Co., Ltd.), etc., dialkylaminobenzophenone, 7-(diethylamino group) a 4-alkyl- 2H-1-benzopyran-2-one (7-(diethylamino)-4-methylloxacin) or the like containing a dialkylamine group Compound, ethyl 4-dimethylamino benzoate (KAYAKIYU EPA, manufactured by Nippon Kayaku Co., Ltd.), 2-dimethylamino benzoic acid ethyl vinegar (Quantacure DMB, manufactured by International Microgas Biotech Co., Ltd.), 4-dimethyl Amino-based benzoic acid (η-butoxy)ethyl (Quantacure®, manufactured by International Microbiological Technology Co., Ltd.), p-dimethylammonium benzoic acid, isoamylethyl ester (KAYAKIYU DMBI, manufactured by Nippon Kayaku Co., Ltd.), 4- Dimethylamino benzoic acid 2-ethylhexanoic acid (Esolc, manufactured by Van Dyk Co., Ltd.) 1 507), 4,4,-diethylaminobenzophenone (EAB, manufactured by Hodogaya Chemical Co., Ltd.) 〇 Among the contents of said 'using preferably a thioxanthone compound and an amine compound 3 stages. When it contains a thioxanthone compound, it is preferable from the viewpoint of deep hardenability and the like, among which 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxene A thioxanthone compound such as a ketone or a 2,4-diisopropylthioxanthone is preferred. The addition ratio of the thioxanthone compound is preferably 20 parts by mass or less, more preferably 1 part by mass or less, based on 100 parts by mass of the carboxylic acid-containing resin (B). When the addition ratio of the thioxanthone compound is too large, the thick film hardenability is lowered, which is also disadvantageous because it causes an increase in cost. -21 - 201003309 A tertiary amine compound, preferably a compound having a dialkylaminobenzene structure, wherein a dialkylaminobenzophenone compound has a maximum absorption wavelength of 350 to 41 nm. The alkylamine-based humectin compound is preferred. A dialkylaminobenzophenone compound such as 4,4'-diethylaminobenzophenone is preferred because it is also less toxic. The herbicidal compound containing a dialkylamine group having a maximum absorption wavelength of 3 to 50 to 410 nm has a color absorption of less color, and forms a photosensitive composition having colorless transparency. When a colorant is used, the color of the body of the colorant can be reacted, and a colored solder resist film can be provided. In particular, 7-(diethylamino)-4-methyl-2H-1-benzopyran-2-one exhibits an excellent sensitizing effect with respect to laser light having a wavelength of 400 to 410 nm. . The addition ratio of the above-mentioned tertiary amine compound is preferably 0.1 to 20 parts by mass, more preferably 0.1 to 1 part by mass, based on 100 parts by mass of the carboxylic acid-containing resin (B). When the addition ratio of the tertiary amine compound is less than 0.1 part by mass, a sufficient sensitizing effect may not be obtained. When the amount is more than 20 parts by mass, a strong light absorption is formed on the surface of the dry solder resist coating film due to the tertiary amine compound, and the deep hardenability tends to be lowered. These photopolymerization initiators, photoinitiator adjuvants, and sensitizers may be used singly or as a mixture of two or more types. (D) Compound having two or more ethylenically unsaturated groups in the molecule The photosensitive resin composition 'of the present invention' is a compound containing a compound (D) having two or more ethylenically unsaturated groups in the molecule. The compound (D)-22-201003309 having two or more ethylenically unsaturated groups in the molecule is such that photohardening is formed by the irradiation of the active energy ray to help the formation of the carboxylic acid-containing resin (B) to be insolubilized in the aqueous alkali solution. 'Or insoluble compounds. Such compounds, such as diacrylates of glycols such as ethylene glycol, methoxytetraethylene glycol, polyethylene glycol, propylene glycol, etc.; hexane diol, trimethylolpropane, pentaerythritol, dipentaerythritol, three a polyhydric alcohol such as a hydroxyethyl tripolyisocyanate or a polyvalent acrylate such as an ethylene oxide adduct or a propylene oxide adduct; a phenoxy acrylate 'bisphenol A diacrylate, and the like Polyol acrylates such as phenolic ethylene oxide adducts or propylene oxide adducts; glycerol diglycidyl ether, glycerol triglycidyl ether, trimethylolpropane triglycidyl ether, three a polyvalent acrylate such as glycidyl ether such as glycidyl tripolyisocyanate; and melamine acrylate; and/or each methacrylate corresponding to the above acrylate. Further, a polyfunctional epoxy resin such as a cresol novolac type epoxy resin, an epoxy acrylate resin obtained by reacting with acrylic acid, or a base of the epoxy acrylate resin, and pentaerythritol An epoxy urethane acrylate compound obtained by reacting a hydroxy acrylate such as a tripropionate or a diisocyanate compound such as isophorone diisocyanate. These epoxy acrylate-based resins can improve the photocurability without causing a decrease in finger-drying properties. The addition ratio of the compound (D) having two or more ethylenically unsaturated groups in the above-mentioned molecules is preferably from 5 to 100 parts by mass based on 1 part by mass of the above-mentioned (B) carboxylic acid-containing resin. Good for! ~70 parts by mass ratio. When the addition ratio is less than 5 parts by mass, the photocurability is lowered, and the development after irradiation with the active energy ray of -23-201003309 is not easy to form a pattern, which is not preferable. Further, when the amount exceeds 1 part by mass, the coating film is embrittled because it lowers the solubility in the aqueous alkali solution, which is also undesirable. (E) Thermosetting component In the photosensitive resin composition of the present invention, (E) a thermosetting component can be added in order to impart heat resistance. Particularly preferred is a thermosetting component (E) having two or more cyclic ether groups and/or cyclic thioether groups (hereinafter, simply referred to as cyclic (thio)ether groups) in the molecule. The thermosetting component (F) having two or more cyclic (thio)ether groups in the molecule is a cyclic ether group having a ring of 3, 4 or 5 members in the molecule, or a cyclic thioether group. One or a compound having two or more kinds of two types of groups, for example, a compound having at least two or more epoxy groups in the molecule, that is, a polyfunctional epoxy compound (E-1) having at least 2 in the molecule More than one propylene oxide-based compound, that is, a polyfunctional propylene oxide compound (E-2), a compound having two or more cyclic thioether groups in the molecule, that is, an episulfide compound (E) -3) Wait. The above-mentioned polyfunctional epoxy compound (E-1), for example, Epikote 828, Epikote 834, Epikotel OOl, Epikotel 004 manufactured by Nippon Epoxy Co., Ltd., Epiclon 840, Epiclon 850, Epiclon 050, and Epiclon 2055 manufactured by Dainippon Ink and Chemicals Co., Ltd., manufactured by Toho Chemical Co., Ltd. Epotooto YD-011, YD-013, YD-127, YD-128, DER 317, DER 331, DER 661, D. E. R. 664, manufactured by Dow Chemical Co., Ltd., Araldite 607 from Ciba Specialty Chemical Company 1 , 24-201003309

Araldite6084、AralditeGY250、AralditeGY260，住友化學 工業公司製之斯密-環氧ESA-011、ESA-014、ELA-115、 ELA-128，旭化成工業公司製之A. E. R. 330、A. E. R. 331、A. E. R. 661、A. E. R_ 664等（皆爲商品名）之雙酚 A型環氧樹脂；日本環氧樹脂公司製之Epik〇teYL903、大 日本油墨化學工業公司製之Epiclonl52、Epiclonl65、東 都化成公司製之EpotootoYDB-400、YDB-500、道化學公 司製之D. E. R. 542、汽巴•特用化學公司製之 Araldi te 8011、住友化學工業公司製之斯密-環氧ESB-400 、ESB-700、旭化成工業公司製之A. E. R. 711、A. E. R. 7 1 4等（皆爲商品名）之溴化環氧樹脂；日本環氧樹脂公 司製之Epikotel52、Epikotel54、道化學公司製之D. Ε· N. 431、D· E. N. 438、大日本油墨化學工業公司製之 EpiclonN-73 0、EpiclonN-770、EpiclonN- 8 65、東都化成 公司製之Epotooto YDCN-70 1、YDCN-704、汽巴·特用化 學公司製之 AralditeECN 1 2 3 5 、 Ar al d i t e E C N 1 2 7 3 、Araldite6084, AralditeGY250, AralditeGY260, Sumi-Epoxy ESA-011, ESA-014, ELA-115, ELA-128, manufactured by Sumitomo Chemical Industries, AER 330, AER 331, AER 661, AE R_ 664 by Asahi Kasei Kogyo Co., Ltd. Bisphenol A type epoxy resin (both trade names); Epik〇teYL903 manufactured by Japan Epoxy Resin Co., Ltd., Epiclonl 52 manufactured by Dainippon Ink Chemical Industry Co., Ltd., Epiclonl 65, Epotooto YDB-400 manufactured by Dongdu Chemical Co., Ltd., YDB- 500, DER 542 manufactured by Dao Chemical Co., Ltd., Araldi te 8011 manufactured by Ciba Specialty Chemicals Co., Ltd., Smith-Epoxy ESB-400 manufactured by Sumitomo Chemical Industries Co., Ltd., ESB-700, AER 711 manufactured by Asahi Kasei Industrial Co., Ltd. Brominated epoxy resin of AER 7 1 4 (both trade names); Epikotel 52, Epikotel 54 manufactured by Japan Epoxy Resin Co., Ltd., D. Ε·N. 431, D·EN 438, Da Nippon Ink manufactured by Dow Chemical Co., Ltd. Epiclon N-73 0, Epiclon N-770, Epiclon N-8 65 manufactured by Chemical Industry Co., Ltd., Epotooto YDCN-70 manufactured by Dongdu Chemical Co., Ltd. 1, YDCN-704, and Araldite ECN manufactured by Ciba Specialty Chemicals Co., Ltd. 1 2 3 5 , Ar al d i t e E C N 1 2 7 3 ,

AralditeECN 1 299、Ar al d i t e XP Y 3 0 7、日本化藥公司製之 EPPN-201、EOCN- 1 025、EOCN- 1 020、EOCN-104S、RE-306、住友化學工業公司製之斯密-環氧ESCN-195X、 ESCN-220、旭化成工業公司製之A. Ε· R· ECN-23 5、ECN-2 99等（皆爲商品名）之酚醛清漆型環氧樹脂；大日本油 墨化學工業公司製之Epicl〇n8 3 0、日本環氧樹脂公司製 Epikote8 07、東都化成公司製之 E p o t ο o t ο Y D F -1 7 0、Y D F-175 、 YDF-2004 、汽巴 •特用化學公司製之 -25- 201003309AralditeECN 1 299, Ar al dite XP Y 3 0 7. EPPN-201, EOCN-1 025, EOCN-1 020, EOCN-104S, RE-306, manufactured by Nippon Kayaku Co., Ltd. Epoxy ESCN-195X, ESCN-220, A. Ε·R· ECN-23, manufactured by Asahi Kasei Kogyo Co., Ltd. 5, ECN-2 99 (all are trade names), novolak-type epoxy resin; Dainippon Ink Chemical Industry Epicl〇n8 3 0 made by the company, Epikote 8 07 made by Japan Epoxy Co., Ltd., E pot ο ot ο YDF -1 7 0, YD F-175, YDF-2004, Ciba Specialty Chemicals Co., Ltd. System-25-201003309

AralditeXPY3 06等（皆爲商品名）之雙酚F型環氧樹脂； 東都化成公司製之 EPotootoST·2004 ' ST-2007、ST-3000 ( B1 emmer 商品名）等氫化雙酚A型環氧樹脂；日本環氧樹脂公司製 之Epikote604、東都化成公司製之EpotootoYH-434、汽巴 •特用化學公司製之AralditeMY720、住友化學工業公司 製之斯密-環氧ELM-120等（皆爲商品名）之縮水甘油胺型 環氧樹脂；汽巴•特用化學公司製之AralditeCY-3 5 0 (商 品名）等之乙內醯脲（Hydant〇in)型環氧樹脂；DAICEL 化學工業公司製之Cerokisaito202 1、汽巴·特用化學公司 製之AralditeCY175、CY179等（皆爲商品名）之脂環式環 氧樹脂；日本環氧樹脂公司製之YL-93 3、道化學公司製之 T. E. N.、EPPN-501、EPPN-502等（皆爲商品名）之三羥 基苯基甲烷型環氧樹脂；日本環氧樹脂公司製之YL-6056 、YX-4000、YL-6121 (皆爲商品名）等之聯二甲苯醇（ bixylenol)型或雙酌型環氧樹脂或該些混合物，日本化藥 公司製EBPS-200、旭電化工業公司製EPX-30、大日本油 墨化學工業公司製之EXA-1514 (商品名）等之雙酚S型環 氧樹脂；曰本環氧樹脂公司製之Epikotel 57S (商品名）等 之雙酚A酚醛清漆型環氧樹脂；日本環氧樹脂公司製之 EpikoteYL-931、汽巴•特用化學公司製之Aralditel63等 (皆爲商品名）之四酚乙烷型環氧樹脂；汽巴•特用化學 公司製之AralditePT81〇、日産化學工業公司製之TEPIC等 (皆爲商品名）之雜環式環氧樹脂；日本油脂公司製 DGT等之二縮水甘油苯甲酸酯樹脂；東都化成公 -26- 201003309 司製ZX-1063等之四縮水甘油二甲苯醯乙烷樹脂；新日鐵 化學公司製ESN-190、ESN-360、大曰本油墨化學工業公 司製HP-403 2、EXA-475 0、EXA-4700等之含萘基之環氧樹 月旨：大日本油墨化學工業公司製HP-72 00、HP-7200H等之 具有二環戊二烯骨架之環氧樹脂；日本油脂公司製CP-50S 、CP-50M等之縮水甘油甲基丙烯酸酯共聚合系環氧樹脂 ;此外，例如環己基馬來醯亞胺與縮水甘油甲基丙烯酸酯 之共聚合環氧樹脂；環氧改質之聚丁二烯橡膠衍生物（例 如DAICEL化學工業製PB-3600等）、CTBN改質環氧樹脂 (例如東都化成公司製之YR-102、YR-450等）等，但並 未限定於該些內容。該些環氧樹脂，可單獨或將2種以上 組合使用。其中，特別是以酚醛清漆型環氧樹脂、雜環式 環氧樹脂、雙酚A型環氧樹脂或其之混合物爲佳。 前述多官能環氧丙烷化合物（E-2)，例如雙〔（3-甲基-3-環氧丙烷甲氧基）甲基〕醚、雙〔（3-乙基-3-環 I 氧丙院甲氧基）甲基〕酸、1,4 -雙〔（3 -甲基-3-環氧丙院 甲氧基）甲基〕苯、1,4-雙〔（3-乙基-3-環氧丙烷甲氧基 )甲基〕苯、（3-甲基-3-環氧丙烷）甲基丙烯酸酯、（3-乙基-3-環氧丙烷）甲基丙烯酸酯、（3 -甲基-3-環氧丙烷 )甲基丙烯酸甲酯、（3 -乙基-3-環氧丙烷）甲基丙烯酸甲 酯或該些低聚物或共聚合體等多官能環氧丙院類以外，例 如環氧丙烷醇與酚醛清漆樹脂、聚（P-羥基苯乙燏）、籠 型雙酚類、杯芳烴類、杯間苯二酚芳烴類、或倍半噁烷等 具有羥基之樹脂之醚化物等。其他，例如具有環氧丙烷環 -27- 201003309 之不飽和單體與（甲基）丙烯酸烷基酯之共聚 環氧硫化合物（E-3 )，例如，日本環氧 之雙酚A型環氧硫樹脂YL7000等。又，亦可使 合成方法，將酚醛清漆型環氧樹脂之環氧基的 原子取代所得之環氧硫樹脂等。 前述分子中，具有2個以上之環狀（硫） 化性成份（E )之添加率，相對於前述（B )含 之羧基1當量，較佳爲0.6〜2.5當量，更佳爲0 之範圍。分子中具有2個以上之環狀（硫）醚 性成份（E )之添加率未達0.6當量時，抗焊阻 留羧基，而會造成耐熱性、耐鹼性、電氣絕緣 而爲不佳。又，超過2.5當量時，低分子量之 醚基將會殘留於乾燥塗膜上，而會造成塗膜之 ，而爲不佳。 本發明之感光性樹脂組成物中，使用含有 具有2個以上之環狀（硫）醚基的熱硬化性成1 形，以含有（F )熱硬化觸媒爲佳。該些熱硬/ ，例如，咪唑、2 -甲基咪唑、2 -乙基咪唑、2-咪唑、2 -苯基咪唑、4 -苯基咪唑、1-氰基乙基 、1- ( 2-氰基乙基）-2-乙基-4-甲基咪唑等味 二氰二醯胺、苄基二甲基胺、4-(二甲基胺； 甲基苄基胺、4 -甲氧基-Ν,Ν -二甲基苄基胺、 二甲基苄基胺等之胺化合物、己二酸二醯肼、 肼等肼化合物；三苯基膦等之磷化合物等，或 物等。 樹脂公司製 用依相同之 氧原子以硫 醚基之熱硬 羧酸之樹脂 .8〜2.0當量 基之熱硬化 劑膜中將殘 性等降低， 環狀（硫） 強度等降低 上述分子中 分（Ε )之情 七觸媒（F ) 乙基-4-甲基 -2 -苯基咪唑 唑衍生物； S ) -Ν，Ν-二 4-甲基-Ν，Ν-癸二酸二醯 市售之產品 -28- 201003309 ，例如四國化成工業公司製之2MZ-A、2MZ-OK、2PHZ、 2P4BHZ、2P4MHZ (任一者皆爲咪唑系化合物之商品名） ' SAN-APRO公司製之 U-CAT3 503N、U-C AT3 5 02T (任一 者皆爲二甲基胺之嵌段異氰酸酯化合物之商品名）、DBU 、DBN、U-CATSA102、U-CAT5002 (任一者皆爲二環式 脒化合物及其鹽）等。 特別是，並未限定於該範圍之中，只要可促進環氧樹 脂或環氧丙烷化合物之熱硬化觸媒，或環氧基及/或環氧 丙烷基與羧基之反應者皆可使用，其可單獨或將2種以上 混合使用皆可。又，可使用胍、甲基胍胺、苯倂胍、三聚 氰胺' 2,4 -二胺基-6-甲基丙烯醯氧乙基-S-三嗪、2 -乙烯 基-2,4-二胺基-S-三嗪、2-乙烯基-4,6-二胺基-S-三嗪•三 聚異氰酸加成物、2,4-二胺基-6-甲基丙烯醯氧乙基-S-三 嗪•三聚異氰酸加成物等之S-三嗪衍生物，較佳爲將其作 爲密著性增強劑之機能化合物而與前述熱硬化觸媒合倂使 用。 該些熱硬化觸媒（F )之添加率，以通常量之比例即 可’例如相對於（B )含羧酸之樹脂或分子中具有2個以上 之環狀（硫）醚基之熱硬化性成份（E ) 100質量份，較佳 爲0.1〜20質量份，更佳爲0.5〜15.0質量份。 本發明之感光性樹脂組成物，爲提高該塗膜之物理性 強度等目的時，可配合其必要性，添加塡料。該些塡料， 可使用公知慣用之無機或有機塡料，特別是以使用硫酸鋇 '球狀二氧化矽與滑石爲佳。此外，可使用酸化鈦或金屬 -29- 201003309 氧化物、氫氧化鋁等之金屬氫氧化物作爲體質顏料之塡料 使用。塡料之添加率，較佳爲組成物全體量之75質量％以 下，更佳爲〇 . 1〜6 0質量％之比例。塡料之添加率’超過組 成物全體量之7 5質量。/。時，會增高絕緣組成物之黏度，降 低塗佈、成形性，使硬化物脆化等，而爲不佳。 此外，本發明之感光性樹脂組成物，於上述（B )含 羧酸之樹脂之合成或製作組成物等目的’或塗佈基板或負 載薄膜時所進行之黏度調整等目的，可使用有機溶劑。 該些有機溶劑，例如酮類、芳香族烴類、甘醇醚類、 甘醇醚乙酸酯類、酯類、醇類、脂肪族烴、石油系溶劑等 。更具體而言，例如甲基乙基酮、環己酮等酮類；甲苯、 二甲苯、四甲基苯等芳香族烴類；溶纖劑、甲基溶纖劑、 丁基溶纖劑、卡必醇、甲基卡必醇'丁基卡必醇、丙二醇 單甲基醚、二丙二醇單甲基醚、二丙二醇二乙基醚、三乙 二醇單乙基醚等甘醇醚類；乙酸乙酯、乙酸丁酯、二丙二 醇甲基醚乙酸酯、丙二醇甲基醚乙酸酯、丙二醇乙基醚乙 酸酯、丙二醇丁基醚乙酸酯、乳酸甲酯、乳酸乙酯、乳酸 丁酯等酯類；乙醇、丙醇、乙二醇、丙二醇等醇類；辛院 、癸烷等脂肪族烴；石油醚、石油腦、氫化石油腦、 So Went石油腦等石油系溶劑等。該些有機溶劑，可單獨或 以2種以上之混合物方式使用。 本發明之感光性性樹脂組成物，更必要時，可添加氫 醌、氫醌單甲基醚、t-丁基兒茶酚、五倍子酚、吩噻哄等 公知慣用之熱聚合阻礙劑 '微粉二氧化矽、有機膨潤土、 -30- 201003309 蒙脫土等公知慣用之增黏劑、聚较氧系、氟系、高分子系 等之消泡劑及/或整平劑、咪唑系、噻唑系、三Π坐系等之 矽院偶合劑、抗氧化劑、抗鏽劑等公知慣用之添加劑類。 【實施方式】 [實施例] 以下將以實施例與比較例對本發明作具體之說明，但 本發明並不受下述實施例所限定。又，以下所稱之「份」 ，於無特別限定下，爲表示「質量份」之意。 〔實施例1〕 <含羧酸之樹脂之合成> 本發明之含羧酸之樹脂（B )係依下述合成例所製作 者。 將甲酚酚醛清漆型環氧樹脂（大日本油墨化學工業（ 株）製、“ Epiclon” （登錄商標）N-695、環氧當量：220 )220份加入附有攪拌機及迴流冷卻器之四口燒瓶中，加 入卡必醇乙酸酯2 1 4份，加熱溶解。 其次，加入作爲聚合阻礙劑之氫醌0 · 4 6份，與作爲反 應觸媒之三苯基膦1.38份。將該混合物加熱至95〜105 °C ，將丙烯酸72份緩緩滴下，進行16小時之反應。將該反應 產物冷卻至80〜90 °C，加入四氫苯甲酸酐106份，進行8小 時之反應’冷卻後，取出反應溶液（亦稱爲蠟（B-1)) 。依前述方式所得之含羧酸之樹脂，其固形物之酸價爲 -31 - 201003309 1 00 mgKOH/ g ’不揮發成份爲65%。 <添加例> 將下述成份以下述添加量於攪拌機中進行預混合後， 使用3輥滾筒硏磨機混練以製作各抗焊阻劑用感光性樹脂 組成物（組成物例1〜8 )。其中，所得之感光性樹脂組成 物的分散度使用Erichsen公司製粒度測試器（Grind Meter )進行粒度測定並進行評估結果’得知其爲丨5 # m以下。 組成物例6〜8中，無論任一·例皆未添加本發明之花系著色 劑（A -1 )之例。 A成份 表1所記載之各著色劑 表1所記載之各質量份 B成份 蠟（B，l) 1 5 4部（固形分1 〇 0份） C成份 2-甲基甲基硫基）苯基]_2_嗎啉代胺基丙院 1 -酮 10份 2,4-二乙基噻噸酮 1份 D成份 二季戊四醇六丙烯酸酯 (DPHA/日本化藥製） 20份 E成份 酚酚醛清漆型環氧樹脂 (道化學公司製DEN-431) 15份 聯二甲苯醇型環氧樹脂 (曰本環氧樹脂公司製YX- 4000) 2 5 份 F成份 二氰二醯胺 0.3份 其他之成份 -32- 201003309 硫酸鋇（堺化學公司製硫酸鋇B3 0) 1 00份 聚矽氧系消泡劑 3份 DPM(二丙二醇單甲基醚） 5份。 [表1] 表1 A成份(著色劑） 例1 例2 例3 例4 例5 例6 例7 例8 茈系著色劑 Solvent Green 5 0.1 0.2 0.1 0.2 0.2 - - - 茈系著色劑 Solvent Orange 55 - - 0.2 - - - - - 茈系著色劑 Pigment black 31 - - - 0.4 - - - - 茈系著色劑 Pigment red 179 - - - - 0.5 - - - 酞菁綠 C.I.Pigment Green 7 0.5 - - - - 0.5 - - 蒽醌系黃色顏料 C.I.Pigment Yellow 147 - 0.1 - - - 0.4 0.8 0.8 酞菁藍 C.I.Pigment Blue 15:3 - 0.4 - 0.3 - - 0.5 - 二酮吡咯倂吡咯紅 C.I.Pigment Red 264 - - 0.3 - - - - 0.5 阻劑性能評估： 〔評估基板之製作方法〕 將依上述方法所得之例1〜8之組成物，於形成有圖型 之銅箔基板使用網版印刷進行全面塗佈，於80°c下乾燥20 分鐘，放冷至室溫。對該基板使用設置有金屬鹵化物燈之 曝光裝置（股份有限公司-奧科製作所製）以最佳曝光量 -33- 201003309 對抗焊阻劑圖型進行曝光，以3 0 °C之1 % Na2C Ο3水溶 噴壓0.2MPa之條件下進行60秒鐘之顯影，得阻劑圖型 該基板於UV輸送爐中，以合計曝光量爲i〇〇〇mj/cm2 件照射紫外線後，於150 °C、60分鐘之條件下加熱使 化。對所得之印刷基板（評估基板）進行以下之特性 〈色調· L*a*b*値〉 依上述評估基板之製作方法，製作例1〜8之感光 脂組成物之硬化塗膜。膜厚以乾燥後之膜厚爲25 ±2 // 厚度進行製作。所得之硬化塗膜以目視方式確認辨別 ，此外，於例2、3、4、7及8中，則使用分光測色計 測色。分光測色計爲使用KONICA MINOLTA公司製 2600d，表色系爲使用CIE L*a*b*。銅箔基板上之均 膜表面上，使用SCI模式所測定之値作爲測色値。其 結果係如表2所示。 此外，爲進行比較，而對具有良好色調之作爲抗 劑之市售品的太陽油墨製造公司製PSR-4000之各種產 依相同方法評估色調及L*a*b*値。其結果係如表3所 又，確認PSR-4000中任一者皆未使用茈系著色劑。 <最佳曝光量> 將鋪銅層合基板使用拋光滾筒硏磨後’經水洗、 ，將例1〜8之感光性樹脂組成物使用網版印刷法進行 液、 。將 之條 其硬 評估 性樹 m之 色調 進行 CM- 勻塗 評估 焊阻 品， 不 0 乾燥 塗佈 -34- 201003309 ’於80C之熱風循環式乾燥爐乾燥30分鐘。乾燥後，藉由 光遮罩（柯達•伊士曼公司製，步進平台Νο·2)，以高壓 水銀燈曝光裝置進行曝光。照射後之基板做爲測試顆粒， 以噴壓2 k g / c m 2之顯影液（碳酸鈉水溶液）進行6 〇秒鐘之 顯影後，以目視判定殘存塗膜之段數。以殘存塗膜之段數 爲6段之曝光量爲最佳曝光量。其評估結果係如表2所示。 <解析性•線路截面形狀> 基板’爲使用銅厚度分別爲35μηι、50/zm、70/zm之 鋪銅層合板上形成有線路/空間爲300/300之電路圖型之 基板上，於進行前處理之拋光滾筒硏磨後，經水洗、乾燥 所得者。將例1〜8之感光性樹脂組成物，於施有前處理之 上述基板上以網版印刷法進行塗佈，再使用8 0 T：之熱風循 環式乾燥爐乾燥3 0分鐘。乾燥後，使用高壓水銀燈曝光裝 置進行曝光。曝光圖型，爲使用於空間部描繪有50/ 60/ 70/80/90/100/zm之線路的圖型。曝光量，爲使用最佳 曝光量評估所得之曝光量。曝光後，以碳酸鈉水溶液進行 顯影形成圖型’使殘留之最小線路之寬度作爲解析性。此 外，經150 °C、60分鐘熱硬化以製得硬化塗膜後，觀察硬 化塗膜之設計値1 0 〇 # m之線路部的截面。 該截面係如圖2所記載之模式圖，將分別評價爲A〜E 等5階段。圖示爲表示發生以下現象時之模式圖。特別是 ，於A評價之情形中，設計値所產生之偏移無論於線路上 部、下部皆爲5/im以内之偏移。其結果如表2所示。其中 -35- 201003309 最佳之評價爲A，最差之評價爲E，C評價爲作爲抗焊阻劑 時仍有改善之空間，但爲可使用之程度。 此外，爲進行比較，對於色調良好之抗焊阻劑之作爲 市售品之太陽油墨製造公司製PSR-4000的各種產品，同樣 的進行70 // m之電路厚度基板所進行之截面評估。其結果 如表3所示。 A評價：如設計寬度所示般之理想狀態 B評價：耐顯影性不足等而造成表面層侵蝕 C評價：底部削減狀態 D評價：因暈開等而發生線路過於擴張 E評價：表面層之線過於擴張與發生底部削減狀態 [表2] 表2Araldite XPY3 06 (all are trade names) bisphenol F-type epoxy resin; Etodoto ST·2004 'ST-2007, ST-3000 (B1 emmer trade name) made by Dongdu Chemical Company, hydrogenated bisphenol A type epoxy resin; Epikote 604 manufactured by Nippon Epoxy Co., Ltd., Epotooto YH-434 manufactured by Dongdu Chemical Co., Ltd., AralditeMY720 manufactured by Ciba Specialty Chemicals Co., Ltd., and Smith-Epoxy ELM-120 manufactured by Sumitomo Chemical Industries Co., Ltd. (all are trade names) Glycidylamine type epoxy resin; Hydant〇in type epoxy resin such as AralditeCY-3 5 0 (trade name) manufactured by Ciba Specialty Chemicals Co., Ltd.; Cerokisaito 202 manufactured by DAICEL Chemical Industry Co., Ltd. 1. The alicyclic epoxy resin of Araldite CY175, CY179, etc. (all of which are trade names) manufactured by Ciba Specialty Chemicals Co., Ltd.; YL-93 manufactured by Japan Epoxy Resin Co., Ltd. 3, TEN, EPPN- manufactured by Dao Chemical Co., Ltd. 501, EPPN-502 (all are trade names) of trishydroxyphenylmethane type epoxy resin; Japan Epoxy resin company YL-6056, YX-4000, YL-6121 (all are trade names), etc. Xylenol type or double-type epoxy Lipid or a mixture thereof, EBPS-200 manufactured by Nippon Kayaku Co., Ltd., EPX-30 manufactured by Asahi Kasei Kogyo Co., Ltd., and EXA-1514 (trade name) manufactured by Dainippon Ink Chemical Industries Co., Ltd.; Bisphenol A novolac type epoxy resin such as Epikotel 57S (trade name) manufactured by Epoxy Epoxy Co., Ltd.; Epikote YL-931 manufactured by Japan Epoxy Resin Co., Ltd., Aralditel 63 manufactured by Ciba Specialty Chemicals Co., Ltd. Trade name) tetraphenol ethane type epoxy resin; Araldite PT81〇 manufactured by Ciba Specialty Chemicals Co., Ltd., TEPIC manufactured by Nissan Chemical Industries Co., Ltd. (all are trade names), heterocyclic epoxy resin; Japan Oil Company Diglycidyl benzoate resin such as DGT; Dongdu Huacheng Gong-26-201003309 Tetraglycidyl xylene oxirane resin such as ZX-1063, manufactured by Nippon Steel Chemical Co., Ltd. ESN-190, ESN-360 HP-403, EXA-475 0, EXA-4700, etc., containing naphthyl-based epoxy resin, manufactured by Otsuka Ink Chemical Industry Co., Ltd.: HP-72 00, HP-7200H, etc. manufactured by Dainippon Ink Chemical Industry Co., Ltd. Epoxy resin having a dicyclopentadiene skeleton; a glycidyl methacrylate copolymerized epoxy resin such as CP-50S or CP-50M; in addition, a copolymerized epoxy resin such as cyclohexylmaleimide and glycidyl methacrylate; epoxy Modified polybutadiene rubber derivatives (for example, PB-3600 manufactured by DAICEL Chemical Industry Co., Ltd.), CTBN modified epoxy resins (such as YR-102 and YR-450 manufactured by Tosho Kasei Co., Ltd.), etc., but are not limited For that content. These epoxy resins may be used singly or in combination of two or more. Among them, a novolak type epoxy resin, a heterocyclic epoxy resin, a bisphenol A type epoxy resin or a mixture thereof is particularly preferable. The above polyfunctional propylene oxide compound (E-2), for example, bis[(3-methyl-3-epoxypropane methoxy)methyl]ether, bis[(3-ethyl-3-ring I oxypropyl) Methoxy)methyl] acid, 1,4-bis[(3-methyl-3-epoxypropyl methoxy)methyl]benzene, 1,4-bis[(3-ethyl-3) - propylene oxide methoxy)methyl]benzene, (3-methyl-3-epoxypropane) methacrylate, (3-ethyl-3-epoxypropane) methacrylate, (3 - Methyl-3-epoxypropane)methyl methacrylate, (3-ethyl-3-epoxypropane) methyl methacrylate or a polyfunctional epoxy-propylene compound such as these oligomers or copolymers For example, a resin having a hydroxyl group such as propylene propanol and novolak resin, poly(P-hydroxyphenylacetamidine), caged bisphenol, calixarene, cup-resorcinol aromatic hydrocarbon, or sesquioxane. Ether and the like. Others, for example, a copolymerized epoxy sulfur compound (E-3) having an unsaturated monomer of propylene oxide ring-27-201003309 and an alkyl (meth)acrylate, for example, Japanese epoxy bisphenol A type epoxy Sulfur resin YL7000 and so on. Further, the synthesis method may be an epoxy epoxide obtained by substituting an atom of an epoxy group of a novolac type epoxy resin. In the above molecule, the addition ratio of the two or more cyclic (sulfur) components (E) is preferably from 0.6 to 2.5 equivalents, more preferably from 0 to 1 equivalent of the carboxyl group contained in the above (B). . When the addition ratio of two or more cyclic (thio)ether-containing components (E) in the molecule is less than 0.6 equivalent, the solder resists the carboxyl group, and heat resistance, alkali resistance, and electrical insulation are not preferable. Further, when it exceeds 2.5 equivalents, the low molecular weight ether group will remain on the dried coating film, which may cause a coating film, which is not preferable. In the photosensitive resin composition of the present invention, a thermosetting property having two or more cyclic (thio)ether groups is used, and it is preferable to contain (F) a thermosetting catalyst. These are hot/hard, for example, imidazole, 2-methylimidazole, 2-ethylimidazole, 2-imidazole, 2-phenylimidazole, 4-phenylimidazole, 1-cyanoethyl, 1-(2- Cyanoethyl)-2-ethyl-4-methylimidazole and the like dicyanodiamide, benzyldimethylamine, 4-(dimethylamine; methylbenzylamine, 4-methoxyl - hydrazine, hydrazine - an amine compound such as dimethylbenzylamine or dimethylbenzylamine; an anthracene compound such as diammonium adipate or hydrazine; a phosphorus compound such as triphenylphosphine; or the like. The company uses a resin of a thermosetting carboxylic acid having a thioether group of the same oxygen atom to reduce the residue and the like in a thermosetting agent film of 8 to 2.0 equivalents, and the cyclic (sulfur) strength and the like lower the molecular component ( Ε) Seven Catalysts (F) Ethyl-4-methyl-2-phenylimidazoleazole derivatives; S) -Ν,Ν-di-4-methyl-oxime, Ν-sebacic acid diterpene -28-201003309, for example, 2MZ-A, 2MZ-OK, 2PHZ, 2P4BHZ, 2P4MHZ (any of which is a brand name of imidazole compound) manufactured by Shikoku Chemical Industry Co., Ltd. -CAT3 503N, UC AT3 5 02T (either is dimethyl The trade name of the amine block isocyanate compound, DBU, DBN, U-CATSA102, U-CAT5002 (either of which is a bicyclic hydrazine compound and a salt thereof). In particular, it is not limited to this range, as long as it can promote a thermosetting catalyst of an epoxy resin or a propylene oxide compound, or a reactor of an epoxy group and/or an oxypropylene group and a carboxyl group, These may be used alone or in combination of two or more. Further, hydrazine, methyl decylamine, benzoquinone, melamine ' 2,4-diamino-6-methylpropenyloxyethyl-S-triazine, 2-vinyl-2,4-di can be used. Amino-S-triazine, 2-vinyl-4,6-diamino-S-triazine•trimeric isocyanate adduct, 2,4-diamino-6-methylpropene oxime The S-triazine derivative such as an ethyl-S-triazine/trimeric isocyanate addition product is preferably used in combination with the above-mentioned thermosetting catalyst as a functional compound as an adhesion enhancer. The addition ratio of the thermosetting catalyst (F) can be, for example, relative to (B) a carboxylic acid-containing resin or a thermosetting hardening having two or more cyclic (thio)ether groups in the molecule. The component (E) is 100 parts by mass, preferably 0.1 to 20 parts by mass, more preferably 0.5 to 15.0 parts by mass. When the photosensitive resin composition of the present invention is used for the purpose of improving the physical strength of the coating film, etc., it is possible to add a dip material in accordance with the necessity. As the materials, conventionally known inorganic or organic materials can be used, and in particular, barium sulphate spheroidal cerium oxide and talc are preferably used. Further, a metal hydroxide of an acid oxide such as titanium oxide or metal -29-201003309, aluminum hydroxide or the like can be used as a pigment for the body pigment. The addition ratio of the mash is preferably 75 mass% or less of the total amount of the composition, more preferably 〇1 to 60% by mass. The addition rate of the dip is 'more than 75 mass of the total amount of the composition. /. In this case, the viscosity of the insulating composition is increased, the coating and formability are lowered, and the hardened material is embrittled, which is not preferable. Further, in the photosensitive resin composition of the present invention, an organic solvent can be used for the purpose of synthesizing or preparing a composition such as the above-mentioned (B) carboxylic acid-containing resin, or adjusting the viscosity of the substrate or the supporting film. . These organic solvents are, for example, ketones, aromatic hydrocarbons, glycol ethers, glycol ether acetates, esters, alcohols, aliphatic hydrocarbons, petroleum solvents, and the like. More specifically, for example, ketones such as methyl ethyl ketone and cyclohexanone; aromatic hydrocarbons such as toluene, xylene, and tetramethylbenzene; cellosolve, methyl cellosolve, butyl cellosolve, and carbene Alcohol, methyl carbitol butyl carbitol, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol diethyl ether, triethylene glycol monoethyl ether and other glycol ethers; Ester, butyl acetate, dipropylene glycol methyl ether acetate, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol butyl ether acetate, methyl lactate, ethyl lactate, butyl lactate And other esters; alcohols such as ethanol, propanol, ethylene glycol, and propylene glycol; aliphatic hydrocarbons such as Xinyuan and decane; petroleum-based solvents such as petroleum ether, petroleum brain, hydrogenated petroleum brain, and So Went petroleum brain. These organic solvents may be used singly or in combination of two or more. In the photosensitive resin composition of the present invention, if necessary, a known conventional thermal polymerization inhibitor such as hydroquinone, hydroquinone monomethyl ether, t-butylcatechol, gallic phenol, or phenothiquinone may be added. Antimony sulphate, organic bentonite, -30-201003309 montmorillonite, etc., known as tackifiers, polyoxo-based, fluorine-based, polymer-based defoamers and/or leveling agents, imidazoles, thiazoles Additives such as broth coupling agents, antioxidants, rust inhibitors, etc., such as Sanchao. [Embodiment] [Examples] Hereinafter, the present invention will be specifically described by way of examples and comparative examples, but the present invention is not limited by the following examples. In addition, the "parts" referred to below are intended to mean "parts by mass" unless otherwise specified. [Example 1] <Synthesis of carboxylic acid-containing resin> The carboxylic acid-containing resin (B) of the present invention was produced according to the following synthesis examples. 220 parts of cresol novolac type epoxy resin ("Epiclon" (registered trademark) N-695, epoxy equivalent: 220) manufactured by Dainippon Ink and Chemicals Co., Ltd. was added to four ports with a blender and a reflux cooler. In the flask, 2 14 parts of carbitol acetate was added and dissolved by heating. Next, 0. 4 6 parts of hydroquinone as a polymerization inhibitor and 1.38 parts of triphenylphosphine as a reaction catalyst were added. The mixture was heated to 95 to 105 ° C, and 72 parts of acrylic acid was gradually dropped, and the reaction was carried out for 16 hours. The reaction product was cooled to 80 to 90 ° C, and 106 parts of tetrahydrobenzoic anhydride was added thereto to carry out a reaction for 8 hours. After cooling, the reaction solution (also referred to as wax (B-1)) was taken out. The carboxylic acid-containing resin obtained in the above manner has an acid value of -31 - 201003309 1 00 mgKOH / g ' of a solid content of 65%. <Additional Example> The following components were premixed in a blender with the following addition amount, and then kneaded by a three-roll drum honing machine to prepare photosensitive resin compositions for each solder resist (composition examples 1 to 8) ). The degree of dispersion of the obtained photosensitive resin composition was measured by particle size measurement using a Grind Meter manufactured by Erichsen Co., Ltd., and the evaluation result was found to be 丨5 #m or less. In the composition examples 6 to 8, the flower coloring agent (A-1) of the present invention was not added in any of the examples. A component of each coloring agent described in Table 1 each mass part B of the component B (B, l) 1 5 4 (solid content 1 〇 0 parts) C component 2-methylmethyl thio) benzene 2] morpholino-aminopropyl 1-ketone 10 parts 2,4-diethyl thioxanthone 1 part D component dipentaerythritol hexaacrylate (DPHA/Nippon Chemical Co., Ltd.) 20 parts E phenol novolac Epoxy resin (DEN-431, manufactured by Dao Chemical Co., Ltd.) 15 parts of xylene glycol epoxy resin (YX-4000 manufactured by Epoxy Epoxy Co., Ltd.) 2 5 parts F component dicyanamide 0.3 parts other ingredients -32- 201003309 Barium sulphate (Barium sulfate B3 0 manufactured by Sigma Chemical Co., Ltd.) 100 parts of polyoxymethane defoamer 3 parts of DPM (dipropylene glycol monomethyl ether). [Table 1] Table 1 A component (colorant) Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Example 8 Barium coloring agent Solvent Green 5 0.1 0.2 0.1 0.2 0.2 - - - Barium coloring agent Solvent Orange 55 - - 0.2 - - - - - Tanning coloring agent Pigment black 31 - - - 0.4 - - - - Tanning coloring agent Pigment red 179 - - - - 0.5 - - - Phthalocyanine green CIPigment Green 7 0.5 - - - - 0.5 - - Lanthanide Yellow Pigment CIPigment Yellow 147 - 0.1 - - - 0.4 0.8 0.8 Phthalocyanine Blue CIPigment Blue 15:3 - 0.4 - 0.3 - - 0.5 - Diketopyrrolepyrrole Red CIPigment Red 264 - - 0.3 - - - - 0.5 Resistance performance evaluation: [Method for producing evaluation substrate] The composition of Examples 1 to 8 obtained by the above method was applied to the copper foil substrate on which the pattern was formed by screen printing. Dry at 80 ° C for 20 minutes and let cool to room temperature. The substrate was exposed to an anti-welding resist pattern using an exposure apparatus (manufactured by AOKO Co., Ltd.) provided with a metal halide lamp, and an exposure amount of -33 - 201003309 was used to expose 1% Na 2 C at 30 ° C. Ο3 water-soluble spray pressure of 0.2MPa for 60 seconds of development, the resist pattern of the substrate in the UV transport furnace, the total exposure is i〇〇〇mj / cm2 parts of the ultraviolet light, at 150 ° C Heated under 60 minutes. The obtained printed circuit board (evaluation substrate) was subjected to the following characteristics: "Hue, L*a*b*値> The cured coating film of the photosensitive resin compositions of Examples 1 to 8 was produced in accordance with the above-described method for producing a substrate. The film thickness was prepared by drying the film thickness to 25 ± 2 // thickness. The obtained cured coating film was visually confirmed and discriminated. Further, in Examples 2, 3, 4, 7, and 8, color measurement was performed using a spectrophotometer. The spectrophotometer was 2600d manufactured by KONICA MINOLTA Co., Ltd., and the color was CIE L*a*b*. On the surface of the film on the copper foil substrate, the enthalpy measured by the SCI mode was used as the color measurement enthalpy. The results are shown in Table 2. Further, for comparison, the color tone and L*a*b*値 were evaluated in the same manner for various products of PSR-4000 manufactured by Sun Ink Co., Ltd., which is a commercial product having a good color tone as an anti-agent. As a result, as shown in Table 3, it was confirmed that none of the PSR-4000 used an anthraquinone coloring agent. <Optimum exposure amount> The copper-clad laminate substrate was honed by a polishing drum, and washed with water, and the photosensitive resin compositions of Examples 1 to 8 were subjected to liquid-screen printing using a screen printing method. The color of the hard evaluation tree m is subjected to CM-leveling evaluation. Solder resistance, not 0 Dry coating -34- 201003309 ' Dry in a hot air circulating oven at 80C for 30 minutes. After drying, exposure was carried out by a high-pressure mercury lamp exposure apparatus by means of a light mask (manufactured by Kodak Eastman, stepping platform Νο·2). The substrate after the irradiation was used as a test pellet, and development was carried out by spraying a developing solution (aqueous sodium carbonate solution) of 2 k g / c m 2 for 6 sec., and then the number of remaining coating films was visually determined. The exposure amount of the number of segments of the remaining coating film is the optimum exposure amount. The evaluation results are shown in Table 2. <Resolvability/Line Cross-Section Shape> The substrate 'is a substrate having a circuit pattern of 300/300 line formed on a copper-clad laminate having copper thicknesses of 35 μm, 50/zm, and 70/zm, respectively. After the polishing drum for pretreatment is honed, it is washed with water and dried. The photosensitive resin compositions of Examples 1 to 8 were applied by screen printing on the substrate subjected to the pretreatment, and dried in a hot air circulating drying oven at 80 °C for 30 minutes. After drying, exposure was carried out using a high pressure mercury lamp exposure apparatus. The exposure pattern is a pattern in which a line of 50/60/70/80/90/100/zm is drawn for use in the space portion. The amount of exposure is the amount of exposure that is estimated using the optimum exposure. After the exposure, development was carried out with an aqueous solution of sodium carbonate to form a pattern, and the width of the remaining minimum line was used as the resolution. Further, after hardening at 150 ° C for 60 minutes to obtain a hardened coating film, the cross section of the line portion of the design of the hard coating film 値 10 〇 # m was observed. This cross section is a schematic diagram as shown in Fig. 2, and is evaluated as five stages of A to E, respectively. The figure shows a pattern diagram showing the following phenomenon. In particular, in the case of the A evaluation, the offset generated by the design 无论 is within 5/im of the upper and lower portions of the line. The results are shown in Table 2. Among them, -35- 201003309, the best evaluation is A, the worst evaluation is E, and C is evaluated as a space for improvement as a solder resist, but it is usable. In addition, for the comparison, a variety of products of the PSR-4000 manufactured by Sun Ink Manufacturing Co., Ltd., which is a commercially available product, were subjected to a cross-sectional evaluation of a substrate thickness of 70 // m. The results are shown in Table 3. A evaluation: ideal state as indicated by design width B evaluation: surface layer erosion caused by insufficient development resistance C evaluation: bottom reduction state D evaluation: line expansion due to halo or the like E evaluation: surface layer line Too much expansion and the occurrence of bottom cuts [Table 2] Table 2

評估 例1 例2 例3 例4 例5 例6 例7 例8 色調 綠 綠 橙 綠 橙 綠 綠 橙 L* - 53 56 46 - - 51 55 a* - -26 34 -14 - - -23 37 b* - 14 36 11 - - 14 31 最佳曝光量(m〗/cm2) 400 500 400 400 400 500 600 500 電路厚度35 // m 解析性(//m) 50 50 50 50 50 60 70 60 線路截面形狀 A A A A A C C C 電路厚度50//m 解析性(//m) 50 60 50 50 50 80 90 80 線路截面形狀 A A A A A E E E 電路厚度70/zm 解析注(㈣ 80 80 70 80 70 NG NG NG 線路截面形狀 C C C C C NG NG NG *NG :未能形成100/zm之畫像。 -36- 201003309 [表3] 表3Evaluation Example 1 Example 2 Case 3 Case 4 Case 5 Case 6 Case 7 Case 8 Tone Green Green Orange Green Orange Green Orange Orange L* - 53 56 46 - - 51 55 a* - -26 34 -14 - - -23 37 b* - 14 36 11 - - 14 31 Optimum exposure (m)/cm2 400 500 400 400 400 500 600 500 Circuit thickness 35 // m Analytical (//m) 50 50 50 50 50 60 70 60 Line section shape AAAAACCC Circuit thickness 50//m Analytical (//m) 50 60 50 50 50 80 90 80 Line section shape AAAAAEEE Circuit thickness 70/zm Resolution note ((iv) 80 80 70 80 70 NG NG NG Line section shape CCCCC NG NG NG * NG: Failure to form a portrait of 100/zm. -36- 201003309 [Table 3] Table 3

PSR-4000G23K PSR-4000GEC50 PSR-4000SP08 色調 綠 綠 綠 L調 54.9 47.7 57.2 a* -22.4 -21.8 -13.3 b* 14.7 13.7 17.7 感度(mJ/cm2) 400 400 500 線路形狀 E E E <焊料耐熱性> 依上述評估基板之製作方法，製作例1〜8之感光性樹 脂組成物之硬化塗膜。膜厚爲以乾燥後之膜厚爲25±2 // m 之方式製作。將其浸漬於加熱至260 °C之焊浴10秒鐘，重 複3次，以目視方式確認塗膜是否發生剝離或變色。其結 果，確認使用例1〜8所製作之評估基板，無論任一個皆未 發生剝離或變色。 〔實施例2〕 將例2及例7之感光性樹脂組成物使用甲基乙基酮稀釋 ，塗佈於負載薄膜上。將其加熱乾燥後形成厚度20/zm之 感光性樹脂組成物層，使用80°C之熱風乾燥器乾燥30分鐘 。隨後，於所得之塗膜上貼合包覆薄膜（CoverFilm)而 得乾薄膜。隨後，將包覆薄膜剝離，於形成圖型之銅箔基 板熱層合所得之薄膜，其次’同樣使用設置有金屬鹵化物 燈之曝光裝置（股份有限公司·奧科製作所製）進行曝光 -37- 201003309 。曝光後，剝離負載薄膜，以150 °C之熱風乾燥器進行60 分鐘加熱硬化，以製作試驗基板。對於具有所得硬化被膜 之試驗基板，依實施例1之試驗方法及評估方法，進行各 種特性之評估試驗。其結果，於實施例1中，例2與例7係 爲相同。 【圖式簡單說明】 [圖1]顯示孟塞爾色相環之圖。 [圖2]顯示感光性樹脂組成物之硬化塗膜所形成之圖型 的截面形狀圖。 -38-PSR-4000G23K PSR-4000GEC50 PSR-4000SP08 Tone Green Green Green L Adjust 54.9 47.7 57.2 a* -22.4 -21.8 -13.3 b* 14.7 13.7 17.7 Sensitivity (mJ/cm2) 400 400 500 Line Shape EEE <Solder Heat Resistance> In the method for producing the evaluation substrate described above, the cured coating film of the photosensitive resin composition of Examples 1 to 8 was produced. The film thickness was produced so that the film thickness after drying was 25 ± 2 // m. This was immersed in a solder bath heated to 260 ° C for 10 seconds, and repeated three times to visually confirm whether or not the coating film was peeled off or discolored. As a result, it was confirmed that the evaluation substrates produced in Examples 1 to 8 were not peeled or discolored in any of them. [Example 2] The photosensitive resin compositions of Examples 2 and 7 were diluted with methyl ethyl ketone and applied onto a supported film. This was dried by heating to form a photosensitive resin composition layer having a thickness of 20 / zm, and dried by a hot air dryer at 80 ° C for 30 minutes. Subsequently, a cover film (CoverFilm) was attached to the obtained coating film to obtain a dry film. Subsequently, the coated film was peeled off, and the film obtained by thermal lamination of the patterned copper foil substrate was used, and the exposure was also carried out using an exposure apparatus (manufactured by AOKO Co., Ltd.) provided with a metal halide lamp. - 201003309. After the exposure, the load film was peeled off and heat-hardened in a hot air dryer at 150 ° C for 60 minutes to prepare a test substrate. For the test substrate having the obtained cured film, the evaluation test of each characteristic was carried out in accordance with the test method and evaluation method of Example 1. As a result, in Example 1, Example 2 and Example 7 were the same. [Simple diagram of the figure] [Fig. 1] shows the map of the Munsell hue circle. Fig. 2 is a cross-sectional view showing a pattern formed by a cured coating film of a photosensitive resin composition. -38-

Claims (1)

201003309 七、申請專利範圍： 1 ·—種感光性樹脂組成物，其特徵爲，含有（Α· 1 ) 茈系著色劑，及（B)含竣酸之樹脂。 2 .如申請專利範圍第丨項之感光性樹脂組成物，其中 ，茈系著色劑（A-1 )爲至少含有染料者。 3 ·如申請專利範圍第1項之感光性樹脂組成物，其中 ’茈系著色劑（A-1 )爲至少含有顏料者。 4 ·如申請專利範圍第2項之感光性樹脂組成物，其中 ，茈系著色劑（A-1 )爲至少含有顏料者。 5 ·如申請專利範圍第1至4項中任一項之感光性樹脂組 成物，其中，色調爲綠色或橙色。 6. 如申請專利範圍第1至4項中任一項之感光性樹脂組 成物，其尙含有（A-2 )酞菁系著色劑。 7. 如申請專利範圍第1至4項中任一項之感光性樹脂組 成物，其爲鹼顯影性光抗焊阻劑。 8 . —種乾薄膜，其特徵爲，將申請專利範圍第1至4項 中任一項之感光性樹脂組成物於負載薄膜上塗佈、乾燥而 製得。 9. 一種硬化物，其特徵爲，將申請專利範圍第1至4項 中任一項之感光性樹脂組成物或該感光性樹脂組成物於負 載薄膜上經塗佈乾燥所得之乾薄膜，於形成電路之基板上 硬化而製得。 10. —種印刷電路基板，其特徵爲，於形成電路之基 板上，具有由申請專利範圍第9項之硬化物所得之抗焊阻 劑層。 -39-201003309 VII. Patent application scope: 1 - A photosensitive resin composition characterized by containing (Α·1) anthraquinone coloring agent, and (B) a tannic acid-containing resin. 2. The photosensitive resin composition according to the ninth aspect of the invention, wherein the lanthanum coloring agent (A-1) is at least a dye. 3. The photosensitive resin composition of claim 1, wherein the oxime coloring agent (A-1) is at least a pigment. 4. The photosensitive resin composition of claim 2, wherein the anthraquinone coloring agent (A-1) is at least a pigment. The photosensitive resin composition according to any one of claims 1 to 4, wherein the color tone is green or orange. 6. The photosensitive resin composition according to any one of claims 1 to 4, further comprising (A-2) a phthalocyanine coloring agent. 7. The photosensitive resin composition according to any one of claims 1 to 4, which is an alkali-developable photo-resist resist. A dry film obtained by coating and drying a photosensitive resin composition according to any one of claims 1 to 4 on a supported film. A cured product obtained by coating and drying a photosensitive resin composition according to any one of claims 1 to 4 or a photosensitive resin composition on a supported film. It is obtained by hardening a substrate on which a circuit is formed. A printed circuit board characterized by having a solder resist layer obtained from a cured product of claim 9 on a substrate on which a circuit is formed. -39-
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