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TW201106097A - Photosensitive composition and solder resist composition - Google Patents

Photosensitive composition and solder resist composition Download PDF

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Publication number
TW201106097A
TW201106097A TW99112235A TW99112235A TW201106097A TW 201106097 A TW201106097 A TW 201106097A TW 99112235 A TW99112235 A TW 99112235A TW 99112235 A TW99112235 A TW 99112235A TW 201106097 A TW201106097 A TW 201106097A
Authority
TW
Taiwan
Prior art keywords
photosensitive composition
inorganic filler
weight
compound
polymerizable
Prior art date
Application number
TW99112235A
Other languages
Chinese (zh)
Other versions
TWI363931B (en
Inventor
Shigeru Nakamura
Takashi Nishimura
Shuuji Kage
Takashi Watanabe
Toshio Takahashi
Original Assignee
Sekisui Chemical Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from JP2009185817A external-priority patent/JP4657358B2/en
Application filed by Sekisui Chemical Co Ltd filed Critical Sekisui Chemical Co Ltd
Publication of TW201106097A publication Critical patent/TW201106097A/en
Application granted granted Critical
Publication of TWI363931B publication Critical patent/TWI363931B/zh

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Classifications

    • 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
    • H05K3/285—Permanent coating compositions
    • H05K3/287—Photosensitive compositions
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/0047—Photosensitive materials characterised by additives for obtaining a metallic or ceramic pattern, e.g. by firing
    • 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
    • H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
    • H05K2201/02—Fillers; Particles; Fibers; Reinforcement materials
    • H05K2201/0203—Fillers and particles
    • H05K2201/0206—Materials
    • H05K2201/0209—Inorganic, non-metallic particles

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

Abstract

Disclosed is a photosensitive composition which is capable of providing a resist film that does not easily suffer from discoloration such as yellowing even when the resist film is exposed to a high temperature around 200 DEG C or more, such as the temperature during solder reflowing. Specifically disclosed is a photosensitive composition which contains either a polymerizable hydrocarbon monomer (A) and/or a polymerizable hydrocarbon polymer (B) and an inorganic filler (C). The inorganic filler (C) is characterized in that when a solution obtained by adding 5 g of the inorganic filler (C) into 100 mL of purified water is kept boiling for 5 minutes and then left at rest until the temperature thereof falls to 23 DEG C so that a boiled solution is obtained, and then water in an amount equal to the amount of water vaporized by the boiling is added to the thus-obtained boiled solution so that the resulting solution is in an amount of 100 mL, the resulting solution has a pH of 6.8-11 (inclusive).

Description

201106097 六、發明說明： 【發明所屬之技術領域】 本發明係關於一種適宜用於在基板上形成防焊膜，或者 在裝載有發光二極體晶片之基板上形成防反射膜之感光性 組合物及防焊組合物。 【先前技術】 作為保護印刷配線基板不受高溫之焊錫之影響的保護 膜’係廣泛使用防焊膜。 作為用以形成上述防焊膜之材料之一例，於下述專利文 獻1中揭示有如下防焊材料’其含有作為丙烯酸酯化合物 之紫外線硬化型預聚物及顏料，且進而含有紫外線硬化型 預聚物、有機聚矽氧烷與鋁螯合化合物之反應產物。 又，於裝載有發光二極體（以下將發光二極體簡稱為 LED(light-emitting diode))晶片之印刷配線基板之表面， 為效率良好地射出由LED發出之光而形成光之反射率高之 白色防焊膜。 上述白色防焊膜由於效率良好地反射對基板表面照射之 LED之光’故可提高由LED產生之光之利用率。 作為用以形成上述白色防焊膜之材料之一例，於下述專 利文獻2中揭示有如下阻劑材料，其含有藉由環氧樹脂與 水解性烷氧基矽烷之脫醇反應而得之含有烷氧基之矽烷改 質環氧樹脂，且進而含有包含不飽和基之聚羧酸樹脂、稀 釋劑、光聚合起始劑、及硬化密著性賦予劑。 於下述專利文獻3中揭示有如下白色防焊材料，其含有 147625.doc 201106097 不具有芳香環之含叛基之樹脂、光聚合起始劑、環氧化合 物、金紅石型氧化鈦、及稀釋劑。 先前技術文獻 專利文獻 [專利文獻1]曰本專利特開昭58-25374號公報 [專利文獻2]曰本專利特開2007-249148號公報 [專利文獻3]曰本專利特開2007-322546號公報 【發明内容】 [發明所欲解決之問題] 上述專利文獻1中記載之防焊材料含有丙烯酸酯化合物 作為主成分。上述專利文獻2中記載之阻劑材料含有將環 氧樹脂以烧氧基料進行改質而成之含有烧氧基之石夕烧改 質環氧樹脂作為主成分。上述專利文獻3中記載之防焊材 料含有環氧化合物1使用含有該等成分之阻劑材料來形 成保護膜之情形時’若暴露於如回流焊時約2GGt以上之 高溫下，則存在保護膜黃變之情形。 又’最上層之保護膜必需於可見光區域具有高反射率 為此，必需於阻劑材料中大量添加填充料。例如，假設; 里使用硬度〶之氧化鈦作為填充料，則存在利用模具等$ 行切割加工時，於保罐胳L * 、保濩膜上產生裂痕或缺損之情形。 本發明之目的在於接扯 ^ 在於松供一種可獲得即便暴露於 時約200°C以上之离、、w τ + n 之同，皿下亦不易產生黃變等變201106097 VI. Description of the Invention: [Technical Field] The present invention relates to a photosensitive composition suitable for forming a solder resist film on a substrate or forming an antireflection film on a substrate on which a light emitting diode wafer is mounted And solder resist composition. [Prior Art] As a protective film which protects a printed wiring board from high-temperature solder, a solder resist film is widely used. As an example of the material for forming the above-mentioned solder resist film, the following Patent Document 1 discloses a solder resist material which contains an ultraviolet curable prepolymer and a pigment as an acrylate compound, and further contains an ultraviolet curable prepreg. The reaction product of a polymer, an organopolyoxane and an aluminum chelate compound. Further, on the surface of the printed wiring board on which the light-emitting diode (hereinafter referred to as a light-emitting diode) is mounted, the light emitted from the LED is efficiently emitted to form a light reflectance. High white solder mask. Since the white solder resist film efficiently reflects the light of the LED irradiated to the surface of the substrate, the utilization of light generated by the LED can be improved. As an example of the material for forming the white solder resist film, Patent Document 2 listed below discloses a resist material containing a dealcoholization reaction of an epoxy resin and a hydrolyzable alkoxysilane. The alkoxy decane-modified epoxy resin further contains a polycarboxylic acid resin containing an unsaturated group, a diluent, a photopolymerization initiator, and a hardening adhesion imparting agent. Patent Document 3 listed below discloses a white solder resist material containing 147625.doc 201106097 a repellent-containing resin having no aromatic ring, a photopolymerization initiator, an epoxy compound, a rutile-type titanium oxide, and a dilution. Agent. [Patent Document 1] Japanese Patent Laid-Open Publication No. Hei. No. Hei. No. Hei. No. Hei. No. 2007-249148. [Explanation] [Problems to be Solved by the Invention] The solder resist material described in Patent Document 1 contains an acrylate compound as a main component. The resist material described in the above Patent Document 2 contains, as a main component, an alkoxy-based modified epoxy resin containing an alkoxy group obtained by modifying an epoxy resin with an aerobic material. When the solder resist material described in the above Patent Document 3 contains the epoxy compound 1 and the resist material containing the components is used to form the protective film, the protective film is present when exposed to a high temperature of about 2 GGt or more as in reflow soldering. The situation of yellowing. Further, the protective film of the uppermost layer must have a high reflectance in the visible light region. Therefore, it is necessary to add a large amount of the filler to the resist material. For example, it is assumed that titanium oxide having a hardness of 〒 is used as a filler, and when it is cut by a mold or the like, cracks or defects may occur in the canal L* and the film. The object of the present invention is to provide a yellowing, which is easy to produce yellowing under the dish, even if it is about 200 ° C or more, and w τ + n.

的感光性組合物. e S 本發明之限定性目 的在於提供一 種可獲得切割加工性優 147625.doc 201106097 * 異之保護膜的感光性組合物。 [解決問題之技術手段] 根據本發明，可提供如下感光性組合物，其含有聚人性 煙早體㈧及聚合性烴聚合物(B)中之至少一者與無機：充 料（c) ’且無機填充料為如 、 rc^ , s ^ 者.對將該無機填充料 )g添加至純水而獲得之溶液進行加熱使其 沸騰5分鐘後，靜置至達到 、 雉“ 為止，獲得沸騰處理液， 繼而於所得之彿騰處理液中加人因彿騰而蒸發之水量之 水’使水量成為100 mL，測定 呈以以上、U以下之值。所传洛液之PH值時，_ 本f 1案說明書中，有時將如下方法稱為煮满 法.對將無機填充料（C)5 g加至純水⑽虹中而獲得之溶 液進行加熱’使其沸騰5分鐘後，靜置至達到坑為止， 獲得彿騰處理液，繼而於所得之沸騰處理液中加入因滞騰 而蒸發之水量之水’使水量成為⑽祉，測定所得 pH值。 上述無機填充料（C)之能帶隙較好的是2 5 ev以上、7 ^ 以下。 較好的是上述無機填充料（c)之465 nmT之折射率為i 8 以上，且無機帛充料(c)為白色填m上述無機填 充料（c)更好的是金紅石型氧化鈦。 上述無機填充料（c)之含量較好的是3重量％以上、8〇重 量％以下。 車乂好的疋至y 1種無機填充料（c)係由鹼性金屬氧化物或 I47625.doc 201106097 鹼性金屬氫氧化物所被覆。 構成上述驗性金屬氧化物或鹼性金屬氫氧化物之金屬元 素較好的是選自由鎂、錯、鈽、锶、銻、鋇及鈣所組成之 群中之至少1種。 上述無機填充料（c)較好的是由含有氧化鉛之被覆材料 所被覆。 本發明之感光性組合物較好的是進而含有可與無機填充 料（C)之酸性部位反應之化合物。 上述無機填充料（C)較好的是由可與該無機填充料（c)之 酸性部位反應之化合物進行表面處理。 可與上述無機填充料之酸性部位反應之化合物較好 的疋鹼性化合物。又，上述鹼性化合物更好的是選自由多 元醇炫·醇胺及烧氧基石夕烧所組成之群中之至少1種。 上述聚合性烴單體（a )較好的是具有2個以上聚合性不飽 和基，並且於乙腈：水=1 :丨（體積比）溶液中，利用附質 譜分析之液相層析法（LC/MS，liquid chr_t〇graphy/mass speCtr〇meter)測定上述聚合性烴單體（A)時，由質譜分析之 碎片峰為500以下之成分所構成之波峰面積為^峰面積 之30%以上。 上述聚合性烴單體（A)之重量平均分子量較好的是7〇〇以 下。 。本發明之感光性組合物較好的是進而含有具有環狀謎骨 架之化合物(D)，並且相對於聚合性烴聚合物(b_重量 份，具有環狀醚骨架之化合物（D)之含量為〇1重量份以 147625.doc 201106097 上、50重量份以下。 上述具有環狀醚骨架之化合 如好的是具有環狀^醚 月架且不具有直鏈㈣架之環氧化合物。 上述環狀鍵骨架較好的是環氧環己烧骨架。 =,感光性組合物較好的是進而含有具有路易斯鹼 氧;Γ 劑。上述抗氧化劑較好的是選自由齡系抗 t藉m氧化劑及胺系抗氧化劑所組成之群中之至 少1種。 乂子的疋上述聚合性烴單體⑷及聚合性烴聚合物⑻中 之至少-者含有“固以上聚合性不飽和基及2個以上叛基， 並且作為聚合性煙單體（A)及聚合性烴聚合物⑻之整體， 重里平均分子量為5,咖〜5()，咖，固體成分酸值為⑽％ 叫K〇H/g ’且雙鍵當量為50〜2,000 g/eq。 於上述聚合性單體⑷及聚合性煙聚合物⑻之合計 1〇〇重量％中，較好的是聚合性烴單體⑷之含量為5重量％ 以上、50重量％以下。 於上述聚合性煙單體⑷i⑽重量％中，較好的是具有醇 性羥基之聚合性烴單體之含量為15重量％以下。 上述無機填充料（C)較好的是滿足下述式（X)。 [U第1無機填充料之莫氏硬度）χ(硬化後之感光性組合物 〇〇體積/〇中之第1無機填充料之含量（體積％))}+{(第2無 機填充料之莫氏硬度）χ(硬化後之感光性組合物100體積％ 中之第2無機填充料之含量（體積％))}+ U第η無機填充 料之莫氏硬度）χ(硬化後之感光性組合物1〇〇體積％中之第η I47625.doc 201106097 無機填充料之含量（體積％))}] $ 4 (χ) 、心月之感光&組合物較好的是進而含有溶劑，且溶劑 之偶極矩為1 Debye以上。 本發明之防焊組合物係依據本發明而構成之感光性組合 物本發明之感光性組合物適宜用作防谭組合物。 [發明之效果] 一本發明之感光性組合&含有聚合性烴單體⑷及聚合性 垣聚合物（B)中之至少—者、與無機填充料（〇,且無機填 充料（c)之利用煮沸法而得之阳值為6 8以上、u以下，故 可獲得即便暴露於高溫下亦不易變色之保護膜。 於上述無機填充料（C)之465 nm下之折射率為i 8以上， 且上述無機填充料（C)為白色填充料之情形時，可獲得反 射性能更高之白色防焊膜。 於至少1種上述無機填充料（c)係由鹼性金屬氧化物或鹼 性金屬氫氧化物所被覆之情形時，幾乎與無機填充料（c) 之種類㈣，而形成在高溫下更不易變色之保護膜。又， 由於可提高樹脂之硬化性’故可提高保護膜之切割加工 性。進❿’由於可抑制具有光氧化作用之無機帛充料（c) 之表面活性，故可形成即便照射光亦難使樹脂劣化之保護 膜。 於感光性組合物含有可與無機填充料（c)之酸性部位反 應之化合物之情形時，可獲得即便暴露於高溫下亦更不易 變色之保護膜。 於如下情形時可確實地抑制保護膜之黃變：上述聚合性 147625.doc 201106097 煙單體㈧具有2個以上之聚合性不飽和基，且 =1:1(體積比)溶液中，利用附質譜分析之液相層二水 (LC蘭嫩上述聚合性烴單體⑷時，由質譜分 峰為5°〇以下之成分所構成之波峰面積為總波峰面積片 30%以上。 久卞®積之 【實施方式】 以下，對本發明進行詳細說明。 本發明之感光性組合物含有聚合性煙 烴聚合物（B)中之至少—去叮过土 ^及聚。性 主乂者。可僅使用聚合性烴單體 聚合性烴聚合物（B)中之—去 n成m )及 之者，亦可使用聚合性烴單體（ 及聚合性烴聚合物（3)之jη 甘人 () _)之兩者。又，聚合性烴單體⑷及聚 «性經聚合物（Β)可分別僅使用m，亦可併用2種以上。 (聚合性烴單體（A)) 作為上述聚合性烴單體⑷，例如可列舉含有聚合 飽和基之單體或含有聚合性環狀縫基之單體。 作為上述聚合性不飽和基’例如可列舉（甲基）丙婦酿基 及乙烯喊基等具有聚合性不飽和雙鍵之官能基。其中，由 於可提高保護膜之交聯密度，故較好的是（甲基、)丙稀酿 基。 上述含有聚合性不飽和基之單體較好的是具有（甲基）丙 烯醯基之化合物。作為上述具有（甲基）丙稀醯基之化合 物可列舉·乙二醇、甲氧基四乙二醇、&乙二醇或丙二 醇等一醇之二（甲基）丙烯酸酯改質物；多元醇、多元醇之 缞氧乙烷加成物或多元醇之環氧丙烷加成物之多元（甲基） 147625.doc 201106097 丙烯酸酯改質物；酚、酚之環氧乙烷加成物或苯酚之環氧 丙烷加成物之（曱基）丙烯酸酯改質物；甘油二縮水甘油醚 或二羥甲基丙烷三縮水甘油醚等縮水甘油醚之（曱基）丙烯 酸酯改質物；或者三聚氰胺（甲基）丙烯酸酯。 作為上述多元醇，例如可列舉己二醇、三羥甲基丙烷、 季戊四醇、二季戊四醇及三_羥基乙基異氰尿酸酯。作為 上述酚之（曱基）丙烯酸酯，例如可列舉苯氧基（曱基）丙烯 酸酯及雙酚A之二（曱基）丙烯酸酯改質物。 「（甲基）丙烯醯基」係指丙烯醯基與甲基丙烯醯基。 「（甲基）丙烯酸」係指丙烯酸與曱基丙烯酸。「（甲基）丙烯 酸酯」係指丙烯酸酯與甲基丙烯酸酯。 (聚合性烴聚合物（B)) 作為上述聚合性煙聚合物（B)，例如可列舉丙稀酸系樹 脂、環氧樹脂及烯烴樹脂。再者，r樹脂」並不限定於固 形樹脂’亦包括液狀樹脂及寡聚物。 上述聚合性烴聚合物（B)較好的是下述含羧基之樹脂 ⑷〜⑷。 (a) 藉由不飽和羧酸與具有聚合性不飽和雙鍵之化合物之 共聚合而獲得之含羧基之樹脂 (b) 藉由含缓基之（甲基）丙稀酸共聚合樹脂（匕”與丨分子中 具有環氧乙烧環及乙浠性聚合性不飽和雙鍵之化合物（b2) 之反應而獲得之含羧基之樹脂 (c) 使不飽和單羧酸，與1分子中具有各為丨個之環氧基及 聚合性不飽和雙鍵之化合物和具有聚合性不飽和雙鍵之化 I47625.doc •10- 201106097 合物的共聚物進行反應後，使飽和或不飽和多元酸針與所 生成之反應物之二級羥基進行反應而獲得之含羧基之樹脂 (d)使飽和或不飽和多元酸酐與含羥基之聚合物反應 . 後’使1分子中具有各為1個之環氧基及聚合性不飽和雙鍵 • 之化合物與所生成之叛酸進行反應而獲得之含經基及緩基 之樹脂 由於可進一步提高保護膜之耐熱性，故聚合性烴聚合物 (B)較好的是上述（b)含羧基樹脂。 上述含缓基之（甲基）丙稀酸共聚合樹脂（b 1)例如可藉由 使（曱基）丙烯酸酯（bb 1 )、與1分子中具有1個不飽和基及至 少1個羧基之化合物（bb2)共聚合而獲得。 作為上述（甲基）丙烯酸酯（bb 1)，可列舉：（曱基）丙婦酸 曱酯、（曱基）丙烯酸乙酯、（甲基）丙烯酸丙酯、（曱基）丙稀 酸丁酯、（曱基）丙烯酸戊酯及（曱基）丙烯酸己酯。進而， 作為上述（曱基）丙稀酸醋（bb 1)，可列舉含經基之（甲美）丙 稀酸酯及二醇改質（曱基）丙烯酸酯。上述（甲基）丙烯酸酿 (bbl)可僅使用1種，亦可併用2種以上。 作為上述含羥基之（曱基）丙烯酸酯，可列舉：（甲基）丙 ' 烯酸2·羥基乙酯、（曱基）丙烯酸羥基丙酯、（甲基）丙缔酸 - 輕基丁醋及己内醋改質（曱基）丙烯酸2-輕基乙醋等。作為 上述二醇改質（甲基）丙烯酸酯，可列舉：曱氧基二乙二醇 (甲基）丙烯酸酯、乙氧基二乙二醇（甲基）丙烯酸g旨、異辛 氧基一乙·一醇（甲基）丙缚酸S旨、苯氧基三乙二醇（甲美）丙 烯酸酯、曱氧基三乙二醇（曱基）丙烯酸酯、及甲氧基聚乙 147625.doc 11 201106097 一醇（甲基）丙稀酸@旨。 作為上述1分子中具有丨個聚合性不飽和基及至少1個羧 基之化合物（bb2)，可列舉：（甲基）丙烯酸、不飽和基與羧 酸之間經鏈延長之改質不飽和單羧酸、（甲基）丙烯酸卜羧 基乙酯、2-丙烯醯氧基乙基琥珀酸、2_丙烯醯氧基乙基六 氫鄰苯二甲酸、藉由内酯改質等而具有酯鍵之不飽和單羧 酸、具有醚鍵之改質不飽和單羧酸、及順丁烯二酸等j分 子中具有2個以上羧基之化合物。上述化合物（bb2)可僅使 用1種，亦可併用2種以上。 作為上述1分子中具有環氧乙烷環及乙烯性不飽和基之 化合物（b2)，例如可列舉：（甲基）丙烯酸縮水甘油酯、（曱 基）丙烯酸α-曱基縮水甘油酯 ' (曱基）丙烯酸3,4-環氧環己 基曱Sa、（曱基）丙烯酸3,4-環氧環己基乙酯、（甲基）丙烯酸 3,4_裱氧環己基丁酯、及丙烯酸3,4_環氧環己基曱基胺基 酯。其中，較好的是（甲基）丙烯酸3,4_環氧環己基曱酯。 上述化合物（b2)可僅使用1種，亦可併用2種以上。 上述聚合性烴單體（A)較好的是具有2個以上聚合性不飽 和基，並且於乙腈：水=1 :〖（體積比）溶液中，利用附質 譜分析之液相層析法（LC/MS)測定上述聚合性烴單體（a) 時，由質譜分析之碎片峰為5〇〇以下之成分所構成之波峰 面積為總波峰面積之30%以上。 作為由質譜分析之碎片峰為5〇〇以下之成分所構成之波 峰面積為總波峰面積之30%以上的聚合性烴單體（A)，例如 可列舉：乙二醇、甲氧基四乙n乙二醇或丙二醇等 147625.doc 12 201106097 二醇之二(甲基)丙烯酸醋改質物；多元醇、 乙烧加成物或多元醇之環氧丙烧加成物之夕-辰一 酸酯改質物；酚、酚之環氧夕M甲基)丙烯 附炙環氧乙烷加成物或酚之 成:之(’基)丙婦酸醋改質物;甘油二縮水甘油趟= ::丙：一縮水甘油醚等縮水甘油喊之(甲基)丙烯酸酯改 質物，或者三聚氰胺（甲基）丙烯酸酯。 作為上述多元醇，例如可枭. θ金…* 〗如1舉.己-醇、三羥甲基丙 酵、二季戊四醇及三-經基乙基異氰尿酸醋。 作為上述紛之（甲基）丙埽酸酿，例如可列舉苯氧基（甲 丙稀酸酯及雙齡A之二（甲基）丙烯酸醋改質物。 土 上述聚合性烴單體（A)之藉由GPC(gel permeati〇n 化麵伽㈣咖，凝膠渗透層析法）測定所求出之以聚苯乙 稀換算之重量平均分子量較好的是700以下。藉由該重量 平均分子量為7G(m下’可更確實地抑制保護膜之黃變。 上述重量平均分子量係使聚合性烴單體⑷15 mg溶解於 THF(tetrahydrofuran’四氫呋喃）i mL中而進行Gpc測定 時，作為以聚苯乙烯換算所得之分子量而測定。 車义好的疋上述聚合性烴單體（A)及聚合性烴聚合物⑺）中 之至一者含有1個以上聚合性不飽和雙鍵及2個以上羧 基，並且作為聚合性烴單體及聚合性烴聚合物之整 體’重量平均分子量為5,〇〇〇〜5〇,〇〇〇，且固體成分酸值為 30〜150 mg KOH/g ’且雙鍵當量為5〇〜2 〇〇〇 g/eq。 右上述重量平均分子量為5,〇〇〇〜50,〇〇〇，固體成分酸值 為30〜150 mg KOH/g，且雙鍵當量為5〇〜2 〇00 g/eq，則感 147625.doc 201106097 光性組合物之顯影性更優異，並且保護膜之切割加工性優 異。 於上述聚合性烴單體（A)及聚合性烴聚合物（b)之合計 100重量％中，聚合性烴單體（A)之含量較好的是5重量％以 上、50重量％以下。若聚合性烴單體⑷之含量在上述範圍 内，則可使感光性組合物充分硬化，且可進—步提高保蠖 膜之切割加工性。進而，保護膜之交聯密度變得適度，可 獲得充分之解像度，且保護膜不易黃變。 於上述聚合性烴單體⑷1〇〇重量％中，具有醇性羥基之 聚合性烴單體之含量較好的是15重量％以下。於此情形 時’容易保持無機填充料（c)之驗性，容易對保護膜進行 切割加工。作為上述聚合性烴單體（A)，可列舉季戊四醇 三（甲基）丙稀酸酯。 (無機填充料（C)) 本發明之感光性組合物中所含之無機填充料⑹藉由煮 沸法所測定之pH值為6 8 , 值為6.8以上、Η以下。於PH值低於6.8 日=4膜汽變’且難以對保護膜進行切割加。又，於 P值门於1 a夺存在感光性組合物之適用期變差之情形。 由於可進一步抑制保*法na > # '、濩Μ之汽變，故上述無機填充料 之利用煮彿法所測定之 、 疋之ΡΗ值較好的是7.0以上，更好的是 7·4以上’進而好的是 疋·1以上❶由於可使感光性組合Photosensitive composition. e S A limited object of the present invention is to provide a photosensitive composition which can obtain a protective film having excellent cutting processability. [Technical means for solving the problem] According to the present invention, there is provided a photosensitive composition comprising at least one of a poly-exposed tobacco precursor (VIII) and a polymerizable hydrocarbon polymer (B) and an inorganic material: (c) And the inorganic filler is, for example, rc^, s ^. The solution obtained by adding the inorganic filler g to pure water is heated to boil for 5 minutes, and then allowed to stand until it reaches, 雉The treatment liquid, and then the water of the amount of water evaporated by the human Ferteng in the obtained Fo Teng treatment liquid is made to make the amount of water 100 mL, and the value is above and below U. The pH value of the solution is _ In the specification of the present invention, the following method is sometimes referred to as the full method. The solution obtained by adding 5 g of the inorganic filler (C) to pure water (10) is heated to "boil for 5 minutes, and then When the pit is reached, the Fo Teng treatment liquid is obtained, and then the water of the amount of water evaporated by the stagnation is added to the obtained boiling treatment liquid to make the water amount (10) 祉, and the obtained pH value is measured. The above inorganic filler (C) The band gap is preferably 2 5 ev or more and 7 ^ or less. The inorganic filler (c) has a refractive index of 465 nmT of i 8 or more, and the inorganic cerium filling (c) is white filled with m. The inorganic filler (c) is more preferably rutile-type titanium oxide. The content of the material (c) is preferably 3% by weight or more and 8% by weight or less. 乂 乂 疋 to y 1 inorganic filler (c) is composed of an alkali metal oxide or I47625.doc 201106097 alkaline The metal hydroxide is coated. The metal element constituting the above-mentioned metal oxide or alkali metal hydroxide is preferably at least one selected from the group consisting of magnesium, argon, lanthanum, cerium, lanthanum, cerium, and calcium. The inorganic filler (c) is preferably coated with a coating material containing lead oxide. The photosensitive composition of the present invention preferably further contains a reactive portion reactive with the inorganic filler (C). The above inorganic filler (C) is preferably subjected to surface treatment with a compound which can react with the acidic portion of the inorganic filler (c). The compound which can react with the acidic portion of the above inorganic filler is preferred. Compound, in addition, the above basic compound More preferably, it is at least one selected from the group consisting of polyhydric alcohols and alkoxylates. The polymerizable hydrocarbon monomer (a) preferably has two or more polymerizable unsaturated groups. And measuring the above polymerizable hydrocarbon monomer by liquid chromatography with a mass spectrometry (LC/MS, liquid chr_t〇graphy/mass speCtr〇meter) in an acetonitrile:water=1:丨 (volume ratio) solution ( In the case of A), the peak area composed of the component having a fragment peak of 500 or less by mass spectrometry is 30% or more of the peak area. The weight average molecular weight of the polymerizable hydrocarbon monomer (A) is preferably 7 Å or less. . . The photosensitive composition of the present invention preferably further contains a compound (D) having a cyclic engraving skeleton, and is a compound (D) having a cyclic ether skeleton with respect to the polymerizable hydrocarbon polymer (b_part by weight). 1 part by weight of 147625.doc 201106097 and 50 parts by weight or less. The above-mentioned compound having a cyclic ether skeleton is preferably an epoxy compound having a cyclic ether pendant and having no linear (tetra) framework. Preferably, the photosensitive ring skeleton is an epoxy ring-fired skeleton. =, the photosensitive composition preferably further contains a Lewis base oxygen; the above-mentioned antioxidant is preferably selected from the group consisting of an anti-t-m-oxidant And at least one of the group consisting of an amine-based antioxidant. The at least one of the polymerizable hydrocarbon monomer (4) and the polymerizable hydrocarbon polymer (8) of the oxime contains "solid polymerizable unsaturated group and two The above-mentioned rebel, and as a whole of the polymerizable tobacco monomer (A) and the polymerizable hydrocarbon polymer (8), the average molecular weight of the weight is 5, coffee ~ 5 (), coffee, solid component acid value (10)% is called K〇H / g 'and double bond equivalent weight is 50~2,000 g/eq. (4) In the total amount of the polymerizable tobacco polymer (8), the content of the polymerizable hydrocarbon monomer (4) is preferably 5% by weight or more and 50% by weight or less. The polymerizable tobacco monomer (4) i (10)% by weight In the above, the content of the polymerizable hydrocarbon monomer having an alcoholic hydroxyl group is preferably 15% by weight or less. The inorganic filler (C) preferably satisfies the following formula (X). [U first inorganic filler Mohs hardness) χ (photosensitive composition after curing 〇〇 volume / content of first inorganic filler (% by volume) in 〇)} + { (Mohs hardness of second inorganic filler) χ (hardening The content (vol%) of the second inorganic filler in 100% by volume of the photosensitive composition after the coating)}+ the Mohs hardness of the U-n inorganic filler) (the photosensitive composition after curing 1% by volume) In the middle of the η I47625.doc 201106097 content of inorganic filler (% by volume))}] $ 4 (χ), heart month photosensitive & composition is better to further contain a solvent, and the solvent's dipole moment is 1 Debye or higher. The solder resist composition of the present invention is a photosensitive composition according to the present invention. The photosensitive group of the present invention The invention is suitable for use as an anti-tank composition. [Effect of the Invention] The photosensitive composition of the present invention contains at least one of a polymerizable hydrocarbon monomer (4) and a polymerizable fluorene polymer (B), and an inorganic filler ( 〇, and the inorganic filler (c) has a positive value of 6 8 or more and u or less by boiling, so that a protective film which is less likely to be discolored even when exposed to a high temperature can be obtained. When the refractive index at 465 nm is i 8 or more, and the inorganic filler (C) is a white filler, a white solder resist film having higher reflectance can be obtained. At least one of the above inorganic fillers (c) When it is covered with an alkali metal oxide or an alkali metal hydroxide, it is almost the same as the type (4) of the inorganic filler (c), and a protective film which is less likely to be discolored at a high temperature is formed. Further, since the curability of the resin can be improved, the cutting workability of the protective film can be improved. Since the surface activity of the inorganic cerium filling (c) having photooxidation can be suppressed, it is possible to form a protective film which is difficult to deteriorate the resin even when irradiated with light. In the case where the photosensitive composition contains a compound which can react with the acidic portion of the inorganic filler (c), a protective film which is less likely to be discolored even when exposed to a high temperature can be obtained. The yellowing of the protective film can be surely suppressed in the following cases: the above-mentioned polymerizable property 147625.doc 201106097 Tobacco monomer (8) has two or more polymerizable unsaturated groups, and in a solution of 1:1 (volume ratio), In the liquid phase layer dihydrate of the mass spectrometry (LC), the peak area composed of the component having a mass spectrum peak of 5° or less is 30% or more of the total peak area sheet. [Embodiment] Hereinafter, the present invention will be described in detail. The photosensitive composition of the present invention contains at least one of the polymerizable hydrocarbon polymer (B) and the like. In the polymerizable hydrocarbon monomer-polymerizable hydrocarbon polymer (B), it is also possible to use a polymerizable hydrocarbon monomer (and a polymerizable hydrocarbon polymer (3). ) Both. Further, the polymerizable hydrocarbon monomer (4) and the poly-based polymer (Β) may be used alone or in combination of two or more. (Polymerizable hydrocarbon monomer (A)) The polymerizable hydrocarbon monomer (4) may, for example, be a monomer containing a polymerizable saturated group or a monomer containing a polymerizable cyclic slit group. The polymerizable unsaturated group 'is, for example, a functional group having a polymerizable unsaturated double bond such as a (meth) propylene group and an ethylene group. Among them, since the crosslinking density of the protective film can be increased, a (methyl) styrene is preferred. The above monomer having a polymerizable unsaturated group is preferably a compound having a (meth) fluorenyl group. Examples of the compound having a (meth) acrylonitrile group include a di(meth)acrylate modified product of an alcohol such as ethylene glycol, methoxytetraethylene glycol, & ethylene glycol or propylene glycol; Polyol (meth) of an alcohol, a polyoxyethylene ethane adduct of a polyol or a propylene oxide adduct of a polyhydric alcohol 147625.doc 201106097 Acrylate modification; phenol, phenol ethylene oxide adduct or phenol a (meth) acrylate modification of a propylene oxide adduct; a glycidyl ether (mercapto) acrylate modification such as glycerol diglycidyl ether or dimethylolpropane triglycidyl ether; or melamine (A) Base) acrylate. Examples of the polyhydric alcohol include hexanediol, trimethylolpropane, pentaerythritol, dipentaerythritol, and tris-hydroxyethyl isocyanurate. Examples of the phenolic (mercapto) acrylate include phenoxy (mercapto) acrylate and bisphenol A bis(indenyl) acrylate modified product. "(Meth)acryloyl fluorenyl" means propylene fluorenyl and methacryl fluorenyl. "(Meth)acrylic acid" means acrylic acid and mercaptoacrylic acid. "(Meth)acrylate" means acrylate and methacrylate. (Polymerizable hydrocarbon polymer (B)) Examples of the polymerizable tobacco polymer (B) include an acrylic resin, an epoxy resin, and an olefin resin. Further, the "r resin" is not limited to the solid resin, and includes a liquid resin and an oligomer. The above polymerizable hydrocarbon polymer (B) is preferably the following carboxyl group-containing resin (4) to (4). (a) a carboxyl group-containing resin obtained by copolymerization of an unsaturated carboxylic acid with a compound having a polymerizable unsaturated double bond (b) by a buffer-containing (meth)acrylic acid copolymerized resin (匕) a carboxyl group-containing resin (c) obtained by a reaction with a compound (b2) having an epoxy group and an ethylidene unsaturated double bond in an anthracene molecule, which has an unsaturated monocarboxylic acid and one molecule A saturated or unsaturated polybasic acid is obtained by reacting a compound of each of the epoxy group and the polymerizable unsaturated double bond with a copolymer having a polymerizable unsaturated double bond of I47625.doc •10-201106097. The carboxyl group-containing resin (d) obtained by reacting the needle with the secondary hydroxyl group of the resulting reactant causes the saturated or unsaturated polybasic acid anhydride to react with the hydroxyl group-containing polymer. After that, one molecule of each molecule is one. The resin containing a base group and a slow base obtained by reacting a compound having an epoxy group and a polymerizable unsaturated double bond with the generated tickic acid can further improve the heat resistance of the protective film, so the polymerizable hydrocarbon polymer (B) The above (b) carboxyl group-containing resin is preferred. The (meth)acrylic acid-containing copolymer resin (b 1 ) having a buffer group can be, for example, obtained by using (fluorenyl) acrylate (bb 1 ), having one unsaturated group in one molecule, and at least one carboxyl group. The compound (bb2) is obtained by copolymerization. As the above (meth) acrylate (bb 1), (mercapto) acetoacetate, ethyl (meth) acrylate, propyl (meth) acrylate And (mercapto) butyl acrylate, (mercapto) pentyl acrylate and (mercapto) hexyl acrylate. Further, as the above (mercapto) acrylic acid vinegar (bb 1), (Kami) acrylate and diol-modified (mercapto) acrylate. The above (meth)acrylic acid (bbl) may be used alone or in combination of two or more. The acrylate may, for example, be (meth)propionic acid 2·hydroxyethyl ester, (mercapto) hydroxypropyl acrylate, (methyl)propionic acid-light butyl vinegar and caprolactone modified ( Mercapto)acrylic acid 2-light ethyl vinegar, etc. As the diol-modified (meth) acrylate, decyloxy diethylene glycol ( Acrylate, ethoxydiethylene glycol (meth)acrylic acid, isooctyloxymonoethylidene (methyl) acrylate acid, phenoxytriethylene glycol (methyl methacrylate) Acrylate, decyloxytriethylene glycol (mercapto) acrylate, and methoxypolyethyl 147625.doc 11 201106097 monool (methyl) acrylic acid @. As one of the above molecules, it has a single polymerizability Examples of the unsaturated group and at least one carboxyl group compound (bb2) include (meth)acrylic acid, a chain-extended modified unsaturated monocarboxylic acid between an unsaturated group and a carboxylic acid, and a (meth)acrylic acid carboxy group. Ethyl ester, 2-propenylmethoxyethyl succinic acid, 2-propenyloxyethylhexahydrophthalic acid, unsaturated monocarboxylic acid having an ester bond by modification of a lactone, etc., having an ether bond A compound having two or more carboxyl groups in the j molecule such as a modified unsaturated monocarboxylic acid or maleic acid. The above compound (bb2) may be used alone or in combination of two or more. Examples of the compound (b2) having an oxirane ring and an ethylenically unsaturated group in the above-mentioned one molecule include glycidyl (meth)acrylate and α-mercapto glycidyl (mercapto)acrylate. Mercapto)acrylic acid 3,4-epoxycyclohexyl hydrazine Sa, (mercapto)acrylic acid 3,4-epoxycyclohexylethyl ester, (meth)acrylic acid 3,4-oxacyclohexyl butyl acrylate, and acrylic acid 3 , 4_epoxycyclohexyldecylamino ester. Among them, preferred is 3,4-epoxycyclohexyldecyl (meth)acrylate. The compound (b2) may be used alone or in combination of two or more. The above polymerizable hydrocarbon monomer (A) preferably has two or more polymerizable unsaturated groups, and is subjected to liquid chromatography using mass spectrometry in an acetonitrile:water = 1: (volume ratio) solution. When the polymerizable hydrocarbon monomer (a) is measured by LC/MS, the peak area composed of the component having a fragment peak of 5 Å or less by mass spectrometry is 30% or more of the total peak area. The polymerizable hydrocarbon monomer (A) having a peak area of a particle size of 5 Å or less by mass spectrometry and having a peak area of 30% or more of the total peak area is, for example, ethylene glycol or methoxytetrazol. N-ethylene glycol or propylene glycol, etc. 147625.doc 12 201106097 diol di(meth)acrylic acid vinegar modified; polyhydric alcohol, ethylene burn adduct or polyol epoxidized calcined adduct Ester modification; phenol, phenolic epoxy oxime M methyl) propylene oxime ethylene oxide adduct or phenolic composition: ('base) propylene vinegar vinegar modified; glycerol diglycidyl hydrazine = :: C: A glycidyl ether such as glycidyl ether is called a (meth) acrylate modifier, or melamine (meth) acrylate. As the above polyhydric alcohol, for example, θ gold...* 〗 〖1. Hexanol, trimethylolpropanyl, dipentaerythritol and tris-ethylidene ethyl isocyanurate. Examples of the above-mentioned (meth)propionic acid brewing include a phenoxy group (methyl acrylate) and a bis-(meth) acrylate vinegar modified product. The above-mentioned polymerizable hydrocarbon monomer (A) The weight average molecular weight in terms of polystyrene determined by GPC (gel permeati 〇 n 面 ( 四 , 凝胶, gel permeation chromatography) is preferably 700 or less. By the weight average molecular weight 7G (m under 'can more reliably suppress yellowing of the protective film. The above weight average molecular weight is obtained by dissolving 15 mg of the polymerizable hydrocarbon monomer (4) in THF (tetrahydrofuran 'tetrahydrofuran) i mL for Gpc measurement. It is measured by the molecular weight obtained by the styrene conversion. The one of the above-mentioned polymerizable hydrocarbon monomer (A) and the polymerizable hydrocarbon polymer (7) contains one or more polymerizable unsaturated double bonds and two or more. a carboxyl group, and as a polymerizable hydrocarbon monomer and a polymerizable hydrocarbon polymer, the overall 'weight average molecular weight is 5, 〇〇〇 5 5 〇, 〇〇〇, and the solid content acid value is 30 〜 150 mg KOH / g ' and The double bond equivalent is 5 〇~2 〇〇〇g/eq. The average molecular weight is 5, 〇〇〇~50, 〇〇〇, the solid component acid value is 30~150 mg KOH/g, and the double bond equivalent is 5 〇~2 〇00 g/eq, then the feeling is 147625.doc 201106097 light The polymerizable hydrocarbon monomer (in the total of 100% by weight of the total of the polymerizable hydrocarbon monomer (A) and the polymerizable hydrocarbon polymer (b), the polymerizable hydrocarbon monomer ( The content of the component A) is preferably 5% by weight or more and 50% by weight or less. When the content of the polymerizable hydrocarbon monomer (4) is within the above range, the photosensitive composition can be sufficiently cured, and the heat retention can be further improved. Further, the cross-linking density of the protective film is moderate, and sufficient resolution can be obtained, and the protective film is not easily yellowed. The polymerizable hydrocarbon monomer (4) has an alcoholic hydroxyl group in an amount of 1% by weight. The content of the polymerizable hydrocarbon monomer is preferably 15% by weight or less. In this case, it is easy to maintain the intrinsic property of the inorganic filler (c), and it is easy to cut the protective film. As the above-mentioned polymerizable hydrocarbon monomer (A) ), pentaerythritol tri (meth) acrylate can be cited. Filler (C)) The inorganic filler (6) contained in the photosensitive composition of the present invention has a pH of 6 8 as measured by a boiling method, and has a value of 6.8 or more and Η or less. The pH is less than 6.8 days = 4 film vaporization' and it is difficult to cut and apply the protective film. Moreover, the application period of the photosensitive composition is deteriorated when the P value gate is 1 a. Since the protection method can be further suppressed, na ># ',汽 汽 汽 , , , , , , 上述 上述 上述 上述 上述 上述 上述 上述 上述 上述 上述 上述 上述 上述 上述 上述 上述 上述 上述 上述 上述 上述 上述 上述 上述 上述 上述 上述 上述 上述 无机 无机 无机 无机 无机 无机 无机 无机 无机 无机Photosensitive combination

適用期變得更良好，故卜、f &R 故上述無機填充料（C)之利用者沸法 所測定之pH值較好的是 ‘、、、，弗法 疋1〇.〇以下’更好的是9.0以下。 所謂上述煮沸法，俦 承払如下方法：對將上述無機填充料 147625.doc 201106097 (c)5 g加至純水100 mL中所得溶液進行加熱，使其沸騰5 分鐘後，靜置直至達到23X：為止，獲得沸騰處理液，繼而 於所得冬沸騰處理液中加入因沸騰而蒸發之水量之水，使 水量成為100 mL ’測定所得溶液之pH值。 上述煮沸法中，具體而言係於具有開口之容器内放入將 上述無機填充料（C)5 g加至純水1〇〇 mL中而獲得之溶液。 藉由加熱上述容器而加熱容器内之溶液’使容器内之溶液 沸騰。開始沸騰後，使沸騰狀態維持5分鐘。其後，於容 器之開口安裝塞體，靜置至達到23t為止，獲得沸騰處理 液。自容器之開口卸除塞體，於所得之滞騰處理液中加入 因沸騰而蒸發之水量之水，使水量成為1〇〇 mL。於容器之 =口安裝塞體，振盪混合丨分鐘後，靜置5分鐘。如此而獲 付測疋溶液。所得之測定溶液之1311值可依據jis z88〇2之7 中記載之操作而測定。 上述無機填充料（c)之能帶隙較好的是2 5 eV以上、7 ev ^下於Ji述能帶隙低於2.5 eVB夺，#在防焊膜之絕緣性 :低之情形。於上述能帶隙高於7 eV時，存在防焊膜若暴 露於高溫下則容易黃變之傾向。 、較好的是上述無機填充料（〇之465 nm下之折射率為Μ 以上，且上述無機填充料（c)為白色填充料。於此情形 時，可獲得適合於L剛印刷配線基板等之白色防焊膜的 感光性組合物。再者，若上述折射率為Μ以上，則可獲 得對用於裝載有LED之基板的白色防焊膜所要求之高反射 147625.doc 15 201106097 作為上述白色填充粗 _ 録、氧化鋅1白二化列舉：氧化鈦、氧化錯、氧化 由於可進-步抑制高：下鉀及鈦酸船等。其中， 化鈦。 之保濩臈之黃變，故較好的是氧 範 上述白色填充料之數量平均粒徑較好的是G.01〜1.0 圍内’更好的是(Μ〜0·5 _之範圍内 上述無機填充料（C)較 石型氧化鈦之情形時， 變。 好的是金紅石型氧化鈦。 防焊膜暴露於高溫下時更 於金紅 不易黃 感光性組合物100重量％中之無機填充料（c)之含量較好 :是3重量％以上、8〇重量％以下。於無機填充料(〇之含 量未達3重量/。時，存在防焊膜暴露於高溫下時容易黃變 之傾向^於無機填充料（c)之含量超出8g重量。之情形時， 存在難以製備具有適合塗佈之黏度的感光性組合物之情 形。感光性組合物1〇〇重量％中之無機填充料（c)之含量之 更佳下限為重量％，更佳上限為75重量％。 為了使表面呈鹼生，較好的是至少!種上述無機填充料 (C)係由鹼性金屬氧化物或鹼性金屬氫氧化物所被覆。於 此情形時，防焊膜暴露於高溫下時，可使防焊膜更不易黃 變。上述鹼性金屬氧化物或鹼性金屬氫氧化物可僅使用^ 種’亦可併用2種以上。 作為上述驗性金屬氧化物或驗性金屬氫氧化物，可列舉 含有鎂、錯、鈽、锶、銻、鋇或鈣等之金屬化合物。由於 可進一步抑制高溫下之防焊膜之黃變，故構成上述鹼性金 147625.doc -16· 201106097 屬氧化物或鹼性金屬氫氧化物之金屬元素較好的是選自由 鎂'锆、鈽、鳃、銻、鋇及鈣所組成之群中之至少i種。 由於可進一步抑制高溫下之防焊膜之黃變，故上述無機填 充料（c)較好的是由含有氧化锆之被覆材料所被覆。作為 上述鹼性金屬氧化物或鹼性金屬氫氧化物，適宜使用氧化 錯0 由上述鹼性金屬氧化物或鹼性金屬氫氧化物所被覆之無 機填充料（C)例如可以下述方式而獲得。 使無機填充料（c)分散於水中或以水為主成分之溶液 中獲得聚料。視需要藉由砂磨機或球磨機等將無機填充 料（C)粉碎。繼而，使漿料之阳值為中性或驗性，視情況 為酸性。其後’將成為被覆材料之原料之水溶性鹽添加至 聚料中，被覆無機填充料(c)之表面。其後，中和毁料， 回收無機填充料（C)。經时之無機填充料（C)可進行乾燥 或乾式粉碎。 又，於本發明之感光性組合物中，除上述無機填充料 ⑹以外，視需要亦可含有碳_、氧化銘、氫氧化铭、 風氧化辞、氧化鋅、氮化銘、氮切、氮㈣、金剛石粉 末、矽酸錯、氧化锆、滑石、硫酸鋇、鈦酸鋇、氧化鈦、 黏土、碳酸鎂、氫氧化鎮'雲母、雲母粉、硫酸船、硫化 鋅、乳化録、氮化鈦、氟化飾及氧化鈽等其他填充料。 上述無機填充料(C)較好的是具有酸性部位。為提高驗 上速無機填充料（C)較好的是由可與無機填充料（C)之 西欠性部位反應之化合物進行表面處理。 147625.doc 201106097 作為可與上述無機填充料（c)之酸性部位反應之化合 物’可列舉··三羥甲基丙烷、三羥甲基乙烷、二-三羥甲 基丙烷、三羥甲基丙烷乙氧化物或季戊四醇等多元醇，·單 乙醇胺I丙醇胺、二乙醇胺、二丙醇胺、三乙醇胺或三 丙醇胺等烷醇胺；氣矽烷及烷氧基矽烷等。 由於可進一步抑制高溫下之保護膜之黃變，故可與上述 無機填充料（c)之酸性部位反應之化合物較好的是鹼性化 合物。於鹼性化合物之情形時，可進一步提高無機填充料 (c)之鹼性。由於可進一步抑制高溫下之保護膜之黃變， 故上述鹼性化合物較好的是選自由多元醇、烷醇胺及烷氧 基矽烷所組成之群中之至少丨種，特別好的是烷醇胺。於 烷醇胺之情形時，保護膜於高溫下極不易黃變。 作為使無機填充料（C)、與可與無機填充料之酸性部 位反應之化合物進行反應之方法，可列舉以下方法等： 於流體能量粉碎機或衝擊粉碎冑等乾式粉碎機中放入上述 化合物與無機填充料（c)，將無機填充料粉碎；（2)使用 亨舍爾混合機或快速混合機等高速搜拌機，將上述化合物 與經乾式粉碎之無機填充料（c)攪拌、混合；以及於無 機填充料（C)之水性漿料中添加上述化合物，加以撥摔。 再者，本發明之感光性組合物除藉由煮彿法而測定之pH 值為6.8以上、η以下之無機填充料(c)以外，亦可含有藉 由煮濟法而測定之PH值未達68,或者該PH值超出 機填充料。 (其他成分） 147625.doc •18· 201106097 為提高上述無機填充料（c)之鹼性，感光性組合物較好 的是含有可與無機填充料（c)之酸·性部位反應之化合物。 作為可與上述無機填充料（C)之酸性部位反應之化合物， 適宜使用用以對無機填充料（C)進行表面處理之可與上述 無機填充料（C)之酸性部位反應之化合物。可與上述無機 填充料（C)之酸性部位反應之化合物可僅使用1種’亦可併 用2種以上。 可與上述無機填充料之酸性部位反應之化合物較好 的疋驗性化合物。又，上述驗性化合物更好的是選自由多 兀醇、烧醇胺及烷氧基矽烷所組成之群中之至少1種。 於感光性組合物含有可與無機填充料（C)之酸性部位反 應之化合物之情形時，於感光性組合物100重量％中可 與上述無機填充料（C)之酸性部位反應之化合物之含量較 好的是(M重量。/。以上、10重量％以下。可與上述無機填充 料（C)之馱性部位反應之化合物之含量在上述較佳範圍内 之情形時’可進—步抑制高溫下之保護膜之黃變。 為了提高保護膜之切割加卫性，感光性組合物較好的是 含有具有環狀醚骨架之化合物（D)。 作為上述具有環狀醚骨牟 月永之化合物（D)，例如可列舉： 雙酚S型環氧樹脂、鄰| _ —甲®欠一縮水甘油醋樹脂、異氰 尿酸三縮水甘油酯等雜璟 衣式％乳树脂、聯二甲苯盼型環氧 樹脂、聯苯酚型環氧榭日t _ g、四lis水甘油基二甲苯酚乙烷樹 脂、雙紛A型環氧樹脂、气μ 虱化雙酚Α型環氧樹脂、雙酚F型 樹脂、溴化雙酚A型環氧椒^ 虱樹知、本酚酚醛型環氧樹脂、甲 147625.doc •19· 201106097 酚酚醛型環氧樹脂、脂環式環氧樹脂、雙酚A之酚醛型環 氧樹脂、螯合物型環氧樹脂、乙二醛型環氧樹脂、含胺基 之環氧樹脂、橡膠改質環氧樹脂、二環戊二稀酚型環氧^ 月曰、聚石夕氧改質環氧樹脂及ε_己内醋改質環氧樹脂。上述 具有環狀醚骨架之化合物（D)可僅使用j種亦可併用2種 以上。 本發明之感光性組合物亦可含有具有環狀醚骨架且不具 有直鏈_之環氧化合物(m)。作為上述環氧化合物 (D1)，可列舉環氧化聚晞烴、二㈣之縮水甘油酯、鄰苯 二甲酸二縮水甘油S旨樹脂、及異氰尿酸三縮水甘油醋等雜 壤式環氧樹料。作為上述二㈣，刊舉己二酸、鄰苯 二甲酸、四氫鄰苯二甲酸及六氫鄰苯二甲酸等。上述環氧 化合物（D1)可僅使用1種，亦可併用2種以上。纟中’與不 使用該等化合物之情形相比較，於使用該等化合物之情形 時，存在保護膜之切割加工性降低之情形。 ^ 玉衣氧化合物（D1)較奸的县目士 ^ V )权好的疋具有2個以上環狀醚骨 架0 :具有環狀喊骨架之化合物⑼之環狀縫骨架較好合 骨架。上述環氧化合物(D1)之環狀驗骨㈣ 氧環己院骨架。作為具有環氧環己院骨架且不肩 骨架之環氧化合物，可列舉:3、4，，_環氧環“ :，Μ環己基甲酉旨、己二酸雙(3,4-環氧環己基甲基 氧乙基-3,4_環氧環己烧、轉檬稀二環氧化物及二 衣一環氧化物。作為該環氧化合物之市售品，可歹, 147625.doc -20· 201106097 舉 Celloxide 2021P(Daicel 公司製造）。 具有環狀醚骨架之化合物（D)與聚合性烴聚合物（B)所具 有之羧基等官能基反應而發揮作用，以使感光性組合物硬 化。 相對於上述聚合性烴聚合物（B)100重量份，上述具有環 狀醚骨架之化合物（D)之含量之較佳下限為0.1重量份，更 佳下限為1重量份，較佳上限為50重量份，更佳上限為30 重量份。當上述具有環狀醚骨架之化合物（D)之含量在上 述較佳範圍内時，可進一步抑制保護膜之黃變。 為減少暴露於高溫下時防焊膜黃變之擔憂，本發明之感 光性組合物較好的是含有抗氧化劑。上述抗氧化劑較好的 是具有路易斯鹼性部位。就進一步抑制保護膜之黃變之觀 點而言，上述抗氧化劑較好的是選自由酚系抗氧化劑、磷 系抗氧化劑及胺系抗氧化劑所組成之群中之至少1種。 作為上述酚系抗氧化劑之市售品，可列舉：Irganox 1010 ' Irganox 1035 ' Irganox 1076 ' Irganox 1135 ' Irganox 245、Irganox 259、及 Irganox 295(以上均由 Ciba Japan公司製造）；Adekastab AO-30、Adekastab AO-40、 Adekastab AO-50、Adekastab AO-60、Adekastab AO-70、 Adekastab AO-80、Adekastab AO-90、及 Adekastab AO-330(以上均由 Adeka 公司製造）；Sumilizer GA-80、 Sumilizer MDP-S、Sumilizer BBM-S、Sumilizer GM、 Sumilizer GS(F)、及Sumilizer GP(以上均由住友化學工業 公司製造）；Hostanox O10、Hostanox 016、Hostanox 147625.doc -21 - 201106097 014、及 Hostanox 03(以上均由 Clariant公司製造）；Antage ΒΗΤ、Antage W-300、Antage W-400、及 Antage W500(以 上均由川口化學工業公司製造）；以及Seenox 224M、及 Seenox 326M(以上均由Shipro Kasei公司製造）等。 作為上述磷系抗氧化劑，可列舉環己基膦及三苯基膦 等。作為上述磷系抗氧化劑之市售品，可列舉：ADK Stab PEP-4C、ADK Stab PEP-8、ADK Stab PEP-24G、ADK Stab PEP-36、ADK Stab HP-10、ADK Stab 2112、ADK Stab 260、ADK Stab 522A、ADK Stab 1178、ADK Stab 1500、ADK Stab C、ADK Stab 135A、ADK Stab 3010、及 ADK Stab TPP(以上均由 Adeka公司製造）；Sandostab P-EPQ及Hostanox PAR24(以上均由Clariant公司製造）；以及 JP-312L、JP-318-0、JPM-308、JPM-313、JPP-613M、 JPP-31、JPP-2000PT及JPH-3800(以上均由城北化學工業公 司製造）等。 作為上述胺系抗氧化劑，可列舉：三乙胺、二氰二胺、 三聚氰胺、乙基二胺基-均三畊、2,4-二胺基-均三畊、2,4-二胺基-6-曱苯基-均三畊、2,4-二胺基-6-二曱苯基-均三畊 及四級銨鹽衍生物等。 本發明之感光性組合物可含有溶劑。溶劑之偶極矩較好 的是1 Debye以上。藉由使用偶極矩為1 Debye以上之溶 劑，可提供適用期優異之感光組合物。 上述無機填充料（C)較好的是滿足下述式（X)。於此情形 時，可進一步提高保護膜之切割加工性。 147625.doc -22· 201106097 機填充料之莫氏硬度)x(硬化後之感光性組合物 機填香租/〇中之第1無機填充料之含量（體積％))} + {(第2無 '枓之莫氏硬度）χ(硬化後之感光性組合物⑽體積％ 之第2無機填充料之含量（體積％)))+ ·.·.·{(第η無機填充 之莫氏硬度）χ(硬化後之感光性組合物_體積％中之第打 無機填充料之含量（體積％))}]客4 ......(X) 為進一步提高感光性，本發明之感光性組合物較好的是 含有光聚合起始劑。 作為上述光聚合起始劑，例如可列舉：酿基氧化鱗、函 甲基化三畊、自曱基化噚二唑、咪唑、安息香、安息香烷 基鍵、，蒽酉昆、苯并蒽嗣、二苯甲酮、苯乙嗣、9_氧硫灿 哇、苯曱酸酯、吖啶、啡畊、二茂鈦、α，基烷基苯酮、 肟、以及該等之衍生物。上述光聚合起始劑可僅使用丄 種’亦可併用2種以上。 於含有上述光聚合起始劑之情形時，相對於上述聚合性 烴單體（A)及上述聚合性烴聚合物之合計1〇〇重量份， 上述光聚合起始劑之含量之較佳下限為〇丨重量份，更佳 下限為1重量份，較佳上限為30重量份，更佳上限為丨5重 1份。於上述光聚合起始劑之含量在上述較佳範圍内之情 形時’可進一步提高感光性組合物之感光性。 又’本發明之感光性組合物亦可含有著色劑、填充劑、 消泡劑、硬化劑、硬化促進劑、脫模劑、表面處理劑、阻 燃劑、黏度調節劑、分散劑、分散助劑、表面改質劑、塑 化劑、抗菌劑、防黴劑、調平劑、穩定劑、偶合劑 '防流 147625.doc -23- 201106097 掛劑或螢光體等。 本發明之感光性組合物例如可藉由將各調配成分授摔混 合後’利用三輥機均勻地混合而製備。 作為用則吏感光性組合物硬化之光源，可列舉發出紫外 線或可見光線等活性能量線之照射裝置。作為上述光源， 例如可列舉：超高壓水銀燈、深紫外線（Deep uv)燈、高 壓水銀燈、低壓水銀燈、金屬_化物燈及準分子雷射。該 等光源係根據感光性組合物之構成成分之感光波長而適當 選擇。光之照射能量係根據所需膜厚或感光性組合物之構 成成分而適當選擇。光之照射能量通常在1〇〜3,〇〇〇 mj/cm2 之範圍内。 (LED元件） 本發明之感光性組合物適宜用於形成LED元件之保護 膜’更適宜用於形成防焊膜。 圖1以部分切口正面剖面圖，示意性地表示包括使用本 發明之一實施形態之感光性組合物而形成之防焊膜的led 元件。 於圖1所示之LED元件1中’於基板2之上表面2a積層有 由感光性組合物形成之保護膜3。保護膜3為圖案膜。因 此，於基板2之上表面2a之一部分區域未形成保護膜3。於 未形成保護膜3之部分之基板2之上表面2a設置有電極4a、 4b。基板2較好的是印刷配線板。 於保護膜3之上表面3a積層有LED晶片7。於基板2上， 隔著保護膜3而積層有LED晶片7。於LED晶片7之下表面7a 147625.doc -24- 201106097 之外周緣設置有端子8a、8b。藉由焊錫9a、9b，端子8a、 8b與電極4a、4b電性連接。藉由該電性連接，可對^^〇晶 片7供給電力。 以下，藉由列舉本發明之具體實施例及比較例而闡明本 發明。本發明並不限定於以下實施例。 準備以下之丙烯酸聚合物1〜6、與無機填充料卜^。 (合成例1)丙烯酸聚合物1 於具備溫度計、攪拌機、滴液漏斗及回流冷凝器之燒瓶 中，添加作為溶劑之乙基卡必醇乙酸酯、及作為觸媒之偶 氮雙異丁腈，於氮氣環境下加熱至80°c，以2小時滴加將 甲基丙烯酸與曱基丙烯酸曱酯以3〇 : 7〇之莫耳比混合而成 之單體。滴加後擾拌1小時，將溫度升至i 2〇。其後進行 冷卻。添加相對於所得樹脂之所有單體單元之總莫耳量的 莫耳比成為10之量之丙烯酸縮水甘油酯，使用溴化四丁基 銨作為觸媒，於1〇〇°C下加熱30小時，使丙烯酸縮水甘油 酯與羧基進行加成反應。冷卻後，自燒瓶中取出，獲得含 有固體成分酸值為60 mg KOH/g、重量平均分子量為 15,000、雙鍵當量為1〇〇〇之含羧基之樹脂5〇重量％(不揮發 成分）的溶液。以下’將該溶液稱為丙烯酸聚合物1。 (合成例2)丙稀酸聚合物2 於具備溫度計、攪拌機、滴液漏斗及回流冷凝器之燒瓶 中’添加作為溶劑之乙基卡必醇乙酸酯、及作為觸媒之偶 氮雙異丁腈’於氮氣環境下加熱至8〇〇c，以2小時滴加將 曱基丙烯酸、曱基丙烯酸曱酯及甲基丙烯酸苄酯以3〇 : 147625.doc •25· 201106097 3〇 . 40之莫耳比混合而成之單體。滴加後，授心小時， 將溫度升至120t。其後’進行冷卻。添加相對於所得樹 脂之所有單體單元之總莫耳量的莫耳比成為1〇之量之丙婦 -夂縮尺甘,“曰’使用溴化四丁基銨作為觸女某，於1 〇〇艽下 加熱30小時’使丙㈣縮水甘油@旨與絲進行加成反應」 、I7後自燒瓶中取出，獲得含有固體成分酸值為叫 顧/g、重量平均分子量為15，_、雙鍵當量為之含 緩基之樹脂50重量％(不揮發成分）的溶液。以下，將該溶 液稱為丙烯酸聚合物2。 (合成例3)丙稀酸聚合物3 於具備溫度計、授拌機、滴液漏斗及回流冷凝器之燒瓶 中，添加作為溶劑之乙基卡必醇乙酸^旨、及作為觸媒之偶 氮雙異丁腈，於氮氣環境下加熱至，以2小時滴加將 甲基丙烯酸、甲基丙烯酸甲醋及甲基丙烯酸节醋以3〇: 3〇 : 40之莫耳比混合而成之單體。滴加後，授拌$小時， 將溫度升至12〇t。錢’進行冷卻。添加㈣於所得樹 脂之所有單體單元之總莫耳量的莫耳比成為1()之量之丙稀 酸縮水甘油醋，使用演化四丁基銨作為觸媒，於1〇〇。〇下 加熱30小時，使丙烯酸縮水甘油酯與羧基進行加成反應。 冷卻後，自燒瓶中取出，獲得含有固體成分酸值為6〇叫 KOH/g、重量平均分子量為1〇〇〇〇〇、雙鍵當量為之 含羧基之樹脂50重量％(不揮發成分）的溶液。以下，將該 溶液稱為丙烯酸聚合物3。 (合成例4)丙稀酸聚合物4 147625.doc • 26· 201106097 於具備溫度計、㈣機、滴液漏斗及回流冷凝器之燒瓶 中’添加作為溶劑之乙基卡必醇乙酸酯、及作為觸媒之偶 氮雙異丁腈’於氮氣環境下加熱至8〇。。，以2小時滴加將 甲基丙烯酸、甲基丙烯酸曱酯及甲基丙烯酸苄酯以Η: 35 ’ 50之莫耳比混合而成之單體。滴加後，攪拌卜"夺， 將溫度升至12G°C。其後，進行冷卻。添加相對於所得樹 脂之所有單體單元之總莫耳量的莫耳比成為1()之量之丙稀 酸縮水甘油S旨’使用漠化四丁基錢作為觸$，於1〇代下 加熱30小時’ &丙稀酸縮水甘油醋與緩基進行加成反應。 冷卻後，自燒瓶中取出，獲得含有固體成分酸值為15叫 OH/g重量平均分子量為14,〇〇〇、雙鍵當量為1〇〇〇之含 羧基之樹脂50重量％(不揮發成分）的溶液。以下，將該溶 液稱為丙烯酸聚合物4。 (合成例5)丙烯酸聚合物5 於具備溫度計、攪拌機、滴液漏斗及回流冷凝器之燒瓶 中，添加作為溶劑之乙基卡必醇乙酸酯 '及作為觸媒之偶 氮雙異丁腈，於氮氣環境下加熱至8〇〇c ,以2小時滴加將 甲基丙烯酸、曱基丙烯酸曱酯及曱基丙烯酸苄酯以85 : 5 : 1 0之莫耳比混合而成之單體。滴加後，攪拌1小時，將 /m度升至120 C。其後，進行冷卻。添加相對於所得樹脂 之所有單體單元之總莫耳量的莫耳比成為1〇之量之丙烯酸 縮水甘油酯，使用溴化四丁基銨作為觸媒，於1〇〇<t下加 熱3 0小時’使丙烯酸縮水甘油酯與羧基進行加成反應。冷 卻後’自燒瓶中取出’獲得含有固體成分酸值為220 mg 147625.doc -27· 201106097 KOH/g、重量平均分子量為17〇〇〇、雙鍵當量為1〇〇〇之含 羧基之樹脂50重量％(不揮發成分）的溶液。以下，將該溶 液稱為丙烯酸聚合物5。 (合成例6)丙烯酸聚合物6 於具備溫度計、攪拌機、滴液漏斗及回流冷凝器之燒瓶 中’添加作為溶劑之乙基卡必醇乙酸酯、及作為觸媒之偶 氮雙異丁腈，於氮氣環境下加熱至8〇〇c，以2小時滴加將 甲基丙烯酸、甲基丙烯酸甲酯及甲基丙烯酸苄酯以22.5 ·· 3 7.5 . 40之莫耳比混合而成之單體。滴加後，攪拌1小 時，將溫度升至12(TC。其後，進行冷卻。添加相對於所 得樹脂之所有單體單元之總莫耳量的莫耳比成為25之量 之丙烯酸縮水甘油§旨，使用溴化四了基敍作為觸媒，於 1〇〇°C下加熱30小時，使丙烯酸縮水甘油酯與羧基進行加 成反應。冷卻後，自燒瓶中取出，獲得含有固體成分酸值 為60 mg KOH/g、重量平均分子量為18 〇〇〇、雙鍵當量為 4,〇〇〇之含羧基之樹脂50重量％(不揮發成分）的溶液。以 下’將該溶液稱為丙烯酸聚合物6。 (無機填充料（C)) 將無機填充料1〜11之詳.細情況示於下述表1中 147625.doc -28- 201106097 η ^ 卜 卜 卜 r- 卜 卜 卜 卜 00 卜 -Ο CN (N 寸 CN 寸· (N (N 寸· (N — (N 寸 CN 卜 CN Tf* ^Τ) CN 家 Μ i 烷醇胺 三經曱基丙烧 三羥甲基丙烷 三羥甲基丙烷 三羥甲基丙烷 1 1 咖 1 1 I 有無 有機處理 碟 媸 碟 經表面處理 之金屬種 Al ' Si ' Zr Al ' Zr 1 < A卜Si Al ' Zr Al ' Si 1 1 1 折射率 465 nm (N (N (N (N (N (N CN (N 〇\ ymmM 寸 CN JO 帶隙能 (eV) Ο rn Ο cn Ο rn 〇 rn Ο rS 〇 cn 〇 rn 〇 rn σ\ 煮沸法 pH值 S 5 Ο 00 Ο 1> 寸 〇 V£> v〇 (N ο ON 寸· 1 1 粒子中具有多數個 酸性部位 粒子中具有多數個 酸性部位 粒子中具有多數個 酸性部位 1 相當於具有酸性部 位之化合物 i相當於具有酸性部 位之化合物 相當於鹼性化合物 1 相當於具有酸性部 位之化合物 堺化學 石原產業 石原產業 Tayca 石原產業 石原產業 石原產業 石原產業 Nippon Talc 曰本稀元素化學 Admatechs D-918 UT771 CR-50-2 R-102 CR-90-2 CR-97 CR-50 CR-90 rn pi CL, W S0-C3 CN m 寸 卜 〇〇 〇\ Ο τ-Η 4 ^ 氧化鍅 二氧化矽 147625.doc -29- Ιί 201106097 於上述幻中，無機填充料卜8相當於由驗性金屬化合物 或驗性金屬氫氧化物所被覆之無機填充料。對無機填充料 進行表面處料，當金屬種相之情料，可使用氮氧化 铭或氧化紹’當金屬種為Si之情形時，可使用氧化石夕，當 金屬種為Zr之情形時’可使用氧化錯。 又於上述表1 _，無機填充料1〜5係由有機材料進行表 面處理。 (其他成分及成分之比重） 下述實施例、比較例及參考例中適宜使用卞述表2所示 之成分。於表2中’將各成分之比重—併表示。 147625.doc 30- 201106097 【<Νΐ L—比重1 寸· r·^ 寸· 1—^ 寸· 寸· 1-Η CN (N (Ν <N p 〇 MMA/MAA/GMA 聚合物 MMA/BzMA/MAA/GMA 聚合物 Mw 為 100,000 酸值為20以下 酸值為20以下 雙鍵當量為1，〇〇〇以上 •Μ «韜 會 ss|· 螭敦 § <〇 12 ^ Μ u ^ nj α -Μ ϊί 容 Ο CO v0 璨 會 s®!· 絮敦 § Φ °孩 VII V jj t 〇 乂乏 ^ Έ 今U U (¾ hj α 利用LC-MS測定之MS之碎片峰$500之面積為30%以下 利用GPC測定之Mw為700以上之聚合性烴單體 偶極矩為1 Debye以上 偶極矩為0.38 Debye 丙烯酸聚合物-1 丙烯酸聚合物-2 丙烯酸聚合物-3 丙烯酸聚合物-4 丙烯酸聚合物-5 丙烯酸聚合物-6 二季戊四醇六丙烯酸酯(DPHA) 三羥甲基丙烷三丙烯酸酯 李戊四醇三丙烯酸酯 二季戊四醇四丙烯酸酯 << C/5 .Ξ S3 Ρύ iJtn 卜i cd <* 旮衾 S制 Celloxide 2021P(Daicel公司製造） 3,4-環氧環己基甲酸(3·，4’-環氧環己基)甲酯 .藏 w溫 << ^ 謝 Ψ 制塄 m w\ Μ 詮S ft ‘ iW $s if 5洛 O粼 〇 Id 乙基卡必醇乙酸酯 曱苯 丙烯酸聚合物 1 -1 丙烯酸單體 環氧化合物 溶劑 -31 - 147625.doc 201106097 (實施例1) 將15重量份之丙烯酸聚合物】、5重量份之DPHa(二季戍 四醇六丙烯酸酯）、40重量份之D_918(金紅石型氧化欽， 堺化學公司製造）、2重量份之光聚合起始劑（τρ〇，光自由 基產生劑，日本Siber Hegner公司製造）' 8重量份之828(雙 酚A型環氧樹脂，Japan Epoxy Resins公司製造）、及重 量份之乙基卡必醇乙酸酯進行調配，利用混合機（練太郎 SP-500，Thinky公司製造）混合3分鐘後，以三輥機進行混 合’從而獲得混合物。其後’使用SP-500，將所得之混人 物消泡3分鐘，藉此獲得作為感光性組合物之阻劑材料。 (實施例2〜47、比較例1〜8及參考例1、2) 除將所使用材料之種類及調配量變更為下述表3〜表9所 示以外，以與實施例1相同之方式獲得阻劑材料。 (評價） (1)測定樣品之製作 準備80 mmx90 mm、厚度為0.8 mmiFR_4之基板。於該 基板上，藉由絲網印刷法，使用i 〇 〇網眼之聚酯斜裁製 版，以整體圖案印刷阻劑材料。印刷後，於80。匸之烘箱内 乾燥20分鐘，於基板上形成阻劑材料層。繼而，經由具有 特疋圖案之光罩，使用紫外線照射裝置，以照射能量成為 4〇0 mJ/cm2之方式，以100 mW/cm2之紫外線照度，對阻劑 材料層照射4秒鐘波長為365 nmi紫外線。其後，為去除 未曝光部之阻劑材料層以形成圖案，而將阻劑材料層浸潰 於碳酸鈉之1重量％水溶液中，進行顯影，從而於基板上 147625.doc •32- 201106097 形成保s蒦膜。其後’於1 5 0 °C之供箱内加熱1小時，使保護 膜進行後硬化’藉此獲得作為測定樣品之保護獏。所得保 護膜之厚度為20 μπι。 (2) 耐熱性 將測定樣品放入加熱烘箱内，於270。(：下加熱5分鐘。 使用色彩·色差計（Konica Minolta公司製造，CR-400)， 測疋經熱處理刚之s平價樣品之L * ' a *、b * ^又，測定經熱 處理後之評價樣品之L*、a*、b*，由該等2個測定值求出 △E*ab。將經熱處理後之評價樣品之△以讣為2以下之情形 評價為「〇〇」’超出2且為3以下之情形評價為「〇」，超出 3且為3.5以下之情形評價為「△」，超出35之情形評價為 「x」，將結果示於下述表3〜表9中。 (3) 耐光性 使用uv照射機，以照射能量成為1〇〇 j/cm2之方式，對 測定樣品照射365 nm之波長之光。 使用色彩-色差計（Konica Minolta公司製造，CR-400)， a*、b*。又，測定經 ，由該等2個測定值求 測定經UV照射前之評價樣品之L* UV照射後之評價樣品之L*、a*、b 出f。將經uv照射後之評價樣品之AE*abs〗以下之情 》平4貝為〇〇」，超出！且為2以下之情形評價為「〇」，超 出「2且為3以下之情形評價為「△」，超出3之情形評價為 「x」’將結果示於下述表3〜表9中。 (4)切割加工性 使用剪切機，對上述⑴中製作之測定樣品（保護膜）進行 147625.doc •33- 201106097 切割後，於2 7 0 C下加熱5分鐘。以目視確認加熱後之測定 樣品之邊緣之裂痕及缺損狀態。以Τ述評價基準判定切割 加工性。 [切割加工性之評價基準] 〇 :以目視完全未確認到裂痕及缺損 △.以目視於切割部確認到部分裂痕或缺損 X .以目視於切割部之整個範圍確認到裂痕或缺損 (5)適用期 利用V型黏度計測定剛製作之阻劑材料、與放置！日後之 阻劑材料之黏度(25。〇’求出點度之變化比。根據變化 比’以下述評價基準判定適用期。 [適用期之評價基準] 〇：變化比未達1.1 △:變化比為1.1以上、未達J 5 x :變化比為1.5以上 (6)顯影性 以目視確5忍測定樣品之顯影圖案，以下述評價基準判定 顯影性。 [顯影性之評價基準] 〇：以目視確認到圖案 x :以目視未確認到圖案 將結果示於下述表3〜9中。 147625.doc -34· 201106097 實施例11 yrt (N 00 m 〇 〇〇 CN 〇 00 〇 < 〇 〇 實施例10 (N oo 〇 rn <N 〇 00 〇 〇 〇 X 〇 〇 實施例9 to ^Τ) <N oo 〇 Ο) 00 〇 〇 as ο 〇 〇 < 〇 〇 實施例8 yrt (N oo 〇 Ο) ON CN 〇 r—Ν 〇 < 〇 〇 實施例7 ITi ί—H CS oo rn €N 〇 〇\ 〇 < 〇 〇 實施例6 CN 00 〇 (N 00 01 〇 寸· 〇 < 〇 〇 實施例5 r-^ (N oo 〇 <N 寸 CN 〇 CN 〇 < 〇 〇 實施例4 CS 00 〇 <N CN 〇 in 〇 < 〇 〇 實施例3 r~^ tN oo 〇 (N (N 〇 VO 〇 < 〇 〇 實施例2 <N oo 〇 CN 〇 CN 〇 〇 ON ο 〇 〇 < 〇 〇 實施例1 κη T—H CN 00 〇 <N OS 〇 〇 On Ο 〇 〇 < 〇 〇 丙烯酸聚合物-1 DPHA o Oh H 00 CN 00 乙基卡必醇乙酸酯 D-918 i UT771 CR-50-2 R-102 CR-90-2 CR-97 CR-50 CR-90 ΓΟ CU ω SO-C3 式(X)之左邊之值 △E*ab △E*ab 丙烯酸聚合物 丙烯酸單體 起始劑 環氧化合物 炒 1 氧化欽 氧化錯 二氧化矽 莫氏硬度指標 对熱性 耐光性 切割加工性 適用期 顯影性 驿®噠Φ〇Ν®Η傘） -35- 147625.doc 201106097 [表4] 比較例1 比較例2 比較例3 參考例1 調 西己 成 分 重 量 丙烯酸聚合物 丙烯酸聚合物-1 15 15 15 15 丙烯酸單體 DPHA 5 5 5 5 起始劑 ΤΡΟ 2 2 2 2 環氧化合物 828 8 8 8 8 溶劑 乙基卡必醇乙酸酯 30 30 30 30 氧化鈦 CR-50 40 CR-90 40 二氧化矽 SO-C3 20 莫氏硬度指標 式(X)之左邊之值 2.1 2.1 1.9 - 評 價 财熱性 △E*ab 3.7 3.7 4.1 3.1 判定 X X X Δ 耐光性 △E*ab 1.1 1.1 1.1 2.2 判定 〇 〇 〇 Δ 切割加工性 判定 X X X Δ 適用期 判定 〇 〇 〇 〇 顯影性 判定 〇 〇 〇 〇 147625.doc ·36· 201106097 【ιπί 實施例22 <N 00 〇 \〇 oi 〇 Ο) 〇 〇 〇 〇 實施例21 Μ κη CN 00 〇 CO 寸 <N 〇 00 ο 〇 〇 0 〇 〇 實施例20 (N oo 〇 σ\ 1—^ Ο) 〇 〇 ο 〇 〇 〇 〇 〇 實施例19 <N 00 〇 〇\ 1—^ v〇 <N 〇 rn 〇 〇 〇 〇 實施例18 iTi (N 00 CO 寸 tN 〇 Ο) 〇 〇 〇 〇 實施例17 t-μ U-5 <N 00 〇 r-i v〇 oi 〇 〇 〇 〇 〇 實施例16 ^Τ) 1—^ in <N 00 〇 <N tN 〇 〇 〇 〇 〇 實施例15 CN oo 〇 <N CN 〇 卜 〇 〇 〇 〇 實施例14 <N 00 〇 CN CN CN 〇 00 »— 〇 〇 〇 〇 實施例13 (N 00 〇 (N 〇 CN 〇 〇 ο 〇 〇 〇 〇 〇 實施例12 <N 00 〇 <N 〇 CN 〇 〇 ο 〇 〇 〇 〇 〇 丙烯酸聚合物-2 DPHA o Oh 00 (N 00 乙基卡必醇乙酸酯 D-918 UT771 CR-50-2 R-102 CR-90-2 CR-97 CR-50 CR-90 ΓΊ cL Oh ω |SO-C3 1式(X)之左邊之值 △E*ab △E*ab 丙烯酸聚合物 丙烯酸單體 起始劑 環氧化合物 效 氧化缺 氧化锆 二氧化矽 莫氏硬度指標 财熱性 对光性 切割加工性 適用期 顯影性 辑齧嘀Φ〇Μ»Η傘） -37- 147625.doc 201106097 [表6] 比較例4 比較例5 比較例6 參考例2 調 配 成 分 t 量 丙烯酸聚合物 丙烯酸聚合物-2 15 15 15 15 丙烯酸單體 DPHA 5 5 5 5 起始劑 TPO 2 2 2 2 環氧化合物 828 8 8 8 8 溶劑 乙基卡必醇乙酸酯 30 30 30 30 氧化鈦 CR-50 40 CR-90 40 二氧化矽 SO-C3 20 莫氏硬度指標 式(X)之左邊之值 2.1 2.1 1.9 - if 耐熱性 △E*ab 4.0 4.1 4.5 3.3 判定 X X X Δ 财光性 AE*ab 1.3 1.3 1.3 2.3 判定 〇 〇 〇 Δ 切割加工性 判定 Δ X X 〇 適用期 判定 〇 〇 〇 〇 顯影性 判定 〇 〇 〇 〇 147625.doc 38- 201106097 【!><〕 ss 9CNi4 辑駟The pot life is better, so the pH value measured by the user boiling method of the above inorganic filler (C) is better than ',,,,,,,,,,,,,,,,,,,,, Better yet is 9.0 or less. The above-mentioned boiling method, the following method: heating the solution obtained by adding the above inorganic filler 147625.doc 201106097 (c) 5 g to 100 mL of pure water, boiling it for 5 minutes, and then standing until it reaches 23X. : The boiling treatment liquid was obtained, and then water of the amount of water evaporated by boiling was added to the obtained winter boiling treatment liquid, and the amount of water was changed to 100 mL 'the pH value of the obtained solution was measured. In the above boiling method, specifically, a solution obtained by adding 5 g of the above inorganic filler (C) to 1 mL of pure water is placed in a container having an opening. The solution in the vessel is heated by heating the vessel to cause the solution in the vessel to boil. After boiling, the boiling state was maintained for 5 minutes. Thereafter, the plug body was attached to the opening of the container, and it was allowed to stand until it reached 23 t to obtain a boiling treatment liquid. The plug body was removed from the opening of the container, and water of the amount of water evaporated by boiling was added to the obtained stagnant treatment liquid to make the amount of water 1 〇〇 mL. Install the plug body at the mouth of the container, shake it for a few minutes, and let it stand for 5 minutes. The test solution is thus obtained. The value of 1311 of the obtained measurement solution can be measured in accordance with the operation described in jis z88〇2, 7. The energy gap of the inorganic filler (c) is preferably 2 5 eV or more, 7 ev ^, and the energy band gap is less than 2.5 eVB, and the insulation property of the solder mask is low. When the above band gap is higher than 7 eV, there is a tendency that the solder resist film is liable to yellow when exposed to a high temperature. It is preferable that the inorganic filler (the refractive index at 465 nm is Μ or more, and the inorganic filler (c) is a white filler. In this case, it is possible to obtain a printed wiring board suitable for an L-shaped printed wiring board or the like. A photosensitive composition of a white solder resist film. Further, when the refractive index is Μ or more, high reflection required for a white solder resist film for a substrate on which an LED is mounted can be obtained as 147625.doc 15 201106097 as the above White filled coarse _ recording, zinc oxide 1 whitening list: titanium oxide, oxidation, oxidation, high inhibition of the step: potassium and titanic acid, etc. Among them, titanium, the yellowing of the protection, Therefore, it is preferred that the number average particle diameter of the above-mentioned white filler is preferably in the range of G.01 to 1.0. Preferably, the above inorganic filler (C) is in the range of Μ~0·5 _. In the case of stone-type titanium oxide, it is good. It is rutile-type titanium oxide. When the solder resist film is exposed to high temperature, it is more than 100% by weight of the inorganic filler (c) in the golden red non-yellow photosensitive composition. Preferably, it is 3% by weight or more and 8% by weight or less. Inorganic filler (When the content of bismuth is less than 3 parts by weight, there is a tendency that the solder resist film is liable to yellow when exposed to high temperature. When the content of the inorganic filler (c) exceeds 8 g by weight, there is a case where it is difficult to prepare a suitable coating. In the case of the photosensitive composition of the viscosity of the cloth, the lower limit of the content of the inorganic filler (c) in the photosensitive composition of 1% by weight is preferably % by weight, more preferably 75% by weight. It is preferred that at least the above-mentioned inorganic filler (C) is coated with an alkali metal oxide or an alkali metal hydroxide. In this case, when the solder resist film is exposed to a high temperature, The solder resist film is less likely to be yellowish. The above-mentioned basic metal oxide or alkali metal hydroxide may be used alone or in combination of two or more. As the above-mentioned test metal oxide or metal hydroxide, A metal compound containing magnesium, argon, lanthanum, cerium, lanthanum, cerium, or calcium is exemplified. Since the yellowing of the solder resist film at a high temperature can be further suppressed, the above-mentioned basic gold 147625.doc -16·201106097 is an oxide. Or a metal element of an alkali metal hydroxide It is preferably at least one selected from the group consisting of magnesium 'zirconium, lanthanum, cerium, lanthanum, cerium, and calcium. The inorganic filler (c) is further inhibited by the yellowing of the solder resist film at a high temperature. Preferably, it is coated with a coating material containing zirconia. As the above-mentioned basic metal oxide or basic metal hydroxide, it is preferable to use oxidization error 0 from the above basic metal oxide or basic metal hydroxide. The coated inorganic filler (C) can be obtained, for example, in the following manner: The inorganic filler (c) is dispersed in water or a solution containing water as a main component, and if necessary, a sand mill or a ball mill or the like is used. The inorganic filler (C) is pulverized. Then, the positive value of the slurry is made neutral or inspective, and is acidic as the case may be. Thereafter, a water-soluble salt which is a raw material of the coating material is added to the polymer to coat the surface of the inorganic filler (c). Thereafter, the material is neutralized and the inorganic filler (C) is recovered. The inorganic filler (C) may be dried or dry pulverized over time. Further, in the photosensitive composition of the present invention, in addition to the above inorganic filler (6), carbon _, oxidized sulphur, sulphuric acid, sulphur oxide, zinc oxide, nitriding, nitrogen cutting, nitrogen may be contained as needed. (4) Diamond powder, bismuth citrate, zirconia, talc, barium sulfate, barium titanate, titanium oxide, clay, magnesium carbonate, oxidized town mica, mica powder, sulfuric acid ship, zinc sulfide, emulsified record, titanium nitride Other fillers such as fluorinated and cerium oxide. The above inorganic filler (C) preferably has an acidic portion. In order to improve the speed-up inorganic filler (C), it is preferred to subject the compound to a surface treatment by reacting with a compound which is reactive with the inorganic filler (C). 147625.doc 201106097 The compound which can react with the acidic site of the above-mentioned inorganic filler (c) is exemplified by trimethylolpropane, trimethylolethane, di-trimethylolpropane, and trimethylol a polyol such as propane ethoxylate or pentaerythritol, an alkanolamine such as monoethanolamine I propanolamine, diethanolamine, dipropanolamine, triethanolamine or tripropanolamine; gas decane or alkoxydecane. Since the yellowing of the protective film at a high temperature can be further suppressed, the compound which can react with the acidic portion of the above inorganic filler (c) is preferably a basic compound. In the case of a basic compound, the basicity of the inorganic filler (c) can be further improved. Since the yellowing of the protective film at a high temperature can be further suppressed, the above basic compound is preferably at least one selected from the group consisting of a polyhydric alcohol, an alkanolamine, and an alkoxydecane, and particularly preferably an alkane. Alcoholamine. In the case of alkanolamines, the protective film is extremely resistant to yellowing at high temperatures. As a method of reacting the inorganic filler (C) with a compound which can react with the acidic site of the inorganic filler, the following method can be mentioned: The above compound is placed in a dry pulverizer such as a fluid energy pulverizer or an impact pulverizer. Mixing the inorganic filler with the inorganic filler (c); (2) stirring and mixing the above compound with the dry-pulverized inorganic filler (c) using a high-speed crawler such as a Henschel mixer or a fast mixer. And adding the above compound to the aqueous slurry of the inorganic filler (C) and dropping it. Further, the photosensitive composition of the present invention may contain a pH value of not less than 6.8 or more and η or less, as measured by a boiled method, and may have a pH value measured by a boiling method. 68, or the pH value exceeds the machine filler. (Other components) 147625.doc • 18· 201106097 In order to increase the alkalinity of the above inorganic filler (c), the photosensitive composition preferably contains a compound which can react with the acid-containing site of the inorganic filler (c). As the compound which can react with the acidic portion of the above inorganic filler (C), a compound which can be surface-treated with the inorganic filler (C) and which reacts with the acidic portion of the above inorganic filler (C) is suitably used. The compound which can be reacted with the acidic site of the inorganic filler (C) may be used alone or in combination of two or more. A compound which is reactive with the acidic portion of the above inorganic filler is preferably a test compound. Further, the above-mentioned test compound is more preferably at least one selected from the group consisting of polynonanol, alkoxylamine and alkoxydecane. When the photosensitive composition contains a compound reactive with an acidic portion of the inorganic filler (C), the compound which can react with the acidic portion of the inorganic filler (C) in 100% by weight of the photosensitive composition It is preferable that (M weight: /. or more, 10% by weight or less. When the content of the compound which can react with the inert part of the inorganic filler (C) is within the above preferred range, the film can be further inhibited. The yellowing of the protective film at a high temperature. In order to improve the cutting and securing property of the protective film, the photosensitive composition preferably contains the compound (D) having a cyclic ether skeleton. D), for example, bisphenol S-type epoxy resin, o- | _-------------------------------------------------- Oxygen resin, biphenol type epoxy 榭 day t _ g, tetra lis glyceryl xylenol ethane resin, double singular A type epoxy resin, gas μ bismuth bisphenol oxime type epoxy resin, bisphenol F type Resin, brominated bisphenol A type epoxy pepper ^ 虱树知Phenolic novolac type epoxy resin, A 147625.doc •19· 201106097 Phenolic novolac type epoxy resin, alicyclic epoxy resin, phenolic epoxy resin of bisphenol A, chelate type epoxy resin, B Dialdehyde type epoxy resin, amine group-containing epoxy resin, rubber modified epoxy resin, dicyclopentadiene phenol type epoxy ^ 曰 曰, poly stone oxime modified epoxy resin and ε_ caprolactone The modified epoxy resin may be used alone or in combination of two or more kinds of the compound (D) having a cyclic ether skeleton. The photosensitive composition of the present invention may further contain a cyclic ether skeleton and have no linear chain. The epoxy compound (m). Examples of the epoxy compound (D1) include an epoxidized polyfluorene hydrocarbon, a di(tetra) glycidyl ester, a phthalic acid diglycidyl S resin, and an isocyanuric acid triglycidyl ester. A mixed-type epoxy resin material such as vinegar, etc. As the above two (four), adipic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, etc. are mentioned. The above epoxy compound (D1) may be only One type may be used, or two or more types may be used in combination. "纟" is compared with the case where these compounds are not used. In the case of using these compounds, there is a case where the cutting processability of the protective film is lowered. ^ The jade oxygen compound (D1) is superior to the county governor ^ V ) and has two or more cyclic ether skeletons 0: The annular seam skeleton of the compound (9) having a ring-shaped skeleton is preferably a skeleton. The ring-shaped bone test of the above epoxy compound (D1) (IV) oxygen ring hexagram skeleton. As the epoxy compound having an epoxy ring structure and a shoulder-free skeleton, there are mentioned: 3, 4, and - epoxy rings ":, anthracene ketone, adipic acid bis (3,4-epoxy) Cyclohexylmethyloxyethyl-3,4-epoxycyclohexene, glucosaliphate and bis-epoxide. Commercially available as the epoxy compound, 147 147625.doc -20 201106097 Celloxide 2021P (manufactured by Daicel Co., Ltd.) The compound (D) having a cyclic ether skeleton reacts with a functional group such as a carboxyl group of the polymerizable hydrocarbon polymer (B) to cause the photosensitive composition to be cured. The preferred lower limit of the content of the compound (D) having a cyclic ether skeleton is 0.1 part by weight, more preferably 1 part by weight, and still more preferably 50% by weight based on 100 parts by weight of the polymerizable hydrocarbon polymer (B). More preferably, the upper limit is 30 parts by weight. When the content of the compound (D) having a cyclic ether skeleton is within the above preferred range, the yellowing of the protective film can be further suppressed. Concerning that the solder film is yellowed, the photosensitive composition of the present invention preferably contains an anti- The antioxidant is preferably a Lewis basic portion. The antioxidant is preferably selected from the group consisting of a phenolic antioxidant, a phosphorus antioxidant, and an amine system from the viewpoint of further suppressing yellowing of the protective film. At least one of the group consisting of antioxidants. As a commercial product of the phenolic antioxidant, Irganox 1010 'Irganox 1035 ' Irganox 1076 ' Irganox 1135 ' Irganox 245, Irganox 259, and Irganox 295 (all of the above) Made by Ciba Japan); Adekastab AO-30, Adekastab AO-40, Adekastab AO-50, Adekastab AO-60, Adekastab AO-70, Adekastab AO-80, Adekastab AO-90, and Adekastab AO-330 (above Produced by Adeka); Sumilizer GA-80, Sumilizer MDP-S, Sumilizer BBM-S, Sumilizer GM, Sumilizer GS (F), and Sumilizer GP (all manufactured by Sumitomo Chemical Industries, Ltd.); Hostanox O10, Hostanox 016, Hostanox 147625.doc -21 - 201106097 014, and Hostanox 03 (all manufactured by Clariant); Antage An, Antage W-300, Antage W-400, and Antage W500 (above) Both are manufactured by Kawaguchi Chemical Industry Co., Ltd.; and Seenox 224M, and Seenox 326M (all manufactured by Shipro Kasei Co., Ltd.). Examples of the phosphorus-based antioxidant include cyclohexylphosphine and triphenylphosphine. As a commercial item of the above-mentioned phosphorus-based antioxidant, ADK Stab PEP-4C, ADK Stab PEP-8, ADK Stab PEP-24G, ADK Stab PEP-36, ADK Stab HP-10, ADK Stab 2112, ADK Stab 260, ADK Stab 522A, ADK Stab 1178, ADK Stab 1500, ADK Stab C, ADK Stab 135A, ADK Stab 3010, and ADK Stab TPP (all manufactured by Adeka); Sandostab P-EPQ and Hostanox PAR24 (all of which are Clariant company); and JP-312L, JP-318-0, JPM-308, JPM-313, JPP-613M, JPP-31, JPP-2000PT and JPH-3800 (all of which are manufactured by Chengbei Chemical Industry Co., Ltd.) . Examples of the amine-based antioxidant include triethylamine, dicyandiamide, melamine, ethyldiamine-average three-dimensional, 2,4-diamino-uniform, and 2,4-diamine. -6-nonylphenyl-average three-till, 2,4-diamino-6-diphenylene-average three-till and quaternary ammonium salt derivatives. The photosensitive composition of the present invention may contain a solvent. The dipole moment of the solvent is preferably 1 Debye or more. By using a solvent having a dipole moment of 1 or more, a photosensitive composition excellent in pot life can be provided. The inorganic filler (C) preferably satisfies the following formula (X). In this case, the cutting processability of the protective film can be further improved. 147625.doc -22· 201106097 Mohs hardness of machine filler) x (content of the first inorganic filler (volume%) in the photosensitive composition after hardening/filling)} + {(2nd) No (Mohs hardness of 枓) χ (content (vol%) of the second inorganic filler (10% by volume of the photosensitive composition after hardening))) ·······(Mr. hardness of the η inorganic filler χ (Photosensitive composition after hardening _ 5% by volume of the content of the first inorganic filler (% by volume))}] 4 (X) To further improve the photosensitivity, the sensitization of the present invention The composition preferably contains a photopolymerization initiator. Examples of the photopolymerization initiator include a oxidized oxidized scale, a functionalized methylation, a self-denylated oxadiazole, an imidazole, a benzoin, a benzoin alkyl bond, a quinone, a benzopyrene. , benzophenone, phenelzine, 9-oxosulfanyl, benzoate, acridine, morphine, titanocene, alpha alkyl benzophenone, anthracene, and derivatives thereof. The photopolymerization initiator may be used alone or in combination of two or more. In the case of containing the photopolymerization initiator, the preferred lower limit of the content of the photopolymerization initiator is 1 part by weight based on the total of the polymerizable hydrocarbon monomer (A) and the polymerizable hydrocarbon polymer. The content is preferably 1 part by weight, more preferably 30 parts by weight, more preferably 丨5 by 1 part. When the content of the photopolymerization initiator is within the above preferred range, the photosensitivity of the photosensitive composition can be further improved. Further, the photosensitive composition of the present invention may further contain a coloring agent, a filler, an antifoaming agent, a hardening agent, a hardening accelerator, a releasing agent, a surface treating agent, a flame retardant, a viscosity adjusting agent, a dispersing agent, and a dispersion aid. Agent, surface modifier, plasticizer, antibacterial agent, antifungal agent, leveling agent, stabilizer, coupling agent 'anti-flow 147625.doc -23- 201106097 Hanging agent or phosphor. The photosensitive composition of the present invention can be produced, for example, by uniformly mixing the respective blending components and then mixing them by a three-roll mill. Examples of the light source used for curing the photosensitive composition include an irradiation device that emits an active energy ray such as ultraviolet rays or visible rays. Examples of the light source include an ultrahigh pressure mercury lamp, a deep ultraviolet lamp, a high pressure mercury lamp, a low pressure mercury lamp, a metal oxide lamp, and an excimer laser. These light sources are appropriately selected depending on the light-receiving wavelength of the constituent components of the photosensitive composition. The irradiation energy of light is appropriately selected depending on the desired film thickness or the composition of the photosensitive composition. The irradiation energy of light is usually in the range of 1 〇 3 to 〇〇〇 mj/cm 2 . (LED element) The photosensitive composition of the present invention is suitably used for forming a protective film of an LED element, and is more suitably used for forming a solder resist film. Fig. 1 is a front cross-sectional view, partially broken away, schematically showing a led device including a solder resist film formed using the photosensitive composition of one embodiment of the present invention. In the LED element 1 shown in Fig. 1, a protective film 3 formed of a photosensitive composition is laminated on the upper surface 2a of the substrate 2. The protective film 3 is a pattern film. Therefore, the protective film 3 is not formed in a partial region of the upper surface 2a of the substrate 2. Electrodes 4a, 4b are provided on the upper surface 2a of the substrate 2 where the protective film 3 is not formed. The substrate 2 is preferably a printed wiring board. An LED chip 7 is laminated on the upper surface 3a of the protective film 3. On the substrate 2, an LED wafer 7 is laminated via a protective film 3. Terminals 8a, 8b are provided on the outer periphery of the lower surface 7a 147625.doc -24- 201106097 of the LED chip 7. The terminals 8a, 8b are electrically connected to the electrodes 4a, 4b by solders 9a, 9b. By this electrical connection, power can be supplied to the wafer 7. Hereinafter, the present invention will be clarified by enumerating specific examples and comparative examples of the invention. The invention is not limited to the following examples. The following acrylic polymers 1 to 6 and inorganic fillers were prepared. (Synthesis Example 1) Acrylic Polymer 1 In a flask equipped with a thermometer, a stirrer, a dropping funnel, and a reflux condenser, ethyl carbitol acetate as a solvent and azobisisobutyronitrile as a catalyst were added. The mixture was heated to 80 ° C under a nitrogen atmosphere, and a monomer obtained by mixing methacrylic acid with decyl methacrylate at a molar ratio of 3 〇: 7 Torr was added dropwise over 2 hours. After the addition, the mixture was stirred for 1 hour, and the temperature was raised to i 2 Torr. It is then cooled. Adding a total molar amount of all the monomer units of the obtained resin to a molar ratio of 10 parts of glycidyl acrylate, using tetrabutylammonium bromide as a catalyst, heating at 1 ° C for 30 hours The glycidyl acrylate is subjected to an addition reaction with a carboxyl group. After cooling, it was taken out from the flask to obtain a 5% by weight (nonvolatile matter) of a carboxyl group-containing resin having a solid content of 60 mg KOH/g, a weight average molecular weight of 15,000, and a double bond equivalent of 1 Å. Solution. Hereinafter, this solution is referred to as acrylic polymer 1. (Synthesis Example 2) Acrylic acid polymer 2 In the flask equipped with a thermometer, a stirrer, a dropping funnel, and a reflux condenser, 'addition of ethyl carbitol acetate as a solvent, and azo double heterogeneity as a catalyst The nitrile was heated to 8 ° C under nitrogen atmosphere, and thioglycolic acid, decyl methacrylate and benzyl methacrylate were added dropwise over 2 hours to 3 〇: 147625.doc •25· 201106097 3〇. 40 The molar ratio of the monomer is mixed. After the addition, the temperature is raised to 120t after the heart is given. Thereafter, cooling is performed. Adding the molar ratio of the total molar amount of all the monomer units of the obtained resin to the amount of 1 〇 丙 夂 夂 , , , , , , , , , , 使用 使用 使用 使用 使用 使用 使用 使用 使用 使用 使用 使用 使用 使用 使用 使用Heating under the armpit for 30 hours 'After the reaction of C (tetra) glycidol @ with silk), I7 was taken out from the flask, and the acid value of the solid content was obtained, and the weight average molecular weight was 15, _, double A solution having a bond equivalent of 50% by weight (nonvolatile component) of the resin containing a slow base. Hereinafter, this solution is referred to as acrylic polymer 2. (Synthesis Example 3) Acrylic acid polymer 3 In a flask equipped with a thermometer, a mixer, a dropping funnel, and a reflux condenser, ethyl carbitol acetic acid as a solvent and azo as a catalyst were added. Double isobutyronitrile, heated to a nitrogen atmosphere, and added a mixture of methacrylic acid, methyl methacrylate and methacrylic acid vinegar in 3 hours: 3〇: 3〇: 40 molar ratio body. After the addition, mix for $hour and raise the temperature to 12 〇t. Money' is cooling. (4) The amount of the total molar amount of all the monomer units of the obtained resin is 1 (1) of acrylic acid glycidol vinegar, using the evolved tetrabutylammonium as a catalyst at 1 Torr. The underarm was heated for 30 hours to carry out an addition reaction of glycidyl acrylate with a carboxyl group. After cooling, it was taken out from the flask to obtain 50% by weight (nonvolatile matter) of a resin containing a solid component having an acid value of 6 KOH/g, a weight average molecular weight of 1 Å, and a double bond equivalent of a carboxyl group-containing resin. The solution. Hereinafter, this solution is referred to as acrylic polymer 3. (Synthesis Example 4) Acrylic acid polymer 4 147625.doc • 26·201106097 'Addition of ethyl carbitol acetate as a solvent to a flask equipped with a thermometer, (4) machine, a dropping funnel and a reflux condenser, and The azobisisobutyronitrile as a catalyst was heated to 8 Torr under a nitrogen atmosphere. . The monomer obtained by mixing methacrylic acid, methacrylic acid methacrylate and benzyl methacrylate in a molar ratio of 35 Å 50 was added dropwise over 2 hours. After the addition, stir the mixture and increase the temperature to 12G °C. Thereafter, cooling is performed. Adding the molar ratio of the total molar amount of all the monomer units of the obtained resin to the amount of 1 () of the acrylic acid glycidol S is intended to use the desertified tetrabutyl money as the touch $, under the 1st generation Heating for 30 hours ' & Acrylic glycidol vinegar and the slow base for the addition reaction. After cooling, it was taken out from the flask to obtain 50% by weight of a carboxyl group-containing resin having an acid value of 15 as an OH/g weight average molecular weight of 14 and a double bond equivalent of 1 Å (nonvolatile matter). )The solution. Hereinafter, this solution is referred to as acrylic polymer 4. (Synthesis Example 5) Acrylic Polymer 5 In a flask equipped with a thermometer, a stirrer, a dropping funnel, and a reflux condenser, ethyl carbitol acetate as a solvent and azobisisobutyronitrile as a catalyst were added. Heating to 8 〇〇c under a nitrogen atmosphere, and adding a monomer obtained by mixing methacrylic acid, decyl methacrylate and benzyl methacrylate with a molar ratio of 85:5:10 in 2 hours. . After the dropwise addition, the mixture was stirred for 1 hour, and the /m degree was raised to 120 C. Thereafter, cooling is performed. The amount of the molar ratio of the total molar amount of all the monomer units of the obtained resin was changed to 1 Torr of glycidyl acrylate, using tetrabutylammonium bromide as a catalyst, at 1 Torr. <T is heated for 30 hours to carry out an addition reaction of glycidyl acrylate with a carboxyl group. After cooling, 'take out from the flask' to obtain a carboxyl group-containing resin having a solid content of 220 mg 147625.doc -27·201106097 KOH/g, a weight average molecular weight of 17 Å, and a double bond equivalent of 1 Å. A solution of 50% by weight (non-volatile). Hereinafter, this solution is referred to as acrylic polymer 5. (Synthesis Example 6) Acrylic Polymer 6 'Addition of ethyl carbitol acetate as a solvent and azobisisobutyronitrile as a catalyst in a flask equipped with a thermometer, a stirrer, a dropping funnel, and a reflux condenser , heated to 8 〇〇c under nitrogen atmosphere, and added a mixture of methacrylic acid, methyl methacrylate and benzyl methacrylate at a molar ratio of 22.5 ··3 7.5.40 in 2 hours. body. After the dropwise addition, the mixture was stirred for 1 hour, and the temperature was raised to 12 (TC. Thereafter, cooling was carried out. The molar ratio of the molar amount of the total molar amount of all the monomer units to the obtained resin was changed to 25 by the amount of acrylic glycidol. The product was heated at 1 ° C for 30 hours using a brominated tetrazide as a catalyst to carry out an addition reaction of glycidyl acrylate with a carboxyl group. After cooling, it was taken out from the flask to obtain an acid value containing a solid component. It is a solution of 60 mg KOH/g, a weight average molecular weight of 18 Å, a double bond equivalent of 4, and 50% by weight of a carboxyl group-containing resin (nonvolatile content). Item 6. (Inorganic Filler (C)) The details of the inorganic fillers 1 to 11 are shown in Table 1 below. 147625.doc -28- 201106097 η ^ 卜卜卜r- 卜卜卜卜 00 -Ο CN (N inch CN inch · (N (N inch N (N - N inch CN Bu CN Tf* ^Τ) CN Μ i alkanolamine tri- thiol-propyl trimethylolpropane trihydroxyl Propane trimethylolpropane 1 1 coffee 1 1 I with or without organic processing discs surface treated metal species Al ' Si ' Zr Al ' Zr 1 < A Bu Si Al ' Zr Al ' Si 1 1 1 Refractive index 465 nm (N (N (N (N (N (N (N (N (N (N (N (N (N (N (N (N (N (N (N (N (N (N (N N N N N N N N N N N N N N N N N N N N N N N N N N N N N N N N N N N N N N N N N N N N N N N N N N N N N N N N N N Rn 〇rn Ο rS 〇cn 〇rn 〇rn σ\ boiling method pH S 5 Ο 00 Ο 1> inch 〇V£> v〇(N ο ON inch · 1 1 particles have a majority of acidic sites with particles Most acidic sites have a plurality of acidic sites. 1 corresponds to an acidic site. Compound i corresponds to an acidic site. The compound corresponds to a basic compound. 1 corresponds to a compound having an acidic site. The chemical stone source industry, the Ishihara industry, Tayca Ishihara, Ishihara. Industry Ishihara Industry Ishihara Industry Nippon Talc 曰本稀稀化学化学 Admatechs D-918 UT771 CR-50-2 R-102 CR-90-2 CR-97 CR-50 CR-90 rn pi CL, W S0-C3 CN m inch 〇〇〇 〇〇〇 Ο τ τ τ ^ ^ ^ ^ 矽 矽 矽 矽 矽 矽 矽 矽 矽 矽 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 Inorganic filler. Surface filling of inorganic filler, In the case of metal species, nitrogen oxide or oxidation can be used. When the metal species is Si, the oxide oxide can be used. When the metal species is Zr, the oxidation error can be used. _, inorganic fillers 1 to 5 are surface-treated with an organic material. (Specific gravity of other components and components) In the following examples, comparative examples and reference examples, the components shown in Table 2 are suitably used. In Table 2, The proportion of each component - and expressed. 147625.doc 30- 201106097 [ <Νΐ L—specific gravity 1 inch · r·^ inch · 1—^ inch · inch · 1-Η CN (N (Ν <N p 〇MMA/MAA/GMA Polymer MMA/BzMA/MAA/GMA Polymer Mw is 100,000 Acid value is 20 or less Acid value is 20 or less Double bond equivalent is 1, 〇〇〇 or more • Μ «韬会ss |· 螭敦§ <〇12 ^ Μ u ^ nj α -Μ ϊί 容Ο CO v0 璨 s®!· 絮 § Φ ° 儿童 VII V jj t 〇乂 ^ ^ 今 Today UU (3⁄4 hj α measured by LC-MS The area of MS fragment peak $500 is 30% or less. The Mw of 700 or more is determined by GPC. The dipole moment of the polymerizable hydrocarbon monomer is 1 Debye or more. The dipole moment is 0.38. Debye Acrylic Polymer-1 Acrylic Polymer-2 Acrylic Polymerization -3 Acrylic Polymer-4 Acrylic Polymer-5 Acrylic Polymer-6 Dipentaerythritol Hexaacrylate (DPHA) Trimethylolpropane Triacrylate Lipentaerythritol Triacrylate Dipentaerythritol Tetraacrylate << C/5 .Ξ S3 Ρύ iJtn 卜 i cd <* 旮衾 S made Celloxide 2021P (manufactured by Daicel) 3,4-epoxycyclohexylcarboxylic acid (3·, 4'-epoxycyclohexyl) methyl ester << ^ 谢Ψ Ψmw\ Μ S S ft ' iW $s if 5 洛O粼〇Id Ethyl carbitol acetate phthalic acid acrylic acid polymer 1 -1 Acrylic monomer epoxy compound solvent -31 - 147625.doc 201106097 (Example 1) 15 parts by weight of acrylic polymer], 5 parts by weight of DPHa (diquaternary tetradecyl hexaacrylate), 40 parts by weight of D_918 (rutile-type oxidized chin, manufactured by 堺Chemical Co., Ltd.) 2 parts by weight of a photopolymerization initiator (τρ〇, photoradical generator, manufactured by Siber Hegner, Japan) 8 parts by weight of 828 (bisphenol A type epoxy resin, manufactured by Japan Epoxy Resins Co., Ltd.), and Ethyl carbitol acetate was added in a portion by weight, and the mixture was mixed by a mixer (Litaro SP-500, manufactured by Thinky Co., Ltd.) for 3 minutes, and then mixed by a three-roller to obtain a mixture. Thereafter, the obtained mixed product was defoamed for 3 minutes using SP-500, whereby a resist material as a photosensitive composition was obtained. (Examples 2 to 47, Comparative Examples 1 to 8 and Reference Examples 1 and 2) In the same manner as in Example 1, except that the type and amount of the materials to be used were changed to those shown in Tables 3 to 9 below. Obtain a resist material. (Evaluation) (1) Preparation of measurement sample A substrate of 80 mm x 90 mm and a thickness of 0.8 mmiFR_4 was prepared. On the substrate, the resist material was printed in a unitary pattern by a screen printing method using a polyester oblique cut plate of i 〇 〇 mesh. After printing, at 80. The inside of the oven was dried for 20 minutes to form a layer of a resist material on the substrate. Then, the resist material layer is irradiated for 4 seconds at a wavelength of 365 by using an ultraviolet ray irradiation device with an ultraviolet ray irradiation device so that the irradiation energy is 4 〇0 mJ/cm 2 and ultraviolet illuminance at 100 mW/cm 2 . Nmi ultraviolet light. Thereafter, in order to remove the resist material layer of the unexposed portion to form a pattern, the resist material layer is immersed in a 1% by weight aqueous solution of sodium carbonate, and developed to form on the substrate 147625.doc •32-201106097蒦 蒦 film. Thereafter, it was heated in a case of 150 ° C for 1 hour to post-harden the protective film, thereby obtaining a protective flaw as a measurement sample. The thickness of the resulting protective film was 20 μm. (2) Heat resistance The measurement sample was placed in a heating oven at 270. (: heating for 5 minutes. Using a color and color difference meter (manufactured by Konica Minolta Co., Ltd., CR-400), measuring the L* ' a *, b * ^ of the heat-treated s-valid sample, and measuring the evaluation after heat treatment ΔE*ab was obtained from the two measured values of L*, a*, and b* of the sample. The Δ of the evaluation sample after the heat treatment was evaluated as "〇〇" by the 讣 of 2 or less. In the case of 3 or less, it is evaluated as "〇", and when it exceeds 3 and is 3.5 or less, it is evaluated as "△", and when it exceeds 35, it is evaluated as "x", and the results are shown in Tables 3 to 9 below. 3) Light resistance Using a uv irradiator, the measurement sample is irradiated with light of a wavelength of 365 nm in such a manner that the irradiation energy is 1 〇〇 j/cm 2 . Using a color-color difference meter (manufactured by Konica Minolta Co., Ltd., CR-400), a *, b*. Further, the measurement results are obtained by measuring the L*, a*, b of the evaluation sample after the L*UV irradiation of the evaluation sample before the UV irradiation by the two measured values. After the AE*abs of the evaluation sample, the following feelings are as follows: "4" is "〇〇", and it is exceeded and the case of 2 or less is evaluated as "〇", which exceeds "2" 3 or less is evaluated as "△", and when it exceeds 3, it is evaluated as "x". The results are shown in the following Tables 3 to 9. (4) Cutting workability The above-mentioned (1) was produced using a shearing machine. The measurement sample (protective film) was subjected to 147625.doc •33-201106097, and then heated at 270 C for 5 minutes. The cracks and the defect state of the edge of the sample after heating were visually confirmed. The cutting was judged by the evaluation criteria. [Processing property. [Evaluation criteria for cutting workability] 〇: No cracks or defects were observed by visual observation. Δ. Partial cracks or defects were visually observed in the cutting portion. X. Cracks or defects were confirmed by visually observing the entire range of the cutting portion ( 5) Applicable period V-type viscometer is used to measure the viscosity of the newly formed resist material and the resist material placed in the future (25. 〇 'determine the change ratio of the point. According to the change ratio', the following evaluation criteria are applied. [Evaluation criteria for the pot life] 〇: The change ratio is less than 1.1 △: The change ratio is 1.1 or more, and the J 5 x is not changed: the change ratio is 1.5 or more. (6) Developability to visually confirm the development pattern of the sample. With the following evaluation basis [Determination of developability] [Evaluation criteria for developability] 〇: The pattern x was visually confirmed: The results were not visually observed. The results are shown in Tables 3 to 9 below. 147625.doc -34·201106097 Example 11 yrt (N 00 m 〇〇〇CN 〇00 〇 < 〇 实施 Example 10 (N oo 〇 rn <N 〇 00 〇 〇 〇 X 〇 实施 Example 9 to ^Τ) <N oo 〇 Ο) 00 〇 〇 as ο 〇 〇 < 〇 实施 Example 8 yrt (N oo 〇 Ο) ON CN 〇 r—Ν 〇 < 〇 实施 Example 7 ITi ί—H CS oo rn €N 〇 〇\ 〇 < 〇 实施 Example 6 CN 00 〇 (N 00 01 〇 inch · 〇 < 〇 实施 Example 5 r-^ (N oo 〇 <N inch CN 〇 CN 〇 < 〇 实施 Example 4 CS 00 〇 <N CN 〇 in 〇 < 〇 实施 Example 3 r~^ tN oo 〇 (N (N 〇 VO 〇 < 〇 实施 Example 2 <N oo 〇 CN 〇 CN 〇 〇 ON ο 〇 〇 < 〇 实施 Example 1 κη T—H CN 00 〇 <N OS 〇 〇 On Ο 〇 〇 < 〇〇Acrylic Polymer-1 DPHA o Oh H 00 CN 00 Ethyl carbitol acetate D-918 i UT771 CR-50-2 R-102 CR-90-2 CR-97 CR-50 CR- 90 ΓΟ CU ω SO-C3 The value of the left side of the formula (X) △E*ab △E*ab Acrylic polymer Acrylic monomer Starting agent Epoxy compound fry 1 Oxidation oxidized erbium dioxide Mohs hardness index for heat Light-resistant cutting processability developable period 驿® 哒Φ〇Ν® Η umbrella) -35- 147625.doc 201106097 [Table 4] Comparative Example 1 Comparative Example 2 Comparative Example 3 Reference Example 1 Weight-adjusted component acrylic polymer Acrylic polymer-1 15 15 15 15 Acrylic monomer DPHA 5 5 5 5 Initiator ΤΡΟ 2 2 2 2 Epoxy compound 828 8 8 8 8 Solvent ethyl carbitol acetate 30 30 30 30 Titanium oxide CR- 50 40 CR-90 40 二2 SO-C3 20 Mohs hardness index (X) on the left side 2.1 2.1 1.9 - Evaluation of the heat △E*ab 3.7 3.7 4.1 3.1 Determination XXX Δ Light fastness △ E*ab 1.1 1.1 1.1 2.2 Determination of 〇〇〇Δ Cutting processability judgment XXX Δ Applicable period judgment 〇〇〇〇 developability Judgment 〇 〇 〇 147 147625.doc · 36· 201106097 [ιπί Example 22 <N 00 〇 \〇 oi 〇 Ο) 〇 〇 〇 实施 Example 21 Μ κη CN 00 〇 CO inch <N 〇 00 ο 〇 〇 0 〇 实施 Example 20 (N oo 〇 σ\ 1—^ Ο) 〇 〇 ο 〇 〇 〇 〇 实施 Example 19 <N 00 〇 〇\ 1—^ v〇 <N 〇 rn 〇 〇 〇 实施 Example 18 iTi (N 00 CO inch tN 〇 Ο) 〇 〇 〇 实施 Example 17 t-μ U-5 <N 00 〇 r-i v〇 oi 〇 〇 〇 〇 实施 Example 16 ^Τ) 1—^ in <N 00 〇 <N tN 〇 〇 〇 〇 实施 Example 15 CN oo 〇 <N CN 〇 卜 〇 〇 〇 实施 Example 14 <N 00 〇 CN CN CN 〇 00 » - 〇 〇 〇 实施 Example 13 (N 00 〇 (N 〇 CN 〇 〇 ο 〇 〇 〇 〇 实施 Example 12 <N 00 〇 <N 〇CN 〇〇ο 〇〇〇〇〇Acrylic polymer-2 DPHA o Oh 00 (N 00 ethyl carbitol acetate D-918 UT771 CR-50-2 R-102 CR-90-2 CR-97 CR-50 CR-90 ΓΊ cL Oh ω |SO-C3 1 The value of the left side of formula (X) △E*ab △E*ab Acrylic polymer acrylic acid monomer initiator epoxide oxidative hypoxia Zirconium dioxide dioxide Mohs hardness index Fibrillation resistance to light cutting processability Applicability development mark 嘀Φ〇Μ»Η umbrella) -37- 147625.doc 201106097 [Table 6] Comparative Example 4 Comparative Example 5 Comparative Example 6 Reference Example 2 Formulation component t Amount Acrylic polymer Acrylic polymer-2 15 15 15 15 Acrylic monomer DPHA 5 5 5 5 Initiator TPO 2 2 2 2 Epoxy compound 828 8 8 8 8 Solvent ethyl carbitol Acetate 30 30 30 30 Titanium oxide CR-50 40 CR-90 40 Cerium oxide SO-C3 20 Mohs hardness index (X) to the left of the value 2.1 2.1 1.9 - if heat resistance △ E*ab 4.0 4.1 4.5 3.3 Judgment XXX Δ Visibility AE*ab 1.3 1.3 1.3 2.3 Determination 〇〇〇 Δ Cutting processability judgment Δ XX 〇 Applicable period judgment〇〇 〇 显影 developability judgment 〇 〇 〇 147 147625.doc 38- 201106097 [!><〕 ss 9CNi4

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X ^f# wl·# Ϊ iiHnff# 尽 if- 147625.doc -40- 201106097 【6ί 實施例47 «/> (Ν 00 ο 〇\ 〇 〇 Ο) 〇 〇 〇 X 〇 實施例46 «η (Ν 00 S ο 〇〇 〇 〇 〇 〇 〇 〇 〇 實施例45 in Vi (Ν 00 2 ο 口 卜 〇 〇 <> 〇 〇 〇 〇 〇 實施例44 V» vr> (Ν 00 5 ο in 〇 〇 »η 〇 〇 〇 〇 〇 實施例43 VJ 〆 (Ν -Η rr •η ο (Ν rj- w> Γ^' 〇 (Ν 〇 X 〇 〇 實施例42 SO ν〇 fS m r»» (Ν 〇 〇 οο 〇 〇 X 〇 〇 實施例41 •D «Λ fS 00 ο σ\ 〇 〇 ΟΝ 〇 〇 <1 〇 〇 實施例40 <Ν 00 S ο ο (Ν 〇 〇 00 ο 〇 〇 〇 〇 χ(溶解） 實施例39 (Ν 00 ο 〇\ 〇 〇 00 ο 〇 〇 〇 〇 x(不溶解） 實施例38 «η fS 00 ο η 〇 〇 〇\ ο 〇 Ο <3 〇 〇 實施例37 s (Ν 00 ο (Ν <Ν 口 〇 (Ν 〇 X 〇 〇 實施例36 iS 00 s ο ΟΝ (Ν 〇 〇 X 〇 〇 丙烯酸聚合物·2 丙烯酸聚合物-3 丙烯酸聚合物·4 丙烯酸聚合物-5 丙烯酸聚合物-6 DPHA Ο α. 00 <Ν 00 Irganox 1010 雄 0 »1 三環己基膦 乙基卡必醇乙酸酯 ί4 &* D-918 式(X)之左邊之值 △E*ab △E*ab W 丙烯酸 聚合物 _i 丙烯酸單體 起始劑 環氧化合物 抗氧化劑 1 氧化鈦 莫氏硬度指標 耐熱性 耐光性 切割加工性 適用期 顯影性 147625.doc •41 · 201106097 〃不含無機填充料之參考例1之感光性組合物之情形相 較 3有上述藉由煮沸法所測定之pH值為6.8以上、i j 以下之鹼性無機填充料的實施例1〜10之感光性組合物幾乎 未黃變，耐熱性良好。進而可知，於含有由表丨所示之有 機材料進行表面處理之無機填充料的實施例1〜5之感光性 組〇物之情形時，可進一步改善黃變。並且可知，於含有 表面處理時使用鹼性烷醇胺之無機填充料的實施例1之感 光性組合物之情形時，可進一步改善黃變。 可知’含有上述藉由煮沸法所測定之pH值未達6 8之酸 性無機填充料的比較例1〜3之感光性組合物之情形較參考 例1之感光性組合物之情形更易黃變。 進而可知’實施例i丨〜47之感光性組合物中，保護膜亦 幾乎未黃變，财熱性良好。 【圖式簡單說明】 圖1係示意地表示包括使用本發明之一實施形態之感光 性組合物而形成之保護膜之LED元件的部分切口正面剖面 圖0 【主要元件符號說明】 1 LED元件 2 基板 2a 上表面 3 保護膜 3a 上表面 4a、4b 電極 147625.doc •42· 201106097 7 7a 8a、8b 9a、9b LED晶片 下表面 端子 焊錫 147625.doc -43 -X ^f# wl·# Ϊ iiHnff# Do as if - 147625.doc -40- 201106097 [6ί Example 47 «/> (Ν 00 ο 〇 〇〇Ο 〇〇Ο) 〇〇〇X 〇 Example 46 «η (Ν 00 S ο 〇〇〇〇〇〇〇〇〇 Example 45 in Vi (Ν 00 2 ο 口卜〇〇<> 〇〇〇〇〇Example 44 V» vr> (Ν 00 5 ο in 〇〇 »η 〇〇〇〇〇Example 43 VJ 〆(Ν -Η rr •η ο (Ν rj- w> Γ^' 〇(Ν 〇X 〇〇Example 42 SO ν〇fS mr»» (Ν 〇〇 Οο 〇〇X 〇〇Example 41 •D «Λ fS 00 ο σ\ 〇〇ΟΝ 〇〇<1 〇〇Example 40 <Ν 00 S ο ο (Ν 〇〇00 ο 〇〇〇〇χ ( Dissolution) Example 39 (Ν 00 ο 〇 〇〇 00 ο 〇〇〇〇 x (insoluble) Example 38 «η fS 00 ο η 〇〇〇 ο 〇Ο 〇Ο <3 〇〇 Example 37 s ( Ν 00 ο (Ν <Ν口〇(Ν 〇〇X 〇〇Example 36 iS 00 s ο ΟΝ (Ν 〇 〇X 〇〇Acrylic polymer·2 Acrylic polymer-3 Acrylic polymer·4 Acrylic polymer-5 Acrylic polymer-6 DPHA Ο α. 00 <Ν 00 Irganox 1010 Male 0 »1 Tricyclohexylphosphine ethyl Carbitol acetate ί4 &* D-918 The value of the left side of the formula (X) △E*ab △E*ab W Acrylic polymer _i Acrylic monomer starter Epoxy compound antioxidant 1 Titanium oxide Hardness index heat resistance light resistance cutting workability pot life developability 147625.doc •41 · 201106097 情形The photosensitive composition of Reference Example 1 containing no inorganic filler is compared with the above by the boiling method. The photosensitive compositions of Examples 1 to 10 having a pH of 6.8 or more and an ij or less basic inorganic filler were hardly yellowed, and the heat resistance was good. Further, it is understood that the yellowing can be further improved in the case of the photosensitive composition of Examples 1 to 5 containing the inorganic filler surface-treated by the organic material shown in Table 。. Further, it is understood that the yellowing can be further improved in the case of the photosensitive composition of Example 1 which uses an inorganic filler of a basic alkanolamine in the surface treatment. It is understood that the photosensitive compositions of Comparative Examples 1 to 3 containing the above-mentioned acidic inorganic filler having a pH of not more than 68 as measured by the boiling method are more susceptible to yellowing than the photosensitive composition of Reference Example 1. Further, it was found that in the photosensitive compositions of Examples i to 47, the protective film was hardly yellowed, and the heat retention property was good. BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a partially cutaway front cross-sectional view of an LED element including a protective film formed using a photosensitive composition according to an embodiment of the present invention. [Main element symbol description] 1 LED element 2 Substrate 2a Upper surface 3 Protective film 3a Upper surface 4a, 4b Electrode 147625.doc • 42· 201106097 7 7a 8a, 8b 9a, 9b LED wafer lower surface terminal solder 147625.doc -43 -

Claims (1)

201106097 七、申請專利範圍： 1. 一種感光性組合物，盆合古 八3有聚合性烴單體及聚合性烴聚 合物中之至少一者與無機填充料，並且 上述無機填充料係如下者：對將該無機填充料5 g加至 屯X 100 mL中而獲知之溶液進行加熱，使其沸騰5分鐘 二’靜置至達到2rc為止’獲得彿騰處理液，繼而於所 得之彿騰處理液中加人因彿騰而蒸發之水量之水，使水 量成為100紅，測定所得溶液之PH值時，pH值呈6.8以 上、11以下之值。 2.如請求項！之感光性組合物，其中上述無機填充料之能 帶隙為2.5 eV以上、7 eV以下。 3·如凊求項1或2之感光性組合物，其中上述無機填充料之 465 nm下之折射率為h8以上，且上述無機填充料為白色 填充料。 4·如請求項3之感光性組合物，其中上述無機填充料為金 紅石型氧化欽。 5. 如請求項1或2之感光性組合物，其中上述無機填充料之 含量為3重量％以上' 80重量％以下。 6. 如請求項1或2之感光性組合物，其中至少丨種之上述無 機填充料係由鹼性金屬氧化物或鹼性金屬氫氧化物所被 覆。 - 7_如請求項6之感光性組合物，其中構成鹼性金屬氧化物 或鹼性金屬氫氧化物之金屬元素為選自由鎂、鍅、飾、 鎖、錄、鋇及辦所組成之群中之至少1種。 147625.doc 201106097 8. 如請求項6之感光性組合物，其中上述無機填充料係由 含有氧化錄之被覆材料所被覆。 9. 如請求項1或2之感光性組合物，其進而含有可與上述無 機填充料之酸性部位反應之化合物。 10. 如請求項9之感光性組合物，其中可與上述無機填充料 之酸性部位反應之化合物為鹼性化合物。 11. 如請求項1 〇之感光性組合物，其中上述鹼性化合物為選 自由多元醇、烷醇胺及烷氧基矽烷所組成之群中之至少 1種。 12. 如請求項1或2之感光性組合物，其中上述無機填充料係 由可與該無機填充料之酸性部位反應之化合物進行表面 處理。 13. 如請求項12之感光性組合物，其中可與上述無機填充料 之酸性部位反應之化合物為鹼性化合物。 14. 如請求項13之感光性組合物，其中上述鹼性化合物為選 自由多元醇、烷醇胺及烷氧基矽烷所組成之群中之至少 1種。 15. 如請求項1或2之感光性組合物，其中上述聚合性烴單體 具有2個以上聚合性不飽和基，且 於乙腈：水=1 : 1(體積比）溶液中，利用附質譜分析之 液相層析法（LC/MS)測定上述聚合性烴單體時，質姚八 析之碎片峰為500以下之成分所構成之波峰面積為ϋ 峰面積之30%以上。 16. 如請求項丨或2之感光性組合物，其中上述聚合性烴單體 147625.doc 201106097 17. 18. 19. 20. 21. 22. 23. 其進而含有上述具有環 之重量平均分子量為700以下。 如請求項1或2之感光性組合物 狀醚骨架之化合物，且 上述具有環 5 0重量份以 相對於上述聚合性烴聚合物1〇〇重量份 狀醚骨架之化合物之含量為〇1重量份以上 下0 如請求項17之感光性組合物，其中上述具有環狀醚骨架 之化合物為具有環狀醚骨架且不具有直鏈醚骨架之環氣 化合物。 如請求項17之感光性組合物，其中上述環狀醚骨架為環 氧環己烷骨架。 ^ 如喷求項1或2之感光性組合物，其進而含有具有路易斯 驗性部位之抗氧化劑。 如請求項20之感光性組合物，其中上述抗氧化劑為選自 由酚系抗氧化劑、磷系抗氧化劑及胺系抗氧化劑所組成 之群中之至少1種。 如請求項1或2之感光性組合物，其中上述聚合性烴單體 及上述聚合性烴聚合物中之至少一者含有丨個以上聚合 性不飽和基及2個以上敌基，並且 作為上述聚合性烴單體及上述聚合性烴聚合物之整 體，重量平均分子量為5,000〜50,000，固體成分酸值為 30〜150 mg KOH/g，且雙鍵當量為 50〜2,〇〇〇 g/eq。 如請求項1或2之感光性組合物，其中於上述聚合性烴單 體及上述聚合性烴聚合物之合計100重量％中，上述聚合 147625.doc 201106097 性煙單體之含量為5重量％以上、5〇重量％以下。 24.如請求項！或2之感光性組合物，其中於上述聚合性煙聚 «物100重1%中，具有醇性羥基之聚合性烴單體之含量 為1 5重量。/。以下。 25·如請求項】或2之感光性組合物，其中上述無機填充料滿 足下述式（X): [{(第1無機填充料之莫氏硬度）x(硬化後之感光性組合 物100體積/。中之第！無機填充料之含量（體積％))}+{(第 2無機填充料之莫氏硬度）x(硬化後之感光性組合物⑽體 積％中之第2無機填充料之含量（體積％))}+…·{(第11無 機填充料之莫氏硬度）x(硬化後之感光性組合物1〇〇體積 %中之第η無機填充料之含量（體積％))}]$ 4 ......(χ)。 26. 如请求項1或2之感光性組合物，其進而含有溶劑，且 上述洛劑之偶極矩為1 Debye以上。 27. —種防焊組合物，其係如請求項丄至26中任一項之感光 性組合物。 147625.doc201106097 VII. Patent application scope: 1. A photosensitive composition comprising at least one of a polymerizable hydrocarbon monomer and a polymerizable hydrocarbon polymer and an inorganic filler, and the inorganic filler is as follows : The solution obtained by adding 5 g of the inorganic filler to 屯X 100 mL was heated and allowed to boil for 5 minutes, and then allowed to stand until 2 rc was reached to obtain the Fo Teng treatment liquid, and then the obtained Fo Teng treatment was carried out. In the liquid, the amount of water evaporated by the human beings is increased to 100 red. When the pH of the obtained solution is measured, the pH is 6.8 or more and 11 or less. 2. As requested! In the photosensitive composition, the inorganic filler has an energy band gap of 2.5 eV or more and 7 eV or less. 3. The photosensitive composition according to claim 1 or 2, wherein the inorganic filler has a refractive index at 465 nm of at least h8, and the inorganic filler is a white filler. 4. The photosensitive composition of claim 3, wherein the inorganic filler is rutile-type oxidized. 5. The photosensitive composition according to claim 1 or 2, wherein the content of the inorganic filler is 3% by weight or more and <80% by weight or less. 6. The photosensitive composition of claim 1 or 2, wherein at least one of the above inorganic fillers is coated with an alkali metal oxide or an alkali metal hydroxide. The photosensitive composition of claim 6, wherein the metal element constituting the basic metal oxide or the alkali metal hydroxide is selected from the group consisting of magnesium, strontium, decoration, lock, record, sputum, and office. At least one of them. 8. The photosensitive composition of claim 6, wherein the inorganic filler is coated with a coating material containing an oxide record. 9. The photosensitive composition of claim 1 or 2, which further comprises a compound which is reactive with the acidic sites of the above inorganic filler. 10. The photosensitive composition of claim 9, wherein the compound reactive with the acidic portion of the inorganic filler is a basic compound. 11. The photosensitive composition of claim 1, wherein the basic compound is at least one selected from the group consisting of a polyhydric alcohol, an alkanolamine, and an alkoxydecane. 12. The photosensitive composition of claim 1 or 2, wherein the inorganic filler is surface-treated with a compound reactive with an acidic portion of the inorganic filler. 13. The photosensitive composition of claim 12, wherein the compound reactive with the acidic portion of the inorganic filler is a basic compound. 14. The photosensitive composition of claim 13, wherein the basic compound is at least one selected from the group consisting of a polyhydric alcohol, an alkanolamine, and an alkoxydecane. 15. The photosensitive composition of claim 1 or 2, wherein the polymerizable hydrocarbon monomer has two or more polymerizable unsaturated groups, and is used in an acetonitrile:water=1:1 (volume ratio) solution. When the polymerizable hydrocarbon monomer was measured by liquid chromatography (LC/MS) for analysis, the peak area of the component having a fragment peak of 500 or less was 30% or more of the peak area. 16. The photosensitive composition of claim 2 or 2, wherein the above polymerizable hydrocarbon monomer is 147625.doc 201106097 17. 18. 19. 20. 21. 22. 23. Further comprising the above weight average molecular weight having a ring is 700 or less. The compound of the photosensitive composition ether skeleton of claim 1 or 2, wherein the content of the compound having 50 parts by weight of the ring and the weight of the ether skeleton of the polymerizable hydrocarbon polymer is 〇1 by weight. The photosensitive composition of claim 17, wherein the compound having a cyclic ether skeleton is a cyclic gas compound having a cyclic ether skeleton and having no linear ether skeleton. The photosensitive composition of claim 17, wherein the cyclic ether skeleton is an epoxycyclohexane skeleton. ^ A photosensitive composition according to claim 1 or 2 which further contains an antioxidant having a Lewis moiety. The photosensitive composition according to claim 20, wherein the antioxidant is at least one selected from the group consisting of a phenolic antioxidant, a phosphorus antioxidant, and an amine antioxidant. The photosensitive composition of claim 1 or 2, wherein at least one of the polymerizable hydrocarbon monomer and the polymerizable hydrocarbon polymer contains one or more polymerizable unsaturated groups and two or more enemy groups, and The polymerizable hydrocarbon monomer and the above polymerizable hydrocarbon polymer as a whole have a weight average molecular weight of 5,000 to 50,000, a solid content acid value of 30 to 150 mg KOH/g, and a double bond equivalent of 50 to 2, 〇〇〇g/ Eq. The photosensitive composition of claim 1 or 2, wherein the content of the polymerization 147625.doc 201106097 soot monomer is 5% by weight in 100% by weight of the total of the polymerizable hydrocarbon monomer and the polymerizable hydrocarbon polymer. Above, 5% by weight or less. 24. As requested! Or a photosensitive composition of 2, wherein the content of the polymerizable hydrocarbon monomer having an alcoholic hydroxyl group is 15% by weight in 1% by weight of the polymerizable tobacco. /. the following. The photosensitive composition according to claim 2 or 2, wherein the inorganic filler satisfies the following formula (X): [{(Mohs hardness of the first inorganic filler) x (photosensitive composition 100 after curing) Volume /. In the content of the inorganic filler (vol%))}+{(Mohs hardness of the second inorganic filler) x (the second inorganic filler in the photosensitive composition (10)% by volume after curing Content (% by volume))}+...·{(Mohs hardness of the 11th inorganic filler) x (content (% by volume) of the η inorganic filler in 1% by volume of the photosensitive composition after curing )}]$ 4 ......(χ). 26. The photosensitive composition according to claim 1 or 2, which further contains a solvent, and wherein the above-mentioned agent has a dipole moment of 1 Debye or more. A solder resist composition according to any one of claims 18 to 26. 147625.doc
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