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TW200811921A - Method of forming resist pattern - Google Patents

Method of forming resist pattern Download PDF

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Publication number
TW200811921A
TW200811921A TW096128962A TW96128962A TW200811921A TW 200811921 A TW200811921 A TW 200811921A TW 096128962 A TW096128962 A TW 096128962A TW 96128962 A TW96128962 A TW 96128962A TW 200811921 A TW200811921 A TW 200811921A
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TW
Taiwan
Prior art keywords
film
photoresist
pattern
light
photoresist film
Prior art date
Application number
TW096128962A
Other languages
Chinese (zh)
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TWI341553B (en
Inventor
Kazunori Kitamura
Kiyoshi Sato
Eiichi Inoue
Original Assignee
San Ei Kagaku Co
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Publication of TW200811921A publication Critical patent/TW200811921A/en
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Publication of TWI341553B publication Critical patent/TWI341553B/en

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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
    • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
    • 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
    • G03F7/0047—Photosensitive materials characterised by additives for obtaining a metallic or ceramic pattern, e.g. by firing
    • 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
    • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
    • G03F7/0382—Macromolecular compounds which are rendered insoluble or differentially wettable the macromolecular compound being present in a chemically amplified negative photoresist composition
    • 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
    • G03F7/095—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having more than one photosensitive layer
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/027—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/027—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34
    • H01L21/0271—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising organic layers
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/0073—Masks not provided for in groups H05K3/02 - H05K3/46, e.g. for photomechanical production of patterned surfaces
    • H05K3/0082—Masks not provided for in groups H05K3/02 - H05K3/46, e.g. for photomechanical production of patterned surfaces characterised by the exposure method of radiation-sensitive masks
    • 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
    • H05K2203/00—Indexing scheme relating to apparatus or processes for manufacturing printed circuits covered by H05K3/00
    • H05K2203/05—Patterning and lithography; Masks; Details of resist
    • H05K2203/0548—Masks
    • H05K2203/0551—Exposure mask directly printed on the PCB
    • 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
    • H05K2203/00—Indexing scheme relating to apparatus or processes for manufacturing printed circuits covered by H05K3/00
    • H05K2203/05—Patterning and lithography; Masks; Details of resist
    • H05K2203/0562—Details of resist
    • H05K2203/0577—Double layer of resist having the same pattern
    • 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
    • H05K2203/00—Indexing scheme relating to apparatus or processes for manufacturing printed circuits covered by H05K3/00
    • H05K2203/06—Lamination
    • H05K2203/066—Transfer laminating of insulating material, e.g. resist as a whole layer, not as a pattern
    • 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
    • H05K2203/00—Indexing scheme relating to apparatus or processes for manufacturing printed circuits covered by H05K3/00
    • H05K2203/10—Using electric, magnetic and electromagnetic fields; Using laser light
    • H05K2203/107—Using laser light
    • 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)
  • Engineering & Computer Science (AREA)
  • General Physics & Mathematics (AREA)
  • Manufacturing & Machinery (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Power Engineering (AREA)
  • Structural Engineering (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Computer Hardware Design (AREA)
  • Architecture (AREA)
  • Chemical & Material Sciences (AREA)
  • Ceramic Engineering (AREA)
  • Materials For Photolithography (AREA)
  • Exposure And Positioning Against Photoresist Photosensitive Materials (AREA)
  • Non-Metallic Protective Coatings For Printed Circuits (AREA)
  • Photosensitive Polymer And Photoresist Processing (AREA)
  • Manufacturing Of Printed Circuit Boards (AREA)
  • Manufacturing Of Printed Wiring (AREA)

Abstract

This invention provides a method of forming a photoresist by which the exposure of a solder resist material can be perfected in a short time and the exposure using the same solder resist material as a known one by laser is possible. The method can be performed by the steps as follows: forming a UV-sensitive solder resist film 7 of which the surface is covered by a covering film 6 on a print circuit board 3, forming in UV-blocked state a visible light sensitive resist film 8 over the UV-sensitive solder resist film 7; exposing by visible light laser 10, exposing a resist pattern 11 on the resist film 8, developing with water to form a mask pattern by means of resist pattern 11 with the hardened film of resist film 8, then making solder resist pattern 5 exposed with UV in the solder resist film 7 by using said mask pattern as a mask, developing with a weak alkali developer liquid, and forming a solder resist pattern 5 by way of the hardened film of solder resist film 7 on the printed circuit board 3.

Description

200811921 九、發明說明： 【發明所屬之技術領域】 本發明係關於光阻圖案之形成方法，特別係關於當對 印刷電路基板施行焊接之際，當預先設置的防焊膜在形成 時’能縮短曝光_，並提升生產力的光_案之形成方 法、及可增加使料防焊膜之自由度的光阻圖案之形成方 0 【先前技術】 料路板的製造方面，供電路形成用輪材 枓、與供電路保護用的防焊材料係使用感光性材料。 p著步成有阻^材料圖案曝光之際，-般係採取 ㈣光性負型圖案的玻璃或薄膜等遮罩（以下亦 ^罩」_*))，施行紫外線照射並顯影的工法。 然而，當使用光罩施行圖 作多種弁置如我π p 仕配*分圖案而製 、斤主、、用共耗時，而頗難對應少量多樣化。 ^，已知有在未隔著光罩的情況下吏 阻材料施行直接曝麵方法（參照專 ^射對光 法’藉由使用雷射對光阻㈣ _ )。依知該方 種光罩的情況下，於同其/接曝先，便可在未製作多 抄二 於同基板上形成多種圖案。 以而，防焊材料通常為負各 於圖案形成部分的大部分成為田也仃接曝光時，由 為少許，因而在利用雷部分’而非曝光部分僅 顧慮。、&仃直接曝光時則有頗為耗時的 再者，當對光阻材料帝 ^用运射施行直接曝光時，則必 319353 5 200811921 需使用具有以往的數倍感度之光阻材料，因而所使用的光 p材料有所限制。例如當在形成圖案之光阻膜的配線基板 -或半導體晶片上安裝其他構件時，配線基板上所接合部分 的構件’必需具有與樹脂或金屬間之密合性，但是此情況 Γΐ同&兼具密合性、與對雷射光的感度之性質的光阻材 ;4成乎不存在’而有光阻材料選擇自由度降低的顧慮。另 :例子係#総膜由對鍍敷液的光阻材料構成_，因為必 •需兼具耐藥性與高感度之感光'!·生，頗難在維持耐荜性的情 •況下而僅提升感度、结果，便有光阻的材料選擇;由= 低之顧慮。 [專利文獻1]曰本專利第2679454號公報 【發明内容】 (發明欲解決的課題） 本發明係有鑑於上述狀況，目的在於提供能縮短光阻 材=的曝光時間，且即便選擇對雷射的感度較低之光阻材 .料¥仍可形成反射雷射曝光之光阻的光阻圖案之形成方 法。 (解決課題的手段） 、解決上述課題的本發明第1態樣的光阻圖案之形成方 去、係包括有··在半導體晶片或配線基板的配線圖案上，形 j感應第1感應波長區域之波長的光之第〗光硬化性光阻 ，的步驟，在上述第i光硬化性光阻膜的上側，形成阻隔 、第1感應波長區域之波長的光且感應第2感應波長區域之 波長的光之第2光硬化性光阻膜的步驟；將含有第2感應 319353 6 200811921 罩長的雷射’對成為第2光硬化性光阻膜之遮 ^木㈣域’施行掃描並曝光的步驟，·以不會 ηΓ 頭影液，對上述第2光硬化性光阻膜 區域之波县“ 的步驟，利用上述第1感應波長 、、，以上述遮罩圖案為遮罩，並對上述第工 光硬化性光阻膜施行圖幸 硬化性先阻— 以及對上述第1光 路圖= 影，而在上述已形成半導體晶片或電 回木2土板上，形成光阻圖案的步驟。 該第1癌樣係利用不會传繁T ^ 波長（即，Mm Μ ^ 絲膜曝光的 將黛Λ 波長區域之波長）的雷射照射，而 光阻膜^更Γ生光阻膜曝光’並利用不會使第1光硬化性 二痛影液，對第2光硬化性光阻膜施行 便可在不致損及第1光硬化性総膜，且不致使第^硬 ^生t阻膜的非曝光部分曝光之情況下，對第1光硬化性 罩圖# ’且可依更短時間實施對第1光硬化性 光阻膜的圖案形成。 =者’使用雷射的曝光係對第2光硬化性光阻膜實 ^ 便可將對雷射的感度較低之第1光阻材料，選擇 硬化性光阻膜材料。即，可在不致降二 本用、1所阻㈣使用材料的自由度情況下’選擇適合原 ^ Μ的H光魏性光㈣，並執行反 的光阻圖案之形成。 ^ ^ 樣所態樣的光阻圖案之形成方法，係在第1態 樣所*己載的光阻圖案之形成方法卜當在上述第！光硬化 319353 7 200811921 :=光阻膜的上侧，形成第2光硬化料阻膜之際，便隔著 ‘第1感應波長區域之波長的光會穿透的覆蓋膜，形成:述 •旦第^硬化性光阻膜，並在對第…更純光阻膜施行顯 衫的乂驟中，最先藉由將上述覆蓋膜剝離而將遮罩圖案去 1^" 〇 便可輕易地將遮 該第2態樣中，藉由將覆蓋膜去除， 罩圖案去除。 本發明第3態樣的光阻圖案之形成方法，係在第i態 樣所記載的光阻圖案之形成方法中，當在上述第！光硬二 光阻膜的上側’形成第2光硬化性光賴之際，便隔著 第1感應波長區域之波長的光會穿透的覆蓋膜，形成上述 ^光硬化性光阻膜，並在對第！光硬化性綠膜施行顯 〜的步驟中，藉由將覆蓋膜剝離而去除遮罩圖案，同時亦 將第1光硬化性光阻膜的非曝光部分去除。 該第3態樣中，藉由將覆蓋膜去除，便可將遮罩圖案 與第1光硬化性光阻膜的非曝光部分（即，非硬化分· 易地去除。 ; 十本發明第4態樣的光阻圖案之形成方法，係在第2或 第3態樣所記載的光阻圖案之形成方法中，使上述覆蓋膜 與第1光硬化性光阻膜積層的積層體設置於上述配線圖案 上之後再於上述覆盍膜上形成第2光硬化性光阻膜。 該第4態樣中，使用薄片狀之第丨光硬化性光阻膜， 依積層法即可輕易地在半導體晶片或電路基板上，設置第 1光硬化性光阻膜，且，藉由使用現有具覆蓋膜的第丨光 319353 8 200811921 硬化性光阻膜’便可省略另外設置覆蓋膜的麻須。 4能=明第5態樣的光阻圖案之形成方法，係在第^至 松中任一項所記載的光阻圖案之形成方法中， 有第2感應波長區域之波長的光之雷射，對要成 案的區_行·，輯要絲上述第2光硬化性== 圖案的區域施行曝光之際，經預先對各配線圖 : 純正之後，對含有第2感應波長區域之波長 光之雷=施行掃描，而在各配線圖案上形成遮罩圖案。 該第5態#中，#所測得配線基板的畸變進行校正之 雷射掃描，並施行遮罩㈣㈣光，便可對具有各種 ~又的夕數半導體晶片、或形成有配線圖案的基板，在益 各種偏移狀態下，高精度地形成遮罩圖案。、 &本發明第6態樣的光阻圖案之形成方法，係在第}至 5態樣中任一項所記載的光阻圖案之形成方法中，第丨光 硬化〖生光阻膜係使用具有紫外線感光性的材料，並利用紫 外線對上述第1光硬化性光阻膜施行曝光，第2光硬化性 光阻膜係使用具可見光感光性的材料，並利用可見光雷射 對上述第2光硬化性光阻膜施行曝光。 該第6態樣中，藉由使用可見光於雷射照射，便可不 致將對紫外線感應的第1光硬化性光阻膜曝光，而僅將第 2光硬化性光阻膜施行曝光。 本务明弟7悲樣的光阻圖案之形成方法，係在第1至 6態樣中任一項所記載的光阻圖案之形成方法中，第2光 硬化性光阻膜至少含有氧化鈦微粒子、碳酸鈣微粒子、及 9 319353 200811921 氧化鋅微粒子中之1種。 2光硬化性光阻膜，附 、以及水溶性與可見光 該第7態樣中，可輕易地 加將第1感應波長區域阻隔的 感光性。 b 本毛明弟8態樣的光阻圓安 樣所記载的光阻圖案之==形成方法’係在第7態200811921 IX. OBJECTS OF THE INVENTION: TECHNICAL FIELD The present invention relates to a method for forming a photoresist pattern, and more particularly to a method for soldering a printed circuit board, when the solder resist film provided in advance is formed Exposure_, and the method of forming a light-increasing product, and the formation of a photoresist pattern capable of increasing the degree of freedom of the solder resist film. [Prior Art] For the manufacture of a material path plate, a wheel for circuit formation感光, and solder resist materials for circuit protection use photosensitive materials. When p is stepped into a resistive material pattern exposure, a method such as a glass or a film such as a photo-negative pattern (hereinafter also referred to as _*)) is used to perform ultraviolet irradiation and development. However, when using a reticle to perform a variety of settings, such as the π p 仕 * 分 分 而 而 斤 斤 斤 斤 斤 斤 斤 斤 斤 斤 斤 斤 斤 斤 。 。 。 。 。 。 。 。 。 。 。 。 ^, It is known that a direct exposure method is applied to the resist material without a photomask (refer to the special method of photo-ray method by using a laser to the photoresist (4) _). In the case of the reticle, it is possible to form a plurality of patterns on the same substrate without making multiple copies. Therefore, the solder resist material is usually negative, and most of the pattern forming portion becomes a field exposure, and is a little, so that the use of the lightning portion instead of the exposed portion is only a concern. , & 仃 direct exposure is quite time-consuming, when direct exposure to the photoresist material is used, it will be 319353 5 200811921 need to use the photoresist with the previous multiple sensitivity, Therefore, the light p material used is limited. For example, when other members are mounted on the wiring substrate or the semiconductor wafer of the patterned photoresist film, the member of the bonded portion on the wiring substrate must have adhesion to the resin or the metal, but this case is the same as & A photoresist material that combines the properties of adhesion and sensitivity to laser light; 4 has no concern of 'there is a decrease in the degree of freedom of choice of photoresist material. Another: the example system #総膜 consists of the photoresist material for the plating solution _, because it must be combined with the resistance and high sensitivity of the photosensitive '! · Health, it is difficult to maintain the temperament of the situation However, only the sensitivity and the result are improved, and there is a choice of materials for the photoresist; [Patent Document 1] Japanese Patent No. 2679454 [Disclosure] The present invention has been made in view of the above circumstances, and an object thereof is to provide an exposure time capable of shortening a photoresist material, and even if a laser is selected The photoresist of the lower sensitivity is formed. The material can still form a resist pattern for reflecting the photoresist of the laser exposure. (Means for Solving the Problem) The formation of the photoresist pattern according to the first aspect of the present invention, which solves the above-described problems, includes forming a first sensing wavelength region on a wiring pattern of a semiconductor wafer or a wiring substrate. a step of light-curing photoresist of the wavelength of light, forming a light blocking the wavelength of the first inductive wavelength region and sensing the wavelength of the second inductive wavelength region on the upper side of the i-th photocurable photoresist film a step of light-curing the second photo-curable photoresist film; and scanning and exposing the laser beam containing the second sensing 319353 6 200811921 hood length to the second photo-curable photoresist film a step of using the masking pattern as a mask for the step of using the first sensing wavelength in the step of "wave state of the second photocurable photoresist film region" without the η Γ cephaloscene liquid The photo-curable photoresist film is subjected to a step of forming a photoresist pattern on the semiconductor wafer or the electro-green wood 2 on the above-mentioned semiconductor wafer or electro-return wood. The first cancerous cell line will not pass through T ^ The wavelength (i.e., Mm Μ ^ the exposure of the silk film to the wavelength of the 黛Λ wavelength region) is irradiated by the laser, and the photoresist film is exposed to the photoresist film and the first photo-curable second pain is not utilized. The liquid can be applied to the second photocurable photoresist film without damaging the first photocurable ruthenium film, and the first light is not exposed to the non-exposed portion of the second resist film. The curable cover pattern #' can be used to form the pattern of the first photocurable photoresist film in a shorter period of time. = The 'exposure system using a laser can be used for the second photocurable photoresist film. For the first photoresist material with low sensitivity of the laser, the curable photoresist film material is selected. That is, the H suitable for the original can be selected without reducing the degree of freedom of the use of the material and the resistance of the material used. The light is light (4), and the formation of the reverse photoresist pattern is performed. ^ ^ The formation method of the photoresist pattern in the sample state is the method for forming the photoresist pattern in the first aspect. Light hardening 319353 7 200811921 :=The upper side of the photoresist film, when the second light hardening film is formed, the first sensing wavelength is separated The light of the wavelength of the domain penetrates the cover film to form: the first hardened photoresist film, and in the step of applying the shirt to the more pure photoresist film, the first step is to cover the above When the film is peeled off and the mask pattern is removed, the second pattern can be easily removed, and the cover film can be removed by removing the cover film. The method for forming the photoresist pattern according to the third aspect of the present invention In the method of forming a photoresist pattern described in the ith aspect, when the second photo-curable light is formed on the upper side of the first light hard resist film, the first sensing wavelength is interposed. a cover film through which light of a wavelength of the region penetrates forms the photo-curable photoresist film, and in the step of performing the photo-curable green film, the mask pattern is removed by peeling off the cover film At the same time, the non-exposed portion of the first photocurable photoresist film is also removed. In the third aspect, by removing the cover film, the mask pattern and the non-exposed portion of the first photocurable photoresist film (that is, the non-hardened portion can be easily removed. In the method of forming a photoresist pattern according to the second or third aspect, the layered body in which the cover film and the first photocurable photoresist film are laminated is provided in the above-described method. A second photocurable photoresist film is formed on the overlying film after the wiring pattern. In the fourth aspect, a flaky photo-curable photoresist film is used, and the semiconductor layer can be easily used in the semiconductor layer. On the wafer or the circuit board, a first photocurable photoresist film is provided, and by using a conventional photomask 319353 8 200811921 curable photoresist film ′ with a cover film, the whisker additionally provided with the cover film can be omitted. A method of forming a photoresist pattern according to any one of the first to sixth aspects of the method for forming a photoresist pattern according to any one of the first to the sixth aspect of the present invention, The area to be completed _ line ·, the silk of the above second light hardenability == pattern area When the exposure is performed, each wiring pattern is preliminarily: after being pure, the light having the wavelength of the second inductive wavelength region is scanned for scanning, and a mask pattern is formed on each wiring pattern. The fifth state #中# The laser scanning of the distortion of the measured wiring substrate is performed, and the mask (4) and (4) light are applied, so that the semiconductor wafer having various kinds of semiconductor wafers or the substrate having the wiring pattern can be used in various offset states. A method of forming a photoresist pattern according to any one of the first to fifth aspects of the present invention, in the method of forming a photoresist pattern according to any one of the first to fifth aspects, Photohardening: a material having ultraviolet ray sensitivity is used for the raw photoresist film, and the first photocurable photoresist film is exposed to light by ultraviolet rays, and a material having visible light sensitivity is used for the second photocurable photoresist film. Exposing the second photocurable photoresist film by visible light laser. In the sixth aspect, by using visible light for laser irradiation, the first photocurable photoresist film that is sensitive to ultraviolet light is not exposed. And only will (2) The photocurable photoresist film is subjected to exposure. The method for forming a photoresist pattern according to any one of the first to sixth aspects is the second method. The photocurable photoresist film contains at least one of titanium oxide fine particles, calcium carbonate fine particles, and 9 319353 200811921 zinc oxide fine particles. 2 Photocurable photoresist film, attached, and water soluble and visible light in the seventh aspect, The sensitivity of the first sensing wavelength region can be easily added. b The photoresist pattern of the photoresist pattern of the 8th aspect of the Mao Mingdi is formed in the seventh state.

舞微粒子、及氧化鋅微粒子中至，乳化鈦微粒子、碳酸 # Π1至0.05# m。 夕種，具有平均粒徑0·01 2光硬化性光阻膜，附 阻隔的機能、以及水溶 該第8態樣中，可輕易地對第 加將第1感應波長區域之波長的光 性與可見光感光性。 案之形成方法，係在第1至 圖木之形成方法中，第2光 的材料，第2顯影液係使用 本發明第9態樣的光阻圖 8態樣中任一項所記載的光阻 硬化性光阻膜係使用可水顯影 水。 _ 該第9態樣申，可在不致損及第】硕,^ 情況:^用水輕易地將第2光硬化性光阻膜施行：的 t弟iG態樣的光阻圖案之形成方法，係在第】 至9恶樣令任-項所記载的光阻圖案之形成 光硬化性光阻膜為防焊膜。 f 罘1 該第i〇態樣尹，使用本發明的光阻圖案之 便可在短時間内輕易地對防焊膜施行圖案的形成\ 、， 本發明第11態樣的光關案之形成方法， 至9態樣中任一項所記載的光阻圖案之形成方法中，第1 319353 10 200811921 光硬化性光阻膜為防錄膜。 該第11態樣中，使用本發明的光阻 便可在紐％間内輕易地對防鍍膜施行圖案的形成。 本發明第12態樣的光阻圖案之形成方法，係在 至9態樣中任—項所記載的光阻圖案之形成方Μ 光硬化性光阻膜為防蝕膜。 該第12態樣中，使用本發明的光阻圖案之形成方法， 便可在短時間内輕易地對防蝕膜施行圖案的形成。/ [發明的效果] ^ 根據本發明可提供能在短時間内施行防谭材料的曝 光’並且不致發生光阻圖案的位移’且可如同以往般的‘ 用防焊材料，利用雷射施行曝光的光阻圖案之形成方 【實施方式】 ' ^ 〇 以下，根據圖式對本發明之實施形態進行說明。另 外，各圖中，同一構成要件便賦予相同的元件符號。 第1圖所示係使用本發明光阻圖案之形成方法， 付之防焊圖案一例。 在由玻璃纖維布（glass cloth)強化環氧樹脂或聚醯亞 胺樹脂等構成的可撓性基板丨上，對設有由銅等導電材料 構成配線圖案2的印刷電路板3，在配線圖案2忠壯 /、 文衣其他 構件的部分，形成具有開口 4的防焊圖案5。將開口 4立 分裸露出的配線焊接其他構件的金屬端子。 ° 本發明的光阻圖案之形成方法可適用於第2圖所示防 焊圖案的形成，可在短時間内施行防焊材料的曝 一、％ ’且亦 319353 11 200811921 了如同以在般的使用防焊材料並利用雷射施行曝光。 本貫施形態中，第1光硬化性光阻膜係使用防焊膜7, 第2光硬化性光阻膜係使用光阻膜8，並在印刷電路板3 上施行防焊圖案5的形成。根據第2圖⑷至⑻，例示本實 施形態的光阻圖案之形成方法流程。 Ί在如帛2目⑷料之樹脂等構成的可撓性基板 上叹有由銅等導電性材料構成配線圖案2的印刷電路 板3上b第2圖⑻所示，依積層法設置表面由覆蓋膜6 覆蓋的乾膜狀防焊膜7(第1光硬化性光阻臈）。本實施形態 所使用的覆蓋膜6係以PET等樹脂為主成分，並具有可見 光與紫外線穿透性，且屬於非感光性、不溶於水，以及明 顯小的透氣性（或透氧性）。 垃人7係如同以往般’可利用適於與其他構件進行 防二膜需屬於適合雷射照射的材質。本實施形態的 f、歧用具有料線硬化性，*溶 用 鹼性顯影液進行顯影的材料（亦稱「材料D。 弱 稱係有如至少含有:聚合物類及/或寡聚物類(以下 、A)」）、單體類及/或有機溶劑（以下稱「成分 」、以及反應起始劑（以下稱「成分（I_C)」）。 成分二::::二分(1’的聚合物類、寡聚物類、以及 料！便具:中’至少一者係具有感光基。藉此，材 鍵、環氧乙院鍵算^化性。此種感光基係有如具有不飽和 舉例如:丙埽酿基、白、,=席飽和鍵的感光基係可 甲基丙烯fe基（以下亦有將該等統稱 319353 12 200811921 「（甲基）丙_基」的情形）、乙稀基、婦丙基、肉桂醯基 (fnnam〇yl)等。此外，具有環氧乙炫鍵的感光基係有如·· %氧基等。》亥等之中，亦可含有一或二種以上之感光基， 亦可使用二種以上具有一或二種以上感光基的成分(ι·α) 與成分（Ι-Β)。 再者’材料1中，成分(LA)的聚合物類、寡聚物類、 以及成分（Ι·Β)的單體類中至少任—者係具有酸性基。藉 此’材料I便具有驗顯影性。此種酸性基係有如省酸基、 磺酸基等’亦可含有該等—或二種以上的酸性基，亦可使 用-種以上具有-或二種以上酸性基的成分（LA)與成分 (Ι-Β) 〇 材料I中’成为（Ι-A)宜為平均分子量2〇〇〇至3〇〇⑻（特 別係5000至20000)者。 成刀（I Α)係兼具有感光基與酸性基等二基，例如在環 氧樹脂的不飽和羧酸加成物中使酸酐產生反應而獲得者 # (以下亦稱「成分（I_A-i)」）。 成刀（I A i)中’環氧樹月旨係可舉例如··酴盤型環氧化合 物[苯酚酚醛型環氧樹脂、甲酚酚醛型環氧樹脂等]、雙^ 型環氧化合物、三苯甲烧型環氧樹脂等。亦可含有該等中 之一或二種以上。 < 成分（I_A_i)中，不飽和羧酸係可舉例如：丙烯酸、甲美 丙烯酸、巴豆酸、肉桂酸，或者飽和Μ飽和二元酸肝（二 如成分的「二元酸酐」等）、與1分子中具有丨個經 基的（曱基）丙烯酸酯類或不飽和單縮水甘油基化合物的半 319353 13 200811921 • 酯類等。 -成分（I-A-i)中，酸酐係可舉例如··二元酸酐[順丁烯二 ,酸酐、琥珀酸酐、衣康酸酐、酞酸酐、四氫酞酸酐、六氫 醜酉欠酐、甲基六氫g太酸酐、内亞甲基四氫酜酸酐、甲基内 亞曱基四氳酞酸酐、六氣内亞曱基四氫酞酸酐、甲基四氫 酞酸酐等]、芳香族多元羧酸酐[偏苯三甲酸酐、均苯四甲 酸酐、二苯基酮四羧酸二酐等]、多元羧酸酐衍生物[5-(2,5_ 翁二酮基（0X0)四氫呋喃基）_3_曱基環己烯羧酸酐 等]等。亦可含有該等中之一或二種以上。 成分（I-A-i)係可使用使環氧樹脂的不飽和羧酸加成物 (即’環氧樹脂與不飽和羧酸的反應物）所具有之每丨個羥 基’與0· 15莫耳以上的酸酐進行反應者。此外，成分 的酸價係 45 至 160mgKOH/g，最好 50 至 140mgKOH/g。 當酸價過小時，鹼溶解性將惡化，反之，若過大，將成為 硬化膜的耐鹼性、電氣特性等光阻特性降低的肇因，因而 敢好均避免。 材料I中，其他成分（Ι-A)的具體例，係有如對不飽和 羧酸（例如成分（I-A-i)的「不飽和羧酸」等）、與不飽和二 元酉欠酐（例如成分(I-A-i)的「二元酸酐」等）的共聚物中所 含致基其中一部分，經加成不飽和單縮水甘油基化合物的 聚合物等。、 材料ί的成分（I-B)中，單體類具體上可舉例如：水溶性 “單體[丙烯酸2-羥乙酯、丙烯酸2-羥丙酯、Ν-乙稀基,比略 义S同、丙烯醯基嗎啉、甲氧基四乙二醇丙烯酸酯、甲氧基 319353 14 200811921 聚乙二醇丙烯酸酯、聚乙二醇二丙烯酸酯、N，N-二甲基丙 烯醯胺、N-羥甲基丙烯醯胺、N，N_二甲胺基丙基丙烯醯 胺、丙烯酸Ν，Ν-二曱胺基乙酯、丙烯酸N，N-二曱胺基丙 酯、或上述丙烯酸酯所對應的各曱基丙烯酸酯類等]、非水 溶性單體[二乙二醇二丙烯酸酯、三乙二醇二丙烯酸酯、丙 二醇二丙浠酸酯、二丙二醇二丙烯酸酯、三丙二醇 酸酯、聚丙二醇二丙烯酸酯、丙烯酸苯氧基乙酯、丙烯酸 四氫糠酯、丙烯酸環己酯、三經曱基丙烧二丙稀酸酯、三 羥甲基丙烷三丙烯酸酯、甘油二縮水甘油醚二丙烯酸醋、 甘油二縮水甘油醚三丙烯酸酯、季戊四醇三丙烯酸酯、季 戊四醇四丙烯酸酯、二季戊四醇五丙烯酸酯、二季戊四醇 六丙烯酸酯或上述丙烯酸酯所對應的各曱基丙烯酸酯類、 多元酸與（甲基）丙烯酸羥基烷酯的單_、二_、二_ 上 聚醋销。亦可含有該等中之一或二種以上上的 材料1的成分（Ι-Β)中，有機溶劑具體係可舉例如：酮類 > [甲乙酮、環己酮等]、芳香族烴類[甲苯、二甲苯等]、溶纖 劑（cell〇solve)類[溶纖劑、丁基溶纖劑等]、卡必醇類[卡必 醇:丁基卡必醇等]、醋酸醋類[醋酸乙酉旨、錯酸丁醋 纖劑醋酸酯、丁基溶纖劑醋酸酯、卡必醇醋酸酯 卡 必醇醋動旨等]。亦可含有該料之-或二種以上。 材料I巾，成分㈣係有如利用紫外線（具體俜波早 綱至_一光)進行照射，便開始進行光:合體的::長 此種成分（Ι-C)具體上可舉例如：2_甲基，_(甲硫 基]·2-嗎琳基丙酮（汽 爪土）本 飞巴起級化學（Ciba · specialty · 15 319353 200811921 ^ Chemicals)&司製、「IRGACURE 907」）、苯偶姻（benzoin) -與其烧醚類[本偶姻、苯偶姻曱醚、苯偶姻乙_、苯偶姻異 ,丙醚等]、乙醯苯類[乙醯苯、2,2-二曱氧基-2-苯基乙醯苯、 2,2-二乙氧基·2-苯基乙醯苯、1，丨_二氯乙醯苯等]、蒽醌 (anthmquincme)類[2-曱基蒽醌、2_乙基蒽醌、2_第三丁基 蒽醌、1-氯蒽醌、2-戊基蒽醌等]、噻噸酮（thi〇xanih〇ne)類 [2,4-二甲基噻噸酮、2,4_二乙基噻噸酮、2_氯噻噸酮、2,4_ 一兴丙基噻噸酮等]、縮酮類[乙醯苯二甲基縮酮、苄基二 曱基鈿酮等]、二苯基酮類、及咕噸酮類等。亦可含有該等 中之一或二種以上。 人 材料I中，其他的添加劑，如：填充劑、增感劑、著 用顏料、密合劑、阻聚劑類、環氧化合物、環氧硬 反應促進劑（苯甲酸系與三級胺系等）、溶劑⑽類、㈣ 嗣類等）、消泡雜油等）、均塗劑、抗滴垂劑等，亦引 配入一或二種以上。 材料I的添加劑中，填充劑之 π 鋇、氧化石夕、滑石、勒土 係可舉例如:硫1 站土、奴酸鈣等。亦可含有誃耸φ」 :種以上。增感劑具體上可舉例如:4-二甲胺二甲; 戊酯等二甲脸其梦^ 奴基本甲画 等中之-或二腊肪族腔類等。亦可含有索 藍、-二二二顏料具體上可舉例如辦. 、、苯虱化鈦•石厌黑等。亦可含有兮玺丄 二=上。密合劑係可舉例如:不飽和磷酸化：物η 二丙稀，等。亦可含有該等中之一或二種聚酷型 阻來劍類具體上可舉例如：氫藏、氫醒單甲_、五倍子 319353 16 200811921 帽等，亦可含有該等中之-或 脂、雙盼Fa;=具體係可舉例如:雙…環氧樹 環氧樹脂、甲齡二4雙紛S型環氧樹脂、苯㈣趁型 脂、或脂琴^」環氧樹脂、N，水甘油基型環氧樹 的環氧化合乳：脂子中含有2個以上環氧基 硬化劑且體上可〜、可含有该等中之—或二種以上。環氧 類、苯㈣ 胺化合物類、味哇化合物類、_ 含有兮等Γ四級銨鹽類、或含經甲基化合物類等。亦可 3有5亥專中之—或二種以上。 宜為Γ=組成中，相對成分(ι都。°重量份，成分㈣ 為02至π 50至200為佳）重量份，成分㈣宜 為0.2至3〇(尤以2至2〇為佳）重量份。 其次，如第2圖⑷所示， 設置具有可水顯影的紫外線遮 膜8(第2光硬化性光阻膜）。 可在覆盍膜6上，依積層法 光性且可見光硬化性的光阻Dance microparticles, and zinc oxide microparticles, emulsified titanium microparticles, carbonic acid # Π1 to 0.05# m. In the evening, the photo-curable photoresist film having an average particle diameter of 0·01 2 , the barrier function, and the water-soluble eighth aspect can easily add light to the wavelength of the first sensing wavelength region. Visible light sensitivity. In the method of forming the first to the wood, the material of the second light, and the second developer are the light described in any one of the aspects of the photoresist pattern of the ninth aspect of the invention. The hardenable photoresist film uses water-developable water. _ The ninth aspect of the application, can not be damaged and the first], ^ situation: ^ easy to use the second photo-curable photoresist film with water: the formation method of the resist pattern of the t-i-i The photocurable photoresist film formed of the resist pattern described in the first to the ninth example is a solder resist film. f 罘1 The i-th aspect, the formation of a pattern of the solder resist film can be easily formed in a short time by using the photoresist pattern of the present invention, and the formation of the optical contact pattern of the eleventh aspect of the present invention In the method for forming a photoresist pattern according to any one of the aspects of the invention, the first 319353 10 200811921 photocurable photoresist film is an anti-recording film. In the eleventh aspect, the pattern of the plating resist can be easily formed in the gap between the New% by using the photoresist of the present invention. A method of forming a photoresist pattern according to a twelfth aspect of the invention is the method for forming a photoresist pattern according to any one of the aspects of the invention, wherein the photocurable photoresist film is an anti-corrosion film. In the twelfth aspect, by using the method for forming a photoresist pattern of the present invention, it is possible to easily form a pattern of the anti-corrosion film in a short time. / [Effects of the Invention] According to the present invention, it is possible to provide an exposure of the anti-tamper material in a short time and to prevent displacement of the photoresist pattern, and to perform exposure using a solder resist material as in the past. [Formation of the photoresist pattern] [Embodiment] Hereinafter, an embodiment of the present invention will be described based on the drawings. In the drawings, the same components are denoted by the same reference numerals. Fig. 1 shows an example of a method of forming a photoresist pattern according to the present invention, and an anti-welding pattern. The printed circuit board 3 in which the wiring pattern 2 is formed of a conductive material such as copper is provided on a flexible substrate 构成 made of a glass cloth reinforced epoxy resin or a polyimide resin, etc., in the wiring pattern 2 Zhong Zhuang /, part of other components of the clothes, forming a solder resist pattern 5 having an opening 4. Weld the openings of the openings 4 to the metal terminals of the other members. The method for forming the photoresist pattern of the present invention can be applied to the formation of the solder resist pattern shown in FIG. 2, and the exposure of the solder resist material can be performed in a short time, and % 319353 11 200811921 is as usual. Use solder resist material and use laser to perform exposure. In the present embodiment, the solder resist film 7 is used for the first photocurable photoresist film, and the photoresist film 8 is used for the second photocurable photoresist film, and the solder resist pattern 5 is formed on the printed circuit board 3. . The flow of the method of forming the photoresist pattern of the present embodiment will be exemplified based on Figs. 2(4) to (8). The printed circuit board 3 in which the wiring pattern 2 is made of a conductive material such as copper is smothered on the flexible substrate made of a resin such as a material (4), as shown in Fig. 2 (8), and the surface is provided by the laminated method. The dry film solder resist film 7 (first photocurable photoresist) covered by the cover film 6. The cover film 6 used in the present embodiment contains a resin such as PET as a main component, and has visible light and ultraviolet light transmittance, and is non-photosensitive, insoluble in water, and significantly small in gas permeability (or oxygen permeability). The 7-series is a material that is suitable for laser irradiation and is suitable for use with other components. In the present embodiment, the material having the material-curable property and the alkali-developing solution is used for the development of the material (also referred to as "material D. The weak term includes at least a polymer and/or an oligomer (hereinafter, , A)"), monomeric and/or organic solvents (hereinafter referred to as "components" and reaction initiators (hereinafter referred to as "components (I_C)"). Component 2:::: two points (1' polymer) Classes, oligomers, and materials! In the case of: at least one of them has a photosensitive group. Thereby, the material bond, the epoxy bond is calculated. Such a photosensitive substrate has such as unsaturated : The base of the acrylonitrile, white, and = saturated bonds can be methacrylic (based on the case of 319353 12 200811921 "(methyl)propyl-yl"), ethylene , propyl propyl, cinnamyl group (fnnam〇yl), etc. In addition, the photosensitive group having an epoxy ethoxy group bond may be, for example, an oxy group, etc., and may contain one or more of them. As the photosensitive group, two or more kinds of components (ι·α) and components (Ι-Β) having one or two or more kinds of photosensitive groups may be used. At least any of the polymer, the oligomer, and the monomer of the component (LA) has an acidic group. Thus, the material I has a testability. The acid group, the sulfonic acid group, etc. may also contain these or two or more acidic groups, and the components (LA) and components having one or more acidic groups may be used. In the bismuth material I, '(-A) is preferably an average molecular weight of 2 〇〇〇 to 3 〇〇 (8) (particularly 5,000 to 20,000). The gong (I Α) system has both a photosensitive group and an acidic group. The dibasic group, for example, is obtained by reacting an acid anhydride in an unsaturated carboxylic acid addition product of an epoxy resin to obtain # (hereinafter also referred to as "ingredient (I_A-i)"). For example, the sputum-type epoxy compound [phenol phenolic epoxy resin, cresol novolac epoxy resin, etc.], bis-epoxy compound, benzophenone-type epoxy resin, etc. One or two or more of these may be contained. In the component (I_A_i), the unsaturated carboxylic acid may, for example, be acrylic acid, methacrylic acid, crotonic acid or meat. Lauric acid, or saturated strontium saturated dibasic acid liver (such as the "dibasic acid anhydride" of the component), and a (mercapto) acrylate or unsaturated monoglycidyl compound having a thiol group in one molecule Half 319353 13 200811921 • Esters, etc. - In the component (IAi), the acid anhydride may, for example, be a dibasic acid anhydride [butylene, acid anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, six Hydrogen ugly oxime anhydride, methyl hexahydrogen g-anhydride, endomethylene tetrahydrophthalic anhydride, methyl endonamidinoic anhydride, hexa-indolylene-tetrahydrophthalic anhydride, methyltetrahydroanthracene An acid anhydride or the like], an aromatic polycarboxylic acid anhydride [p-trimellitic anhydride, pyromellitic anhydride, diphenylketone tetracarboxylic dianhydride, etc.], a polycarboxylic acid anhydride derivative [5-(2,5-ononedione) 0X0) tetrahydrofuranyl)_3_fluorenylcyclohexenecarboxylic acid anhydride, etc.]. One or more of these may also be contained. The component (IAi) may be an unsaturated carboxylic acid adduct of an epoxy resin (ie, a reactant of 'epoxy resin and an unsaturated carboxylic acid) having a hydroxyl group of '······ The anhydride is reacted. Further, the acid value of the component is from 45 to 160 mgKOH/g, preferably from 50 to 140 mgKOH/g. When the acid value is too small, the alkali solubility is deteriorated. On the other hand, if it is too large, it will cause a decrease in the photoresist characteristics such as alkali resistance and electrical properties of the cured film, and thus it is avoided. In the material I, specific examples of the other component (Ι-A) include, for example, an unsaturated carboxylic acid (for example, an "unsaturated carboxylic acid" of the component (IAi)), and an unsaturated binary hydrazine anhydride (for example, a component ( A part of the radical contained in the copolymer of "dibasic acid anhydride" or the like of IAi), a polymer obtained by adding an unsaturated monoglycidyl compound, or the like. In the component (IB) of the material ί, the monomer may specifically be, for example, a water-soluble "monomer [2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, fluorene-ethene, and the same as the S , propylene decylmorpholine, methoxytetraethylene glycol acrylate, methoxy 319353 14 200811921 polyethylene glycol acrylate, polyethylene glycol diacrylate, N, N-dimethyl decylamine, N - hydroxymethyl acrylamide, N,N-dimethylaminopropyl acrylamide, hydrazine acrylate, hydrazine-diguanidinoethyl ester, N,N-diallylammonium acrylate, or the above acrylate Corresponding thiol esters, etc.], water-insoluble monomers [diethylene glycol diacrylate, triethylene glycol diacrylate, propylene glycol dipropionate, dipropylene glycol diacrylate, tripropylene glycol acid Ester, polypropylene glycol diacrylate, phenoxyethyl acrylate, tetrahydrofurfuryl acrylate, cyclohexyl acrylate, tri-propyl mercapto-propylene diacrylate, trimethylolpropane triacrylate, glycerol condensate Glycerol ether diacrylate vinegar, glycerol diglycidyl ether triacrylate, pentaerythritol triacrylate, season Tetrahydrin tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate or each of the above acrylates, polybasic acid and hydroxyalkyl (meth) acrylate mono-, di-, and _ The upper vinegar pin. The component (Ι-Β) of the material 1 of one or more of the above may be contained, and the organic solvent may specifically be, for example, a ketone > [methyl ethyl ketone, cyclohexanone, etc. ], aromatic hydrocarbons [toluene, xylene, etc.], cellulolytic agents (cell solvates) [cellosolve, butyl cellosolve, etc.], carbitol [carbitol: butyl carbitol, etc.] Acetic acid vinegar [acetate acetate, acid butyl vinegar acetate, butyl cellosolve acetate, carbitol acetate carbitol, etc.] may also contain - or more than two. The material I towel, the component (4) is irradiated with ultraviolet light (specific 俜波早纲至_一光), and the light is started: the combined:: long such component (Ι-C), for example, 2_ Methyl, _(methylthio)·2-morphinylacetone (screw-claw soil) Benfica grading chemistry (Ciba · specialty · 15 3193 53 200811921 ^ Chemicals) & system, "IRGACURE 907"), benzoin (benzoin) - and its ethers [本偶姻, benzoin oxime ether, benzoin B, benzoin, C Ether, etc.], acetophenone benzene [acetamidine, 2,2-dioxaoxy-2-phenylethyl benzene, 2,2-diethoxy-2-phenyl acetophenone, 1, hydrazine _Dichloroethyl benzene, etc.], ant (anthmquincme) [2-mercaptopurine, 2_ethylhydrazine, 2_t-butylhydrazine, 1-chloroindole, 2-pentylhydrazine醌,] thioxanthone (thi〇xanih〇ne) [2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4_ Yixing Examples include propyl thioxanthone, etc., ketals such as acetophenone ketal and benzyl dimethyl fluorenone, diphenyl ketones, and xanthone. One or more of these may also be included. In human material I, other additives such as fillers, sensitizers, pigments, adhesives, polymerization inhibitors, epoxy compounds, epoxy hard reaction accelerators (benzoic acid and tertiary amine systems, etc.) ), solvents (10), (4) oximes, etc., defoaming oils, etc.), leveling agents, anti-dripping agents, etc., are also introduced into one or more. In the additive of the material I, the filler π 钡, the oxidized rock eve, the talc, and the terracotta may be, for example, sulfur 1 station or calcium citrate. It can also contain 誃 φ ”: more than one species. The sensitizer may specifically be, for example, 4-dimethylamine dimethyl; pentyl ester, etc., a dimethyl face, a dream, a slave, a basic painting, or the like. Further, it may contain, for example, a sapphire or a bismuth pigment, for example, benzophenone hydride, stone black, and the like. It can also contain 兮玺丄 two = up. The adhesive agent may, for example, be unsaturated phosphorylation: η dipropylene, or the like. It may also contain one or two of the types of snails, such as hydrogen reservoir, hydrogen awake 甲, gallnut 319353 16 200811921 cap, etc., and may also contain such - or fat For example, a double epoxide epoxy resin, a two-year-old S-type epoxy resin, a benzene (tetra) yttrium-type grease, or a scented epoxy resin, N, An epoxidized emulsion of a glycerin-based epoxy tree: the lipid contains two or more epoxy hardeners, and the body may be ~, or may contain one or more of them. Epoxy, benzene (tetra) amine compounds, savory compounds, _ containing quaternary ammonium salts such as hydrazine, or methylated compounds. Also 3 have 5 Hai special - or more than two. It should be Γ= composition, the relative components (ι.° parts by weight, component (4) is preferably 02 to π 50 to 200) by weight, and the component (iv) should be 0.2 to 3 〇 (especially 2 to 2 〇 is preferred) Parts by weight. Next, as shown in Fig. 2 (4), a water-developable ultraviolet ray shielding film 8 (second photo-curable photoresist film) is provided. Photoreceptive and visible light curable photoresist can be formed on the cover film 6

精由對該光阻膜8施行曝光與顯影而形成的圖宰 成為下側防焊膜7的遮罩。所以，當光阻膜8曝光之 必需依使位於光阻膜8下侧的紫外線硬化性防焊膜7 被感光的方式，使光阻膜8具有紫外線遮光性。 ，將 際， 不會 此種光阻膜8所使用之具有能水顯影的紫外線遮光性 且可見光硬化性的材料（亦稱「材们L )，係至少含 如聚合物類及/或寡聚物類（以下稱「成分（Π_Α)」）、單體 颏（乂下稱成分（Π·Β)」）、反應起始劑（以下稱「成分 (n_c)」）、以及紫外線遮光性材料（以下稱「成分（ii_d)」）。 319353 17 200811921 ㈣:=*成分(Π,有如水溶性樹脂。此種成分 ϋ 重㈣合單心，具㈣水基及/或親水性 化學構造的樹脂。親水基係 基齡、磺酸基等)及1:(二!:如=基、"基、酸性 彳、疏（竣1§曰、％酸酯等）、鹼性基（胺 及鹽(銨等)。亦可含有該等中之一或二種以上的親 水基。親水性化學構造係有㈣鍵（氧化埽基等）、醋鍵、The pattern formed by exposing and developing the photoresist film 8 serves as a mask for the lower solder resist film 7. Therefore, when the photoresist film 8 is exposed, the ultraviolet curable solder resist film 7 located on the lower side of the photoresist film 8 is required to be light-sensitive, so that the photoresist film 8 has ultraviolet light blocking properties. In addition, the water-developing ultraviolet light-shielding and visible light-curable material (also referred to as "L") used in such a photoresist film 8 does not contain at least a polymer and/or an oligomer. (hereinafter referred to as "component (Π_Α)"), monomer 颏 (hereinafter referred to as component (Π·Β)), reaction initiator (hereinafter referred to as "component (n_c)"), and ultraviolet light-shielding material ( Hereinafter referred to as "ingredient (ii_d)"). 319353 17 200811921 (4): = * Component (Π, like water-soluble resin. This component is heavy (4) combined with a single heart, with (4) water-based and / or hydrophilic chemical structure of the resin. Hydrophilic base age, sulfonic acid groups, etc. And 1: (two!: such as = base, " base, acid hydrazine, sparse (竣1§曰, % acid ester, etc.), basic group (amine and salt (ammonium, etc.). may also contain such One or more hydrophilic groups. Hydrophilic chemical structures are (four) bonds (yttrium oxide groups, etc.), vinegar bonds,

=胺鍵、酸酿胺鍵、乙内酿服（hydantoin)骨架、料咬酉同 月架等。亦可含有該等中之一或二種以上。 、體而σ成刀（Π_Α)係、有如下述合成樹脂、天然高 2類、及半合成樹脂等。即，成分(ΙΙ_Α)中的合成樹脂係 可舉例如：聚乙_(隱）、聚甲基乙制、聚乙稀基料 咬酮、聚乙婦縮丁路、聚環氧乙燒、水溶性騎脂、水溶 性二聚氰胺樹脂、水溶性聚s旨樹脂、水溶性㈣胺樹脂等， 最好為水溶性聚酯樹脂、水溶性聚醯胺樹脂等。亦含 該等中之一或二種以上。 • &分（II-A)的合成樹脂一例之PVA，最好為例如聚合 度100至5000(尤以500至25〇〇為佳)者。若聚合度過低口， 將有成膜性降低的情況。反之，若聚合度過高，將有無法 獲得充分顯影性的情況。此外，PVA最好為皂化度6〇莫 耳％以上（尤以70莫耳％以上為佳）者。若皂化度過低，將 有無法充分獲得顯影性的情況。 成分（11-A)的合成樹脂一例之聚甲基乙烯醚，最好為 例如分子量20000至5000000(尤以100000至1〇〇〇〇〇〇為 佳）者。若分子量過小，將有無法充分獲得硬化薄膜強度的 319353 18 200811921 ^ 情況。反之，若分子量過大，將有無法充分獲得顯影性的 情況。 ，成分（II-A)的合成樹鹿一例之聚乙烯基吼洛咬酮，最 好為例如分子量5000至5000000(尤以500000至1500000 為佳）者。若分子量過小，將有無法充分獲得硬化薄膜強度 的情況。反之，若分子量過大，將有無法充分獲得顯影性 的情況。 成分（II-A)的合成樹脂一例之聚乙烯醇縮丁醛，最好 馨為丁基化度5至40(尤以10至20為佳）莫耳％者。若丁化 度過低，將有顯影耐性降低的情況。反之，若過高，將有 顯影性降低的情況。平均聚合度最好為100至3000(尤以 600至2000為佳）者。若平均聚合度過小，將有顯影耐性 降低的情況。反之，若過大，將有顯影性降低的情況。 成分（Π-A)之合成樹脂一例的聚環氧乙烷，最好為例 如分子量20000至5000000(尤以100000至1000000為佳） 馨者。若分子量過小，將有無法充分獲得硬化薄膜強度的情 況。反之，若分子量過大，將有無法充分獲得顯影性的情 況。 成分（Π-A)之合成樹脂一例的水溶性盼樹脂，係有如 曱紛型紛樹脂。合成樹脂中的水溶性三聚氣胺樹脂，係有 如高經甲基化三聚氰胺（六經曱基三聚氰胺、五經曱基三聚 氰胺等）。 成分（Π-A)之合成樹脂一例的水溶性聚酯樹脂，係有 如由二元酸與二醇類所獲得的樹脂。二元酸係有如：順丁烯 19 319353 200811921 •二酸、酞酸、衣康酸等，二醇類係有如：乙二醇本身、二乙 二醇等。具體的水溶性聚酯樹脂係可使用例如Ar〇n Melt PES-iOOO、Aron Melt PES_2_(均為東亞合成（股）公司製） 等市售物。 成分（II-A)之合成樹脂一例的水溶性聚醯胺樹脂，係 有如將聚醯胺樹脂利用環氧乙烷等施行改性的樹脂。具體 上，水溶性聚醯胺樹脂係可使用例如AQ尼龍A_9〇、 尼龍P-70(均為TORAY(股)公司製）等市售物。 • 成分（II-A)中’天然樹脂係可舉例如：澱粉、糊精、蛋 白質（明膠、骨膠(glue)、酿蛋白等）。天然高分子類中，殿 粉與糊精最好為分子量10000至5〇〇〇〇〇(尤以2〇〇〇〇至 200000為佳）者。蛋白質最好為分子量％⑻至5〇的〇(尤以 10000至20000為佳）者。若分子量過小，將有成膜性降低 的十月況。反之，若分子量過大，將有顯影性降低的情況。 成分(Π-A)中，半合成樹脂係有如改性纖維素（甲基纖 鲁維素、經乙基纖維素等）。經乙基纖維素最好為例如聚合度 50至i 000(尤以200至700為佳）者。若聚合度過小，塗膜 強度將嫌不足’反之，若過大，將有顯影性降低的情況。 再者，成分（II-A)係可使用具有感光基的水溶性樹脂 (以下簡稱「感光性水溶性樹脂」）。當使减光性水溶性 樹脂時’將有提升顯影耐性的效果。 上述感光基係有如上述材料！中之例示物。例如成分 (Π-A)—例的感光性水溶性樹脂，係有如：下述含（甲基）丙 稀醯基樹脂、含環氧基樹脂、含乙縣樹脂等。感光性水 319353 20 200811921 溶性樹脂中的含（甲基）丙烯醯基樹脂，係有如在水溶性樹 脂中使不飽和脂肪酸產生反應者。水溶性樹脂係有如：多元 醇树月a (P VA、聚乙稀醇縮丁醒樹脂等）、聚_樹脂等。不 飽和脂肪酸係有如：不飽和脂肪酸（丙稀酉复、甲基丙婦 酸等）、衣康酸、肉桂酸等。亦可含有該等中之 具體上’感光性水溶性樹脂中，含（甲基）丙烯酿基樹 脂係有如在PVA中加成不飽和脂肪酸者。^不 飽和脂肪酸亦可在PVA中加成羥基例如5至40莫耳％(尤 以10至30 |耳％為隹）。若不飽和脂肪酸的加成量過少， 將有顯影耐性提升效果降低的情形，反之，若過多，將有= amine bond, acid-brown amine bond, hydantoin skeleton, material bite, and moon frame. One or more of these may also be contained. The body is formed into a knife (Π_Α), such as the following synthetic resin, natural high-grade, and semi-synthetic resin. That is, the synthetic resin in the component (ΙΙ_Α) may, for example, be polyethylene (hidden), polymethylethylene, polyethylene glycol ketone, polyethyl condensate, polyepoxybutene, water soluble The salty fat, the water-soluble melamine resin, the water-soluble polystyrene resin, the water-soluble (tetra)amine resin, and the like are preferably a water-soluble polyester resin or a water-soluble polyamide resin. It also contains one or more of these. • PVA of an example of a synthetic resin of (II-A) is preferably, for example, a polymerization degree of 100 to 5,000 (especially preferably 500 to 25 Å). If the degree of polymerization is too low, the film formability may be lowered. On the other hand, if the degree of polymerization is too high, sufficient developability cannot be obtained. Further, it is preferable that the PVA has a saponification degree of 6 〇 mol% or more (especially preferably 70 mol% or more). If the degree of saponification is too low, the developability may not be sufficiently obtained. The polymethyl vinyl ether of a synthetic resin of the component (11-A) is preferably, for example, a molecular weight of 20,000 to 5,000,000 (especially preferably 100,000 to 1 Torr). If the molecular weight is too small, there will be a case where the strength of the cured film cannot be sufficiently obtained 319353 18 200811921 ^. On the other hand, if the molecular weight is too large, the developability may not be sufficiently obtained. A polyvinyl ketone which is a case of the synthetic tree deer of the component (II-A), preferably, for example, a molecular weight of 5,000 to 5,000,000 (especially preferably 500,000 to 1,500,000). If the molecular weight is too small, the strength of the cured film may not be sufficiently obtained. On the other hand, if the molecular weight is too large, the developability may not be sufficiently obtained. The polyvinyl butyral which is an example of the synthetic resin of the component (II-A) is preferably a butyl group having a degree of butylation of 5 to 40 (especially preferably 10 to 20). If the degree of butylation is too low, development resistance will be lowered. On the other hand, if it is too high, there will be a case where the developability is lowered. The average degree of polymerization is preferably from 100 to 3,000 (especially from 600 to 2,000). If the average degree of polymerization is too small, development resistance will be lowered. On the other hand, if it is too large, there will be a case where the developability is lowered. The polyethylene oxide of a synthetic resin of the component (Π-A) is preferably, for example, a molecular weight of 20,000 to 5,000,000 (especially 100,000 to 1,000,000). If the molecular weight is too small, the strength of the cured film may not be sufficiently obtained. On the other hand, if the molecular weight is too large, the developability may not be sufficiently obtained. A water-soluble resin which is an example of a synthetic resin of the component (Π-A) is a resin such as a resin. The water-soluble trimeric urethane resin in the synthetic resin is, for example, a highly methylated melamine (hexa- fluorenyl melamine, penta-pyridyl melamine or the like). The water-soluble polyester resin which is an example of the synthetic resin of the component (Π-A) is a resin obtained from a dibasic acid and a glycol. The dibasic acid is as follows: cis-butene 19 319353 200811921 • Diacid, citric acid, itaconic acid, etc., and glycols such as ethylene glycol itself and diethylene glycol. As the specific water-soluble polyester resin, commercially available products such as Ar〇n Melt PES-iOOO and Aron Melt PES_2_ (all manufactured by Toagosei Co., Ltd.) can be used. The water-soluble polyamine resin which is an example of the synthetic resin of the component (II-A) is a resin which is modified by using an epoxy resin or the like. Specifically, as the water-soluble polyamine resin, commercially available products such as AQ nylon A_9 〇 and nylon P-70 (both manufactured by TORAY Co., Ltd.) can be used. • In the component (II-A), the natural resin may, for example, be starch, dextrin, or protein (gelatin, glue, brewed protein, etc.). Among the natural polymers, it is preferable that the powder and the dextrin have a molecular weight of 10,000 to 5 Å (especially 2 to 200,000). The protein is preferably one having a molecular weight of from (8) to 5 Å (especially preferably from 10,000 to 20,000). If the molecular weight is too small, there will be a ten month condition in which the film formability is lowered. On the other hand, if the molecular weight is too large, the developability may be lowered. In the component (Π-A), the semi-synthetic resin is modified cellulose (methyl cellulose, ethyl cellulose, etc.). The ethyl cellulose is preferably, for example, a polymerization degree of 50 to 1,000 (especially preferably 200 to 700). If the degree of polymerization is too small, the film strength will be insufficient. On the contrary, if it is too large, the developability will be lowered. Further, as the component (II-A), a water-soluble resin having a photosensitive group (hereinafter referred to as "photosensitive water-soluble resin") can be used. When the light-reducing water-soluble resin is used, there is an effect of improving development resistance. The above photosensitive base has the above materials! An example in the middle. For example, the photosensitive water-soluble resin of the component (Π-A) is, for example, the following (meth) acrylonitrile-containing resin, epoxy-containing resin, and resin containing B. Photosensitive water 319353 20 200811921 The (meth)acrylonitrile-containing resin in the soluble resin is a compound which reacts with an unsaturated fatty acid in a water-soluble resin. The water-soluble resin may be, for example, a polyol tree a (P VA, a polyethylene shortening resin, etc.), a poly-resin or the like. Examples of the unsaturated fatty acid include unsaturated fatty acids (acrylic acid, methacrylic acid, etc.), itaconic acid, and cinnamic acid. Further, among the photosensitive water-soluble resins, the (meth)acryl-containing resin may be added with an unsaturated fatty acid as in PVA. ^Unsaturated fatty acids may also be added to the hydroxyl group in PVA, for example, 5 to 40 mol% (especially 10 to 30% by volume). If the amount of unsaturated fatty acid added is too small, there will be a case where the development resistance improvement effect is lowered. On the other hand, if too much, there will be

顯影性降低的情形。聚合度最好為⑽至测 至2500為佳）等。 UU 其他含（甲基）丙烯ϋ基樹脂係有如在經基纖維素中加 成u·不餘和㈣酸者。n不飽和脂肪酸亦可在 #纖維素中加成經基例如5至25莫耳％(尤以1〇至2〇莫= 為佳）。料飽和脂肪酸的氧化量過少，將錢影耐性° ^感光性水溶性樹脂一例的含環氧基樹腊係有如在水 ;谷性樹脂使環氧化人物妄& 一… 應者。水溶性樹脂係有 = VA、名酿樹脂等。亦可含有該等中之一或二種以上。 環氧化合物係有如環氧氯丙烷（epichl〇r〇hydrin)等。。 具體上，係有如在PVA中加成環氧氯丙烧者。環氧氯 ，果降低的情形，反之，若過多，將有顯影性降低的情形。 聚合度可為20至1000(尤以5〇至5〇〇為佳）等。 319353 21 200811921 丙烷最好在P VA中加成羥基例如5 佳）蕈。4严γ — 主刊（尤以W至30為 =吴耳/。。錢魏丙㈣加成量過少，將 升效果降低的情形，反 了性徒 形。〒人斧可a 1Λ 多，將有顯影性降低的情 二2 至_(尤以5。°至25。。為佳）等。 服、;、二 氧基樹脂係有如:1，3-二縮水甘油乙内酿 以上。 g脲專。亦可含有該等中之一或二種 感光性水洛性樹脂一例的含乙稀基樹脂，係 乙基纖維素中加成素r^ 、 在經 的經基例如5至^ ^“氣乙稀最好加成絲纖維素 的加成量過少，將〇為佳）莫耳％。若氯乙烯 若過多，將二^ 提升效果降低的情形。反之， ::將有頒衫性降低的情形。聚合 以200至7〇〇為佳）等。 主川00(尤 材料II中，成分（ΙΙ-Β)係 有如在上述材料！中之例示物。例如者。感光基係 宫能基（甲基）丙稀酸酉旨類（即，單 刀(^)係有如：單 基)丙烯酸酷類係有如下式(化二=:)中’早官能基 Γ化1 1 观 /co〇r1 R2 (化-1) h2c= 〔式中’ R!係指燒基或脂環 ·〆 丄 ’工暴，R2係指 <筒或甲其ΊThe case where the developability is lowered. The degree of polymerization is preferably from (10) to 2500, and the like. Other UU-containing (meth) acrylonitrile-based resins are those which add u· and (iv) acid to the cellulose. The n-unsaturated fatty acid may also be added to the cellulose in the range of, for example, 5 to 25 mol% (especially 1 to 2 mol%). The amount of saturated fatty acid in the material is too small, and it will be resistant to money. ^The epoxy-containing wax of one example of the photosensitive water-soluble resin is as in water; the phenolic resin makes the epoxidized character 妄 & The water-soluble resin is VA, a famous resin, and the like. One or more of these may also be contained. The epoxy compound is, for example, epichlorohydrin (epichl〇r〇hydrin). . Specifically, it is added as an epoxy chlorinated product in PVA. Epoxy chlorine, if the fruit is lowered, on the other hand, if it is too much, there will be a case where the developability is lowered. The degree of polymerization may be from 20 to 1,000 (especially from 5 to 5), and the like. 319353 21 200811921 Propane is preferably added to a hydroxyl group such as 5 蕈 in P VA. 4 Yan γ - Main issue (especially W to 30 = Wu Er / .. Qian Wei Bing (four) the amount of addition is too small, the effect of lowering the effect of the rise, the opposite of the shape. The axe can be a 1 Λ more, will There are cases where the developability is lowered, 2 to _ (especially 5. 5 to 25.), etc., and the dioxy resin is as follows: 1,3- diglycidyl B or more. A vinyl-containing resin which may be one of the one or two photosensitive water-repellent resins, which is an addition product of ethyl cellulose, such as 5 to ^^ It is best to add less than the amount of cellulose added to the air, and it will be better. If the amount of vinyl chloride is too much, the effect of lowering the lift will be reduced. Conversely, :: will reduce the shirting property. In the case of polymerization, it is preferably 200 to 7 Å.) Main 00 (In particular, the component (ΙΙ-Β) is an example of the above material! For example, the photosensitive group is a uterine energy base. The (meth)acrylic acid hydrazine type (ie, the single-knife (^) is as follows: mono-group) acrylic cool class has the following formula (chemical ==) in the 'early functional group 11 1 view / co〇r1 R2 (chemical -1) h2c= Wherein 'R means the burning or alicyclic · 〆 Shang!' Workers storm, R2 means < A cartridge or its Ί

Ri中，烧基係有如C1至c 12去& 主L12者。脂環族烴基係有如 319353 200811921 單或多環烷基、或單或多環烯基等。此外，烷基或脂環族 烴基亦可具有取代基（羥基、烷氧基、羧基等）。 具體而言，成分（Π-Β)的單官能基（曱基）丙烯酸酯類係 有如：（曱基）丙烯酸羥乙酯、（甲基）丙烯酸乙氧基乙酯、(甲 基）丙烯酸二環戊烯酯、（曱基）丙烯酸異冰片酯等。亦可含 有該等中之一或二種以上。 ^ 、，工、厂^，叹日曰糊诉韦如多元 醇、與（曱基）丙烯酸的部分酯化物或全酯化物等。多 係可舉例如：二醇類（乙二醇、- · 斤、朴 —乙一.寻）、甘油類（甘油 :)、其他的三醇類(三經甲基丙烷等)、四醇類(季戊四醇 :)、五醇類(山梨糖醇、甘露糖醇等)、六醇類(二季戊四醇 寺）°亦可含有該等中之一或二種以上。 知 係可二::言，成分(ΙΙ·Β)中的多官能基(甲基)丙她類 係可舉例如：乙二醇二㈣）丙稀酸醋油 = 酸酯、三羥甲基丙烷二（甲 由一（甲基）丙烯 苴、工e (甲基）丙烯酸酯、二季戊四醇田 旬丙缔酸醋等。亦可含有該等中之 戊四I、(甲 τ4*、八 /ττ ^ ?里以上。 型者#右如-的另一具體例係有如脂環式型者。浐产彳 嫩所示物。此外，依式體係有如下式（化姐（化 2至50(尤以2至30所不物，式中的Μ最好為 主J〇為佳）的整數者。 【化2】In Ri, the base is as follows: C1 to c12 to & main L12. The alicyclic hydrocarbon group is, for example, 319353 200811921 mono or polycycloalkyl, or mono or polycycloalkenyl or the like. Further, the alkyl group or the alicyclic hydrocarbon group may have a substituent (hydroxy group, alkoxy group, carboxyl group, etc.). Specifically, the monofunctional (fluorenyl) acrylate of the component (Π-Β) is, for example, hydroxyethyl (meth) acrylate, ethoxyethyl (meth) acrylate, or (meth) acrylate Cyclopentenyl ester, isobornyl (mercapto)acrylate, and the like. One or more of these may also be included. ^,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,, For example, diols (ethylene glycol, - jin, pu-yi-1), glycerol (glycerol:), other triols (trimethylpropane, etc.), and tetraols (for example) Pentaerythritol:), pentaol (sorbitol, mannitol, etc.), hexaol (dipentaerythritol) may also contain one or more of these. Knowing that the polyfunctional (meth) propyl group in the composition (ΙΙ·Β) can be, for example, ethylene glycol di(tetra) acetoacetic acid = acid ester, trimethylol Propane di(A) is a (meth) propylene oxime, an industrial e (meth) acrylate, dipentaerythritol, a celinated vinegar, etc. It may also contain pentylene I, (Aτ4*, 八/ More than ττ ^ ?. Another specific example of the type #右如- is like the alicyclic type. The 浐 彳 彳 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 Especially 2 to 30, the Μ in the formula is preferably the integer of J〇 is the best.

【化3】 (it-2) 319353 23 200811921 ο:[化3] (it-2) 319353 23 200811921 ο:

ο ο ,ΟΗ2〇〇(〇Η2)4^〇〇Η： ch3 h3cο ο ,ΟΗ2〇〇(〇Η2)4^〇〇Η: ch3 h3c

:〇 (化一3) 【化4】 ?:〇 (化一3) 【化4】 ?

，CH20 - (化一 4) 【化5】 ^CH —CH2 o (化一 5) 【化6】 〇-, CH20 - (化一 4) [化5] ^CH -CH2 o (化一5) [化6] 〇-

-H-H

」MM

O 〇· (化一 6〉 成分（II-B)再另一具體例係有如下式（化-7)與（化·8)之 所示物。 【化7】 h2c>=ch-coch II 〇O 〇 · (Chemical One 6) Component (II-B) Another specific example is the following formula (Chemical-7) and (Chemical 8). [Chemical 7] h2c>=ch-coch II 〇

O-CH2O--G -ch=ch2 II ο (化一7) 【化8】 CH3 Ο I QH2/PH2CH3O-CH2O--G -ch=ch2 II ο (化一7) 【化8】 CH3 Ο I QH2/PH2CH3

H2C=CH—CO—CH2—C — HC C iht3 °~CH2 ch2~oc-ch=ch2 〇 (化一 8) 亦可含有上述化學式所示物中之一或二種以上。 24 319353 200811921 成分（II-B)之另一具體例係有如水溶性單體[成分（LB) 1 中所例示之物等]。 ， 成分（Π_Β)係就顯影耐性的觀點，最好感光基個數具2 個以上（尤以3至6個為佳）。且就從塗佈性層面的觀點， 最好在常溫下呈液體之物，特別以成為成分（Π_Α)的溶劑者 為佳。具體而言，此種成分（Π_Β)最好具有感光基3至6 個，尤以二季戊四醇六（甲基）丙烯酸酯等為佳。 材料π中，成分(II-C)係有如利用可見光（例如波長400 至800nm的光）的照射，而開始進行光自由基聚合者。此 種成分（II-C)係在可見光區域中具有大吸收，具體上， 舉例如：2_[2_(5_甲基呋π南-2-基）乙炔基]-4,6-雙（王氯甲 基）-s-三畊（tdazine)(三和化學公司製、「ΤΜΕ·三畊」）等三 氯曱基-s-三畊類；节酯、α_萘烷、苊烷（acenaphthane)、 Μ’-二甲氧基苄酯、4,4’_二環苄酯等苄酯化合物；莰醌 (camphorquinone)等醌化合物；2_氯噻噸酮、2,4_二乙氧基 φ噻噸酮、曱基噻噸酮等噻噸酮化合物；三曱基苯曱醯基二 苯基氧化膦等醯基氧化膦系化合物；二茂鈦⑽麵二)： ^物等。最好為2,4,6_三(三氯甲基）_s_三哄、與3,3，^基 雙(7-一乙胺基）香豆素(c〇umadn)(增感色素）的組合等。 材料II中，成分（II-D)最好係可見光能穿透，並阻隔 紫外線者。具體而言，成分(n-D)係有如：氧化鈦、碳酸約、 氧化鋅等，亦可含有該等中之一種或二種以上。此外，氧 化鈦係可使用金紅石型、銳鈦礦型中任一種。相較於氧化 鈦’雖然碳酸㈣紫外線遮蔽性懸，但是就可見光穿透 319353 200811921 性而言則具有優越特性。最 材料最好為微粒子狀形態（粒，、、、平^與氧化辞。遮光性 以。.。_至。.。_為丄).一至。.5…尤 μΓ、3圖所不係分散媒為使用噴漆(lacquer)塗料時，氧 私尸^ 圖中，a係針對具有〇.2#m平均 ^破粒子的測定結果，b係針對具有〇.〇3至0.05㈣平 —㈣粒子的測定結果’ e係針對具有0.CH至0.03_ 千均粒控微粒子的測定結果。依此得知，雖粒徑越大，將 越能遮蔽可見光（波長約4_m以上的光），但是粒徑越 i則可見光將越▲穿透，且有越能遮蔽紫外線（波長小於 約35〇nm❸光）的傾向。纟此種實驗的結果，本案發明者 等發現為了滿足可見光穿透性與紫外線遮蔽性，只要將微 粒子的平均粒子大小設定在Q 5_以下（尤以&心瓜以 下為佳）便可。 在材料II中亦可調配一或二種以上材升斗工中所例示的 φ添加劑，即，如：填充劑、增感劑、著色用顏料、密合劑、 阻聚劑類、環氧化合物、環氧硬化劑、反應促進劑（苯甲酸 系與二級胺系等）、溶劑（醚類、酯類、酮類等）、消泡劑（矽 油等）、均塗劑、抗滴垂劑等。 再者’材料II的添加劑中，增感劑藉由與成分 併用’便可較單獨成分（n-c)時更能將光聚合活化，具體上 宜為：曱基丙烯酸二曱胺基乙酯、4-二曱胺基苯甲酸異戊 醋、正丁胺、三乙胺等胺系化合物；三乙基__正丁膦等膦類； 悬頓（thioxanthene)糸、咕嘲（xanthene)系、_系、硫代°比喃 26 319353 200811921 * 鏽GhioPy1^11聰）鹽系、苯乙烯（base styryl)系、部花青素 ' (merocyamne)系、3·取代香豆素系、3,4_取代香豆素系、花 * 青素（cyanme)系、吖啶（acridine)系、噻畊(thiazine)系、啡 噻啡系、蒽系、蔻（coronene)系、苯并蒽系、茈（perylene) 系、酮香豆素系、富馬鹼（fumarine)系、硼酸酯系等。亦可 含有該等中之一或二種以上。 材料II的組成中，相對成分（π-Α)1〇〇重量份，成分 (ΙΙ-Β)最好含有5〇至3〇〇(尤以8〇至15〇為佳）重量份，成 分(II-C)取好含有！至2〇(尤以6至1〇為佳）重量份，以及 成分（II-D)最好含有4〇至1〇〇(尤以5〇至8〇為佳）重量份。 依如上述所調製得的材料Π，通常可見光穿透率係 60%以上’且紫外線穿透率低於4〇0/。。 其-人’從由上述材料η所構成的光阻膜8形成光阻圖 木本卷明光阻圖案之形成方法，因為係利用雷射施行曝 光而形成遮罩圖案，因而可配合各個可撓性基板1的畸 _變，調整雷射照射位置俾施行高精密曝光。 以往係當隔著已形成有遮光性負型圖案的玻璃或薄 膜:施行圖案形成的情況，頗難使曝光位置對應於因基板 %艾所&成各配線圖案2的位移。且，亦無法對應於因基 板崎變所造成配線圖案2的縱橫比變化、及X|^y㈣ 角之變化等。 調整雷射照射位置，而 圖案形成的問題，可施 如以下所說明，本發明中藉由 形成光阻圖案，便可解決上述以往 行而精密曝光。 319353 200811921 本實施形態中，為了配合各個可撓性基板！的實際位 置，调整雷射照射位置並施行曝光，而在曝光前便施行畸 變的測定。畸變值係在複數地方所預設的基準點9座標進 行測定，並從與基準位置間的誤差便可求得。 將所求得值輸入於雷射曝光的控制裝置中，並反映於 基準的雷射照射控制數據，而調整雷射照射位置，並如第 2圖（d)所示般的施行雷射曝光。 可見光硬化性光阻膜8的曝光係使用可見光雷射忉 實施。此時，位於光阻膜8下方的防焊膜7係紫外線感光 性材料’而實際上對可見光不感光。本實施形態中，可見 光係利用400 i 8〇〇nm的可見光，例如由g線或氯雷射 (488nm)及FD_Nd/YAG雷射（Μ2·)等雷射所產生的可 光0 經曝光過的光阻膜8係使用水進行顯影。更詳言之， 將 1 〇 至 8 0 C (最好 t 4取对至30C)的水，以10至300秒（最好 10至60秒）施行噴霧便可進行顯影。光阻膜 顯影的狀態係如第2_所示。另外，因為防焊二t: 7::。’因而此處所使用顯影液的水便不會對防焊膜 經利用水顯影而形成光阻圖案n之後，便如 所:般’料刷電路板3上整面施行紫外線12照射。^ 开兄成遮^具有紫外線遮光性的光阻圖案U物膜； /、“、、罩圖案，因而防焊膜7位於光阻圖案u下方 便成為非曝光部分(非硬化部分)13，其他部分的防焊膜〜 319353 200811921 則將硬化。藉此，便可形成防焊圖案5。 供施行紫外線照射的光源與紫外線照射量等停件，可 選擇適合防焊膜7的條件。具體上在本實施形態中，紫外 線係使用波長200 S4GGnm的光，例如由低.中· 廢水銀燈、氣燈或金屬函素燈、雷射等所產生的紫外線了 經紫外線12照射後，便藉由將非感光性覆蓋膜。剝 離’而如第2圖（g)所示般的將光阻圖案u去除，然後再 使用驗性顯影液將防焊膜7施行顯影，而將非曝光部分13 ^除’便可如第2 _所示般的形成防焊圖案5。驗性頻 影液係有如0.5至3%碳酸鈉水溶液等。 藉由依如上述流程，對防焊膜7施行圖案形成，便不 ^要針對各曝光圖案分別製造—個曝光遮罩板或曝光遮罩 溥片、纟°果，便可提升曝光精度、及縮短防焊的曝光時間， 、可防止光阻圖案的位移情況。此外，即便防焊材料沿用 、《所使用的材料，屬於對雷射的感度較低之防焊材料， ❿仍可施行反射雷射曝光的光阻圖#形成。即，可在不致降 低第1光硬化性光阻膜所使用材料自由度的情況下，選擇 適用原本用途性質的第i光硬化性光阻膜，可施行反射雷 射曝光的光阻圖案形成。 另卜印刷龟路板3、第1光硬化性光阻膜、第2光 更化14光阻膜、及薄片等的種類、材質、構造、及設置方 法等，均未僅侷限於本實施形態所例示。 λ例如本實施形態中，印刷電路板3係使用在可撓性基 々反1上，w又置由銅等導電材料所構成的配線圖案2，但是 319353 29 200811921 :=剛性基板，且導電材料亦可為紹或金等。此 面或雙面印刷電路板、或單層❹層印刷電路板等 防焊本實料Μ聽第1切純総膜為使用 膜=7’並形成能因應使用焊錫等的覆晶接 =案二成製程為例進行說明，惟本發明的㈣ 钮圖案、防鑛敷圖案、玻璃遮罩等防 光阻圖案之形成方法最好適用=焊成二：:本;明的 積比例明顯多於非曝光面積比例的情況。+'’ ^面 本實施形態中，第i光硬化 顯影液進行顯影的乾膜狀防關用弱驗 光阻膜，亦可將液狀或溶膠狀光為酉夂顯影型之 等方式進行設置。當使用酸顯影型之第：硬:：噴塗 時，便選擇不會㈣2 & 性先阻膜 材料。 疋更化性先阻肤的顯影液所顯影之 :二且，亦可使用利用酸進行_的材料 點在於第i光硬化：：因駄而顯影的耐酸性物。即，重 係使用依照不同㈣=膜與第2光硬化性光阻膜，分別 針對# 進行顯影的材料。 …木用為弟】光阻材料或第2光阻材料的酸顯影 319353 30 200811921 •性材料，進行以下的詳細說明。 * 酸顯影性材料之至少 人 > ，體類辑錢溶_成# 7 =物類、與早 分⑴或成分⑼構成之物十“ f物仏有如僅由以下成 成分π)#ί ⑴與成分⑼構成之物。 ()係#曰聚合物類及/戋寬平 者，成分⑻係指聚合物類、夷;;有驗性構造 具有驗性基者。 h物類、及單體類中任一者 上述成分（i)的情況，聚合物類 氧胺系樹脂[三聚氰鞍樹脂、 j係有如.二承 聚氰胺•酚樹脂 艰氰胺•脲樹脂等]、苯胺樹脂等H2C=CH—CO—CH2-C—HC C iht3 °~CH2 ch2~oc-ch=ch2 〇 (Chem. 1) may also contain one or more of the above chemical formulas. 24 319353 200811921 Another specific example of the component (II-B) is, for example, a water-soluble monomer [the substance exemplified in the component (LB) 1 and the like]. The component (Π_Β) is preferably two or more photosensitive groups (especially 3 to 6) from the viewpoint of developmental resistance. Further, from the viewpoint of the coating property, it is preferable to use a liquid at a normal temperature, and it is particularly preferable to use a solvent which is a component (Π_Α). Specifically, such a component (Π_Β) preferably has 3 to 6 photosensitive groups, particularly preferably dipentaerythritol hexa(meth)acrylate or the like. In the material π, the component (II-C) is one which starts photoradical polymerization using irradiation with visible light (for example, light having a wavelength of 400 to 800 nm). Such a component (II-C) has a large absorption in the visible light region, specifically, for example, 2_[2_(5-methylfuro π-nan-2-yl)ethynyl]-4,6-double (king Chloromethyl)-s-three-till (tdazine) (manufactured by Sanwa Chemical Co., Ltd., "ΤΜΕ·三耕") and other trichloroindolyl-s-three-plowing; esters, α-decalin, decane (acenaphthane) Benzyl ester compound such as Μ'-dimethoxybenzyl ester or 4,4'-bicyclobenzyl ester; anthracene compound such as camphorquinone; 2-chlorothioxanthone, 2,4-diethoxy a thioxanthone compound such as φ thioxanthone or decyl thioxanthone; a fluorenyl phosphine oxide compound such as tridecyl phenyl fluorenyl diphenyl phosphine oxide; and a titanocene (10) surface 2): a compound or the like. Preferably, it is 2,4,6-tris(trichloromethyl)_s_triterpene, and 3,3,^-bis(7-monoethylamino)coumarin (c〇umadn) (sensitizing pigment) The combination and so on. In the material II, the component (II-D) is preferably a person whose visible light can penetrate and block ultraviolet rays. Specifically, the component (n-D) may be, for example, titanium oxide, carbonic acid or zinc oxide, or may contain one or more of these. Further, as the titanium oxide type, any of a rutile type and an anatase type can be used. Compared to titanium oxide, although carbonic acid (IV) is UV-shielded, it has superior properties in terms of visible light penetration 319353 200811921. The most preferred material is in the form of fine particles (granules, , , , flat and oxidized. The opacity is .. _ to . . . _ is 丄). .5... Especially Γ Γ 3 3 3 3 3 为 为 为 为 为 为 为 为 为 lac lac lac lac lac lac lac lac lac lac lac lac lac lac lac 氧 lac lac lac lac lac 氧 lac 氧 lac 氧 氧 氧 氧 氧 氧 氧 氧 氧〇.〇3 to 0.05(四)平—(4) Measurement results of the particles 'e system for the measurement results with 0.CH to 0.03_ thousand average particle size control particles. From this, it is known that the larger the particle size, the more visible light (light having a wavelength of about 4 mm or more) is shielded, but the more the particle diameter is i, the more visible light will penetrate, and the more ultraviolet light can be shielded (the wavelength is less than about 35 〇). The tendency of nm twilight). As a result of such an experiment, the inventors of the present invention found that in order to satisfy the visible light transmittance and the ultraviolet shielding property, the average particle size of the fine particles may be set to be Q 5 or less (especially preferably & In the material II, the φ additive exemplified in one or more materials, such as a filler, a sensitizer, a pigment for coloring, an adhesive, a polymerization inhibitor, an epoxy compound, Epoxy curing agent, reaction accelerator (such as benzoic acid and secondary amine), solvent (ether, ester, ketone, etc.), antifoaming agent (such as eucalyptus), coating agent, anti-dripping agent, etc. . Furthermore, in the additive of the material II, the sensitizer can be photopolymerized more than the individual component (nc) by using the combination of the components, and specifically, it is preferably: decylaminoethyl decyl acrylate, 4 - an amine compound such as diamyl benzoic acid isoamyl vinegar, n-butylamine or triethylamine; a phosphine such as triethyl __n-butylphosphine; thioxanthene oxime, xanthene system, _ Department, thio-pyrene ratio 26 319353 200811921 * rust GhioPy1^11 Cong) salt system, styrene (base styryl), merocyanin ' (merocyamne), 3 · substituted coumarin system, 3, 4_ Replacing coumarin, cyanme, acridine, thiazine, morphine, coronene, benzopyrene, anthraquinone Perylene), ketocoumarin, fumarine, borate, and the like. One or more of these may also be included. In the composition of the material II, the relative component (π-Α) is 1 part by weight, and the component (ΙΙ-Β) preferably contains 5 to 3 inches (especially 8 to 15 inches) by weight, and the composition ( II-C) Take the inclusion! The parts by weight to 2 〇 (especially 6 to 1 〇), and the component (II-D) preferably contain 4 Å to 1 Torr (especially 5 Å to 8 Å) by weight. According to the material 调制 prepared as described above, the visible light transmittance is generally 60% or more and the ultraviolet ray transmittance is lower than 4 〇 0 /. . The method for forming a photoresist pattern 8 formed of the above-mentioned material η forms a photoresist pattern, and forms a mask pattern by laser exposure, thereby being compatible with each flexibility. The distortion of the substrate 1 is adjusted, and the laser irradiation position is adjusted to perform high-precision exposure. In the past, when a glass or a film having a light-shielding negative pattern was formed and a pattern was formed, it was difficult to make the exposure position correspond to the displacement of each of the wiring patterns 2 by the substrate. Further, it is not possible to cope with the change in the aspect ratio of the wiring pattern 2 due to the change in the substrate, and the change in the X|^y (four) angle. The problem of pattern formation can be adjusted by adjusting the position of the laser irradiation, and the above-described conventional exposure can be solved by forming the photoresist pattern in the present invention. 319353 200811921 In this embodiment, in order to match each flexible substrate! The actual position, the position of the laser irradiation is adjusted and exposure is performed, and the measurement of the distortion is performed before the exposure. The distortion value is measured at a predetermined reference point 9 in a plurality of places, and can be obtained from the error from the reference position. The obtained value is input to the laser exposure control device, and is reflected on the reference laser irradiation control data, and the laser irradiation position is adjusted, and the laser exposure is performed as shown in Fig. 2(d). The exposure of the visible light curable resist film 8 is carried out using a visible light laser. At this time, the solder resist film 7 located under the photoresist film 8 is an ultraviolet photosensitive material' and is actually not sensitive to visible light. In the present embodiment, the visible light is exposed to visible light of 400 i 8 〇〇 nm, for example, by a laser such as a g-line or a chloro-ray (488 nm) and an FD_Nd/YAG laser (Μ2·). The photoresist film 8 is developed using water. More specifically, water is applied from 1 Torr to 80 ° C (preferably t 4 to 30 C) for 10 to 300 seconds (preferably 10 to 60 seconds) for development. The state in which the photoresist film is developed is as shown in the second step. In addition, because of solder resist two t: 7::. Therefore, the water of the developing solution used herein does not irradiate the solder resist film with the water to form the photoresist pattern n, and then the ultraviolet ray 12 is irradiated on the entire surface of the brush circuit board 3. ^ 兄 成 ^ 具有 具有 具有 具有 具有 具有 具有 具有 具有 具有 具有 具有 具有 具有 具有 具有 具有 具有 具有 具有 具有 具有 具有 具有 具有 具有 具有 具有 具有 具有 具有 具有 具有 具有 具有 具有 具有 具有 具有 具有 具有 具有 具有 具有 具有 具有Part of the solder mask 319353 200811921 will be hardened. Thereby, the solder resist pattern 5 can be formed. For the light source to be irradiated with ultraviolet light and the amount of ultraviolet irradiation, etc., the conditions suitable for the solder resist film 7 can be selected. In the present embodiment, the ultraviolet light is light having a wavelength of 200 S4 GGnm, for example, ultraviolet light generated by a low-medium, a waste water silver lamp, a gas lamp, a metal element lamp, a laser or the like is irradiated with ultraviolet rays 12, and then The photosensitive cover film is peeled off and the photoresist pattern u is removed as shown in Fig. 2(g), and then the solder resist film 7 is developed using an in-progress developing solution, and the non-exposed portion 13 is removed. The solder resist pattern 5 can be formed as shown in the second embodiment. The photorefractive liquid solution is, for example, a 0.5 to 3% aqueous solution of sodium carbonate, etc. By patterning the solder resist film 7 as described above, it is not To create an exposure mask for each exposure pattern Or by exposing the mask to the enamel and 纟°, it can improve the exposure accuracy and shorten the exposure time of the solder resist, and prevent the displacement of the photoresist pattern. In addition, even if the solder resist material is used, the material used belongs to The solder resist material with low sensitivity to the laser can be formed by the resistive pattern # of the reflective laser exposure, that is, without reducing the degree of material used for the first photocurable photoresist film, The i-th photocurable photoresist film to which the original use property is applied can be formed by performing a resist pattern for reflection laser exposure. Further, the turtle plate 3, the first photocurable photoresist film, and the second photo-transformation film are printed. The type, material, structure, and installation method of the photoresist film, the sheet, and the like are not limited to those exemplified in the embodiment. λ. For example, in the present embodiment, the printed circuit board 3 is used in a flexible substrate. On the 1st, w is further provided with a wiring pattern 2 made of a conductive material such as copper, but 319353 29 200811921 := a rigid substrate, and the conductive material may also be a ruthenium or gold, etc. This side or double-sided printed circuit board, or a single layer Solder masks such as tantalum printed circuit boards The material of the first cut pure ruthenium film is formed by using a film = 7 ′ and can be formed by using a flip chip connection method such as soldering, etc., but the (4) button pattern and the anti-mineral pattern of the present invention are The method of forming a photoresist mask such as a glass mask is preferably applied = welding into two:: the present; the proportion of the product of the bright is significantly larger than the ratio of the non-exposure area. +'' ^ embodiment, the ith photohardening The dry film-like weak-proof photoresist film for developing a developing solution may be set such that the liquid or sol-like light is a sputum developing type. When the acid developing type is used: Hard:: spraying, Then choose not (4) 2 & first film material. 疋 性 先 先 先 先 先 : : : : : : : : : : : : : : : : : : : 显影 显影 显影 显影 显影 显影 显影 显影 显影 显影 显影 显影 显影 显影 显影 显影 显影 显影 显影 显影 显影Developed acid resistant material. That is, a material which is developed for # in accordance with the different (4) = film and the second photocurable photoresist film, respectively, is used. ...wood for the brother] acid development of the photoresist material or the second photoresist material 319353 30 200811921 • For the material, the following detailed description is given. * At least one of the acid-developable materials, the body type, the money-soluble _ into # 7 = the object, and the composition of the early (1) or the composition (9) ten "f-like matter is only composed of the following components π) #ί (1) It is composed of the component (9). () is a polymer and a 戋 戋, a component (8) is a polymer, and a test structure has an experimental basis. In the case of the above component (i), a polymer oxyamine resin [cyanide resin, j system such as melamine, phenol resin, cyanamide, urea resin, etc.], aniline resin Wait

二聚氣胺—來氰胺•醇酸（alkyd)樹脂、 —=本开胍胺(~_、三聚氛胺甲W 亦可含有該等中之一或二種以上 .級及三 種以上 、上述成分⑴）的情況，驗性基係有如：一級、 、及胺基、以及四級銨基等，亦可含有該等之一或 的M·生基。最好驗性基係二級及三級胺基。< 右‘目Γ成77 (11)的^況’聚合物類、寡聚物類、單體類係 基者^^性基的成分(I_A)中’將酸性基取代為上述驗性 二為t :f#酉夂性基的成分(I_B)單體類中’將酸性基取 且:性基者’或成分（Π·Α)内具有鹼性基者，或在未 =㈣：的成分㈣與 基者寻。亦可含有該等中之一或二種以上。 τ盘Tff顯影性材料中，亦可調配人—種以上之上述材料 /、II中所例示之添加劑。 酸顯影性材料且具紫外線硬化性物，係有如在至少由 319353 31 200811921 上述聚合物類及/或窠平4 構成的樹脂組成物中二二、广單體類及/或有機溶劑所 5 w、一來合物類、寡聚物類、及單體類中 物二且t二備Γ光基(例如在上述材料1中所敘述之 物）且更调配入成分（I_C)者。 、心 化性影性材料且具有紫物^ 盘單體在至4由上述聚合物類及/或寡聚物類、 ► 等）等酸顯影液係可舉例如：有機酸（蘋果酸等）、無機酸(鱗酸 但是，本發明中，第2光硬化 第光:r光阻膜所感光的波長的光遮蔽之材二 賴無法使用對第1光硬化性光阻膜曝光 吏用波長具感光的材料，㈣無法㈣與第丨光硬 ，阻膜曝光相同波長的光’對第2光硬化性光阻膜施行曝 :以’弟1光硬化性光阻膜係只要選擇具有第！光硬 化性光阻膜所必要性質的材料，並使用適於該材料的波長 之先施行曝光便可。此外，帛2光硬化性光阻膜則只要選 擇可使用與第1光硬化性光阻膜曝光時所使用波長不同的 波長的光’且第2光硬化性光阻膜不會遮光之波長的光進 行曝光的材料，並進行曝光便可。 鑑於此情形，不僅侷限於上述實施形態，其他的實 施形態尚有如下述。例如亦可在第丨光硬錄紐膜（防& 膜7)使用能進行水顯影’且具有紫外線遮光性與可見光硬 319353 200811921 化ί1生的材料（材料π等），而在第2光硬化性光阻膜（光阻膜 ··· 8)則使用具有可見光遮光性與紫外線硬化性，且不溶於水 ，中亚能利用弱鹼性顯影液進行顯影的材料，分別利用該等 材料形成，且在第1光硬化性光阻膜的曝光時使用可 光，而在第2光硬化性光阻膜的曝光時使用紫外線。 再者，賦予可見光遮光性與紫外線硬化性的方法，係 有如在感光性材料中調配人著色顏料（尤其是碳 法等。 ’乃 、本貫施形態的覆蓋膜係使用具有可見光與紫外線穿 透，物，但疋亦可僅使第！光硬化性光阻膜硬化的感應波 ，區域的光（例如紫外線）穿透。此外，本實施形態中厂覆 置膜係使用預先設置於第丨光硬化性光阻膜（防烊膜）上 者，但是亦可使用未被覆蓋膜覆蓋的第1光硬化性光阻膜 積層覆蓋膜，或者亦可積層已形成有第2光硬化性光阻膜 的覆蓋膜。此外’亦可在第i光硬化性光阻膜上，將液狀 ♦或溶膠狀覆蓋膜原料利用塗佈、印刷、喷塗等進行設置等 方式，而分別設置第1光硬化性光阻膜與覆蓋膜。此情況 下，復盍膜亦可如本實施形態所示，進行剝離並去除，亦 I利用藥物等進行去除。將覆蓋膜去除的藥物係使用由不 會對光阻膜、配線、基板等造成侵蝕的材料所構成之物。 本實施形態中，經圖案曝光的第丨光硬化性光阻膜之 非曝光部分，將利用顯影而去除，但是亦可如第4圖所示， 在覆蓋膜6剝離時，便將防焊膜（第丨光硬化性光阻膜)、的 非曝光部分13其中—部分或全部，黏貼於覆蓋膜6上、，並 319353 33 200811921 與覆盘膜6 —起去除。 Μ再者’亦可不使用覆蓋膜。當未制覆蓋膜時，便可 如弟5圖所不，將級圖案η在第！光硬化 進行 顯影之同時去除。 H订 士當覆蓋膜在光阻膜之外另行設置時、或未使用覆蓋膜 日守’便必f採取因環境所造成絲膜品f劣 、 [實施例] 了朿Dimer amine-cyanamide/alkyd resin, —= open decylamine (~_, trimeric amine W) may also contain one or more of these, grades and more than three, In the case of the above component (1)), the test group may be, for example, a primary group, an amine group, a quaternary ammonium group or the like, or may contain one or more M. groups. It is best to test the secondary and tertiary amine groups. < Right's view of 77 (11) in the 'polymers, oligomers, and monomeric groups' components (I_A) in the 'acidic group substituted with the above-mentioned test two In the component of the t:f# oxime group (I_B), the component having the acidic group and the base group or the component (Π·Α) has a basic group, or the component is not = (4): (4) Seeking with the basics. One or more of these may also be contained. In the τ disk Tff developable material, an additive exemplified in the above materials /, II may be blended. An acid-developable material having an ultraviolet curable material, such as a resin composition composed of at least 319353 31 200811921, a polymer composition and/or a bismuth 4 , a broad monomer, and/or an organic solvent 5 w A compound, an oligomer, and a monomeric intermediate, and a t-substrate (for example, those described in the above material 1), and further blended into the component (I_C). Examples of the acid developing material such as the above-mentioned polymers and/or oligomers, and the like may be organic acid (malic acid, etc.). In addition, in the present invention, the second light-curing light: the light-shielding material of the wavelength which is exposed by the r-resist film cannot be used for the exposure of the first light-curable photoresist film. Photosensitive material, (4) Unable to (4) Hard to light with the third light, and to expose the same wavelength of light to the film. 'Exposed to the second photo-curable photoresist film: To select the light with the first light-curable photoresist film A material having a property necessary for the curable photoresist film may be exposed first using a wavelength suitable for the material. Further, the 帛2 photocurable photoresist film may be selected and used as the first photocurable photoresist film. It is only necessary to use a material which exposes light having a wavelength of a different wavelength at the time of exposure and which is not exposed to light of the second photo-curable photoresist film, and exposes it. In this case, it is not limited to the above embodiment, and other The embodiment is as follows. For example, the third light can also be used. The hard-recorded film (anti-film 7) uses a material that can perform water development and has ultraviolet light-shielding properties and visible light hard 319353 200811921 (material π, etc.), and a second photo-curable photoresist film (light) Resist film ································································································ The photoresist is exposed to light when exposed to light, and ultraviolet light is used for exposure of the second photocurable photoresist film. Further, a method of imparting visible light blocking property and ultraviolet curing property is to mix people in a photosensitive material. A coloring pigment (especially a carbon method, etc..) The coating film of the present embodiment is an inductive wave having a visible light and an ultraviolet ray, but the enamel can only harden the opaque photo-curable film. In the present embodiment, the factory-coated film is used in advance on the first light-curable photoresist film (anti-mite film), but may be used without being covered with a cover film. 1st The curable photoresist film may be laminated to cover the film, or a cover film in which the second photocurable photoresist film is formed may be laminated. Further, it may be a liquid ♦ or sol on the ith photocurable photoresist film. The cover film material is provided by coating, printing, spraying, or the like, and the first photocurable resist film and the cover film are separately provided. In this case, the retanning film may be peeled off as shown in the embodiment. Further, it is removed by using a drug or the like. The drug for removing the cover film is made of a material which does not corrode the photoresist film, the wiring, the substrate, or the like. In the present embodiment, the pattern is exposed. The non-exposed portion of the calender-curable photoresist film is removed by development, but as shown in FIG. 4, when the cover film 6 is peeled off, the solder resist film (the first photo-curable photoresist film) is used. The non-exposed portion 13 of the non-exposed portion 13 is partially or entirely adhered to the cover film 6, and 319353 33 200811921 is removed together with the cover film 6. It is also possible to use no cover film. When the film is not made, you can use the level pattern η in the first! Photohardening is removed while developing. H. When the cover film is separately set outside the photoresist film, or if the cover film is not used, the defensive film will be taken due to the environment. [Examples]

以下，針對本發明使用第 行更具體的說明。 (實施例1) 6圖與苐7圖，依實施例進 首先，將均勻分散著下述配方組成υ的樹脂組成物， 在f __的ΡΕ薄膜14上，使用150篩網聚輯網版施 仃Ρ刷，並在80C下進行15分鐘乾燥。依此便在ρΕ薄膜 14上形成第2光硬化性光阻膜8。㈣，在該第2光硬化 性光阻膜8上面，積層著厚25//m的ρΕΤ覆蓋膜6。依此 籲，製得由ΡΕ薄膜Η、第2光硬化性光阻膜8、及ρΕτ覆 蓋膜6所構成的3層體（參照第6圖（a))。 後 另一方面，在已形成有配線圖案2的印刷電路板3 上’將下述配方組成2)的鹼顯影型防焊劑施行網版印刷， 便在印刷電路板3上形成帛i光硬化性光阻膜7(參昭第6 圖（b)) 〇 其次，在上述印刷電路板3上的第i光硬化性光阻膜 7上’隔著PET覆蓋膜6積層上述3層體。然後，如第6 圖（c)所示，將該積層體最上層的PE薄膜14剝離，而裸露 319353 34 200811921 出第2光硬化性光阻膜8(參照第6圖⑷及第、（ 其將432nm雷射光1G照射於雷射照射位置15處昭第7 圖⑷），而描繪出既定圖案（參照第6圖⑷）。描績時間 2〇秒。接著，利用流水施行2〇秒鐘顯影，便形成第2来、 硬化光阻圖案11(參照第7圖（b))。 削4，使用高壓水銀燈’從上方朝印刷電路板整面施 的外線η照射（參照第6圖⑼，而僅殘留第u硬化光 阻膜中位於光阻圖案η下方的非曝光部分13，其他部分 則硬化（第6圖（g))。紫外線12的照射時間係3〇秒。接著刀， ，第2光硬化光阻圖# n與pET覆蓋膜6—起剝離（參照 第6圖（h))。然後，使用3〇。〇的1%碳酸鈉水溶液，將弟工 光硬化性光阻膜中的非曝光部分13施行顯影去除。 依此便獲得被具有與第2光硬化光阻圖案u相反圖 案的第1光硬化光阻圖案5所被覆的印刷電路板（參照第6 圖（i)、第 7 圖（c))。 _ 、該κ施例1中，因為利用雷射1 〇施行的描緣時間縮 短為20秒，且利用高壓水銀燈所產生紫外線12的照射係 利用其他裝置實施，因而生產力極為優異。此外，因為利 用雷射10施行描繪，因而便可利用測量長度而進行校正。 、、、°果，便可在基板上的正確位置處形成（被覆）有光阻圖案 5，且位置精度極為優異。另外，本實施例中，各光硬化光 阻膜的材料係使用下述1)、2)配方組成，但是即便含有除 上述本發明光硬化光阻膜所使用外的其他成分，仍可獲得 相同的結果。 319353 35 200811921 1) 配方組成： 丙烯酸酯寡聚物（曰本化藥製「ZAA_178」）1〇〇重量 份、一季戊四醇六丙稀酸S旨（單體）25重量份、三經甲基丙 烧三丙烯酸酯（單體)1 〇重量份、三畊系反應起始劑（三和化 學製「ΤΜΕ-三哄」）2.5重量份、雙酮香豆素（增感色素、 山本化成製「KCD」）0.15重量份、超微粒子氧化鈦（υν遮 蔽劑、平均粒徑0.03/zm、石原產業製「TTO_55」）2〇重 里伤、聚一曱基石夕氧烧（消泡劑、Shin-Etsu Silicones製 ⑩「KS-66」)0·5重量份。 2) 配方組成： 四氫酞酸酐改性三苯曱烷型環氧丙烯酸酯寡聚物（日 本化樂製「TCR-1041」）150重量份、二季戊四醇六丙烯酸 酯（單體）25重量份、2_甲基-一(甲硫基）苯基]_2_嗎啉基 丙烧-1-酮巴超級化學公司製r IRGACURE 907」）20重 量份、異氰脲酸（isocyanurate)三縮水甘油酯（日產化學製 ⑩「TEPIC」)30重量份、三聚氰胺（日產化學製三聚氰胺）4 重量份、硫酸鋇（堺化學製「Barifine⑧1〇〇」）15〇重量份、 聚二曱基矽氧烷（消泡劑、Shin_Etsu SiHc〇nes製 「KS-66」）0.5重量份、綠色顏料〇 〇5重量份。 (比較例1) 以下，針對比較例1根據第8圖進行說明。 在已形成有配線圖案2的印刷電路板3上，將上述配 方組成2)的鹼顯影型防焊劑施行網版印刷，而形成第1光 硬化性光阻膜7。 319353 36 200811921 接著，對該第1光硬化性光阻膜7，於與實施例Μ 第1光硬化光阻圖案5相同圖案區域中，將365nm紫外線 雷射16施行描繪（照射）。描繪時間係2分3〇秒。 然後’利用3(TC的1%碳酸鈉水溶液，將第】光硬化 性光阻膜中，因未被前期雷射所照射到，而未硬化並殘留 的非曝光部分U顯影去除，便獲得由以光硬化光阻圖案 5所被覆的印刷電路板[(參照第8圖（c))]。 該比較例1中，因為利用紫外線雷射16施行描緣， 因而位置糈度較優越，但是描繪時間卻長達2分3〇 產力差。 (比較例2) 以下，針對比較例2根據第9圖進行說明。 在已形成有配線圖案2的印刷電路板3上，將上述配 方組成2)的鹼顯影型防焊劑施行網版印刷，便 工 硬化性光阻膜7。 >〜接著’在該第！光硬化性光阻膜7上，密合著具有盘 貫施例1的第2光硬化光阻圖案u /、 卞（為相同圖案的負型薄膜 ^後’隔者該負型薄膜17’利用高屢水銀燈，將紫外 穿線照射於第i光硬化性光阻膜7整面。照射時間 杪0 性光的1%碳酸納水溶液，將第1光硬化 部分13顯影去除，便獲得由第1光硬 光阻圖木5被覆的印刷電路板（參照第9圖⑷）。 只比孝乂例2因為係利用高屋水銀燈施行整面照射，因 319353 37 200811921 而生產力較優越，但是負型薄膜17將因溫濕度而發生尺寸 變化等情形，因而導致基板上的光硬化光阻圖案5對 配線圖案2的位置不正確，造成位置精度變差。 【圖式簡單說明】 第1圖係使用本發明光阻圖案之形成方法，所製得之 防焊圖案一例的剖面示意圖。 第2圖（a)至（h)係本實施形態的本發明緣圖案之形 成方法流程之剖面示意圖。 弟3圖係氧化欽微粒子的穿透光譜。 第4圖係將第2圖所示防焊膜的非曝光部分施行去除 的步驟之另一例的剖面示意圖。 第5圖係當第2圖中未使用覆蓋膜時，利用光阻膜的 硬化膜去除遮罩圖案之方法的剖面示意圖。 第6圖（a)至⑴係實施例1中本發明光阻圖案之形成方 法流程之剖面示意圖。 第7圖⑷至⑷分別係第6圖（d)、⑴及⑴中之印刷電 路板俯視圖。即，各截線Α_Α，、Β_Βι、及c_c，所截開的截 面圖，分別對應於第6圖（d)、（f)、及⑴。 第8圖（a)至（c)係比較例1的光阻圖案之形成方法流程 之剖面不意圖。 第9圖（a)至（c)係比較例2的光阻圖案之形成方法流程 之剖面不意圖。 【主要元件符號說明】 1 可撓性基板 319353 38 200811921 2 配線圖案 3 印刷電路板 4 開口 5 防焊圖案 6 覆蓋膜 7 防焊膜 8 光阻膜 9 基準點 10 可見光雷射 11 光阻圖案 12 紫外線 13 非曝光部分(非硬化部分) 14 PE薄膜 15 照射預定位置 16 紫外線雷射 17 負型薄膜 39 319353Hereinafter, a more specific explanation will be used for the present invention. (Example 1) Fig. 6 and Fig. 7, according to the examples, firstly, a resin composition in which the following formulation is composed of ruthenium is uniformly dispersed, and on the ΡΕ film 14 of f__, a sieve mesh of 150 mesh is used. The brush was applied and dried at 80 C for 15 minutes. Thus, the second photocurable resist film 8 is formed on the ? film 14 . (4) On the upper surface of the second photo-curable resist film 8, a ρΕΤ cover film 6 having a thickness of 25/m is laminated. In response to this, a three-layered body composed of a tantalum film, a second photocurable resist film 8, and a ρΕτ cover film 6 was obtained (see Fig. 6(a)). On the other hand, on the printed circuit board 3 on which the wiring pattern 2 has been formed, the alkali-developing type solder resist of the following formulation composition 2 is screen-printed to form 帛i photocurability on the printed circuit board 3. The resist film 7 (refer to Fig. 6 (b)) Next, the above-mentioned three-layer body is laminated on the i-th photocurable resist film 7 on the printed circuit board 3 via the PET cover film 6. Then, as shown in Fig. 6(c), the PE film 14 of the uppermost layer of the laminate is peeled off, and the second photocurable resist film 8 is exposed 319353 34 200811921 (refer to Fig. 6 (4) and The 432 nm laser light 1G is irradiated to the laser irradiation position 15 (Fig. 7 (4)), and a predetermined pattern is drawn (see Fig. 6 (4)). The time is 2 seconds. Then, the development is performed by running water for 2 seconds. Then, the second resistive resist pattern 11 is formed (see Fig. 7(b)). The cut 4 is irradiated with an outer line η applied from the upper side to the entire surface of the printed circuit board using a high-pressure mercury lamp (refer to Fig. 6 (9)). Only the non-exposed portion 13 located under the photoresist pattern η in the u-hardened photoresist film remains, and the other portions are hardened (Fig. 6(g)). The irradiation time of the ultraviolet light 12 is 3 sec. Next, the knife, the second The photohardenable photoresist pattern #n is peeled off from the pET cover film 6 (refer to Fig. 6(h)). Then, using a 3% aqueous solution of sodium carbonate, a 1% sodium carbonate aqueous solution is used in the photohardenable photoresist film. The non-exposed portion 13 is subjected to development removal. Accordingly, the first photo-hardening having the opposite pattern to the second photo-curing photoresist pattern u is obtained. The printed circuit board covered by the photoresist pattern 5 (see FIGS. 6(i) and 7(c)). _ In the κ embodiment 1, the stroke time by the laser 1 缩短 is shortened to 20 In the second, and the irradiation of the ultraviolet ray 12 generated by the high-pressure mercury lamp is performed by another device, the productivity is extremely excellent. Further, since the drawing is performed by the laser 10, the measurement length can be used for correction. The photoresist pattern 5 can be formed (covered) at the correct position on the substrate, and the positional accuracy is extremely excellent. In addition, in the present embodiment, the materials of the photohardenable photoresist films are composed of the following formulas 1) and 2). However, the same result can be obtained even if it contains other components than those used in the above-mentioned photohardenable photoresist film. 319353 35 200811921 1) Formulation composition: Acrylate oligomer ("ZAA_178" manufactured by Sakamoto Chemical Co., Ltd.) 1 part by weight, pentaerythritol hexapropanoic acid S (monomer) 25 parts by weight, trimethyl methacrylate Burning triacrylate (monomer) 1 part by weight, 2.5 parts by weight of three-tillage reaction initiator (Sanwa Chemical "ΤΜΕ-三哄"), diketone coumarin (sensitizing dye, Yamamoto Chemicals Co., Ltd.) KCD") 0.15 parts by weight, ultrafine titanium oxide (υν masking agent, average particle diameter 0.03/zm, "TTO_55" manufactured by Ishihara Sangyo Co., Ltd.) 2 〇 里 、 、 、 、 、 、 、 、 、 、 、 ( ( ( ( ( ( ( ( ( ( ( ( ( 10" KS-66" manufactured by Silicones) 0.5 parts by weight. 2) Formulation composition: tetrahydrophthalic anhydride modified triphenyl decane type epoxy acrylate oligomer ("TCR-1041" manufactured by Nippon Chemical Co., Ltd.) 150 parts by weight, dipentaerythritol hexaacrylate (monomer) 25 parts by weight , 2_Methyl-mono(methylthio)phenyl]_2-morpholinylpropan-1-one-keto-super-chemical company r IRGACURE 907") 20 parts by weight, isocyanurate triglycidyl 30 parts by weight of ester (10" TEPIC" manufactured by Nissan Chemical Co., Ltd., 4 parts by weight of melamine (melamine produced by Nissan Chemical Co., Ltd.), 15 parts by weight of barium sulfate ("Barifine 81" manufactured by Seiko Chemical Co., Ltd.), polydidecyloxane ( 0.5 parts by weight of an antifoaming agent, "KS-66" manufactured by Shin_Etsu SiHc〇nes, and 5 parts by weight of a green pigment 〇〇. (Comparative Example 1) Hereinafter, a comparative example 1 will be described based on Fig. 8 . On the printed circuit board 3 on which the wiring pattern 2 has been formed, the alkali-developing type solder resist of the above-described composition 2) is screen-printed to form the first photo-curable resist film 7. 319353 36 200811921 Next, in the first photocurable resist film 7, the 365 nm ultraviolet laser 16 is drawn (irradiated) in the same pattern region as the first photo-curing resist pattern 5 of the embodiment. The drawing time is 2 minutes and 3 seconds. Then, using 3 (TC 1% sodium carbonate aqueous solution, the first photo-curable photoresist film), which is not irradiated by the previous laser and is not hardened and remains, the non-exposed portion U is removed and developed, A printed circuit board covered with the photo-curing resist pattern 5 [(see FIG. 8(c))]. In the comparative example 1, since the edge is applied by the ultraviolet laser 16, the position is excellent, but the drawing is performed. The time is as long as 2 minutes and 3 minutes. (Comparative Example 2) Hereinafter, the second embodiment will be described with reference to Fig. 9. On the printed circuit board 3 on which the wiring pattern 2 has been formed, the above formula is composed 2) The alkali-developing type solder resist is screen-printed to facilitate the work of the curable resist film 7. >~Next' in the first! The photocurable photoresist film 7 is adhered to the second photocured photoresist pattern u /, 卞 having the same example of the first embodiment (the negative film of the same pattern is used) The high-time mercury lamp is irradiated with ultraviolet rays on the entire surface of the i-th photo-curable photoresist film 7. The first light-cured portion 13 is developed and removed by irradiating a 1% sodium carbonate aqueous solution with a time of 杪0 light, thereby obtaining the first light. Hard printed circuit board 5 printed circuit board (refer to Figure 9 (4)). Only for the case of filial piety 2, because the whole house is illuminated by high-rise mercury lamps, the productivity is superior due to 319353 37 200811921, but the negative film 17 will be When the dimensional change occurs due to temperature and humidity, the position of the photo-cured photoresist pattern 5 on the substrate is not correct for the wiring pattern 2, and the positional accuracy is deteriorated. [Simplified Schematic] FIG. 1 uses the light of the present invention. FIG. 2(a) to FIG. 2(h) are schematic cross-sectional views showing the flow of the method for forming the edge pattern of the present invention in the present embodiment. The penetration spectrum of the granules. Fig. 4 is a schematic cross-sectional view showing another example of the step of removing the non-exposed portion of the solder resist film shown in Fig. 2. Fig. 5 is a cured film using a photoresist film when the cover film is not used in Fig. 2. Fig. 6(a) to (1) are schematic cross-sectional views showing a flow of a method for forming a photoresist pattern of the present invention in Embodiment 1. Fig. 7 (4) to (4) are respectively Fig. 6(d) The top view of the printed circuit board in (1) and (1), that is, the cross-sectional views of the respective cut lines Α_Α, Β_Βι, and c_c, corresponding to Fig. 6(d), (f), and (1), respectively. Figs. (a) to (c) are cross-sectional views showing a flow of a method for forming a photoresist pattern of Comparative Example 1. Fig. 9(a) to (c) are cross sections showing a flow of a method for forming a photoresist pattern of Comparative Example 2. Intent. [Main component symbol description] 1 Flexible substrate 319353 38 200811921 2 Wiring pattern 3 Printed circuit board 4 Opening 5 Solder mask pattern 6 Cover film 7 Solder mask 8 Photoresist film 9 Reference point 10 Visible light laser 11 Resistor Pattern 12 UV 13 Non-exposed part (non-hardened part) 14 PE film 15 Irradiation scheduled position 16 Ultraviolet laser 17 Negative film 39 319353

Claims (1)

200811921 ' 十、申請專利範圍： 1 · 一種光阻圖案之形成方法，係包括有： 在半v體晶片或配線基板的配線圖案上，形成感 應第1感應波長區域之波長的光之第丨光硬化性光阻 膜的步驟； 、在該第1光硬化性光阻膜的上側，形成阻隔第i 感應波長區域之波長的光且感應第2感應波長區域之 φ 波長的光之第2光硬化性光阻膜的步驟； 將含有第2感應波長區域之波長的光之雷射，對 要成為第2光硬化性光阻膜之遮罩圖案的區域，施行 掃描並曝光的步驟； 二—以不會使第1光硬化性光阻膜顯影的顯影液，對 該第2光硬化性光阻膜施行顯景卜形成遮 驟； 利用該第1感應波長區域之波長的光，以該遮罩 ♦圖案為遮罩，對該第U硬化性光阻膜施行圖案曝光 的步驟；以及 對該第1光硬化性光阻膜施行顯影，而在該已形 牛驟導體曰曰片或電路圖案的基板上’形成光阻圖案的 m。 2·=請專利範圍第！項之光阻圖案之形成方法，其中， ^該第1純化性光阻朗上側，形成第2光硬化 ★读阻""之際，隔著第1感應波長區域之波長的光會 牙透的覆蓋膜，形成該第2光硬化性光阻膜； 319353 40 200811921 對第1ί硬化性光阻膜施行顯影的步驟中， 3. 4. 5· 取猎由將該覆蓋膜剝離而將遮罩圖突去陕 Γ請專利範圍第1項之光阻圖案之；成：法中 1光硬化性光阻膜的上側形成第2光硬化性 際’隔著第！感應波長區域之波長的光會穿 透的復盍膜，形成該第2光硬化性光阻膜； “並在對第厂光硬化性光阻膜施行顯影的步驟中， 猎由將覆蓋膜剝離而將遮罩圖案錢，同時亦將第工 光硬化性光阻膜的非曝光部分去除。 如申請專利範圍第2項之光阻圖案之形成方法，其中， 使該覆蓋膜與第1光硬化性光阻_層_層體設置 於該配線圖案上之後’再於該覆蓋臈上形成第2 化性光阻膜。 如申請士利範圍第3項之光阻圖案之形成方法，其中， 使該覆蓋膜與f 1光硬化性光阻膜積層的積層體設置 於該配線圖案上之後，再於該覆蓋膜上形成第^硬 化性光阻膜。 6.如申請專利範圍第…項中任一項之光阻圖案之形 成方法’其中’當將含有第2感應波長區域之波長的 光之雷射，對要成為遮罩圖案的區域施行掃插，並對 成為該第2光硬化性光阻膜之遮罩圖案的區域施行曝 光之際， I 經預先對各配線圖案施行位移校正之後，對含有 第2感應波長區域之波長光的雷射施行掃描，而在各 319353 41 200811921 配線圖案上形成遮罩圖案。 :7.如申請專利範圍第！至5項中任—項之光阻圖案之形 成方法’其令’第1光硬化性光阻膜係使用具有紫外 線感光性的材料，並利用紫外線對該第丨光硬化性光 阻膜施行曝光，第2光硬化性光阻膜係使用具可見光 感光性的材料，並利用可見光雷射對該第2光硬化性 光阻膜施行曝光。 _ 如申明專利範圍第1至5項中任一項之光阻圖案之形 成=法，其中，第2光硬化性光阻膜係至少含有氧化 鈦微粒子、碳酸鈣微粒子、及·氧化鋅微粒子中之丨種。 9· ^申請專利範圍第8項之光阻圖案之形成方法，其中， 虱化鈦微粒子、碳酸鈣微粒子、及氧化鋅微粒子中之 至/ 1種’具有平均粒徑0.01 # m至〇·〇5 # m 0 、申明專利範圍第1至5項中任一項之光阻圖案之形 癱 成方法，其中，第2光硬化性光阻膜係使用可水顯影 的材料，第2顯影液係使用水。 ' ll 4fn 、申明專利範圍第1至5項中任一項之光阻圖案之形 12成方法，其中，第1光硬化性光阻膜係防焊膜。 如申凊專利範圍第1至5項中任一項之光阻圖案之形 13 、方去其中，第1光硬化性光阻膜係防鍍膜。 、申明專利範圍第1至5項中任一項之光阻圖案之形 成方去’其中，第1光硬化性光阻膜係防蝕膜。 319353 42200811921 ' X. Patent application scope: 1 . A method for forming a photoresist pattern, comprising: forming a third light of a light that induces a wavelength of a first sensing wavelength region on a wiring pattern of a half-v body wafer or a wiring substrate a step of forming a curable photoresist film; and forming a second photo-curing light that blocks light of a wavelength of the i-th sensing wavelength region and induces light of a φ wavelength of the second inductive wavelength region on the upper side of the first photo-curable photoresist film a step of forming a photoresist; and irradiating and exposing a region of the region of the mask pattern to be the second photocurable photoresist film; The developing solution that does not develop the first photocurable photoresist film is subjected to a development of the second photocurable photoresist film; and the light of the wavelength of the first inductive wavelength region is used as the mask. ♦ a pattern as a mask, a step of patterning the U-curable photoresist film; and performing development on the first photo-curable photoresist film, and in the shaped bob-conductor chip or circuit pattern 'formation on the substrate M barrier pattern. 2·=Please patent scope! In the method of forming a photoresist pattern of the first photosensitive photo-resistance, when the second photo-curing is formed, the wavelength of the first inductive wavelength region is separated by the wavelength of the first inductive wavelength region. The second photocurable resist film is formed by the transparent cover film; 319353 40 200811921 In the step of performing development on the first curable resist film, 3. 4. 5 · removing the cover film by peeling off the cover film The cover picture protrudes to Shaanxi to request the photoresist pattern of the first item of the patent range; into: the upper side of the photo-curable photoresist film in the middle of the law forms the second photo-curing property' through the first! a retanning film that penetrates the wavelength of the wavelength region to form a second photocurable photoresist film; "and in the step of developing the photo-curable photoresist film of the first factory, the stalk is peeled off by the cover film The mask is patterned and the non-exposed portion of the photo-curable photoresist film is also removed. The method for forming a photoresist pattern according to claim 2, wherein the cover film is cured with the first light. After the photoresist layer _ layer layer is disposed on the wiring pattern, a second photoresist film is formed on the cover layer. For example, the method for forming a photoresist pattern according to item 3 of the 士利范围范围, After the laminate of the cover film and the f 1 photocurable photoresist film is provided on the wiring pattern, a second curable photoresist film is formed on the cover film. A method for forming a photoresist pattern in which a laser having a wavelength of a second inductive wavelength region is irradiated, and a region to be a mask pattern is swept and inserted into the second photocurable light. The area of the mask pattern of the resist film is exposed Then, after the displacement correction is performed on each of the wiring patterns in advance, the laser beam containing the wavelength light of the second sensing wavelength region is scanned, and a mask pattern is formed on each of the 319353 41 200811921 wiring patterns. The method for forming a photoresist pattern according to any one of the items of the fifth aspect of the present invention, wherein the first photocurable photoresist film is made of a material having ultraviolet light sensitivity, and the first light curable photoresist is used for ultraviolet light. The film is exposed to light, and the second photocurable photoresist film is made of a material having visible light sensitivity, and the second photocurable photoresist film is exposed by visible light laser. _ As stated in claims 1 to 5 of the patent scope In the formation of the photoresist pattern according to any one of the methods, the second photocurable photoresist film contains at least titanium oxide fine particles, calcium carbonate fine particles, and zinc oxide fine particles. A method for forming a photoresist pattern of eight items, wherein: one of titanium telluride fine particles, calcium carbonate fine particles, and zinc oxide fine particles has an average particle diameter of 0.01 # m to 〇·〇5 # m 0 , The method for forming a photoresist pattern according to any one of the items 1 to 5, wherein the second photocurable photoresist film is a water-developable material, and the second developer liquid is water. ' ll 4fn The method for forming a photoresist pattern according to any one of the first to fifth aspects of the invention, wherein the first photocurable photoresist film is a solder resist film, as in the first to fifth patent claims. The shape of the photoresist pattern is 13 and the first photo-curable photoresist film is coated. The formation of the photoresist pattern according to any one of claims 1 to 5 is to be The first photocurable photoresist film is an anti-corrosion film. 319353 42
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