TW201139469A - Curable resin composition and printed wiring board using the same - Google Patents

Curable resin composition and printed wiring board using the same Download PDF

Info

Publication number
TW201139469A
TW201139469A TW99145522A TW99145522A TW201139469A TW 201139469 A TW201139469 A TW 201139469A TW 99145522 A TW99145522 A TW 99145522A TW 99145522 A TW99145522 A TW 99145522A TW 201139469 A TW201139469 A TW 201139469A
Authority
TW
Taiwan
Prior art keywords
group
resin composition
curable resin
meth
compound
Prior art date
Application number
TW99145522A
Other languages
Chinese (zh)
Other versions
TWI510505B (en
Inventor
Masahiro Tsuchiya
Akira Kitamura
Keita Harashima
Original Assignee
Tamura Seisakusho Kk
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
Application filed by Tamura Seisakusho Kk filed Critical Tamura Seisakusho Kk
Publication of TW201139469A publication Critical patent/TW201139469A/en
Application granted granted Critical
Publication of TWI510505B publication Critical patent/TWI510505B/en

Links

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
    • H05K3/30—Assembling printed circuits with electric components, e.g. with resistor
    • H05K3/32—Assembling printed circuits with electric components, e.g. with resistor electrically connecting electric components or wires to printed circuits
    • H05K3/34—Assembling printed circuits with electric components, e.g. with resistor electrically connecting electric components or wires to printed circuits by soldering
    • H05K3/3452—Solder masks
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
    • C08F290/06—Polymers provided for in subclass C08G
    • C08F290/062—Polyethers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/08—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated side groups
    • C08F290/12—Polymers provided for in subclasses C08C or C08F
    • 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
    • G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
    • G03F7/033—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. vinyl polymers
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
    • G03F7/0388—Macromolecular compounds which are rendered insoluble or differentially wettable with ethylenic or acetylenic bands in the side chains of the photopolymer
    • 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
    • H05K2201/20—Details of printed circuits not provided for in H05K2201/01 - H05K2201/10
    • H05K2201/2054—Light-reflecting surface, e.g. conductors, substrates, coatings, dielectrics

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Physics & Mathematics (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Manufacturing & Machinery (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • General Physics & Mathematics (AREA)
  • Materials For Photolithography (AREA)
  • Macromonomer-Based Addition Polymer (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Non-Metallic Protective Coatings For Printed Circuits (AREA)

Abstract

Disclosed is a curable resin composition which enables the production of a solder resist film that does not undergo the deterioration in reflectance caused by the passage of time or thermal history and has flexibility and low warpage properties. The curable resin composition is characterized by comprising: (A-1) a copolymer resin that is produced by the reaction of a compound represented by general formula (I) with a compound represented by general formula (II) and/or a compound represented by general formula (III), or (A-2) a copolymer resin that is produced by adding a compound having an oxirane ring and an ethylenically unsaturated bond to one or some of carboxyl groups in a copolymer produced by the reaction of a compound represented by general formula (I) with a compound represented by general formula (II) and/or a compound represented by general formula (III); (B) a curing agent; and (C) a diluent.

Description

201139469 六、發明說明： 【發明所屬之技術領域】 本發明係關於適用於印刷配線板之防焊光阻劑或各種 光阻劑等之硬化性組成物，及被覆使之硬化而成之硬化物 '的印刷配線板。 【先前技術】 印刷配線板係在基板上形成導體電路之圖型，在該圖 型之焊接焊錫線道（land)上焊接電子零件而搭載使用，去 除該焊接焊錫之線道之電路部分以作爲永久保護皮膜之防 焊光阻膜被覆。據此，將電子零件焊接於印刷配線板上 時，可防止焊劑附著於不必要之部份，同時防止電路導體 直接暴露於空氣中因氧化或濕度造成之腐蝕。 此處，專利文獻1揭示可使用作爲安定性、耐熱性、 耐藥品性優異之可藉稀鹼性水溶液顯像之一液型液狀光阻 劑之感光性樹脂組成物。 又，印刷配線板亦可使用作爲發光二極體元件（LED) 等之安裝用基板，於安裝面上形成之防焊光阻膜被要求有 提高來自光源之光的反射率之功能》該等用途主要使用白 ' 色防焊光阻劑作爲形成防焊光阻膜之防焊光阻組成物。 然而，白色防焊光阻劑之情況下，將塗膜加熱而硬化 時會有引起變色之虞，使光反射率下降。尤其，於白色防 焊光阻劑之情況下，變色及反射率下降更顯著，而使商品 價値降低。因此，專利文獻2中提案可抑制變色與反射率 -5- 201139469 下降之防焊光阻組成物。 另外，近年來，隨著電子設備之小型化、內部構造之 複雜化等之進展，而在具有柔軟構造之可撓性配線板上使 用防焊光阻劑。該情況下，爲了對可撓性配線板上賦予柔 軟構造，對於防焊光阻劑不僅要求抑制反射率降低，亦要 求可撓性、低翹曲性，但對於上述防焊光阻劑仍有必要進 一步改良上述特性。 [先前技術文獻] [專利文獻] [專利文獻1]特開平3 - 1 723 0 1 [專利文獻2]特開2007-322546 【發明內容】 [發明欲解決之課題] 鑑於上述問題，本發明之目的係提供一種可形成可防 止經時及因熱過程引起之反射率降低及黃化且有柔軟性' 低翅曲性、難燃性之防焊光阻膜之硬化性樹脂組成物。 [用以解決課題之手段] 本發明之第一樣態爲一種硬化性樹脂組成物，其特徵 爲含有： (A-1)使以通式（I)表示之化合物， 201139469 【化1】[Technical Field] The present invention relates to a hardenable composition suitable for a solder resist of a printed wiring board, various photoresists, and the like, and a hardened material which is hardened by coating 'Printed wiring board. [Prior Art] A printed wiring board is a pattern in which a conductor circuit is formed on a substrate, and an electronic component is soldered on the soldering land of the pattern, and the circuit portion of the wiring of the soldering solder is removed. The solder mask of the permanent protective film is covered. Accordingly, when the electronic component is soldered to the printed wiring board, the solder can be prevented from adhering to an unnecessary portion while preventing the circuit conductor from being directly exposed to the air due to oxidation or humidity. Here, Patent Document 1 discloses that a photosensitive resin composition which is one of liquid-based liquid photoresists which can be developed by dilute alkaline aqueous solution, which is excellent in stability, heat resistance and chemical resistance, can be used. Further, as the printed wiring board, a mounting substrate such as a light emitting diode element (LED) can be used, and a solder resist film formed on the mounting surface is required to have a function of improving the reflectance of light from the light source. The purpose is mainly to use a white color solder resist as a solder resist composition for forming a solder resist film. However, in the case of a white solder resist, when the coating film is heated and hardened, there is a possibility of causing discoloration, and the light reflectance is lowered. In particular, in the case of a white solder resist, the discoloration and reflectance are more markedly lowered, and the commercial price is lowered. Therefore, Patent Document 2 proposes a solder resist resist composition which suppresses discoloration and reflectance from -5 to 201139469. In addition, in recent years, with the progress of miniaturization of electronic equipment and complication of internal structure, a solder resist is used on a flexible wiring board having a flexible structure. In this case, in order to provide a flexible structure to the flexible wiring board, it is required to prevent not only a decrease in reflectance but also flexibility and low warpage for the solder resist resist, but there is still a solder resist for the above solder resist. It is necessary to further improve the above characteristics. [Prior Art Document] [Patent Document 1] [Patent Document 1] JP-A No. 3 - 1 723 0 1 [Patent Document 2] JP-A-2007-322546 [Disclosure] [Problems to be Solved by the Invention] In view of the above problems, the present invention It is an object of the invention to provide a curable resin composition which can form a solder resist film which can prevent a decrease in reflectance and yellowing due to a thermal process and which has a softness, low finness and flame retardancy. [Means for Solving the Problem] The first aspect of the present invention is a curable resin composition characterized by comprising: (A-1) a compound represented by the formula (I), 201139469 [Chemical Formula 1]

(式中，R1表不氫原子或甲基），與以通式（II)表示之 化合物， 【化2】(wherein R1 represents a hydrogen atom or a methyl group), and a compound represented by the formula (II), [Chemical 2]

(式中，R1表不氫原子或甲基，R2表不苯基、α -異丙 苯基、碳數1〜1〇之烷氧基、烷基之碳數1~1〇之醯基、第 三丁基、金剛烷基或三氟甲基，m爲0或1〜3之整數）， 及/或以通式（III)表示之化合物反應而得之共聚合樹脂，(wherein R1 represents a hydrogen atom or a methyl group, and R2 represents a phenyl group, an α-isopropylphenyl group, an alkoxy group having a carbon number of 1 to 1 fluorene, and an alkyl group having a carbon number of 1 to 1 fluorene, a tert-butyl group, an adamantyl group or a trifluoromethyl group, m is an integer of 0 or 1 to 3), and/or a copolymerized resin obtained by reacting a compound represented by the formula (III),

【化3】 R1 Q[Chemical 3] R1 Q

(式中，R1表示氫原子或甲基，R2表示苯基、α-異丙 苯基、碳數1〜10之烷氧基、烷基之碳數1〜10之醯基、第 三丁基、金剛烷基或三氟甲基，Α1表示含有直鏈或環狀 骨架之碳數2〜10之伸烷基或碳數3〜10之羥基伸烷基，m 爲0或1~3之整數，p爲1〜5之整數）， 或（A-2)於使通式（I)之化合物， 【化4】(wherein R1 represents a hydrogen atom or a methyl group, and R2 represents a phenyl group, an α-isopropylphenyl group, an alkoxy group having 1 to 10 carbon atoms, a decyl group having 1 to 10 carbon atoms of an alkyl group, and a tributyl group; , adamantyl or trifluoromethyl, Α 1 represents a linear or cyclic skeleton having 2 to 10 carbon atoms or a carbon number of 3 to 10 alkyl, m is 0 or an integer of 1 to 3. , p is an integer of 1 to 5), or (A-2) is a compound of the formula (I),

(式中，R1表示氫原子或甲基），與以通式（II)表示之 201139469 化合物， 【化5】 H2C』~^r2)， (式中，R1表示氫原子或甲基，R2表示苯基、α-異丙 基苯基、碳數1~1〇之烷氧基、烷基之碳數1〜10之醯基、 第三丁基、金剛烷基或三氟甲基，m爲0或卜3之整 數），及/或以通式（HI)表示之化合物反應而得之共聚物之 羧基之一部分上’加成具有環氧乙烷環及乙烯性不飽和鍵 之化合物的共聚合樹脂’ 【化6】(wherein R1 represents a hydrogen atom or a methyl group), and a compound of the formula 3939469 represented by the formula (II), wherein R1 represents a hydrogen atom or a methyl group, and R2 represents a phenyl group, an α-isopropylphenyl group, an alkoxy group having 1 to 1 carbon atom, an alkyl group having 1 to 10 carbon atoms, a third butyl group, an adamantyl group or a trifluoromethyl group, m is 0 or an integer of 3), and/or a part of a carboxyl group of a copolymer obtained by reacting a compound represented by the general formula (HI), which is added to a compound having an oxirane ring and an ethylenically unsaturated bond. Polymer resin 'Chemical 6】

(式中，R1表示氫原子或甲基，R2表示苯基、α-異丙 基苯基、碳數1〜10之烷氧基、烷基之碳數1〜10之醯基、 第三丁基、金剛烷基或三氟甲基，Α1表示含有直鏈或環 狀骨架之碳數2〜10之伸烷基或碳數3〜10之羥基伸烷基， m爲0或1~3之整數，ρ爲1〜5之整數）， (B )硬化劑；及 (C)稀釋劑。 亦即，（A-1)之共聚合樹脂爲以上述通式（I)表示之化 合物與以上述通式（Π)表示之化合物及/或以上述通式（III) 表示之化合物之共聚物’爲具有芳香環之含有羧基之共聚 合樹脂。且，（A-2)之共聚合樹脂係在共聚物的上述（A-1) 201139469 上進一步加成具有環氧乙烷環與乙烯性不飽和鍵之化合 而獲得’爲具有芳香環之含有羧基之共聚合樹脂。 本發明之第二樣態爲一種硬化性樹脂組成物，其特 爲前述具有環氧乙烷環與乙烯性不飽和鍵之化合物爲以 式（IV)表示之化合物， 【化7】 R1 H2C=C—COO-(a2-O^CH2-CH—CH2 〇V)(wherein R1 represents a hydrogen atom or a methyl group, R2 represents a phenyl group, an α-isopropylphenyl group, an alkoxy group having 1 to 10 carbon atoms, an alkyl group having a carbon number of 1 to 10, and a third group; Base, adamantyl or trifluoromethyl, Α1 represents an alkylene group having a carbon number of 2 to 10 or a hydroxyalkylene group having a carbon number of 3 to 10, which has a linear or cyclic skeleton, and m is 0 or 1 to 3 An integer, ρ is an integer from 1 to 5), (B) a hardener; and (C) a diluent. That is, the copolymerized resin of (A-1) is a copolymer of a compound represented by the above formula (I) and a compound represented by the above formula (Π) and/or a compound represented by the above formula (III). 'is a copolymerized resin containing a carboxyl group having an aromatic ring. Further, the copolymerized resin of (A-2) is further added to the above-mentioned (A-1) 201139469 of the copolymer to have a combination of an oxirane ring and an ethylenically unsaturated bond to obtain a content having an aromatic ring. a copolymerized resin of a carboxyl group. The second aspect of the present invention is a curable resin composition characterized in that the compound having an oxirane ring and an ethylenically unsaturated bond is a compound represented by the formula (IV), and R1 H2C= C-COO-(a2-O^CH2-CH-CH2 〇V)

Q (式中’ R1表示氫原子或甲基，A2表示碳數2~10 伸烷基，q爲0或1~5之整數）。 本發明之第三樣態爲一種硬化性樹脂組成物，其特 爲前述（A-1)共聚合樹脂及前述（A-2)共聚合樹脂具有5~ 質量％之芳香族烴骨架。亦即，（A -1 )共聚合樹脂、（A 共聚合樹脂中，各含有5 ~40質量％之各種芳香族烴 架。本發明之第四樣態爲一種硬化性樹脂組成物，其特 爲（A-1)共聚合樹脂之酸價及（A-2)共聚合樹脂之酸價 3 0~150 mg KOH/g。 本發明之第五樣態爲一種硬化性樹脂組成物，其特 爲進而含有（D)無機白色顏料。本發明之第六樣態爲一 硬化性樹脂組成物，其特徵爲前述（D)無機白色顔料爲 紅石型氧化鈦。 本發明之第七樣態爲一種硬化性樹脂組成物，其特 爲前述（B)硬化劑包含自一分子中具有兩個以上環氧基 化合物、三聚氰胺及三聚氰胺衍生物所組成組群選擇之 少一種，本發明之第八樣態爲一種硬化性樹脂組成物， -9 - 物 徵 通 之 徵 40 2) 骨 徵 爲 徵 種 金 徵 之 至 其 201139469 特徵爲前述（C)稀釋劑包含一分子中具有一個以上乙烯性 不飽和基之化合物，本發明之第九樣態爲一種硬化性樹脂 組成物’其特徵爲前述（C)稀釋劑爲具有兩個以上（甲基） 丙烯酸基且（甲基）丙烯酸基當量爲200g/eq以上之化合 物。 本發明之第十樣態爲一種硬化性樹脂組成物，其特徵 爲進而含有（E)光聚合起始劑，本發明之第十一樣態爲一 種硬化性樹脂組成物，其特徵爲進而含有（F)磷系難燃 劑’本發明之第十二樣態爲一種硬化性樹脂組成物，其特 徵爲進而含有（G)金屬氫氧化物，本發明之第十三樣態爲 一種印刷配線板，其被覆有使用上述硬化性樹脂組成物所 形成之防焊光阻膜。 [發明之效果] 依據本發明之第一、第二樣態，藉由以（甲基）丙烯酸 作爲共聚物之構成要素，使共聚合樹脂之羧基特定於源自 (甲基）丙烯酸之構造，可抑制硬化塗膜之變色，尤其可抑 制於銅配線上形成硬化塗膜時之主要因熱造成之硬化塗膜 之變色。且，如通式（II)、通式（III)所示，聚合後，以於 芳香族烴骨架之側鏈α位上不具有氫原子之化合物成爲共 聚合樹脂之構成要素，亦即，使相對於芳香族烴骨架之側 鏈之α位上不具有氫原子之化合物，或相對於芳香族烴骨 架之α位之氫原子成爲存在於主鏈上而成之化合物作爲共 聚合樹脂之構成要素，故而可抑制硬化塗膜之變色。 -10- 201139469 依據本發明之第三樣態，（A_l)共聚合樹脂及（A_2)共 聚合樹脂具有5~40質量％之芳香族烴骨架，故耐熱性、 難燃性優異，且藉由與（C)稀釋劑具有相溶性，使得作爲 鹼顯像類型之感光性防焊光阻劑使用時，鹼顯像性亦優 異，同時由於良好之光硬化性與熱硬化性因而塗膜之柔軟 性亦優異，故配線板製造時之作業性獲得提高。 基於上述特性，本發明可形成鹼顯像性優異，且具有 柔軟性、低翹曲性、難燃性之防焊光阻膜，故不僅可用於 貼銅層合板等印刷配線板，亦可使用於要求可撓性之印刷 配線板中。另外，由於可防止調配無機系白色顔料，例如 金紅石型氧化鈦之防焊光阻膜之經時及因熱過程造成之反 射率下降及防止由白色變成黃色之變色，故可更提高安裝 發光二極體元件之配線板之照度β 【實施方式】 以下，針對本發明之硬化性樹脂組成物加以說明。本 發明之硬化性樹脂組成物之特徵爲含有（A- 1 )使以上述通 式（I)表示之化合物與以上述通式（II)表示之化合物及/或以 上述通式（III)表示之化合物反應而得之共聚合樹脂，或 (Α-2)於使以上述通式（I)表示之化合物與以上述通式（II)表 示之化合物及/或以上述通式（III)表示之化合物反應而得 之共聚物之羧基之一部分上加成具有環氧乙烷環及乙烯性 不飽和鍵之化合物的共聚合樹脂，（Β)硬化劑，及（C)稀釋 劑之硬化性樹脂組成物。 -11 - 201139469 (A-l)、（A-2):共聚合樹脂 (A-1)之共聚合樹脂係使以通式⑴表示之丙烯酸或甲 基丙烯酸，與以通式（II)表示之具有芳香環之乙烯性不飽 和單體及/或以通式（ΙΠ)表示之具有芳香環之（甲基）丙烯酸 酯共聚合而得。又，（A-2)之共聚合樹脂爲於使通式（I)與 通式（Π)及/或通式（III)共聚合獲得之（A-1)之共聚物之羧 基之一部份上加成具有環氧乙烷環與乙烯性不飽和鍵之化 合物而得。 以通式（II)表示之具有芳香環之乙烯性不飽和單體可 列舉爲例如苯乙烯、α-甲基苯乙烯、對·甲氧基苯乙烯、 間-第三丁氧基苯乙烯、對-第三丁氧基苯乙烯、對- (1-乙 氧基乙氧基）苯乙烯、對-氟苯乙烯等。該等化合物可單獨 使用，亦可混合兩種以上使用。 以通式（III)表示之具有芳香環之（甲基）丙烯酸酯可列 舉爲例如（甲基）丙烯酸苯氧基乙酯及（甲基）丙烯酸2-(2-苯 氧基乙氧基）乙酯等苯氧基聚乙二醇（甲基）丙烯酸酯，（甲 基）丙烯酸苯氧基丙酯及（甲基）丙烯酸2-苯氧基丙酯等苯 氧基聚丙二醇（甲基）丙烯酸酯，苯基縮水甘油醚（甲基）丙 烯酸酯、（甲基）丙烯酸4-α-異丙苯基苯氧基乙基酯等之4-α-異丙苯基苯氧基聚乙二醇（甲基）丙烯酸酯，以及（甲基） 丙烯酸2-苯基苯氧基乙酯等之2-苯基苯氧基聚乙二醇（甲 基）丙烯酸酯等。該等化合物可單獨使用，亦可混合兩種 以上使用。 -12- 201139469 又，就獲得（A-l)、（A-2)之共聚合樹脂而言，可使用 以通式（II)表示之具有芳香環之乙烯性不飽和單體或以通 式（III)表示之具有芳香環之（甲基）丙烯酸酯之任一者，亦 可混合二者使用。 至於具有環氧乙烷與乙烯性不飽和鍵之化合物，只要 爲具有環氧乙烷與乙烯性不飽和鍵之化合物則無特別限 制，列舉爲例如以上述通式（IV)表示之化合物，更具體而 言，列舉爲（甲基）丙烯酸縮水甘油酯、（甲基）丙烯酸4-羥 基丁酯縮水甘油醚、（甲基）丙烯酸羥基烷酯縮水甘油醚、 (甲基）丙烯酸β·甲基縮水甘油酯、（甲基）丙烯酸（3,4-環氧 基環己基）甲酯等之（甲基）丙烯酸之環氧基環己基衍生物 類’（甲基）丙烯酸酯之脂環環氧衍生物類等。該等化合物 可單獨使用，亦可混合兩種以上使用。 另外，依據需要，亦可於以通式（II)表示之具有芳香 環之乙烯性不飽和單體、以通式（III)表示之具有芳香環之 (甲基）丙烯酸酯中，添加不具有芳香環亦不具有羧基之乙 烯性不飽和單體，與以通式（I)表示之丙烯酸或甲基丙烯 酸共聚合。不具有芳香環亦不具有羧基之乙烯性不飽和單 體可列舉爲例如（甲基）丙烯酸甲酯、（甲基）丙烯酸乙酯、 (甲基）丙烯酸正丙酯 '丙烯酸異丙酯 '(甲基）丙烯酸正丁 酯、（甲基）丙烯酸異丁酯、（甲基）丙烯酸正己酯、（甲基） 丙烯酸環己酯、（甲基）丙烯酸正辛酯、（甲基）丙烯酸2-乙 基己酯、（甲基）丙烯酸二環戊酯、（甲基）丙烯酸二環戊烯 酯、（甲基）丙烯酸二環戊烯基氧基乙酯、（甲基）丙烯酸異 -13- 201139469 冰片酯、（甲基）丙烯酸1-金剛烷酯、（甲基）丙烯酸2-甲 基-2-金剛烷酯及（甲基）丙烯酸2-乙基-2-金剛烷酯等之具 有直鏈、分支或脂環骨架之（甲基）丙烯酸烷酯，（甲基）丙 烯酸2-羥基乙酯、（甲基）丙烯酸2-羥基丙酯、（甲基）丙烯 酸3-羥基丙酯、（甲基）丙烯酸2-羥基丁酯、（甲基）丙烯酸 4-羥基丁酯、環己烷二甲醇單（甲基）丙烯酸酯及壬二醇單 (甲基）丙烯酸酯等之羥基單（甲基）丙烯酸酯，四氫糠基（甲 基）丙烯酸酯、環狀三羥甲基丙烷縮甲醛（甲基）丙烯酸酯 及烷氧基化四氫糠基（甲基）丙烯酸酯等之含有環狀醚骨架 之（甲基）丙烯酸酯，（甲基）丙烯酸2·羥基乙酯•己內酯加 成物及（甲基）丙烯酸2-羥基丙酯•己內酯加成物等之羥基 單（甲基）丙烯酸酯·己內酯加成物，聚乙二醇單（甲基）丙 烯酸酯、聚丙二醇單（甲基）丙烯酸酯、聚丙二醇單（甲基） 丙烯酸酯、聚（乙二醇丙二醇）單（甲基）丙烯酸酯、聚（乙二 醇•四伸甲基二醇）單（甲基）丙烯酸酯及聚（丙二醇·四伸甲 基二醇）單（甲基）丙烯酸酯等之聚烷二醇改質之羥基單（甲 基）丙烯酸酯，甲氧基聚乙二醇單（甲基）丙烯酸酯、甲氧 基聚丙二醇單（甲基）丙烯酸酯及乙氧基聚乙二醇單（甲基） 丙烯酸酯等之烷基末端聚烷二醇單（甲基）丙烯酸酯，（甲 基）丙烯酸2,2,2-三氟甲酯、（甲基）丙烯酸2-(全氟丁基）乙 酯、（甲基）丙烯酸3-(全氟丁基）-2-羥基丙酯及（甲基）丙烯 酸2-(全氟己基）乙酯等之含氟（甲基）丙烯酸酯，N-環己基 馬來醯亞胺及N-(甲基）丙烯醯氧基乙基六氫苯二醯亞胺等 含有醯亞胺基之（甲基）丙烯酸酯，以及具有二甲基矽氧烷 -14- 201139469 骨架之單（甲基）丙烯酸酯等之（甲基）丙烯酸矽氧化合物 等。 有關上述之（A-1)共聚合樹脂及（A-2)共聚合樹脂之芳 香族烴骨架之各別含量’其下限値就難燃性及與（c)稀釋 劑等之相溶性之觀點而言較好爲5質量％，最好爲1 〇質 量％。另外，其上限値就防焊光阻膜之柔軟性之觀點而言 較好爲4 0質量％，最好爲3 0質量％。 (A-1)共聚合樹脂、（A-2)共聚合樹脂可以習知之溶液 聚合法合成。使用之溶劑只要是對自由基聚合爲惰性者即 無特別限制。其例列舉爲乙酸乙醋、乙酸異西醋、溶纖素 乙酸酯、丁基溶纖素乙酸酯等乙二醇單烷基醚乙酸酯類； 二乙二醇單甲基醚乙酸酯、卡必醇乙酸酯、丁基卡必醇乙 酸酯等二乙二醇單烷基醚乙酸酯類；丙二醇單烷基醚乙酸 酯類、二丙二醇單烷基醚乙酸酯類等之乙酸酯類；二乙二 醇二烷基醚類、甲基卡必醇、乙基卡必醇、丁基卡必醇等 二乙二醇二烷基醚類；三乙二醇二烷基醚類；丙二醇二烷 基醚類；二丙二醇二烷基醚類：I，4-二噁烷、四氫呋喃等 醚類；丙酮 '甲基乙基酮、甲基異丁基酮、環己酮等酮 類；苯、甲苯、二甲苯、辛烷、癸烷等烴類；石油醚、石 油腦、氫化石油腦、溶劑石腦油（Solvent naphtha)等石油 系溶劑；乳酸甲酯、乳酸乙酯、乳酸丁酯等乳酸酯類；二 甲基甲醯胺、N-甲基吡咯烷酮等。該等溶劑可單獨使用， 亦可混合兩種以上使用。溶劑之使用量相對於共聚合樹脂 1〇〇質量份爲30〜1000質量份，較好爲50〜800質量份。 -15- 201139469 溶液聚合法中使用之自由基聚合起始劑並無特別限 制，可使用例如有機過氧化物或偶氮化合物。具體例可使 用苯甲醯基過氧化物、二異丙苯過氧化物、二異丙基過氧 化物、二第三丁基過氧化物、第三丁基過氧基苯甲酸酯、 第三己基過氧基苯甲酸酯、第三丁基過氧基-2-乙基己酸 酯、第三己基過氧基-2-乙基己酸酯、1,1-雙（第三丁基過 氧基）-3,3,5-三甲基環己烷、2,5-二甲基-2,5-雙（第三丁基 過氧基）己基-3, 3·異丙基過氧化氫、第三丁基過氧化氫、 二異丙苯過氧化物、二異丙苯過氧化氫、乙醯基過氧化 物、雙（4-第三丁基環己基）過氧基二碳酸酯、二異丙基過 氧基二碳酸酯、異丁基過氧化物、3,3,5-三甲基己醯基過 氧化物、月桂基過氧化物、1，1-雙（第三丁基過氧基）3,3,5-三甲基環己烷、1,1-雙（第三己基過氧基）3,3,5-三甲基環己 烷、偶氮雙異丁腈、偶氮雙碳醯胺等。自由基聚合起始劑 係依據聚合溫度適宜選擇適當之半衰期者。自由基聚合起 始劑之使用量相對於自由基聚合性不飽和化合物之合計 1〇〇質量份爲0.5〜20質量份，較好爲1〜10質量份。 聚合方法可爲將不飽和單體與自由基聚合起始劑滴加 於升溫之溶劑中後攪拌，亦可將不飽和單體與自由基聚合 起始劑溶解於溶劑中且邊攪拌邊升溫進行聚合反應。另 外，亦可將自由基聚合起始劑添加於溶劑中且於升溫中滴 加不飽和單體。 藉由使具有環氧乙烷環與乙烯性不飽和鍵之化合物加 成反應於由上述聚合方法獲得之（A-1)之共聚合樹脂中之 -16 - 201139469 羧基之一部份上，可獲得（A-2)之共聚合樹脂。相對於（A-1)之共聚合樹脂中之羧基1當量，具有環氧乙烷環與乙烯 性不飽和鍵之化合物之加成量，其下限値就確保充分感光 性之觀點而言爲0.1當量，較好爲0.2當量。且其上限値 就避免羧基之量過少而使顯像性變不足之觀點而言爲0.8 當量，較好爲0.6當量。 且，（A-1)之共聚合樹脂中之羧基與具有環氧乙烷環 及乙烯性不飽和鍵之化合物之反應中使用之觸媒爲舉出有 例如三苯基膦、環烷酸鋰、環烷酸銷、環烷酸鉻、乙醯基 丙酮酸鉻、氯化鉻等。另外，聚合抑制劑可列舉爲甲氧基 氫醌等。反應可以習知方法進行，列舉爲例如，將以上述 聚合反應獲得之溶劑中之（A-1)之共聚合樹脂設定成特定 溫度後，混合具有環氧乙烷環與乙烯性不飽和鍵之化合 物、前述觸媒、前述聚合抑制劑，且進行攪拌之方法。此 時’觸媒之使用量相對於（A-1)共聚合樹脂及具有環氧乙 烷環與乙烯性不飽和鍵之化合物之合計爲0.01〜1質量％。 聚合抑制劑之使用量相對於（A-1)共聚合樹脂及具有環氧 乙烷環與乙烯性不飽和鍵之化合物之合計爲〇.〇1〜；！質量 %。另外’反應溫度爲60〜15 0°C，反應時間爲3〜60小 時。 有關（A-1)共聚合樹脂之重量平均分子量，其下限値 就硬化塗膜之強韌性及指觸乾燥性之觀點而言爲3 000， 較好爲5 0 0 0。另一方面，其上限値，就與（c)稀釋劑等之 相溶性及鹼顯像性之觀點而言爲200000，較好爲50000。 -17- 201139469 另外，有關（A-2)共聚合樹脂之重量平均分子量，其下限 値就硬化塗膜之強韌性及指觸乾燥性之觀點而言爲 3000’較好爲5〇〇〇。另一方面，其上限値，就與（c)稀釋 劑等之相丨谷性及驗顯像性之觀點而言爲2 0 0 0 〇 〇，較好爲 50000 〇 所得（A-1)共聚合樹脂及（A-2)共聚合樹脂之酸價分別 較好在30〜150mgKOH/g之範圍內。此係因爲酸價未達 3 0mg KOH/g時’與（B)硬化劑成分之硬化性下降，或者以 稀鹼性水溶液難以去除未硬化樹脂組成物，超過 1 5 0 m g Κ Ο H / g時，硬化皮膜之耐濕性、電特性變差。 (B)硬化劑 硬化劑爲用於提高硬化塗膜之交聯密度，獲得充分硬 化塗膜者，例如添加環氧樹脂。至於環氧樹脂，可列舉爲 例如雙酚A型環氧樹脂、酚醛清漆型環氧樹脂（酚酚醛清 漆型環氧樹脂、鄰甲酚酚醛清漆型環氧樹脂、對第三丁基 酚酚醛清漆型等）、對雙酚F或雙酚S反應表氯醇而得之 雙酚F型或雙酚S型環氧樹脂、雙酚E型環氧樹脂、2,5-二第三丁基氫醌型環氧樹脂、聯苯型環氧樹脂、以及具有 氧化環己烯基、氧化三環癸基、氧化環戊烯基等之脂環式 環氧樹脂、核氫化雙酚A型環氧樹脂、核氫化聯苯型環 氧樹脂等之核氫化型環氧樹脂，參（2,3-環氧基丙基）異氛 脲酸酯、三縮水甘油基參（2-羥基乙基）異氰脲酸酯等具有 三嗪環之三縮水甘油基異氰脲酸酯、二環戊二烯型環氧樹 -18- 201139469 脂、金剛院型環氧樹脂、苯二甲酸酐二縮水甘油酯、六氫 苯二甲酸酐二縮水甘油酯等酯型環氧樹脂，三聚氰胺、甲 基化經甲基三聚氰胺、丁基化羥甲基三聚氰胺、咪唑、二 氰二醯胺等。該等化合物可單獨使用，亦可混合兩種以上 f吏用"硬化劑之使用量就硬化後獲得充分塗膜之觀點而 言，相對於共聚合樹脂100質量份爲10〜100質量份，較 好爲20〜50質量份。 (C)稀釋劑 稀釋劑爲例如光聚合性單體，係用以使硬化性樹脂之 光硬化變充分，以獲得具有耐酸性、耐熱性、耐鹼性等防 焊光阻膜所使用者。光聚合性單體可列舉爲例如1，4-丁二 醇二（甲基）丙烯酸酯、1，6_己二醇二（甲基）丙烯酸酯、新 戊二醇二（甲基）丙烯酸酯、聚乙二醇二（甲基）丙烯酸酯、 二季戊四醇六丙烯酸酯、雙酚A型EO改質之二（甲基）丙 烯酸酯、雙酚A型PO改質之二（甲基）丙烯酸酯、己內酯 改質之二季戊四醇六丙烯酸酯、EO改質之二季戊四醇六 丙基酸酯，例如藉由使（甲基）丙烯酸基與具有一個以上羥 基之化合物及具有一個以上異氰酸酯基之化合物反應獲得 之胺基甲酸酯系丙烯酸化合物等。稀釋劑之使用量相對於 共聚合樹脂100質量份爲2.0-150質量份，較好爲10〜80 質量份。且，具有兩個以上（甲基）丙烯酸基之稀釋劑時， 其（甲基）丙烯酸當量就柔軟性及低翹曲性之觀點而言較好 爲200g/eq以上，最好爲300g/eq以上。又，本說明書中 -19- 201139469 之（甲基）丙烯酸當量意指每一個（甲基）丙烯醯基之分子 量。 本發明除上述個成分以外，亦可視需要調配下述成 分。 (D)無機白色顏料 無機白色顏料係爲使塗膜白化者，可列舉爲例如銳鈦 礦型氧化鈦、金紅石型氧化鈦。銳鈦礦型氧化鈦與金紅石 型氧化鈦比較雖爲白色度高者，但由於具有光觸媒活性， 故有引起硬化性樹脂組成物中樹脂變色之情況。相對於 此，金紅石型氧化鈦幾乎沒有光觸媒活性，故就可防止防 焊光阻膜變色之觀點而言較佳。金紅石型氧化鈦粒子之平 均粒徑並無特別限制，但通常爲0.0 1 ~ 1 μηι。另外，金紅 石型氧化鈦粒子之表面處理劑亦無特別限制。金紅石型氧 化鈦可使用例如富士鈦工業（股）製造之「TR-600」、 「TR-700」、「TR-7 5 0」、「TR-840」，石原產業（股）製 造之「R-550」、「R-580」、「R-630」、「R-820」、 「CR-50」、「CR-60」、「CR-90」、「CR-93」，鈦工 業（股）製造之「KR-270」、「KR-310」、「KR-380」， TAYCA(股）製造之「JR- 1 000」等。金紅石型氧化鈦之使 用量相對於共聚合樹脂100質量份爲30〜800質量份，較 好爲50~500質量份。 (Ε)光聚合起始劑 -20- 201139469 光聚合起始劑只要是一般使用者即無特別限制，有例 如肟系起始劑、苯偶因、苯乙酮、2-羥基-2-甲基-1_苯基 丙-1-酮、1-羥基環己基苯基酮、二苯甲酮等。光聚合起 始劑之使用量相對於共聚合樹脂1 00質量份爲5〜20質量 份，較好爲8〜1 5質量份。 (F)磷系難燃劑 磷系難燃劑爲用於對硬化性樹脂組成物賦予難燃性 者’列舉爲例如’參（氯乙基）磷酸酯、參（2,3-二氯丙基） 憐酸酯、參（2_氯丙基）磷酸酯、參（2,3-溴丙基）磷酸酯、 參（溴氯丙基）磷酸酯、2,3-二溴丙基-2,3-氯丙基磷酸酯、 參（三溴苯基）磷酸酯、參（二溴苯基）磷酸酯、參（三溴新戊 基）磷酸酯等之含鹵系磷酸酯：三甲基磷酸酯、三乙基磷 酸醋、三丁基磷酸酯、三辛基磷酸酯 '三丁氧基乙基磷酸 醋等無鹵系脂肪族磷酸酯；三苯基磷酸酯、甲苯基二苯基 磷酸酯、二甲苯基苯基磷酸酯、三甲苯基磷酸酯、三-二 甲本基磷酸酯、二甲苯基二苯基磷酸酯、參（異丙基苯基） 隣酸醋、異丙基苯基二苯基磷酸酯、二異丙基苯基苯基磷 酸酯、參（二甲基苯基）磷酸酯、參（第三丁基苯基）磷酸 酯、羥基苯基二苯基磷酸酯、辛基二苯基磷酸酯等無鹵系 芳香族磷酸酯；參-二乙基次磷酸鋁、參甲基乙基次磷酸 鋁、參-二苯基次磷酸鋁、雙二乙基次磷酸鋅、雙甲基乙 基;人磷酸鋅、雙一苯基次磷酸鋅、雙二乙基次磷酸鈦、肆 二乙基次磷酸鈦、雙甲基乙基次磷酸鈦、肆甲基乙基次磷 -21 - 201139469 酸鈦、雙二苯基次磷酸鈦、肆二苯基次磷酸 金屬鹽，9，10-二氫-9-氧雜-10-磷雜菲-10-寒 爲HCA)、HCA與丙烯酸酯之加成反應產物 樹脂之加成反應產物、HCA與氫醌之加成 HC A改質型化合物，二苯基乙烯基氧化膦 膦、三烷基氧化膦、參（羥基烷基）氧化膦等 物等。該等中，就抑制環境負荷之觀點而言 系之磷酸酯、次磷酸之金屬鹽、HCA改質 化膦系化合物，就少量而言，不僅是難燃性 性、耐變色性優異之觀點而言，最好爲次磷 磷系之難燃劑之使用量相對於共聚合樹脂 3〜20質量份，就一方面確保充分難燃性， 制防焊光阻膜之機械強度降低之觀點而言， 質量份。 金屬氫氧化物係作爲難燃助劑所調配者 如氫氧化鋁等。其使用量，相對於共聚合相 份，爲1〜100質量份。 又，於本發明，依據需要，可進而適當 成分例如消泡劑、分散劑、體質顏料、無機 有機溶劑等。消泡劑可使用習知者，可舉 系、烴系、丙烯酸系等。分散劑舉例有矽 系、氧化鋁系等偶合劑。體質顏料係爲了提 光阻膜之物理強度者，可舉例有例如氧化矽 化鋁、紈氧化鋁、滑石、雲母等。至於無機 鈦等次磷酸之 民化物（以下稱 、HCA與環氧 反應產物等之 、三苯基氧化 氧化膦系化合 ，較好爲無鹵 型化合物、氧 ，且就耐滲出 酸之金屬鹽。 100質量份爲 一方面確實抑 較好爲4〜15 ，可舉例爲例 If脂100質量 調配各種添加 離子捕捉劑、 例爲例如矽氧 院系：鈦酸酯 高塗佈之防焊 、硫酸鋇、氧 離子捕捉劑， -22- 201139469 可舉例有磷酸銷系化合物等。 有機溶劑係爲了調節硬化性樹脂組成物之黏度或乾燥 性者，可舉例有例如甲基乙基酮、環己酮等酮類，甲苯、 二甲苯等芳香族烴類，甲醇、異丙醇、環己醇等之醇類， 環己烷、甲基環己烷等之脂環式烴類，石油醚、石油腦等 石油系溶劑，溶纖劑、丁基溶纖劑等之溶纖劑類，卡必 醇、丁基卡必醇等之卡必醇類，乙酸乙酯、乙酸丁酯、溶 纖劑乙酸酯、丁基溶纖劑乙酸酯、卡必醇乙酸酯、丁基卡 必醇乙酸酯等之乙酸酯類等。 上述本發明之硬化性樹脂組成物之製造方法雖未限定 於特定方法，但可藉由例如將上述各成分以特定比例調配 後’以攪拌機預先混合，於室溫利用三根輥予以混合分散 而製造。 接著’就上述本發明之硬化性樹脂組成物之塗佈方法 加以說明。於使如上述所得之本發明之硬化性樹脂組成物 熱硬化時，例如可於具有使貼銅層合板之銅箔經蝕刻而形 成電路圖型之印刷配線板上，使用網版印刷法、噴_塗佈 法等方法’塗佈成所需厚度後，以130〜170。(：之熱風循環 式乾燥機等加熱20〜80分鐘，使硬化性樹脂組成物熱硬 化’在印刷配線板上形成目的之防焊光阻膜。 於使如上述所得之本發明之硬化性樹脂組成物光硬化 時’例如可於具有使銅箔經蝕刻而形成電路圖型之撓性配 線板上，使用網版印刷法、噴霧塗佈法等方法，塗佈成所 需厚度後’在用以使硬化性樹脂組成物中之溶劑揮發之 -23- 201139469 60〜80°C左右之溫度加熱15〜60分鐘左右進行預備乾燥。 隨後，於所塗佈之硬化性樹脂組成物上，密著具有對前述 電路圖型之線道以外爲透光性之圖型之負型薄膜，自其上 照射紫外線。接著，利用稀鹼水溶液去除對應於前述線道 之非曝光區域，藉此使塗膜顯像。顯像方法，係使用噴霧 法、淋洗法等，所使用之稀鹼水溶液一般爲0.5〜5%碳酸 鈉水溶液，但亦可使用其他鹼。接著，以1 3 0〜1 7 (TC之熱 風循環式乾燥機等進行2 0〜80分鐘之預烘烤，藉此於撓性 配線板上形成目的之防焊光阻膜。 於如此所得之由防焊光阻膜被覆之撓性配線板上，利 用噴流焊接方法、回焊焊接方法等焊接電子零件，藉此形 成電子電路單元。 [實施例] 以下說明本發明之實施例，但本發明只要不超越其精 神主旨’則不受該等實施例之限制。 (A-l) (A-2)具有芳香環之含有羧基之共聚合樹脂之合成 合成例1 於安裝攪拌機、溫度計、回流管之500mL四頸燒瓶 中投入二丙二醇單甲基醚（以下稱DPM)，在氮氣氛圍下升 溫至120 °C後’以約一小時內滴加甲基丙烯酸 17.2g(0.2mol)、甲基丙烯酸苯氧基乙酯（Sart〇mer公司製 造之 SR-3 40，以下稱爲 PEMA) 92.8g(0,45m〇1)、2,2，_偶 -24- 201139469 氮雙（2-甲基丙酸）二甲酯（和光純藥製造之V-601，以下稱 爲DMAMP)4.6g及DPM 10g之混合溶液，在120°C下攪拌 3小時’生成含有約4 9質量％之合成例1之共聚合樹脂之 DPM溶液，獲得合成例1之共聚合樹脂》該具有芳香環 之含羧基之共聚合樹脂之重量平均分子量爲約2 5000(聚 苯乙烯換算），固體成分酸價爲98mgKOH/g。 合成例2 於安裝攪拌機、溫度計、回流管之50 0mL四頸燒瓶 中投入二丙二醇單甲基醚（以下稱DPM) 125g，在氮氣氛 圍下升溫至 1 2 0 °C後，以約一小時內滴加甲基丙烯酸 34.4g (0.4mol)、ΡΕΜΑ 82.5g(0.4mol)、DMAMP 5.5g 及 DPM lOg之混合溶液，在120°C下攪拌3小時，獲得具有 羧基之共聚物。 接著，使燒瓶內之溫度降至1 〇〇t後，於燒瓶內邊以 200mL/min通入空氣與氮氣之混合氣體，邊添加甲基丙烯 酸縮水甘油酯（日本油脂製造之PRENMER GH，以下稱爲 GMA) 21.3g(0.15mol)、作爲反應觸媒之三苯膦（以下稱爲 TPP) 〇.3g、作爲聚合抑制劑之甲氧基氫醌（以下稱爲 MEHQ) 0· 1 g，在1 00 °C反應5小時後，在1 1 5°C下持續反 應直至酸價停止下降，生成含約52質量％之合成例2之 共聚合樹脂之DPM溶液，獲得合成例2之共聚合樹脂。 重量平均分子量爲約18000(聚苯乙烯換算），固體成分酸 價爲 97mgKOH/g。 -25- 201139469 合成例3 除將合成例 2之 PBM82.5g(0.4mol)替換成 74.2g (0.36mol)，將 GMA 21.3g(〇.15mol)替換成丙烯酸 4-羥基 丁酯縮水甘油醚（日本化成製造之4-HB AGE，以下稱爲4-HBGE) 30.0g(0.15mol)以外’餘與合成例2同樣，生成含 約52質a %之合成例3之共聚合樹脂之DPM溶液，獲得 合成例3之共聚合樹脂。重量平均分子量爲約1 6000(聚 苯乙烯換算），固體成分酸價爲97mgKOH/g。 合成例4 除將合成例2之DPM 1 25g替換成1 60g，將甲基丙烯 酸 34.4g (0.4mol)替換成 56_8g(0.66mol)，將 ΡΕΜΑ 82.5g (0.4mol)替換成 47.4g(0.23mol)，將 DMAMP 5.5g 替換成 6.5g，再將 GMA 21 .3g(0.15mol)替換成 4-HBAGE 70.1 g (0.35mol)以外，餘與合成例2同樣，生成含約52質量％ 之合成例4之共聚合樹脂之DPM溶液，獲得合成例4之 共聚合樹脂。重量平均分子量爲約1 9000(聚苯乙烯換 算），固體成分酸價爲96mgK〇H/g。 合成例5 除將合成例2之ΡΕΜΑ 82.5g(0.4mol)替換成甲基丙烯 酸2-(2-苯氧基乙氧基）乙酯（日油製PRENMER PAE-100, 以下稱2PEEMA)85.1g (〇.34mol)以外，餘與合成例2同 -26- 201139469 樣，生成含約52質量％之合成例5之共聚合樹脂之DPM 溶液，獲得合成例5之共聚合樹脂。重量平均分子量爲約 1 8000(聚苯乙烯換算），固體成分酸價爲96mgKOH/g。 合成例6 除將合成例2之ΡΕΜΑ 82.5g(0.4m〇l)替換2PEEMA 75.1g (0.3mol)以外，餘與合成例2同樣，生成含約52質 量％之合成例6之共聚合樹脂之DPM溶液’獲得合成例6 之共聚合樹脂。重量平均分子量爲約2 000 0(聚苯乙烯換 算），固體成分酸價爲97mgKOH/g。 合成例7 除將合成例2之DPM 125g替換成105g，將甲基丙烯 酸 34.4g(0.4mol)替換成 2 5.8 g ( 0 · 3 m ο 1)，將 ΡΕΜΑ 82.5g(0.4mol)替換爲苯乙烯 42.7g(0.4mol)及甲基丙烯酸 正丁酯（三菱縲縈公司製之丙烯酸酯BMA，以下稱nBMA) 15.6g(0.1mol)，進而將 GMA21.3g(0.15mol)替換爲 4-HBAGE 22.0g(0.11mol)以外，餘與合成例2同樣，生成含 約47質量％之合成例7之共聚合樹脂之DPM溶液，獲得 合成例7之共聚合樹脂。重量平均分子量爲約14〇〇〇(聚 苯乙烯換算）’固體成分酸價爲95mgK〇H/g。 合成例8 除將合成例2之DPM 125g替換成110g，將甲基丙烯 -27- 201139469 酸 34.4g(〇.4m〇l)替換爲丙烯酸 25 2g(〇 35ηι〇υ，將 pema 82.5g(0.4m〇l)替換爲 59.8g(0.29m〇1)，將 dmamp 5 5g 替 換爲4g以外’餘與合成例2同樣，生成含約48質量％之 合成例8之共聚合樹脂之DPM溶液，獲得合成例8之共 聚合樹脂。重量平均分子量爲約16〇〇〇(聚苯乙烯換算）， 固體成分酸價爲101mgKOH/g。 合成例9 除將合成例2之甲基丙烯酸34.4g(0.4mol)替換爲丙 烯酸 23.8g(0.33mol)，將 ΡΕΜΑ 82.5g(0.4mol)替換爲 2PEEMA 57.6g(0.23mol)，將 DMAMP 5.5g 替換爲 4.0g 以 外，餘與合成例2同樣，生成含約48質量％之合成例9 之共聚合樹脂之DPM溶液，獲得合成例9之共聚合樹 脂。重量平均分子量爲約15000(聚苯乙烯換算），固體成 分酸價爲94mgKOH/g。 下述表1中，顯示上述合成例1~9之樹脂原料比（莫 耳）、芳香族烴骨架比率（質量％)及酸價（mgKOH/g)。 -28 - 201139469 【ml <7> 1 s ο 1 1 S 1 to o I r- CO 1 s ο 1 〇» Csl 1 1 to . 5 1 〇 r- CO 1 1 1 i 1 5 CO S CO 1 1 1 CO 1 1 ΙΟ 5 Γ- σ> irt 1 1 1 5 c> 1 i〇 5 1 σ» σ> 寸 o 1 1 S 〇 1 1 1 s ο ο «ο σ> CO 1 1 〇 1 1 ΙΑ 5 S (Ο 〇> Csl 1 1 々 1 1 in 〇 1 CM σ> e\i 1 1 S 1 1 1 1 S m 链 <n 雔 s? r 糊 κ- 趙 线 线 K3 < § CL |2PEEMA 1 < CD C < <D [4-HBAGE 1 豳 細* 糊 羝 猫 掛 m 邻 K-© ^km- mm <[Q 明Q K·淞 线 K3 赵 mm mm- Κ)«Ν 獬越 耻遨 ^κ- 褂 Η 眯 翅2 tm 酸價(mg KOH/g) 11 -29 - 201139469 比較合成例1 於安裝有攪拌機、溫度計、回流管之500mL四頸燒 瓶中，投入丙二醇二乙酸酯（以下稱爲PGDA)8 0g，在氮氣 氛圍下升溫至90 °C後，以約1小時時間滴加 GMA 28.4g(0.2mol)、甲基丙烯酸2 -羥基乙酯之己內酯加成物 (平均加成 1 mol，DAICEL化學工業製造之 PRAXCELL FM1D) 49.9g (0.2mol)、DMAMP lg、硫基丙酸 2 -乙基己 酯（堺化學工業製，EHMP)lg及PGDA 80g之混合溶液 後，於90°C攪拌8小時，獲得具有環氧基之共聚物。 接著，邊於燒瓶內以200mL/min通入空氣與氮氣之 混合氣體（氮氣體積對空氣體積比爲1比2)，邊添加丙烯 酸72.02g (0.21mol)、作爲反應觸媒之TPP 0.5g、作爲聚 合抑制劑之MEHQ 0.2g，在100°C反應5小時後，在1 15 °C繼續反應至酸價停止降低爲止，進行共聚物之環氧基與 丙烯酸之羧基之加成反應。酸價成爲2以下後，將燒瓶內 溫度降低至90°C後，添加琥珀酸酐16.0g(0.16mol)反應8 小時以上，進行酸酐之開環加成反應。以IR見到酸酐之 峰消失之時點作爲反應終點，獲得不具有芳香族烴骨架之 比較合成例1之共聚合樹脂溶液。該樹脂溶液之固體成分 約爲40質量％，重量平均分子量約爲1 2000(聚苯乙烯換 算）、固體成分酸價爲78mg KOH/g。 比較合成例2 於安裝有攪拌機、溫度計、回流管之500mL四頸燒 -30- 201139469 瓶中，投入DPM 105g，在氮氣氛圍下升溫至12〇°C後， 以約1小時時間滴加甲基丙烯酸4 3.0 g (0.5 m ο 1)、π - Β Μ A 21.3g (0_15mol)、DMAMP 4.5g 及 DPM lOg 之混合溶液 後，於1 2 0 °C攪拌3小時，獲得具有羧基之共聚物β 接著，使燒瓶內溫度降低至1 〇〇 °C之後’邊於燒瓶內 以200mL/min通入空氣與氮氣之混合氣體（氮氣體積對空 氣體積比爲1比2)，邊添加〇厘八14.28(0.1：11〇1)及間，對-甲苯基縮水甘油醚（坂本藥品製，m，p-CGE) 32.8g(0.2mol)、作爲反應觸媒之三苯膦（以下稱 TPP) 〇.3g、作爲聚合抑制劑之甲氧基氫醌（以下稱 MEHQ) 〇.lg，在l〇〇°C反應5小時後，在1 15°C繼續反應至酸價 停止降低爲止，生成含有約48質量％之具有羧基、於側 鏈之α位具有氫原子之芳香族烴骨架及甲基丙烯酸基之共 聚合樹脂之DPM溶液，獲得比較合成例2之共聚合樹. 脂。重量平均分子量約爲15000(聚苯乙烯換算）' 固體成 分酸價爲96mg KOH/g。 比較合成例3 除了將比較合成例2之GMA 14.2g(0.1mol)及間，對-甲苯基縮水甘油醚 32.8g(0.2mol)替換爲 GMA 4 2.6 g (0.3 m ο 1)以外，與比較合成例2同樣地，生成含有約 49質量％之具有羧基及甲基丙燃酸基但不具有香族煙骨架 之共聚合樹脂之DPM溶液，獲得比較合成例3之共聚合 樹脂。重量平均分子量約爲15000(聚苯乙烯換算）、固體 -31 - 201139469 成分酸價爲l〇〇mg KOH/g。 實施例1〜25、比較例1〜9 將下述表2、3、4所示 示之調配比例調配，以攪拌 室溫混合分散，調製實施例 硬化性樹脂組成物》接著， 如下進行塗佈製作試驗片。 表示質量份。 之各成分以下述表2、3、4所 機預備混合後，使用3根輥於 卜25、比較例1〜9中使用之 將所調製之硬化性樹脂組成物 下述表2、3、4所示之調配量 -32- 201139469 【Ϊ1 比較例 CO Ο r- ΙΟ CM co 8 8 o s CNJ Ο m s S 200 r— ο in CM CO s s o s 實施例 100 in s 200 CO ο lO CM CO s s o s CNJ Ο in 8 o s 100 in CNJ CO s o CSI 合成例1 合成例2 比較合成例1 比較合成例2 EPICOTE 828 三聚氰胺 DPHA DPM 金紅石型氧化鈦 1 KS-66 (Α-1)(Α-2)共聚合樹脂 (B)硬化劑 (c)稀釋劑 (D)無機白色顔料 消泡劑 -33- 201139469 表2中， EPICOTE 828:日本環氧樹脂（股）製之雙酚A型環氧 樹脂， DPHA:日本化藥（股）製之二季戊四醇六丙烯酸酯， DPM ’·協和發酵工業（股）製造之二丙二醇單甲基醚， 金紅石型氧化鈦：石原產業公司製[CR-80]， KS 66 :信越矽氧公司製之矽氧油。 -34- 201139469Q (wherein R1 represents a hydrogen atom or a methyl group, A2 represents a carbon number of 2 to 10 alkyl groups, and q is 0 or an integer of 1 to 5). The third aspect of the present invention is a curable resin composition, which is characterized in that the (A-1) copolymer resin and the (A-2) copolymer resin have an aromatic hydrocarbon skeleton of 5 to 5% by mass. In other words, the (A-1) copolymerized resin and the (A copolymerized resin each contain 5 to 40% by mass of various aromatic hydrocarbon carriers. The fourth aspect of the present invention is a curable resin composition, The acid value of the (A-1) copolymer resin and the acid value of the (A-2) copolymer resin are 30 to 150 mg KOH/g. The fifth aspect of the present invention is a curable resin composition, which is characterized by Further, (D) an inorganic white pigment is contained. The sixth aspect of the present invention is a curable resin composition characterized in that the (D) inorganic white pigment is a redstone-type titanium oxide. The seventh aspect of the present invention is a The curable resin composition is characterized in that the (B) hardener comprises one selected from the group consisting of two or more epoxy compounds, melamine and melamine derivatives in one molecule, and the eighth aspect of the present invention Is a curable resin composition, -9 - sign of the sign 40 2) The bone sign is the gold levy to its 201139469. The feature is that the (C) diluent contains more than one ethylenically unsaturated group in one molecule. The compound of the present invention is the ninth aspect of the present invention. The curable resin composition is characterized in that the (C) diluent is a compound having two or more (meth)acrylic groups and having a (meth)acrylic group equivalent of 200 g/eq or more. The tenth aspect of the present invention is a curable resin composition characterized by further comprising (E) a photopolymerization initiator, and the tenth aspect of the invention is a curable resin composition characterized by further comprising (F) Phosphorus-based flame retardant The twelfth aspect of the present invention is a curable resin composition characterized by further containing (G) a metal hydroxide, and the thirteenth aspect of the present invention is a printed wiring The plate is coated with a solder resist film formed using the above curable resin composition. [Effects of the Invention] According to the first and second aspects of the present invention, the carboxyl group of the copolymer resin is specific to the structure derived from (meth)acrylic acid by using (meth)acrylic acid as a constituent element of the copolymer. The discoloration of the hardened coating film can be suppressed, and in particular, discoloration of the hardened coating film mainly caused by heat when the hard coating film is formed on the copper wiring can be suppressed. Further, as shown in the general formula (II) or the general formula (III), a compound having no hydrogen atom at the α-position of the side chain of the aromatic hydrocarbon skeleton after polymerization is a constituent element of the copolymer resin, that is, A compound having no hydrogen atom at the α position of the side chain of the aromatic hydrocarbon skeleton or a hydrogen atom having an α position with respect to the aromatic hydrocarbon skeleton is a constituent of the copolymerized resin which is present in the main chain. Therefore, the discoloration of the hardened coating film can be suppressed. -10- 201139469 According to the third aspect of the present invention, the (A-1) copolymer resin and the (A_2) copolymer resin have an aromatic hydrocarbon skeleton of 5 to 40% by mass, so that heat resistance and flame retardancy are excellent, and It is compatible with the (C) diluent, so that it is excellent in alkali developability when used as a photosensitive solder resist of the alkali development type, and at the same time, it is soft due to good photocurability and thermosetting property. The workability is also excellent, so the workability at the time of manufacturing the wiring board is improved. Based on the above characteristics, the present invention can form a solder resist film having excellent alkali developability and having flexibility, low warpage, and flame retardancy, and therefore can be used not only for a printed wiring board such as a copper laminate but also for use. In printed wiring boards that require flexibility. In addition, since the inorganic white pigment can be prevented from being mixed, for example, the time of the solder resist film of the rutile type titanium oxide and the reflectance due to the thermal process are lowered, and the discoloration from white to yellow is prevented, so that the mounting light can be further improved. Illuminance β of the wiring board of the diode element [Embodiment] Hereinafter, the curable resin composition of the present invention will be described. The curable resin composition of the present invention is characterized by containing (A-1) a compound represented by the above formula (I) and a compound represented by the above formula (II) and/or represented by the above formula (III) a copolymerized resin obtained by reacting the compound, or (Α-2), a compound represented by the above formula (I) and a compound represented by the above formula (II) and/or represented by the above formula (III) a copolymerized resin of a compound having an oxirane ring and an ethylenically unsaturated bond, a hardening resin of (C) a diluent, a part of a carboxyl group of the copolymer obtained by the reaction of the compound Composition. -11 - 201139469 (Al), (A-2): the copolymerized resin of the copolymerized resin (A-1) is obtained by using the acrylic acid or methacrylic acid represented by the formula (1) and the formula (II) An aromatic ring-containing ethylenically unsaturated monomer and/or a copolymerization of a (meth) acrylate having an aromatic ring represented by the formula (ΙΠ). Further, the copolymerized resin of (A-2) is one of the carboxyl groups of the copolymer of (A-1) obtained by copolymerizing the general formula (I) with the general formula (Π) and/or the general formula (III). The compound is obtained by adding a compound having an oxirane ring and an ethylenically unsaturated bond. The ethylenically unsaturated monomer having an aromatic ring represented by the formula (II) may, for example, be styrene, α-methylstyrene, p-methoxystyrene or m-butoxystyrene. p-Tertibutoxystyrene, p-(1-ethoxyethoxy)styrene, p-fluorostyrene, and the like. These compounds may be used singly or in combination of two or more. The (meth) acrylate having an aromatic ring represented by the formula (III) may, for example, be phenoxyethyl (meth)acrylate or 2-(2-phenoxyethoxy)(meth)acrylate. Phenoxypolyethylene glycol (meth) acrylate such as ethyl ester, phenoxy propylene glycol (meth) acrylate and phenoxy polypropylene glycol (methyl) such as 2-phenoxypropyl (meth) acrylate 4-α-isopropylphenylphenoxypolyethylene acrylate, phenyl glycidyl ether (meth) acrylate, 4-α-cumyl phenoxyethyl (meth) acrylate An alcohol (meth) acrylate, and a 2-phenylphenoxy polyethylene glycol (meth) acrylate such as 2-phenylphenoxyethyl (meth)acrylate. These compounds may be used singly or in combination of two or more. -12- 201139469 Further, in order to obtain a copolymerized resin of (Al) or (A-2), an ethylenically unsaturated monomer having an aromatic ring represented by the formula (II) or a formula (III) may be used. Any of the (meth) acrylates having an aromatic ring may be used in combination. The compound having an ethylene oxide and an ethylenically unsaturated bond is not particularly limited as long as it is a compound having an ethylene oxide and an ethylenically unsaturated bond, and is exemplified by, for example, a compound represented by the above formula (IV). Specifically, it is exemplified by glycidyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate glycidyl ether, hydroxyalkyl (meth)acrylate glycidyl ether, and β-methyl (meth)acrylate. Ethoxycyclohexyl derivative of (meth)acrylic acid such as glycidyl ester or (meth)acrylic acid (3,4-epoxycyclohexyl) methyl ester Derivatives, etc. These compounds may be used singly or in combination of two or more. Further, if necessary, the ethylenically unsaturated monomer having an aromatic ring represented by the formula (II) and the (meth) acrylate having an aromatic ring represented by the formula (III) may be added without The aromatic ring also has an ethylenically unsaturated monomer having no carboxyl group, and is copolymerized with acrylic acid or methacrylic acid represented by the general formula (I). Examples of the ethylenically unsaturated monomer having no aromatic ring or carboxyl group include, for example, methyl (meth)acrylate, ethyl (meth)acrylate, and n-propyl (meth)acrylate 'isopropyl acrylate' ( N-butyl methacrylate, isobutyl (meth)acrylate, n-hexyl (meth)acrylate, cyclohexyl (meth)acrylate, n-octyl (meth)acrylate, 2-(meth)acrylate Ethylhexyl ester, dicyclopentanyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, iso-13-(meth)acrylate 201139469 Borneol ester, 1-adamantyl (meth)acrylate, 2-methyl-2-adamantyl (meth)acrylate and 2-ethyl-2-adamantyl (meth)acrylate An alkyl (meth)acrylate of a chain, a branched or an alicyclic skeleton, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, ( 2-hydroxybutyl methacrylate, 4-hydroxybutyl (meth) acrylate, cyclohexane dimethanol ( Hydroxy mono (meth) acrylate such as acrylate and decanediol mono (meth) acrylate, tetrahydroindenyl (meth) acrylate, cyclic trimethylolpropane formal (methyl) a (meth) acrylate containing a cyclic ether skeleton such as an acrylate or an alkoxylated tetrahydroindenyl (meth) acrylate, a (meth)acrylic acid 2·hydroxyethyl ester/caprolactone adduct and Hydroxy mono(meth)acrylate·caprolactone adduct of 2-hydroxypropyl (meth)acrylate/caprolactone adduct, polyethylene glycol mono(meth)acrylate, polypropylene glycol single (meth) acrylate, polypropylene glycol mono (meth) acrylate, poly (ethylene glycol propylene glycol) mono (meth) acrylate, poly (ethylene glycol • tetramethyl glycol) mono (methyl) Polyalkylene glycol modified hydroxy mono(meth)acrylate such as acrylate and poly(propylene glycol·tetramethyl glycol) mono(meth)acrylate, methoxypolyethylene glycol mono(methyl) Acrylate, methoxypolypropylene glycol mono(meth)acrylate and ethoxypolyethylene glycol single Alkyl-terminated polyalkylene glycol mono(meth)acrylate such as methacrylate or the like, 2,2,2-trifluoromethyl (meth)acrylate, 2-(perfluorobutyl)(meth)acrylate a fluorine-containing (meth) acrylate such as ethyl ester, 3-(perfluorobutyl)-2-hydroxypropyl (meth)acrylate or 2-(perfluorohexyl)ethyl (meth)acrylate, N - (meth) acrylate containing quinone imine, such as cyclohexylmaleimide and N-(meth) propylene methoxyethyl hexahydrobenzidine, and having dimethyl methoxy oxane -14- 201139469 A (meth)acrylic acid oxime compound such as a single (meth) acrylate of a skeleton. The respective contents of the above-mentioned (A-1) copolymerized resin and (A-2) copolymerized resin, the respective contents of the aromatic hydrocarbon skeleton, the lower limit 难, the flame retardancy, and the compatibility with the (c) diluent and the like It is preferably 5% by mass, and more preferably 1% by mass. Further, the upper limit 较好 is preferably 40% by mass, and more preferably 30% by mass, from the viewpoint of flexibility of the solder resist film. (A-1) Copolymerized resin, (A-2) copolymerized resin can be synthesized by a conventional solution polymerization method. The solvent to be used is not particularly limited as long as it is inert to radical polymerization. Examples thereof include ethylene glycol monoalkyl ether acetates such as ethyl acetate, isoacetic acid acetate, cellosolve acetate, and butyl cellosolve acetate; diethylene glycol monomethyl ether acetate; Diethylene glycol monoalkyl ether acetates such as carbitol acetate and butyl carbitol acetate; acetates such as propylene glycol monoalkyl ether acetates and dipropylene glycol monoalkyl ether acetates Diethylene glycol dialkyl ethers such as diethylene glycol dialkyl ethers, methyl carbitol, ethyl carbitol, butyl carbitol, etc.; triethylene glycol dialkyl ethers; a propylene glycol dialkyl ether; a dipropylene glycol dialkyl ether: an ether such as I,4-dioxane or tetrahydrofuran; a ketone such as acetone 'methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone; Hydrocarbons such as benzene, toluene, xylene, octane and decane; petroleum solvents such as petroleum ether, petroleum brain, hydrogenated petroleum brain, solvent naphtha, etc.; methyl lactate, ethyl lactate, butyl lactate And other lactates; dimethylformamide, N-methylpyrrolidone, and the like. These solvents may be used singly or in combination of two or more. The amount of the solvent to be used is 30 to 1000 parts by mass, preferably 50 to 800 parts by mass, per part by mass of the copolymerized resin. -15- 201139469 The radical polymerization initiator used in the solution polymerization method is not particularly limited, and for example, an organic peroxide or an azo compound can be used. Specific examples may include benzammonium peroxide, diisopropylbenzene peroxide, diisopropyl peroxide, ditributyl peroxide, t-butylperoxybenzoate, Trihexylperoxybenzoate, tert-butylperoxy-2-ethylhexanoate, third hexylperoxy-2-ethylhexanoate, 1,1-double (third -based oxy)-3,3,5-trimethylcyclohexane, 2,5-dimethyl-2,5-bis(t-butylperoxy)hexyl-3,3.isopropyl Hydrogen peroxide, tert-butyl hydroperoxide, diisopropylbenzene peroxide, diisopropylbenzene hydroperoxide, acetyl peroxide, bis(4-t-butylcyclohexyl)peroxy Carbonate, diisopropylperoxydicarbonate, isobutyl peroxide, 3,3,5-trimethylhexyl peroxide, lauryl peroxide, 1,1-double Tributylperoxy)3,3,5-trimethylcyclohexane, 1,1-bis(t-hexylperoxy)3,3,5-trimethylcyclohexane, azobis Nitrile, azobiscarbamide, and the like. The radical polymerization initiator is a person who appropriately selects an appropriate half life depending on the polymerization temperature. The total amount of the radical polymerization initiator to be used is 0.5 to 20 parts by mass, preferably 1 to 10 parts by mass, based on the total of the radically polymerizable unsaturated compound. The polymerization method may be carried out by adding an unsaturated monomer and a radical polymerization initiator to a solvent heated at a temperature, followed by stirring, or dissolving the unsaturated monomer and the radical polymerization initiator in a solvent and heating while stirring. Polymerization. Further, a radical polymerization initiator may be added to the solvent and the unsaturated monomer may be added dropwise at elevated temperature. By reacting a compound having an oxirane ring and an ethylenically unsaturated bond with a part of the carboxyl group of -16 - 201139469 in the copolymerized resin of (A-1) obtained by the above polymerization method, A copolymerized resin of (A-2) was obtained. The addition amount of the compound having an oxirane ring and an ethylenically unsaturated bond with respect to 1 equivalent of the carboxyl group in the copolymerized resin of (A-1), the lower limit 値 is 0.1 in terms of ensuring sufficient photosensitivity The equivalent weight is preferably 0.2 equivalent. Further, the upper limit 0.8 is 0.8 equivalent, preferably 0.6 equivalent, from the viewpoint that the amount of the carboxyl group is too small and the development property is insufficient. Further, the catalyst used in the reaction of the carboxyl group in the copolymerized resin of (A-1) with the compound having an oxirane ring and an ethylenically unsaturated bond is exemplified by, for example, triphenylphosphine or lithium naphthenate. , naphthenic acid pin, chromium naphthenate, chromium acetyl acetonate, chromium chloride, and the like. Further, the polymerization inhibitor may, for example, be methoxyhydroquinone or the like. The reaction can be carried out by a conventional method, and, for example, the copolymerized resin of (A-1) in the solvent obtained by the above polymerization reaction is set to a specific temperature, and then mixed with an oxirane ring and an ethylenically unsaturated bond. A method of stirring a compound, the above-mentioned catalyst, and the above polymerization inhibitor. In this case, the amount of the catalyst used is 0.01 to 1% by mass based on the total of the (A-1) copolymer resin and the compound having an ethylene oxide ring and an ethylenically unsaturated bond. The polymerization inhibitor is used in an amount of 〇.〇1~; with respect to (A-1) the copolymerized resin and the compound having an oxirane ring and an ethylenically unsaturated bond; Quality %. Further, the reaction temperature is 60 to 150 ° C, and the reaction time is 3 to 60 hours. The weight average molecular weight of the (A-1) copolymer resin is 3,000, preferably 5,000, from the viewpoint of the toughness of the cured coating film and the dryness of the touch. On the other hand, the upper limit 为 is 200,000, preferably 50,000, from the viewpoint of compatibility with (c) a diluent or the like and alkali developability. Further, the lower limit 値 of the weight average molecular weight of the (A-2) copolymerized resin is preferably 3000 Å from the viewpoint of the toughness of the cured coating film and the dryness of the touch. On the other hand, the upper limit 値 is 2, 000 〇〇, preferably 50,000 〇 (A-1) from the viewpoint of (c) thinner and the like. The acid value of the polymer resin and the (A-2) copolymer resin is preferably in the range of 30 to 150 mgKOH/g. This is because the acidity of the (B) hardener component is lowered when the acid value is less than 30 mg KOH/g, or the uncured alkaline resin composition is difficult to remove the uncured resin composition, and more than 150 mg Κ Ο H / g At the time, the moisture resistance and electrical properties of the hardened film deteriorate. (B) Hardener The hardener is used to increase the crosslinking density of the cured coating film, and to obtain a sufficiently hard coating film, for example, an epoxy resin is added. As the epoxy resin, for example, bisphenol A type epoxy resin, novolak type epoxy resin (phenol novolac type epoxy resin, o-cresol novolak type epoxy resin, p-tert-butylphenol novolac type varnish) Type, etc., bisphenol F or bisphenol S type epoxy resin, bisphenol E type epoxy resin, 2,5-di-tert-butyl hydrogen obtained by reacting epichlorohydrin with bisphenol F or bisphenol S Anthraquinone type epoxy resin, biphenyl type epoxy resin, and alicyclic epoxy resin having cyclohexene oxide, tricyclodecanyl group, oxidized cyclopentenyl group, etc., hydrogenated bisphenol A type epoxy resin , nuclear hydrogenated epoxy resin such as nuclear hydrogenated biphenyl type epoxy resin, ginseng (2,3-epoxypropyl) isocyanurate, triglycidyl ginseng (2-hydroxyethyl) isocyanide a triglycidyl triglycidyl isocyanurate such as a urethane, a dicyclopentadiene type epoxy tree-18-201139469 fat, a diamond-type epoxy resin, a phthalic anhydride diglycidyl ester, Ester-type epoxy resin such as hexahydrophthalic anhydride diglycidyl ester, melamine, methylation via methyl melamine, butylated hydroxymethyl trimerization Amines, imidazoles, dicyandiamide Amides like. These compounds may be used singly or in combination of two or more kinds thereof. The amount of the curing agent used is from 10 to 100 parts by mass based on 100 parts by mass of the copolymerized resin, from the viewpoint of obtaining a sufficient coating film after curing. It is preferably from 20 to 50 parts by mass. (C) Diluent The diluent is, for example, a photopolymerizable monomer, which is used to sufficiently harden the photocurable resin to obtain a solder resist film having acid resistance, heat resistance and alkali resistance. The photopolymerizable monomer may, for example, be 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate. , polyethylene glycol di(meth)acrylate, dipentaerythritol hexaacrylate, bisphenol A type EO modified di(meth)acrylate, bisphenol A type PO modified di(meth)acrylate a caprolactone-modified dipentaerythritol hexaacrylate, an EO-modified dipentaerythritol hexapropyl acid ester, for example, by using a (meth)acrylic group with a compound having one or more hydroxyl groups and a compound having one or more isocyanate groups The urethane-based acrylic compound obtained by the reaction or the like. The amount of the diluent to be used is 2.0 to 150 parts by mass, preferably 10 to 80 parts by mass, per 100 parts by mass of the copolymerized resin. Further, when a diluent having two or more (meth)acrylic groups is used, the (meth)acrylic equivalent is preferably 200 g/eq or more, and preferably 300 g/eq from the viewpoint of flexibility and low warpage. the above. Further, the (meth)acrylic equivalent of -19-201139469 in the present specification means the molecular weight of each (meth)acryl fluorenyl group. In addition to the above components, the present invention may be formulated as needed. (D) Inorganic white pigment The inorganic white pigment is an anatase type titanium oxide or a rutile type titanium oxide, for example, to whiten the coating film. The anatase type titanium oxide is higher in whiteness than the rutile type titanium oxide. However, since it has photocatalytic activity, it may cause discoloration of the resin in the curable resin composition. In contrast, rutile-type titanium oxide has almost no photocatalytic activity, so that it is preferable from the viewpoint of preventing discoloration of the solder resist film. The average particle diameter of the rutile-type titanium oxide particles is not particularly limited, but is usually 0.01 to 1 μm. Further, the surface treatment agent for the rutile-type titanium oxide particles is also not particularly limited. For the rutile-type titanium oxide, for example, "TR-600", "TR-700", "TR-7 50", "TR-840" manufactured by Fujitsu Industries Co., Ltd., and "Ishihara Industry Co., Ltd." can be used. R-550", "R-580", "R-630", "R-820", "CR-50", "CR-60", "CR-90", "CR-93", Titanium Industry ( "KR-270", "KR-310", "KR-380" manufactured by TAYCA, and "JR-1 000" manufactured by TAYCA. The amount of the rutile-type titanium oxide used is 30 to 800 parts by mass, preferably 50 to 500 parts by mass, per 100 parts by mass of the copolymerized resin. (Ε) Photopolymerization initiator -20- 201139469 The photopolymerization initiator is not particularly limited as long as it is a general user, and is, for example, an oxime-based initiator, benzoin, acetophenone, 2-hydroxy-2-methyl Base-1_phenylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, benzophenone, and the like. The amount of the photopolymerization initiator to be used is 5 to 20 parts by mass, preferably 8 to 15 parts by mass, per 100 parts by mass of the copolymerized resin. (F) Phosphorus-based flame retardant The phosphorus-based flame retardant is used for imparting flame retardancy to a curable resin composition, and is exemplified by, for example, ginseng (chloroethyl) phosphate and ginseng (2,3-dichloropropane). Base) pity acid ester, ginseng (2_chloropropyl) phosphate, ginseng (2,3-bromopropyl) phosphate, ginseng (bromochloropropyl) phosphate, 2,3-dibromopropyl-2 , a halogen-containing phosphate such as 3-chloropropyl phosphate, ginseng (tribromophenyl) phosphate, ginseng (dibromophenyl) phosphate, or bis(tribromoneopentyl) phosphate: trimethyl Halogen-free aliphatic phosphate such as phosphate ester, triethylphosphoric acid vinegar, tributyl phosphate, trioctyl phosphate "tributyloxyethyl phosphate vinegar"; triphenyl phosphate, tolyl diphenyl phosphate Ester, xylyl phenyl phosphate, tricresyl phosphate, tri-dimethyl methacrylate, xylyl diphenyl phosphate, cis (isopropylphenyl) o- vinegar, cumene Diphenyl phosphate, diisopropylphenyl phenyl phosphate, ginseng (dimethylphenyl) phosphate, cis (tributylphenyl) phosphate, hydroxyphenyl diphenyl phosphate, Octyldiphenylphosphine Halogen-free aromatic phosphate such as ester; ginsyl aluminum hypophosphite, ginsyl aluminum ethyl hypophosphite, ginseng diphenyl hypophosphite, zinc diethyl phosphinate, bismethyl ethyl ; human zinc phosphate, zinc bis-phenyl hypophosphite, titanium bis-diethyl hypophosphite, titanium bis-diethyl hypophosphite, titanium bisethyl ethyl hypophosphite, hydrazine methyl ethyl phosphorous-21 - 201139469 acid Titanium, titanium diphenylphosphoric acid, metal phthalate, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-cold HCA), HCA and acrylate Addition reaction product of reaction product resin, addition of HCA and hydroquinone to HC A modified type compound, diphenylvinylphosphine oxide phosphine, trialkylphosphine oxide, hydroxy(hydroxyalkyl)phosphine oxide, etc. . In view of the environmental load, the phosphate ester, the metal salt of hypophosphorous acid, and the HCA-modified phosphine compound are not only excellent in flame retardancy and discoloration resistance. In other words, it is preferable that the amount of the phosphorous-phosphorus-based flame retardant is 3 to 20 parts by mass based on the copolymerized resin, thereby ensuring sufficient flame retardancy and reducing the mechanical strength of the solder resist film. , parts by mass. The metal hydroxide is formulated as a flame retardant auxiliary such as aluminum hydroxide. The amount thereof to be used is 1 to 100 parts by mass based on the copolymerization phase. Further, in the present invention, an appropriate component such as an antifoaming agent, a dispersing agent, an extender pigment, an inorganic organic solvent or the like may be further added as needed. As the antifoaming agent, those skilled in the art can be used, and examples thereof include a hydrocarbon system and an acrylic resin. The dispersing agent is exemplified by a coupling agent such as a lanthanide or an alumina system. The extender pigment may be exemplified by, for example, aluminum oxyhydroxide, ruthenium oxide, talc, mica or the like in order to increase the physical strength of the photoresist film. As a compound of hypophosphorous acid such as inorganic titanium (hereinafter referred to as HCA and an epoxy reaction product, a triphenylphosphine oxide phosphine compound, preferably a halogen-free compound or oxygen, and a metal salt resistant to exudation. 100 parts by mass is, on the one hand, preferably 4 to 15 , and can be exemplified by the example of the fat 100 mass compounding various ion trapping agents, such as, for example, an oxygen-based system: titanate high-coated solder resist, barium sulfate In the organic solvent, for example, methyl ethyl ketone, cyclohexanone, etc. may be mentioned, for example, methyl ketone or cyclohexanone. Aromatic hydrocarbons such as ketones, toluene and xylene; alcohols such as methanol, isopropanol and cyclohexanol; alicyclic hydrocarbons such as cyclohexane and methylcyclohexane; petroleum ether, petroleum brain, etc. Petroleum solvent, cellosolve, cellosolve, etc., carbitol, carbitol, butyl carbitol, ethyl acetate, butyl acetate, cellosolve acetate, butyl Fibrous acetate, carbitol acetate, butyl The method of producing the curable resin composition of the present invention is not limited to a specific method, but may be premixed by a mixer, for example, by blending the above components in a specific ratio. This is produced by mixing and dispersing three rolls at room temperature. Next, the method of applying the curable resin composition of the present invention will be described. When the curable resin composition of the present invention obtained as described above is thermally cured, for example, It can be applied to a desired thickness by a method such as a screen printing method or a spray coating method on a printed wiring board having a copper foil in which a copper-clad laminate is etched to form a circuit pattern, and is 130 to 170. (The hot air circulation type dryer or the like is heated for 20 to 80 minutes, and the curable resin composition is thermally cured to form a desired solder resist film on the printed wiring board. The curable resin of the present invention obtained as described above is obtained. When the composition is photocured, for example, it can be applied to a flexible wiring board having a circuit pattern formed by etching a copper foil by a screen printing method or a spray coating method. After the thickness is required, it is heated for about 15 to 60 minutes at a temperature of about -23 to 2011 39469 at 60 to 80 ° C for volatilization of the solvent in the curable resin composition. Subsequently, the cured resin is applied. On the composition, a negative film having a light transmissive pattern other than the line of the circuit pattern is adhered, and ultraviolet rays are irradiated thereon. Then, the non-exposed area corresponding to the above-mentioned lane is removed by using a dilute aqueous alkali solution. Thereby, the coating film is developed. The development method uses a spray method, a rinsing method, etc., and the dilute alkali aqueous solution used is generally 0.5 to 5% aqueous sodium carbonate solution, but other alkalis may be used. Next, 1 3 0 to 1 7 (The hot air circulating dryer of TC is pre-baked for 20 to 80 minutes to form a target solder resist film on the flexible wiring board. On the flexible wiring board coated with the solder resist film thus obtained, an electronic circuit unit is formed by soldering electronic parts by a jet welding method or a reflow soldering method. [Examples] The examples of the present invention are described below, but the present invention is not limited by the embodiments as long as it does not go beyond its spirit. (Al) (A-2) Synthetic Synthesis Example 1 of a carboxyl group-containing copolymer resin having an aromatic ring. Dipropylene glycol monomethyl ether (hereinafter referred to as DPM) was placed in a 500 mL four-necked flask equipped with a stirrer, a thermometer, and a reflux tube. After raising the temperature to 120 ° C in a nitrogen atmosphere, 17.2 g (0.2 mol) of methacrylic acid and phenoxyethyl methacrylate (SR-3 40 manufactured by Sart〇mer Co., Ltd.) were added dropwise in about one hour. Is PEMA) 92.8g (0,45m〇1), 2,2,_even-24- 201139469 Nitrogen bis(2-methylpropionic acid) dimethyl ester (V-601 manufactured by Wako Pure Chemical Industries, hereinafter referred to as DMAMP) A mixed solution of 4.6 g and DPM 10 g was stirred at 120 ° C for 3 hours to form a DPM solution containing about 49% by mass of the copolymerized resin of Synthesis Example 1 to obtain a copolymerized resin of Synthesis Example 1. The weight average molecular weight of the carboxyl group-containing copolymer resin of the ring was about 25,000 (in terms of polystyrene), and the solid content acid value was 98 mgKOH/g. Synthesis Example 2 125 g of dipropylene glycol monomethyl ether (hereinafter referred to as DPM) was placed in a 50 mL four-necked flask equipped with a stirrer, a thermometer, and a reflux tube, and the temperature was raised to 1,200 ° C in a nitrogen atmosphere for about one hour. A mixed solution of 34.4 g (0.4 mol) of methacrylic acid, 82.5 g (0.4 mol) of hydrazine, 5.5 g of DMAMP and DPM 10 g was added dropwise, and the mixture was stirred at 120 ° C for 3 hours to obtain a copolymer having a carboxyl group. Next, after the temperature in the flask was lowered to 1 〇〇t, a mixed gas of air and nitrogen was introduced into the flask at 200 mL/min, and glycidyl methacrylate (PRENMER GH manufactured by Nippon Oil & Fats Co., Ltd., hereinafter referred to as hereinafter) was added. GMA) 21.3 g (0.15 mol), triphenylphosphine (hereinafter referred to as TPP) as a reaction catalyst, 3 g, and methoxyhydroquinone (hereinafter referred to as MEHQ) 0·1 g as a polymerization inhibitor. After reacting at 100 ° C for 5 hours, the reaction was continued at 1 15 ° C until the acid value was stopped to decrease, and a DPM solution containing about 52% by mass of the copolymerized resin of Synthesis Example 2 was obtained to obtain a copolymerized resin of Synthesis Example 2. . The weight average molecular weight was about 18,000 (in terms of polystyrene), and the solid content acid value was 97 mgKOH/g. -25- 201139469 Synthesis Example 3 In place of replacing 82.5 g (0.4 mol) of PBM of Synthesis Example 2 with 74.2 g (0.36 mol), GMA 21.3 g (〇.15 mol) was replaced with 4-hydroxybutyl acrylate glycidyl ether ( In the same manner as in Synthesis Example 2, 4-HB AGE manufactured by Nippon Kasei Co., Ltd., hereinafter referred to as 4-HB AGE, 30.0 g (0.15 mol), was formed into a DPM solution containing a copolymerization resin of Synthesis Example 3 of about 52% by mass. The copolymerized resin of Synthesis Example 3 was obtained. The weight average molecular weight was about 16,000 (in terms of polystyrene), and the solid content acid value was 97 mgKOH/g. Synthesis Example 4 In place of replacing DPM 1 25g of Synthesis Example 2 with 1 60 g, 34.4 g (0.4 mol) of methacrylic acid was replaced with 56-8 g (0.66 mol), and 82.5 g (0.4 mol) of ruthenium was replaced with 47.4 g (0.23 mol). In the same manner as in Synthesis Example 2, a synthesis example containing about 52% by mass was produced, except that DMAMP 5.5g was replaced by 6.5 g, and GMA 21.3 g (0.15 mol) was replaced by 4-HBAGE 70.1 g (0.35 mol). The DPM solution of the copolymerized resin of 4 gave the copolymerized resin of Synthesis Example 4. The weight average molecular weight was about 1 9000 (polystyrene conversion), and the solid content acid value was 96 mg K 〇 H / g. Synthesis Example 5 In place of 82.5 g (0.4 mol) of hydrazine of Synthesis Example 2, 2-(2-phenoxyethoxy)ethyl methacrylate (PRENMER PAE-100, hereinafter referred to as 2PEEMA) 85.1 g was replaced. In the same manner as in Synthesis Example 2, -26-201139469, a DPM solution containing a copolymerization resin of Synthesis Example 5 of about 52% by mass was produced to obtain a copolymerized resin of Synthesis Example 5. The weight average molecular weight was about 1 8000 (in terms of polystyrene), and the solid content acid value was 96 mgKOH/g. Synthesis Example 6 A copolymer resin of Synthesis Example 6 containing about 52% by mass was produced in the same manner as in Synthesis Example 2 except that 82.5 g (0.4 m〇l) of the synthesis example 2 was replaced by 2PEEMA 75.1 g (0.3 mol). DPM solution 'The copolymerized resin of Synthesis Example 6 was obtained. The weight average molecular weight was about 2,000 (polystyrene conversion), and the solid content acid value was 97 mgKOH/g. Synthesis Example 7 In place of replacing 125 g of DPM of Synthesis Example 2 with 105 g, 34.4 g (0.4 mol) of methacrylic acid was replaced with 2 5.8 g (0 · 3 m ο 1 ), and ΡΕΜΑ 82.5 g (0.4 mol) was replaced with benzene. 42.7 g (0.4 mol) of ethylene and n-butyl methacrylate (acrylate BMA manufactured by Mitsubishi Corporation, hereinafter referred to as nBMA) 15.6 g (0.1 mol), and further replaced GMA21.3 g (0.15 mol) with 4-HBAGE. A DPM solution containing a copolymerization resin of Synthesis Example 7 of about 47% by mass was produced in the same manner as in Synthesis Example 2 except for 22.0 g (0.11 mol) to obtain a copolymer resin of Synthesis Example 7. The weight average molecular weight was about 14 Å (in terms of polystyrene), and the solid content acid value was 95 mg K 〇 H / g. Synthesis Example 8 In place of replacing 125 mg of DPM of Synthesis Example 2 with 110 g, 34.4 g of methacryl-27-201139469 acid (〇.4m〇l) was replaced with 25 2 g of acrylic acid (〇35ηι〇υ, pema 82.5 g (0.4) m 〇 l) was replaced with 59.8 g (0.29 m 〇 1), and dmamp 5 5g was replaced by 4 g. The same as in Synthesis Example 2, a DPM solution containing about 48% by mass of the copolymerized resin of Synthesis Example 8 was obtained. The copolymerized resin of Synthesis Example 8. The weight average molecular weight was about 16 Å (in terms of polystyrene), and the solid content acid value was 101 mgKOH/g. Synthesis Example 9 In addition to the methacrylic acid of Synthesis Example 2, 34.4 g (0.4 mol) 23.8 g (0.33 mol) of acrylic acid, 82.5 g (0.4 mol) of ruthenium, 57.6 g (0.23 mol) of 2PEEMA, and 5.5 g of DMAMP were replaced with 4.0 g, and the same as in Synthesis Example 2, the formation was about 48. The DPM solution of the copolymerized resin of Synthesis Example 9 was obtained as the copolymerized resin of Synthesis Example 9. The weight average molecular weight was about 15,000 (in terms of polystyrene), and the acid value of the solid content was 94 mgKOH/g. , showing the resin raw material ratio (mole) and aromatic hydrocarbon skeleton ratio of the above Synthesis Examples 1 to 9 (% by mass) And acid value (mgKOH/g) -28 - 201139469 [ml <7> 1 s ο 1 1 S 1 to o I r- CO 1 s ο 1 〇» Csl 1 1 to . 5 1 〇r- CO 1 1 1 i 1 5 CO S CO 1 1 1 CO 1 1 ΙΟ 5 Γ- σ> irt 1 1 1 5 c> 1 i〇5 1 σ» σ> inch o 1 1 S 〇1 1 1 s ο ο «ο σ> CO 1 1 〇1 1 ΙΑ 5 S (Ο 〇&gt ; Csl 1 1 々1 1 in 〇1 CM σ> e\i 1 1 S 1 1 1 1 S m chain <n 雔 s? r paste κ- Zhao line K3 < § CL |2PEEMA 1 < CD C <<D [4-HBAGE 1 豳 fine* paste 羝 cat hanging m neighbor K-© ^km- mm <[Q 明QK·淞线K3 赵mm mm- Κ)«Ν 獬 遨 遨 遨 κ κ κ κ κ κ 2 t t t t 2 tm acid value (mg KOH / g) 11 -29 - 201139469 Comparative Synthesis Example 1 for installation In a 500 mL four-necked flask equipped with a stirrer, a thermometer, and a reflux tube, 80 g of propylene glycol diacetate (hereinafter referred to as PGDA) was charged, and after heating to 90 ° C in a nitrogen atmosphere, GMA 28.4 g was added dropwise over about 1 hour. (0.2 mol), a caprolactone adduct of 2-hydroxyethyl methacrylate (average addition of 1 mol, PRAXCELL FM1D manufactured by DAICEL Chemical Industry) 49.9 g (0.2 mol), DMAMP lg, thiopropionic acid 2 After a mixed solution of ethylhexyl ester (EHMP, manufactured by Seiko Chemical Industry Co., Ltd., EHMP) and PGDA (80 g), the mixture was stirred at 90 ° C for 8 hours to obtain a copolymer having an epoxy group. Next, a mixed gas of air and nitrogen (nitrogen volume to air volume ratio of 1 to 2) was introduced into the flask at 200 mL/min, and 72.02 g (0.21 mol) of acrylic acid and 0.5 g of TPP as a reaction catalyst were added. 0.2 g of MEHQ as a polymerization inhibitor was reacted at 100 ° C for 5 hours, and then the reaction was continued at 1 15 ° C until the acid value was stopped to decrease, and the addition reaction of the epoxy group of the copolymer with the carboxyl group of acrylic acid was carried out. After the acid value was 2 or less, the temperature in the flask was lowered to 90 ° C, and then 16.0 g (0.16 mol) of succinic anhydride was added and reacted for 8 hours or more to carry out a ring-opening addition reaction of the acid anhydride. When the peak of the acid anhydride disappeared as the end point of the reaction, the copolymerized resin solution of Comparative Synthesis Example 1 having no aromatic hydrocarbon skeleton was obtained. The resin solution had a solid content of about 40% by mass, a weight average molecular weight of about 12,000 (polystyrene conversion), and a solid content acid value of 78 mg KOH/g. Comparative Synthesis Example 2 In a 500 mL four-necked -30-201139469 bottle equipped with a stirrer, a thermometer, and a reflux tube, 105 g of DPM was charged, and after heating to 12 ° C in a nitrogen atmosphere, methyl group was added dropwise over about 1 hour. Acrylic acid 4 3.0 g (0.5 m ο 1), π - Β Μ A 21.3 g (0-15 mol), DMAMP 4.5 g and DPM lOg mixed solution, and stirred at 120 ° C for 3 hours to obtain a copolymer having a carboxyl group β Next, after the temperature in the flask was lowered to 1 〇〇 ° C, a mixed gas of air and nitrogen was introduced into the flask at 200 mL/min (nitrogen volume to air volume ratio was 1 to 2), and 〇 八 八 14.28 was added. (0.1:11〇1) and p-tolyl glycidyl ether (m,p-CGE, manufactured by 坂本药) 32.8g (0.2mol), triphenylphosphine (hereinafter referred to as TPP) as a reaction catalyst. 3g, methoxyhydroquinone (hereinafter referred to as MEHQ) 〇.lg as a polymerization inhibitor, after reacting at 10 ° C for 5 hours, the reaction is continued at 1 15 ° C until the acid value stops decreasing, and the formation contains about 48. a mass% of a copolymerized resin having a carboxyl group, an aromatic hydrocarbon skeleton having a hydrogen atom at the alpha position of the side chain, and a methacrylic group DPM was obtained in Comparative Synthesis Example 2 Copolymerization of tree resin. The weight average molecular weight is about 15,000 (in terms of polystyrene), and the solid component acid value is 96 mg KOH/g. Comparative Synthesis Example 3 except that 14.8 g (0.1 mol) of GMA of Comparative Synthesis Example 2 and 32.8 g (0.2 mol) of p-tolyl glycidyl ether were replaced with GMA 4 2.6 g (0.3 m ο 1 ), In the same manner as in Synthesis Example 2, a DPM solution containing about 49% by mass of a copolymer resin having a carboxyl group and a methylpropane acid group but having no aromatic tobacco skeleton was produced, and a copolymer resin of Comparative Synthesis Example 3 was obtained. The weight average molecular weight is about 15,000 (in terms of polystyrene), and the solid -31 - 201139469 component has an acid value of 10 mg KOH/g. Examples 1 to 25 and Comparative Examples 1 to 9 The blending ratios shown in the following Tables 2, 3, and 4 were blended, and the mixture was mixed and dispersed at room temperature to prepare a curable resin composition of the example. Next, coating was carried out as follows. Make a test piece. Indicates the part by mass. Each of the components was prepared by mixing in the following Tables 2, 3, and 4, and the prepared curable resin composition was used in the following two sheets, in the following Tables 2, 3, and 4; The amount shown is -32-201139469 [Ϊ1 Comparative Example CO Ο r- ΙΟ CM co 8 8 os CNJ Ο ms S 200 r — ο in CM CO ssos Example 100 in s 200 CO ο lO CM CO ssos CNJ Ο in 8 os 100 in CNJ CO so CSI Synthesis Example 1 Synthesis Example 2 Comparative Synthesis Example 1 Comparative Synthesis Example 2 EPICOTE 828 Melamine DPHA DPM Rutile Titanium 1 KS-66 (Α-1) (Α-2) Copolymerized Resin ( B) Hardener (c) Thinner (D) Inorganic White Pigment Defoamer-33- 201139469 In Table 2, EPICOTE 828: bisphenol A epoxy resin made by Japan Epoxy Resin Co., DPHA: Nipponization Dipentaerythritol hexaacrylate manufactured by Pharmacy Co., Ltd., dipropylene glycol monomethyl ether manufactured by DPM 'Concord Fermentation Industry Co., Ltd., rutile type titanium oxide: manufactured by Ishihara Sangyo Co., Ltd. [CR-80], KS 66: Shin-Etsu Oxygenated oil made by the company. -34- 201139469

【eM 比較例 1 CO § in CM CO in S s CM CM in 〇 CO in S s CNJ CM 〇 in CM CO in s § CM r· m 叶 100 m CSJ CO m >r— s g CM 04 CO 〇 in CM CO m s s CM CM T— CM 〇 m CM Γ0 m s s CSJ CM 100 m CM CO m s § OJ CM 产 〇 〇 Τ— in CM CO in s s CM CM T— Μ 〇» 〇 m CVJ CO o s s CM CSi CO 〇 l〇 CM CO LC s s Csi CM 卜 ο CO to s § Oi CM 产 co ο lO CM CO m r— s s CSJ CSi r·» in o T— m CM CO in C>J 8 g CM CM <α 合成例2 合成例3 合成例4 合成例5 合成例6 合成例7 合成例8 合成例9 比較合成例1 比較合成例2 EPICOTE 828 YX-8000 三聚氰胺 DPHA 0PM 金紅石型氧化鈦 CR-80 TPO BAPO KS-66 x—v t〇3 ^<π 5* (B)硬化劑 (c)稀釋劑 (D)無機白色顔料 (E)光聚合起始劑 w m -35- 201139469 表3中 YX-8000:日本環氧樹脂（股）製之核氫化雙酚A型環 氧樹脂 TPO: 2,4,6-三甲基苯甲醯基-二苯基氧化膦 BAPO:雙（2,4,6-三甲基苯甲醯基）-苯基氧化膦 -36- 201139469 【寸m】 比較例 .1 σ> 1 _ 100 I O 严 o o CO to s in s CSI eg o GO § 1— o o o CO in s tn § CM CM O T· r- o o o o CO in s in s CM CS| o 實施例 1 «s o o o o C9 in s m s CM o s o o o o CO m s in s .CM e\i o CO Ol s s o o o CO (A 8 m s Cs* m ο in CM CSj o o o o CO in s in s CM CM o s I 100 I o Q o CO u> 8 m s CM CM o S ο o 〇 o CO O in g CS C>i o CD Ο o 〇 o c〇 \r> s m s 〇» «Μ o CO Ο o Ψ» 〇 o CO o s s CM o 卜 ο in 1*^ 8 C3 s g CM CM o CO s S 〇 s o l〇 io s CNJ CM o in T— S s o 〇 o CO in IO s CM CM o P 合成例〗 Ί Γ-ί 链 1 合成例3 ] | 合成例4 1 | 合成例5 I | 合成例6 I I 合成例7 I I 合成例8 | I 合成例9 I 链 An 1 -比較合成例3 1 | ACA-2250 I I EPICOTE 828 | I EPICOTE 1004F | | YDC-1312 Π I 三聚氛胺 I BP-4EA: (甲基)丙烯酸當量約 255g/eq AH-600: (甲基)丙烯酸當量約 305e/ea g$s 51 ll| 逛 Ifl 想 〇|S §11 金紅石型氧化鈦 CR-80 | SPEEDCURE TPO | IRGACURE819 ] 叁二乙基次磷酸鋁 淫 m 擀 ΠΙ | Ks-ββ | (A-1XA-2) 共聚合樹脂 (B)硬化劑 (c)稀釋劑 (D憮機白色顔料 (E)光聚合起始劑 (F)磷系難燃劑 唾 § 1 消泡劑 1 -37- 201139469 表4中 ACA-Z2 5 0 ： DAICEL化學工業（股）製之樹脂溶液（具 有脂環式骨架，不具有芳香族烴骨架，具有羧基及丙烯酸 基） EPICOTE1 004F ：日本環氧樹脂（股）製之雙酚A型環 氧樹脂 YDC-1312 :東都化成（股）製造之二-第三丁基氫醌改 質之環氧樹脂 BP4EA ：共榮社化學公司製造之EO改質之雙酚A型 丙烯酸酯（EO = 4) AH-6 00 :共榮社化學公司製造 2官能胺基甲酸酯改 質之環氧丙烯酸酯 EBECRYL3 708 ： DAICEL SCIENTIC(股）製 2 官能環 氧丙烯酸酯 UF-8 001 G :共榮社化學公司製造 2官能胺基甲酸酯 丙烯酸酯 SPEEDCURE TPO ：日本 DKSH Japan 公司製 IGRACURE819:汽巴特用化學品公司製 試驗片製作步驟1(實施例1〜4、比較例3) 係製作用以評價經熱硬化塗膜之反射率及變色性之試 驗片製作步驟，於藉由分段硏磨進行表面處理之貼銅層合 板上以網版印刷法，塗佈硬化性樹脂組成物後，於BOX 爐內於1 50°C進行60分鐘固化，形成硬化塗膜。固化後 -38- 201139469 之硬化塗膜厚度爲2 0-23 // m。 試驗片製作步驟2(實施例5~14、比較例4~6) 係製作用以評價形成於硬質基板上之硬化塗膜之反射 率及變色性之試驗片製作步驟，於藉由分段硏磨進行表面 處理之貼銅層合板上以網版印刷法，塗佈硬化性樹脂組成 物後，於BOX爐內於80 °C進行20分鐘預備乾燥。預備 乾燥後’於塗膜上以曝光裝置（OAK公司製造之HMW-680GW)曝光500mJ/cm2後，以30°C、1%碳酸鈉水溶液顯 像後’於BOX爐內於150°C進行60分鐘固化，於貼銅層 合板上形成硬化塗膜。硬化塗膜厚度爲20〜23 // m。 試驗片製作步驟3(實施例1 5〜25、比較例7〜9) 係製作用以評價形成於可撓性基板上之硬化塗膜之反 射率及變色性之試驗片製作步驟，於藉由稀硫酸（3%)進行 表面處理之可撓性基板（新日鐵化學公司製，ESP AN EX MB系列）之銅體上以網版印刷法，塗佈硬化性樹脂組成物 後，於BOX爐內於8(TC進行20分鐘預備乾燥。預備乾 燥後，於塗膜上以曝光裝置（OAK公司製造之 HMW_ 68 0GW)曝光5 00mJ/cm2後，以30°C、1%碳酸鈉水溶液顯 像後，於BOX爐內於15(TC進行60分鐘固化，於可撓性 基板上形成硬化塗膜。硬化塗膜厚度爲2 0〜23 M m。 試驗片製作步驟4(實施例15〜25、比較例7~9) -39- 201139469 係製作用以評價形成於可撓性基板上之硬化塗膜之鹼 顯像性 '翹曲性、難燃性之試驗片製作步驟，於聚醯亞胺 膜（TORAY DUPONT(股）製造之 CAPTON 100H)上形成銅 體電路圖型之可撓性基板藉由稀硫酸（3 %)表面處理後，以 網版印刷法，塗佈硬化性樹脂組成物後，於B OX爐內於 8〇t進行20分鐘預備乾燥。預備乾燥後，於塗膜上以曝 光裝置（OAK公司製造之 HMW-680GW)曝光 500mJ/cm2 後，以30°C、1 %碳酸鈉水溶液顯像後，於BOX爐內於 150°C進行60分鐘固化，於可撓性基板上形成硬化塗膜。 硬化塗膜厚度爲20〜23 # m。 (1 )反射率 使用分光光度計U-3 4 10(日立製作所（股）製造： φ60πιηι積分球），測定於450nm之反射率。且所謂「初 期」意指固化後，所謂「熱劣化後」意指回焊處理後，所 謂「光劣化後」意指UV照射5(H/cm2後，所謂「加溫加 濕後」意指在85°C、85%RH放置1 000小時後。 (2)目視 係針對硬化塗膜外觀，用以藉目視確認由白色變色至 黃色之程度之指標，以下列4個階段評價’：◎:完全未見 到黃色變色而爲白色度高之外觀，〇：稍見到黃色變色但 仍爲白色外觀，△:稍見到黃色變色爲帶有黃色樣之外 觀，X:強烈見到黃色變色爲茶黃色外觀。 -40- 201139469 (3 )鹼顯像性 係在顯像後，以目視評價銅體上及聚醯亞胺上有無殘 留物者，以下列3個階段評價：〇：銅體上、聚醯亞胺上 均無殘留物，△:銅體上雖無殘留物，但聚醯亞胺上稍殘 留有殘留物，X:銅體上及聚醯亞胺均殘留有殘留物。 (4 )柔軟性 係針對曝光後之塗膜，利用圓筒形芯軸法，以目視及 以χ2〇0之光學顯微鏡觀察塗膜之柔軟性加以評價者，以 下列3個階段評價：〇：於直徑2mm以下無異常，△: 於直徑4mm雖無異常，但在直徑2mm以下有龜裂、剝離 等異常，X :於直徑4mm以上有龜裂、剝離等異常。 (5)翹曲性 將試驗片切出2cm x2.5cm後，於水平台上以上面成 爲凹狀平穩地放置試驗片，以未特別施加外力之方式，以 直尺測量四處角落與平台間之垂直間隔測量至1 mm之單 位，以其最大値作爲翹曲量。關於測定結果，以下述三個 階段評價：〇：未達5mm之翹曲量，△ : 5〜8mm之曲 量，X :超過8mm之翅曲量。 (6)難燃性 針對試驗片，依據UL94規格進行垂直燃燒試驗。評 201139469 價係基於UL94規格，以VTM-0〜燃燒表示。 實施例1〜2 5、比較例1〜9之測定結果示於下表5、 [表5] 實方 _ 比較例 1 2 3 4 1 2 3 反射率(450nm) 初期 87 90 86 89 78 79 84 熱劣化後 86 88 85 87 65 63 70 光劣化後 84 87 83 86 75 78 75 目視 初期 ◎ ◎ ◎ ◎ △ Δ 0 熱劣化後 ◎ ◎ ◎ ◎ X X Δ 光劣化後 ◎ ◎ ◎ ◎ △ △ Δ -42- 201139469 【9*】 比較例 1 <〇 % ιο 〇 < < 1〇 CO ES CO < X < JO s co <1 X < 握 CNJ 00 s § ◎ ◎ ◎ CO OJ 00 ω ◎ ◎ ◎ CM eg 00 ◎ ◎ ◎ CNJ 00 ◎ ◎ ◎ 〇 CM 00 ◎ ◎ ◎ 胸 〇> CNJ 00 § % ◎ ◎ ◎ 00 CM 00 « ◎ ◎ ◎ 卜 <Si 00 § ◎ ◎ ◎ CO CM 00 ◎ ◎ ◎ 1〇 CO 00 % s ◎ ◎ ◎ 初期 熱劣化後 光劣化後 初期 熱劣化後 光劣化後 反射率(450nm) 目視 -43- 201139469 比較例 1 σ> CM 00 s ◎ ◎ ◎ X X X 燃焼 CO g CO ΙΟ ◎ ο 〇 <1 < 0 燃焼 卜 CO s < X < < 0 燃焼 實施例 ir> CM s « ◎ ◎ © 0 0 0 VTM-0 Si CM 00 5 g ◎ ◎ ◎ 0 〇 〇 VTM-0 CO CM » S CO ◎ 0 0 0 0 VTM-0 CN4 CM csi oo » » ◎ ◎ ◎ 〇 0 〇 VTM-0 CO 00 5 s ◎ ◎ ◎ 〇 〇 〇 VTM-0 s 00 00 ◎ ◎ ◎ 〇 〇 〇 VTM-0 cr> CO 00 s § ◎ ◎ ◎ 〇 0 〇 I VTM-0 | 00 CM 00 5 « ◎ ◎ ◎ 0 0 0 1 VTM-0 I 卜 τ— CM 00 00 s ◎ ◎ ◎ 0 0 0 I VTM-0 I to CM CO 5 ◎ ◎ ◎ 0 0 〇 1 VTM-Cl ip n 00 » s ◎ ◎ ◎ 〇 0 〇 1 VTM-0 1 初期 熱劣化後(回焊） 加锶加渴後 初期 熱劣化後(回焊） 加溫加濕後 i 1£ /*- ㉔ 目視 鹼顯像性 柔軟性 租 m 1 難燃性 丨 -44- 201139469 使本發明之硬化性樹脂組成物熱硬化時，由實施例 1〜4及比較例1、2可知，藉由使用（甲基）丙烯酸爲共聚物 之原料可抑制硬化皮膜之反射率降低及變色。且，由實施 例1〜4及比較例3可知，藉由使用聚合後，於芳香族烴骨 架之側鏈α位不具有氫原子之通式（II)及通式（III)，可抑 制硬化皮膜之反射率降低及變色。另一方面，於藉由加成 間，對-甲苯基縮水甘油醚，使得含有聚合後於側鏈α位有 氫原子之芳香族烴之比較例3，於初期（固化後）雖可抑制 硬化皮膜之.反射率降低及變色發生，但即使使用甲基丙燃 酸作爲共聚物之原料，於熱劣化後（回焊後）及光劣化（UV 照射5 OJ/cm2後），硬化皮膜之反射率亦降低且亦發生變 色。 使本發明之硬化性樹脂組成物於印刷基板上經光硬化 時，由實施例5〜1 4及比較例4、5可知，藉由使用（甲基） 丙烯酸爲共聚物之原料可抑制硬化皮膜之反射率降低及變 色。且，由實施例5~14及比較例6可知，藉由使用聚合 後，於芳香族烴骨架之側鏈α位不具有氫原子之通式（II) 及通式（III)，可抑制硬化皮膜之反射率降低及變色。另一 方面，於藉由加成間，對-甲苯基縮水甘油醚，使得含有聚 合後於側鏈α位有氫原子之芳香族烴之比較例6，於初期 (後固化後）雖可抑制硬化皮膜之反射率降低及變色發生， 但即使使用甲基丙烯酸作爲共聚物之原料，於光劣化後 (回焊後）及光劣化（UV照射50J/cm2後），硬化皮膜之反射 率亦降低且亦發生變色。 -45- 201139469 使本發明之硬化性樹脂組成物於撓性基板上經光硬化 時，由實施例1 5~25、比較例8、9與比較例7之對比可 知’藉由使用（甲基）丙烯酸爲共聚物之原料可抑制硬化皮 膜之反射率降低及變色。且，於實施例1 5〜25，鹼顯像 性、柔軟性、低翹曲性及難燃性均優異。另一方面，於比 較例7、8由於未含有芳香族烴骨架，故與（C)稀釋劑等之 相溶性變差，而使鹼顯像性降低，且難燃性及柔軟性亦降 低。由责施例〗5〜25及比較例9可知，藉由使用（甲基）丙 烯酸爲共聚物之原料，雖然不含有芳香族烴骨架亦可減小 反射率之降低且抑制變色發生，但由於不含芳香族烴骨架 而含有脂環式骨架，故與（C)稀釋劑等之相溶性差，鹼顯 像性降低，難燃性及柔軟性亦降低。且，於比較例9，翹 曲增大翹曲性亦差。 [產業之可能利用性] 本發明之硬化性樹脂組成物，可形成可防止經時及因 熱過程引起之反射率降低且具有柔軟性、低翹曲性之硬化 塗膜，故於印刷配線板之防焊光阻膜，尤其是於發光二極 體元件（LED)等之安裝用基板之防焊光阻膜領域之利用價 値高。 -46 -[eM Comparative Example 1 CO § in CM CO in S s CM CM in 〇CO in S s CNJ CM 〇in CM CO in s § CM r· m Leaf 100 m CSJ CO m >r- sg CM 04 CO 〇in CM CO mss CM CM T— CM 〇m CM Γ0 mss CSJ CM 100 m CM CO ms § OJ CM calving — in CM CO in ss CM CM T — Μ 〇» 〇m CVJ CO oss CM CSi CO 〇l 〇CM CO LC ss Csi CM ο o to § Oi CM production co ο lO CM CO mr — ss CSJ CSi r·» in o T— m CM CO in C> J 8 g CM CM < α Synthesis Example 2 Synthesis Example 3 Synthesis Example 4 Synthesis Example 5 Synthesis Example 6 Synthesis Example 7 Synthesis Example 8 Synthesis Example 9 Comparative Synthesis Example 1 Comparative Synthesis Example 2 EPICOTE 828 YX-8000 Melamine DPHA 0PM Rutile Titanium Oxide CR-80 TPO BAPO KS-66 X—vt〇3 ^<π 5* (B) hardener (c) thinner (D) inorganic white pigment (E) photopolymerization initiator wm -35- 201139469 Table 3 YX-8000: Japan epoxy Resin (stock) nuclear hydrogenation double Phenol type A epoxy resin TPO: 2,4,6-trimethylbenzimidyl-diphenylphosphine oxide BAPO: bis(2,4,6-trimethylbenzylidene)-phenylphosphine oxide -36- 201139469 [inch m] Comparative example.1 σ> 1 _ 100 IO strict oo CO to s in s CSI eg o GO § 1— ooo CO in s tn § CM CM OT· r- oooo CO in s in s CM CS| o Example 1 «soooo C9 in sms CM osoooo CO ms in s .CM e\io CO Ol ssooo CO (A 8 ms Cs* m ο in CM CSj oooo CO in s in s CM CM os I 100 I o Q o CO u> 8 ms CM CM o S ο o 〇o CO O in g CS C>io CD Ο o 〇oc〇\r> sms 〇» «Μ o CO Ο o Ψ» 〇o CO oss CM o卜ο in 1*^ 8 C3 sg CM CM o CO s S 〇sol〇io s CNJ CM o in T— S so 〇o CO in IO s CM CM o P Synthesis Example Ί Γ-ί Chain 1 Synthesis Example 3 ] Synthesis Example 4 1 | Synthesis Example 5 I | Synthesis Example 6 Synthesis Example 7 II Synthesis Example 8 | I Synthesis Example 9 I Chain An 1 - Comparative Synthesis Example 3 1 | ACA-2250 II EPICOTE 828 | I EPICOTE 1004F | | YDC-1312 Π I Trimeric amine I BP-4EA: (meth)acrylic equivalent of about 255g/eq AH-600: (meth)acrylic equivalent of about 305e/ea g$s 51 ll| Visit Ifl Think 〇|S §11 Rutile Titanium CR- 80 | SPEEDCURE TPO | IRGACURE819 ] 叁 diethylaluminum hypophosphite m m 擀ΠΙ | Ks-ββ | (A-1XA-2) copolymer resin (B) hardener (c) thinner (D 怃 machine white pigment ( E) Photopolymerization initiator (F) Phosphorus-based flame retardant § 1 Defoamer 1 -37- 201139469 ACA-Z2 in Table 4 5 0 : Resin solution made by DAICEL Chemical Industry Co., Ltd. (with alicyclic Skeleton, does not have an aromatic hydrocarbon skeleton, has a carboxyl group and an acrylic group. EPICOTE1 004F: Japanese epoxy resin (share) bisphenol A type epoxy resin YDC-1312: Dongdu Huacheng (share) manufacturing second - third Base Hydrogenated Epoxy Resin BP4EA: EO-modified bisphenol A acrylate manufactured by Kyoeisha Chemical Co., Ltd. (EO = 4) AH-6 00 : Co-Professional Chemical Co., Ltd. Epoxy acrylate modified EBECRYL3 708 : 2-functional epoxy acrylate UF-8 001 G manufactured by DAICEL SCIENTIC Co., Ltd.: 2-functional urethane acrylate SPEEDCURE TPO: IGRACURE 819 manufactured by DKSH Japan Co., Ltd.: Test piece preparation step 1 (Examples 1 to 4, Comparative Example 3) manufactured by Kabbat Chemical Co., Ltd. Preparation of test piece for evaluating reflectance and discoloration property of thermosetting film In the step of coating the copper-clad laminate by surface honing, the curable resin composition is applied by screen printing, and then cured in a BOX furnace at 150 ° C for 60 minutes to form a hard coating. membrane. The cured film thickness after curing -38- 201139469 is 2 0-23 // m. Test piece production step 2 (Examples 5 to 14, Comparative Examples 4 to 6) A test piece preparation step for evaluating the reflectance and discoloration of the cured coating film formed on the rigid substrate was carried out by sectioning The surface-treated copper-clad laminate was subjected to screen printing, and the curable resin composition was applied, and then pre-dried at 80 ° C for 20 minutes in a BOX furnace. After pre-drying, the film was exposed to 500 mJ/cm 2 on an exposure apparatus (HMW-680GW manufactured by OAK Co., Ltd.), and then developed at 30 ° C in a 1% sodium carbonate aqueous solution and then dried at 150 ° C in a BOX furnace. After curing for a minute, a hardened coating film is formed on the copper-clad laminate. The thickness of the hardened coating film is 20 to 23 // m. Test piece production step 3 (Examples 15 to 25, Comparative Examples 7 to 9) A test piece preparation step for evaluating the reflectance and discoloration property of the cured coating film formed on the flexible substrate was carried out by In a copper plate of a flexible substrate (ESP AN EX MB series manufactured by Nippon Steel Chemical Co., Ltd.), which is surface-treated with dilute sulfuric acid (3%), a curable resin composition is applied by a screen printing method, and then a BOX furnace is applied. Into 8 (TC was pre-dried for 20 minutes. After preliminary drying, after exposure to an exposure apparatus (HMW_680 0 GW by OAK) on the coating film, it was exposed to 500 ° C, and then imaged with a 1% sodium carbonate aqueous solution at 30 ° C. Thereafter, it was cured in a BOX furnace at 15 (TC for 60 minutes to form a cured coating film on a flexible substrate. The thickness of the cured coating film was 20 to 23 M m. Test piece production step 4 (Examples 15 to 25, Comparative Example 7 to 9) -39-201139469 A test piece preparation step for evaluating the alkali developability of warpage and flame retardancy of a cured coating film formed on a flexible substrate, in polyimine A flexible substrate on which a copper circuit pattern is formed on a film (CAPTON 100H manufactured by TORAY DUPONT Co., Ltd.) by dilute sulfuric acid ( After the surface treatment, the curable resin composition was applied by screen printing, and then pre-dried in a B OX oven at 8 Torr for 20 minutes. After preliminary drying, an exposure apparatus (OAK) was applied to the coating film. The HMW-680GW manufactured by the company was exposed to 500 mJ/cm2, and then developed at 30 ° C and 1% sodium carbonate aqueous solution, and then cured at 150 ° C for 60 minutes in a BOX furnace to form a hardened coating film on a flexible substrate. The thickness of the hardened coating film is 20 to 23 # m. (1) The reflectance is measured by a spectrophotometer U-3 4 10 (manufactured by Hitachi, Ltd.: φ60πιηι integrating sphere), and the reflectance at 450 nm is measured. After the curing, the term "after thermal deterioration" means after the reflow process, "after photodegradation" means UV irradiation 5 (after H/cm2, the so-called "after warming and humidification" means at 85 °C. After the 85% RH was placed for 1 000 hours, (2) The visual system was used to visually confirm the appearance of the degree of white discoloration to yellow, and the evaluation was performed in the following four stages: ': ◎: not seen at all Yellow discoloration and white appearance, 〇: slightly yellow discoloration but still white appearance, △: The yellow color is slightly changed to have a yellow-like appearance, and X: the yellow color is strongly seen to be a tea-yellow appearance. -40- 201139469 (3) The alkali imaging system is visually evaluated on the copper body after development. And the presence or absence of residues on the polyimine, evaluated in the following three stages: 〇: no residue on the copper body, polyimine, △: no residue on the copper, but on the polyimide The residue remains slightly, and X: remains on both the copper body and the polyimide. (4) The softness is evaluated by the cylindrical mandrel method by visual observation and the softness of the coating film by an optical microscope of χ2〇0, and evaluated in the following three stages: 〇: There is no abnormality in the diameter of 2 mm or less. △: There is no abnormality in the diameter of 4 mm, but there are abnormalities such as cracks and peeling in the diameter of 2 mm or less. X: There are abnormalities such as cracks and peeling at a diameter of 4 mm or more. (5) Warpage After the test piece was cut out by 2 cm x 2.5 cm, the test piece was placed on the water platform so as to be concavely placed on the water platform, and the distance between the four corners and the platform was measured by a ruler without particularly applying an external force. The vertical interval is measured to a unit of 1 mm, with the maximum 値 as the amount of warpage. Regarding the measurement results, evaluation was made in the following three stages: 〇: amount of warpage not exceeding 5 mm, Δ: volume of 5 to 8 mm, and X: amount of fins exceeding 8 mm. (6) Flame retardancy For the test piece, the vertical burning test was carried out in accordance with the UL94 specification. Comment 201139469 The price is based on the UL94 specification and is expressed in terms of VTM-0~ combustion. Examples 1 to 2 5. The measurement results of Comparative Examples 1 to 9 are shown in Table 5 below, [Table 5] Real_Comparative Example 1 2 3 4 1 2 3 Reflectance (450 nm) Initial 87 90 86 89 78 79 84 After thermal deterioration 86 88 85 87 65 63 70 After light deterioration 84 87 83 86 75 78 75 Visual initial ◎ ◎ ◎ ◎ Δ Δ 0 After thermal deterioration ◎ ◎ ◎ ◎ XX Δ After photodegradation ◎ ◎ ◎ ◎ △ △ Δ -42 - 201139469 [9*] Comparative Example 1 <〇% ιο 〇<< 1〇CO ES CO < X < JO s co <1 X < grip CNJ 00 s § ◎ ◎ ◎ CO OJ 00 ω ◎ ◎ ◎ CM eg 00 ◎ ◎ ◎ CNJ 00 ◎ ◎ ◎ 〇 CM 00 ◎ ◎ ◎ 〇 〇 CN CN CN CN CN CN 00 00 00 00 00 00 00 00 ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ CO CM 00 ◎ ◎ 〇 1〇CO 00 % s ◎ ◎ ◎ Reflectance after light deterioration after initial thermal deterioration after initial thermal deterioration (450 nm) Visual-43-201139469 Comparative Example 1 σ> CM 00 s ◎ ◎ ◎ XXX Burning CO g CO ΙΟ ◎ ο 〇<1 < 0 焼 焼 CO CO s < X << 0 combustion example ir> CM s « ◎ ◎ © 0 0 0 VTM-0 Si CM 00 5 g ◎ ◎ ◎ 0 〇〇VTM-0 CO CM » S CO ◎ 0 0 0 0 VTM-0 CN4 CM csi oo » » ◎ ◎ ◎ 〇0 〇 VTM-0 CO 00 5 s ◎ ◎ ◎ 〇〇〇VTM-0 s 00 00 ◎ ◎ ◎ 〇〇〇VTM-0 cr> CO 00 s § ◎ ◎ ◎ 〇0 〇I VTM-0 | 00 CM 00 5 « « ◎ ◎ ◎ 0 0 0 1 VTM-0 I τ CM 00 00 s ◎ ◎ ◎ 0 0 0 I VTM-0 I to CM CO 5 ◎ ◎ ◎ 0 0 〇1 VTM-Cl ip n 00 » s ◎ ◎ ◎ 〇0 〇1 VTM-0 1 After initial thermal deterioration (reflow) After twisting and adding thirst, initial heat deterioration (reflow) After warming and humidifying i 1£ /*- 24 Visual alkali-developing soft rent m 1 flame retardant 丨-44-201139469 When the curable resin composition of the present invention is thermally cured, it is understood from Examples 1 to 4 and Comparative Examples 1 and 2 that (meth)acrylic acid is used as a raw material of the copolymer. It can suppress the decrease in reflectance and discoloration of the hardened film. Further, as is apparent from Examples 1 to 4 and Comparative Example 3, it is possible to suppress hardening by using the general formula (II) and the general formula (III) having no hydrogen atom in the α-position of the side chain of the aromatic hydrocarbon skeleton after polymerization. The reflectance of the film is reduced and discolored. On the other hand, Comparative Example 3 containing an aromatic hydrocarbon having a hydrogen atom in the side chain α after polymerization by the addition of p-tolyl glycidyl ether can suppress hardening at the initial stage (after curing) The film has a decrease in reflectance and discoloration, but even if methyl propionate is used as a raw material of the copolymer, after thermal deterioration (after reflow) and photodegradation (after UV irradiation of 5 OJ/cm2), the reflection of the hardened film The rate is also reduced and discoloration also occurs. When the curable resin composition of the present invention is photocured on a printing substrate, it is understood from Examples 5 to 14 and Comparative Examples 4 and 5 that the hardening film can be suppressed by using (meth)acrylic acid as a raw material of the copolymer. The reflectance is reduced and discolored. Further, from Examples 5 to 14 and Comparative Example 6, it is understood that the curing can be suppressed by using the general formula (II) and the general formula (III) having no hydrogen atom in the α-position of the side chain of the aromatic hydrocarbon skeleton after polymerization. The reflectance of the film is reduced and discolored. On the other hand, Comparative Example 6 containing an aromatic hydrocarbon having a hydrogen atom in the side chain α after polymerization was inhibited by the addition of p-tolyl glycidyl ether in the initial stage (after post-cure). The reflectance of the hardened film is lowered and discoloration occurs. However, even if methacrylic acid is used as a raw material of the copolymer, the reflectance of the hardened film is lowered after photodegradation (after reflow) and photodegradation (after UV irradiation of 50 J/cm 2 ). Discoloration also occurred. -45-201139469 When the curable resin composition of the present invention is photocured on a flexible substrate, it can be seen from the comparison of Examples 15 to 25, Comparative Examples 8 and 9 and Comparative Example 7 'by using (methyl) Acrylic acid is a raw material of the copolymer, which can suppress the decrease in reflectance and discoloration of the hardened film. Further, in Examples 15 to 25, alkali developability, flexibility, low warpage, and flame retardancy were excellent. On the other hand, in Comparative Examples 7 and 8, since the aromatic hydrocarbon skeleton is not contained, the compatibility with the (C) diluent or the like is deteriorated, the alkali developability is lowered, and the flame retardancy and flexibility are also lowered. From the examples of the examples 5 to 25 and the comparative example 9, it is understood that the use of (meth)acrylic acid as a raw material of the copolymer can reduce the decrease in reflectance and suppress the occurrence of discoloration without using an aromatic hydrocarbon skeleton. Since the aromatic hydrocarbon skeleton is not contained and the alicyclic skeleton is contained, the compatibility with the (C) diluent or the like is poor, the alkali developability is lowered, and the flame retardancy and flexibility are also lowered. Further, in Comparative Example 9, warpage and warpage were also poor. [Industrial Applicability] The curable resin composition of the present invention can form a cured coating film which can prevent deterioration of reflectance due to heat and time and has flexibility and low warpage. The solder resist film is particularly expensive in the field of solder resist film of a mounting substrate such as a light emitting diode element (LED). -46 -

Claims (1)

201139469 七、申請專利範圍： 1 · 一種硬化性樹脂組成物，其特徵爲含有·· (A-1)使以通式（I)表示之化合物， 【化1】201139469 VII. Patent application scope: 1 · A curable resin composition characterized by containing (A-1) a compound represented by the general formula (I), [Chemical Formula 1] (式中，R1表示氫原子或甲基），與以通式（II)表示之 化合物， 【化2】(wherein R1 represents a hydrogen atom or a methyl group), and a compound represented by the formula (II), [Chemical 2] (式中，R1表示氫原子或甲基，R2表示苯基、α-異丙 基苯基、碳數1〜10之烷氧基、烷基之碳數1~10之醯基、 第三丁基、金剛烷基或三氟甲基，m爲〇或1~3之整 數）’及/或以通式（III)表示之化合物反應而得之共聚合樹 【化3】 R1 0(wherein R1 represents a hydrogen atom or a methyl group, R2 represents a phenyl group, an α-isopropylphenyl group, an alkoxy group having 1 to 10 carbon atoms, an alkyl group having a carbon number of 1 to 10, and a third group; a copolymerized tree obtained by reacting a compound represented by the general formula (III) with a radical, an adamantyl group or a trifluoromethyl group, m is hydrazine or an integer of 1 to 3) and R1 0 (式中，R1表示氫原子或甲基，R2表示苯基、Π 基苯基、碳數1〜10之烷氧基、烷基之碳數1〜1〇之醯基、 第三丁基、金剛烷基或三氟甲基，Α1表示含有直鏈或胃 狀骨架之碳數2〜10之伸烷基或碳數3〜10之羥基伸院基’ m爲0或1〜3之整數，ρ爲1〜5之整數）， 或（A-2)於使通式（I)之化合物， -47- 201139469 【化4】(wherein R1 represents a hydrogen atom or a methyl group, R2 represents a phenyl group, a nonylphenyl group, an alkoxy group having 1 to 10 carbon atoms, a decyl group having 1 to 1 carbon atom of an alkyl group, a third butyl group, Adamantyl or trifluoromethyl, Α1 represents an alkyl group having a linear or gastric skeleton having 2 to 10 carbon atoms or a hydroxyl group having a carbon number of 3 to 10, m is 0 or 1 to 3, ρ is an integer of 1 to 5), or (A-2) is a compound of the formula (I), -47- 201139469 [Chemical 4] COOH (I) (式中，R1表示氫原子或甲基），與以通式（II)表示之 化合物， 【化5】COOH (I) (wherein R1 represents a hydrogen atom or a methyl group), and a compound represented by the formula (II), (式中，R1表示氫原子或甲基，R2表示苯基、α-異丙 基苯基、碳數1~1〇之烷氧基、烷基之碳數1〜10之醯基、 第三丁基、金剛烷基或三氟甲基，m爲0或1〜3之整 數），及/或以通式（III)表示之化合物反應而得之共聚物之 羧基之一部分上，加成具有環氧乙烷環及乙烯性不飽和鍵 之化合物的共聚合樹脂， 【化6】 R，P(wherein R1 represents a hydrogen atom or a methyl group, R2 represents a phenyl group, an α-isopropylphenyl group, an alkoxy group having 1 to 1 carbon atom, a decyl group having 1 to 10 carbon atoms of an alkyl group, and a third Butyl, adamantyl or trifluoromethyl, m is 0 or an integer of 1 to 3), and/or a part of the carboxyl group of the copolymer obtained by reacting the compound represented by the formula (III), the addition has a copolymerized resin of a compound of an oxirane ring and an ethylenically unsaturated bond, [Chem. 6] R, P (式中，R1表示氫原子或甲基，R2表示苯基、α-異丙 基苯基、碳數1~1〇之烷氧基、烷基之碳數1〜10之醯基、 第三丁基、金剛烷基或三氟甲基，A1表示含有直鏈或環 狀骨架之碳數2~10之伸烷基或碳數3~10之羥基伸烷基， m爲0或1〜3之整數，p爲1~5之整數）’ (B) 硬化劑；及 (C) 稀釋劑。 2.如申請專利範圍第1項之硬化性樹脂組成物，其 -48 - 201139469 中目U述具有環氧乙烷環與乙烯性不飽和鍵之化合物爲以通 式（IV)表示之化合物， 【化7】 h2c R1 =C —C00-(a2-0^CH2-(wherein R1 represents a hydrogen atom or a methyl group, R2 represents a phenyl group, an α-isopropylphenyl group, an alkoxy group having 1 to 1 carbon atom, a decyl group having 1 to 10 carbon atoms of an alkyl group, and a third Butyl, adamantyl or trifluoromethyl, A1 represents a 2 to 10 carbon alkyl group having a linear or cyclic skeleton or a 3 to 10 carbon alkyl group, m is 0 or 1 to 3 The integer, p is an integer from 1 to 5)' (B) hardener; and (C) thinner. 2. The curable resin composition of claim 1, wherein the compound having an oxirane ring and an ethylenically unsaturated bond is a compound represented by the formula (IV). [7] h2c R1 = C - C00-(a2-0^CH2- m .(式中’ R1表示氫原子或甲基，A2表示碳數2〜10之 伸垸基’ q爲0或1〜5之整數）。 3 _如申請專利範圍第1項之硬化性樹脂組成物，其 中前述（A-1)共聚合樹脂及前述（A_2)共聚合樹脂具有5〜4〇 質量％之芳香族烴骨架。 4. 如申請專利範圍第1項之硬化性樹脂組成物，其 中前述（A-1)共聚合樹脂之酸價及前述（A_2)共聚合樹脂之 酸價爲 30〜150 mgKOH/g。 5. 如申請專利範圍第1項之硬化性樹脂組成物，其 中進而含有（D)無機白色顏料。 6-如申請專利範圍第5項之硬化性樹脂組成物，其 中前述（D)無機白色顏料爲金紅石型氧化鈦。 7. 如申請專利範圍第1項之硬化性樹脂組成物，其 中前述（B)硬化劑包含自一分子中具有兩個以上環氧基之 化合物、三聚氰胺及三聚氰胺衍生物所組成組群選擇之至 少一種。 8. 如申請專利範圍第1項之硬化性樹脂組成物，其 中前述（C)稀釋劑包含一分子中具有一個以上乙烯性不飽 和基之化合物。 -49- 201139469 9. 如申請專利範圍第1或8項之硬化性樹脂組成 物，其中前述（C)稀釋劑爲具有兩個以上（甲基）丙烯酸基 且（甲基）丙烯酸基當量爲2 00g/eq以上之化合物。 10. 如申請專利範圍第1項之硬化性樹脂組成物，其 中進而含有（E)光聚合起始劑。 11. 如申請專利範圍第1項之硬化性樹脂組成物，其 中進而含有（F)磷系難燃劑。 12. 如申請專利範圍第1項之硬化性樹脂組成物，其 中進而含有（G)金屬氫氧化物《> 13. 一種印刷配線板，其被覆有使用如申請專利範圍 第1至1 2項中任一項之硬化性樹脂組成物所形成之防焊 光阻膜。 -50- 201139469 四、指定代表圖： (一） 本案指定代表圖為：無 (二） 本代表圖之元件符號簡單說明：無 201139469 五 本案若有化學式時，請揭示最能顯示發明特徵的化學 式：無m. (wherein R1 represents a hydrogen atom or a methyl group, and A2 represents an alkyl group having a carbon number of 2 to 10, and q is an integer of 0 or 1 to 5). The curable resin composition of the first aspect of the invention, wherein the (A-1) copolymer resin and the (A_2) copolymer resin have an aromatic hydrocarbon skeleton of 5 to 4% by mass. 4. The curable resin composition according to claim 1, wherein the acid value of the (A-1) copolymer resin and the acid value of the (A_2) copolymer resin are 30 to 150 mgKOH/g. 5. The curable resin composition of claim 1, further comprising (D) an inorganic white pigment. 6 - The curable resin composition of claim 5, wherein the (D) inorganic white pigment is rutile-type titanium oxide. 7. The curable resin composition of claim 1, wherein the (B) hardener comprises at least one selected from the group consisting of a compound having two or more epoxy groups in one molecule, a melamine, and a melamine derivative. One. 8. The curable resin composition of claim 1, wherein the (C) diluent comprises a compound having one or more ethylenically unsaturated groups in one molecule. The hardening resin composition of claim 1 or 8, wherein the (C) diluent has two or more (meth)acrylic groups and the (meth)acrylic group equivalent is 2 A compound of 00 g/eq or more. 10. The curable resin composition of claim 1, further comprising (E) a photopolymerization initiator. 11. The curable resin composition of claim 1, further comprising (F) a phosphorus-based flame retardant. 12. The curable resin composition of claim 1, further comprising (G) a metal hydroxide "> 13. A printed wiring board coated with use as in claims 1 to 12 A solder resist film formed of the curable resin composition of any one of them. -50- 201139469 IV. Designation of Representative Representatives: (1) The representative representative of the case is: No (2) Simple description of the symbol of the representative figure: No 201139469 If there is a chemical formula in the case, please disclose the chemical formula that best shows the characteristics of the invention. :no
TW099145522A 2009-12-28 2010-12-23 A hardened resin composition and a printed wiring board using the same TWI510505B (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP2009298570A JP5749886B2 (en) 2009-12-28 2009-12-28 Curable resin composition and printed wiring board using the same

Publications (2)

Publication Number Publication Date
TW201139469A true TW201139469A (en) 2011-11-16
TWI510505B TWI510505B (en) 2015-12-01

Family

ID=44226462

Family Applications (1)

Application Number Title Priority Date Filing Date
TW099145522A TWI510505B (en) 2009-12-28 2010-12-23 A hardened resin composition and a printed wiring board using the same

Country Status (3)

Country Link
JP (1) JP5749886B2 (en)
TW (1) TWI510505B (en)
WO (1) WO2011081055A1 (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104516203A (en) * 2013-09-30 2015-04-15 太阳油墨制造株式会社 White curable composition for printed circuit board, cured coating film using the same, and printed circuit board

Families Citing this family (35)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5668348B2 (en) * 2009-07-24 2015-02-12 東洋インキＳｃホールディングス株式会社 Photosensitive composition
JP5676889B2 (en) * 2010-02-12 2015-02-25 互応化学工業株式会社 Photosensitive resin composition, solder resist composition and printed wiring board
JP2011170050A (en) * 2010-02-17 2011-09-01 Taiyo Holdings Co Ltd Solder resist composition and printed circuit board
JP4975834B2 (en) * 2010-02-17 2012-07-11 太陽ホールディングス株式会社 Solder resist composition and printed wiring board
JP2011215384A (en) * 2010-03-31 2011-10-27 Taiyo Holdings Co Ltd Solder resist composition and printed-circuit board
JP2011227308A (en) * 2010-04-20 2011-11-10 Taiyo Holdings Co Ltd Solder resist composition and print circuit board
JP5611769B2 (en) * 2010-10-29 2014-10-22 株式会社カネカ Novel white photosensitive resin composition and use thereof
JP5855405B2 (en) * 2011-09-26 2016-02-09 株式会社タムラ製作所 Photosensitive resin composition
WO2013077358A1 (en) * 2011-11-22 2013-05-30 日立化成株式会社 Photosensitive resin composition, photosensitive resin film produced using said composition, and electronic component produced using said composition or said film
JP5964608B2 (en) * 2012-02-20 2016-08-03 株式会社タムラ製作所 UV curable transparent resin composition
JP6217296B2 (en) * 2013-01-22 2017-10-25 東洋インキＳｃホールディングス株式会社 Photosensitive resin composition and coating film using the same
JP6069021B2 (en) * 2013-02-21 2017-01-25 株式会社日本触媒 Curable resin composition for plastic substrate and use thereof
JP6216133B2 (en) * 2013-03-25 2017-10-18 互応化学工業株式会社 Two-component mixed type main agent and curing agent, and method for producing printed wiring board
JP6163876B2 (en) * 2013-05-24 2017-07-19 株式会社村田製作所 Photosensitive paste
JP5872650B2 (en) * 2013-09-30 2016-03-01 株式会社タムラ製作所 Photosensitive resin composition
JP6263955B2 (en) * 2013-10-28 2018-01-24 日立化成株式会社 Photosensitive resin composition, photosensitive element and method for forming resist pattern
JP5643416B1 (en) * 2013-12-24 2014-12-17 互応化学工業株式会社 Manufacturing method of coated wiring board
JP6019065B2 (en) * 2014-07-08 2016-11-02 太陽ホールディングス株式会社 Solder resist composition and printed wiring board
JP6517477B2 (en) * 2014-07-18 2019-05-22 オキツモ株式会社 Alkali-soluble resist ink composition having high emissivity, light reflectance and heat resistance
JP6463370B2 (en) * 2014-09-30 2019-01-30 太陽インキ製造株式会社 Photosensitive resin composition, dry film and cured film thereof, and printed wiring board using them
JP5992027B2 (en) * 2014-10-28 2016-09-14 互応化学工業株式会社 Photosensitive resin composition, composition for solder resist, and printed wiring board
JP2015173269A (en) * 2015-04-03 2015-10-01 太陽インキ製造株式会社 White curing type composition for printed wiring boards, cured coating film arranged by use thereof, and printed wiring board
EP3135704A1 (en) 2015-08-26 2017-03-01 Evonik Degussa GmbH Use of certain polymers as charge storage
EP3136410A1 (en) 2015-08-26 2017-03-01 Evonik Degussa GmbH Use of certain polymers as charge storage
WO2017032582A1 (en) 2015-08-26 2017-03-02 Evonik Degussa Gmbh Use of certain polymers as a charge store
KR101989727B1 (en) 2015-08-26 2019-06-14 에보니크 데구사 게엠베하 Use of specific polymers as charge carriers
JP6530281B2 (en) * 2015-08-31 2019-06-12 ダイセル・オルネクス株式会社 Active energy ray curable composition for photoresist
JP6114799B2 (en) * 2015-10-20 2017-04-12 株式会社タムラ製作所 Photosensitive resin composition, printed wiring board having cured film of photosensitive resin composition, and method for producing reflection sheet
JP6112691B1 (en) * 2016-03-16 2017-04-12 互応化学工業株式会社 Liquid solder resist composition and printed wiring board
JP5997860B1 (en) 2016-03-16 2016-09-28 互応化学工業株式会社 Liquid solder resist composition and printed wiring board
JP6154942B1 (en) * 2016-07-11 2017-06-28 互応化学工業株式会社 Liquid solder resist composition and printed wiring board
KR20180063731A (en) * 2016-12-02 2018-06-12 삼성전기주식회사 Thermo-curable resin composition for controlling board warpage and cured product thereof
JP6325729B1 (en) * 2017-08-09 2018-05-16 綜研化学株式会社 Epoxy resin composition and cured product
JP7108391B2 (en) * 2017-09-30 2022-07-28 株式会社ネオス Urethane acrylate curable resin composition
CN112859520A (en) * 2021-01-20 2021-05-28 深圳市撒比斯科技有限公司 Low-energy-curing photoresist, resist pattern and preparation method thereof

Family Cites Families (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4620600B2 (en) * 2006-02-06 2011-01-26 富士フイルム株式会社 Photosensitive composition, photosensitive film, and permanent pattern forming method
JP5223207B2 (en) * 2006-02-24 2013-06-26 日立化成株式会社 Photosensitive resin composition, resist pattern forming method using the same, and printed wiring board manufacturing method
JP2008088394A (en) * 2006-09-07 2008-04-17 Showa Highpolymer Co Ltd Alkali-developable photosensitive resin and photosensitive resin composition comprising the same
JP4990605B2 (en) * 2006-12-11 2012-08-01 ニチゴー・モートン株式会社 Photosensitive resin composition, photosensitive resin laminate and resist dry film using the same
JP2008166313A (en) * 2006-12-26 2008-07-17 Nichigo Morton Co Ltd Method for forming resist pattern
JP5151446B2 (en) * 2007-07-18 2013-02-27 日立化成工業株式会社 Photosensitive resin composition, photosensitive element, resist pattern forming method and printed wiring board manufacturing method
JP2009167234A (en) * 2008-01-11 2009-07-30 Showa Highpolymer Co Ltd Curable flame-retardant resin composition
JP2009194222A (en) * 2008-02-15 2009-08-27 Denki Kagaku Kogyo Kk White alkali-developable photocurable and thermosetting solder resist composition, and metal-base circuit substrate using the same
JP2009271445A (en) * 2008-05-09 2009-11-19 Kaneka Corp New photosensitive resin composition and its application
JP5134449B2 (en) * 2008-06-10 2013-01-30 互応化学工業株式会社 Water-based photosensitive resin composition, method for manufacturing water-based photosensitive resin composition, and method for manufacturing printed wiring board
JP5504738B2 (en) * 2009-08-05 2014-05-28 東洋インキＳｃホールディングス株式会社 Photosensitive composition

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104516203A (en) * 2013-09-30 2015-04-15 太阳油墨制造株式会社 White curable composition for printed circuit board, cured coating film using the same, and printed circuit board

Also Published As

Publication number Publication date
WO2011081055A1 (en) 2011-07-07
TWI510505B (en) 2015-12-01
JP2011138037A (en) 2011-07-14
JP5749886B2 (en) 2015-07-15

Similar Documents

Publication Publication Date Title
TW201139469A (en) Curable resin composition and printed wiring board using the same
TWI637238B (en) Solder resist composition and coated printed wiring board
JP4584839B2 (en) Photosensitive resin composition and cured product thereof
TWI574105B (en) An alkali developing type photosensitive resin composition, a dry film and a cured product, and a printed circuit board
TWI819431B (en) Solder resist composition, dry film, printed wiring board and method for producing them
JP2008015285A (en) Photosensitive thermosetting resin composition
JP4634905B2 (en) Photosensitive resin composition, cured product and printed wiring board
JPWO2009150769A1 (en) Curable composition containing carboxyl group-containing resin, cured product thereof, and method for obtaining carboxyl group-containing resin
JP5134449B2 (en) Water-based photosensitive resin composition, method for manufacturing water-based photosensitive resin composition, and method for manufacturing printed wiring board
JP5161661B2 (en) Water-based photosensitive resin composition, method for manufacturing water-based photosensitive resin composition, and method for manufacturing printed wiring board
CN1898299A (en) Polyamide acid resin having unsaturated group, photosensitive resin composition using same, and cured product thereof
TWI787305B (en) Photosensitive resin composition, dry film, cured product and printed wiring board
JP3503910B2 (en) Photo solder resist ink, printed circuit board and method of manufacturing the same
JP6748478B2 (en) Dry film, cured product and printed wiring board
KR102501591B1 (en) Curable resin composition, dry film, cured product and printed wiring board
JP5739609B2 (en) Photosensitive resin composition, solder resist composition and printed wiring board
TWI656163B (en) Liquid solder resist composition and coated printed wiring board (2)
JP7216480B2 (en) Photocurable thermosetting resin composition, dry film, cured product, and printed wiring board
JP2004359729A (en) Curable composition containing carboxyl-group-containing photosensitive resin
JP5878913B2 (en) Photosensitive resin composition, composition for solder resist, printed wiring board, and method for producing photosensitive resin composition
JP5625721B2 (en) Photosensitive resin composition and photosensitive element using the same
JP6055029B2 (en) Photosensitive resin composition, solder resist composition and printed wiring board
JP6055028B2 (en) Photosensitive resin composition, solder resist composition and printed wiring board
JP2021144097A (en) Curable resin composition, dry film, cured product, and electronic component
WO2023051726A1 (en) Curable resin composition, laminate, cured product, and electronic component