TW201230908A - Method for producing tape carrier package and method for producing flexible circuit board for tape carrier package - Google Patents

Method for producing tape carrier package and method for producing flexible circuit board for tape carrier package Download PDF

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Publication number
TW201230908A
TW201230908A TW100135535A TW100135535A TW201230908A TW 201230908 A TW201230908 A TW 201230908A TW 100135535 A TW100135535 A TW 100135535A TW 100135535 A TW100135535 A TW 100135535A TW 201230908 A TW201230908 A TW 201230908A
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Taiwan
Prior art keywords
resin
pigment
denatured
compound
atom
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TW100135535A
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Chinese (zh)
Inventor
Ryoichi Takasawa
Yukinori Kohama
Miharu Nakagawa
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Ube Industries
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Publication of TW201230908A publication Critical patent/TW201230908A/en

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    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L22/00Testing or measuring during manufacture or treatment; Reliability measurements, i.e. testing of parts without further processing to modify the parts as such; Structural arrangements therefor
    • H01L22/10Measuring as part of the manufacturing process
    • H01L22/12Measuring as part of the manufacturing process for structural parameters, e.g. thickness, line width, refractive index, temperature, warp, bond strength, defects, optical inspection, electrical measurement of structural dimensions, metallurgic measurement of diffusions
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00Polymeric products of isocyanates or isothiocyanates
    • C08G18/06Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08Processes
    • C08G18/0804Manufacture of polymers containing ionic or ionogenic groups
    • C08G18/0819Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups
    • C08G18/0823Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups containing carboxylate salt groups or groups forming them
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00Polymeric products of isocyanates or isothiocyanates
    • C08G18/06Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/2805Compounds having only one group containing active hydrogen
    • C08G18/2815Monohydroxy compounds
    • C08G18/282Alkanols, cycloalkanols or arylalkanols including terpenealcohols
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00Polymeric products of isocyanates or isothiocyanates
    • C08G18/06Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40High-molecular-weight compounds
    • C08G18/42Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/44Polycarbonates
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00Polymeric products of isocyanates or isothiocyanates
    • C08G18/06Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/65Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66Compounds of groups C08G18/42, C08G18/48, or C08G18/52
    • C08G18/6633Compounds of group C08G18/42
    • C08G18/6659Compounds of group C08G18/42 with compounds of group C08G18/34
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00Polymeric products of isocyanates or isothiocyanates
    • C08G18/06Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72Polyisocyanates or polyisothiocyanates
    • C08G18/74Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/75Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
    • C08G18/751Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
    • C08G18/752Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
    • C08G18/753Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
    • C08G18/755Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00Polymeric products of isocyanates or isothiocyanates
    • C08G18/06Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72Polyisocyanates or polyisothiocyanates
    • C08G18/74Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/75Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
    • C08G18/758Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing two or more cycloaliphatic rings
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00Details of semiconductor or other solid state devices
    • H01L23/48Arrangements for conducting electric current to or from the solid state body in operation, e.g. leads, terminal arrangements ; Selection of materials therefor
    • H01L23/488Arrangements for conducting electric current to or from the solid state body in operation, e.g. leads, terminal arrangements ; Selection of materials therefor consisting of soldered or bonded constructions
    • H01L23/498Leads, i.e. metallisations or lead-frames on insulating substrates, e.g. chip carriers
    • H01L23/4985Flexible insulating substrates
    • HELECTRICITY
    • H05ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05KPRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00Apparatus or processes for manufacturing printed circuits
    • H05K3/30Assembling printed circuits with electric components, e.g. with resistor
    • H05K3/32Assembling printed circuits with electric components, e.g. with resistor electrically connecting electric components or wires to printed circuits
    • H05K3/34Assembling printed circuits with electric components, e.g. with resistor electrically connecting electric components or wires to printed circuits by soldering
    • H05K3/3452Solder masks
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/0001Technical content checked by a classifier
    • H01L2924/0002Not covered by any one of groups H01L24/00, H01L24/00 and H01L2224/00
    • HELECTRICITY
    • H05ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05KPRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00Printed circuits
    • H05K1/02Details
    • H05K1/0266Marks, test patterns or identification means
    • H05K1/0269Marks, test patterns or identification means for visual or optical inspection
    • HELECTRICITY
    • H05ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05KPRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00Printed circuits
    • H05K1/18Printed circuits structurally associated with non-printed electric components
    • H05K1/189Printed circuits structurally associated with non-printed electric components characterised by the use of a flexible or folded printed circuit
    • HELECTRICITY
    • H05ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05KPRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K2201/00Indexing scheme relating to printed circuits covered by H05K1/00
    • H05K2201/10Details of components or other objects attached to or integrated in a printed circuit board
    • H05K2201/10613Details of electrical connections of non-printed components, e.g. special leads
    • H05K2201/10621Components characterised by their electrical contacts
    • H05K2201/10681Tape Carrier Package [TCP]; Flexible sheet connector

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Computer Hardware Design (AREA)
  • Power Engineering (AREA)
  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Laminated Bodies (AREA)

Abstract

One aspect of the present invention relates to a method for producing a tape carrier package which can firmly mount, with sufficient tear strength, electronic parts, having a length of 1.2mm or shorter on a short side thereof, onto connection terminals of a wiring pattern in a flexible circuit board for a tape carrier package. Another aspect of the present invention relates to a method for producing a flexible circuit board for the tape carrier package wherein pigment without any chlorine atom or bromine atom is adopted for coloring insulation films, and deterioration in inspection efficiency due to false detection can be restrained so as to reduce inspection failure rate, and wherein a process for inspecting the produced flexible circuit board for the tape carrier package by using optical automatic tester is included.

Description

201230908 六、發明說明: 【發明所屬之技術領域】 本發明之一態樣係關於輸送膠帶封装體之製造方法、及 適於當做輸送膠帶封裝體(更具體而言為輸送膠帶封裝體用 撓性電路板)之絕緣膜使用之變性聚胺甲酸酯樹脂組成物。尤 其’係關於能夠將如短邊長度為1.2mm以下之微小半導體晶 片的電子零件理想地安裝的輸送膠帶封裝體之製造方法、= 於如此的製造方法中適用於當做輸送膠帶封裝體之絕緣膜的 變性聚胺曱酸酯接}脂組成物。 制f發明之另一態樣係關於輸送膠帶封裝體用撓性電路板 方法、及適於當做輸送膠帶封裝體用撓性電路板之絕 髁册if的硬化性絕緣膜用樹脂組成物。尤其關於—種輸送 二ϊίί職性電路板之s造方法,其包含將製造之輸送 二驟、、體用撓性電路板以光學式自動檢查裝置予以檢查之 ί料:絕緣膜著色之顏料係不含氯原子及溴原;之 “率測所致檢查效率降低,可減少檢查 體用撓性電路;的製造方法中翻的輸送膠帶封裝 电路板用之硬化性絕緣膜用樹脂組成物。 【先如技術】 成由導雜金屬構 膠帶封裝體職性I齡、广翻撓性電路板(也稱為輸送 ΤΑΒ cof 之輸送膠帶縣體用撓性件而成的封裝體。在此使用 電性金屬構成之電路圖牵板,係在絕緣膜上形成有由導 電子零件的連接端子部心在用於安裝半導體晶片等 膜用樹脂組成物,复多的电路圖案面,塗佈硬化性絕緣 者。 /、夂硬化而形成有絕緣膜(絕緣保護膜) 201230908 帶封賴可料纽町步驟而適#製造,即. 性電ίίί賴上具有以導金_紅電路圖案的撓 將t彳t電路板之至少連接端子部以外的電路圖案面塗佈 更化性树驗成物,並且其相加熱處 硬化膜(絕緣健膜)、 t化而七成 .ΐί得之輸送’難體賴性電路板之電路圖案之連 接鳊子部分安裝半導體晶片等電子零件、 ' 底声膜裝之電子零件&amp;導體晶片)的間隙注入 層填充材硬化而固定電子零件。 低 專利文獻1〜4記載:使用變性聚胺甲酸 膜之硬化性樹脂組成物,二=官 人有基之賴聚胺甲酸輯脂當做前述變性聚 月:甲酉夂醋樹脂。,又二專利文獻5記載:使用聚酿亞胺石夕氧炫樹 月曰組成物當做形成前述絕緣保護膜之硬化性樹脂組。 ,宜使用變性聚胺甲酸酯樹脂組成物 或挈酏亞胺矽氧烷树知組成物的理由在於:硬化性、、 電絕緣性、舰、低硬化收縮性、低㈣性、低黏性、耐藥 品性、焊料耐熱性等耐熱性、與底層填充材之黏 等絕緣保護膜通常要求的各特性為優異。五1〈⑴口 [先前技術文獻] [專利文獻] [專利文獻1]日本特開2006-104462號公報 [專利文獻2]日本特開2〇〇6_3〇7183號公報 [專利文獻3]日本特開2〇〇7_154134號公報 [專利文獻4]日本特開2〇〇8_297536號公報 [專利文獻5]曰本特開2〇〇4_211〇64號公報 【發明内容】 201230908 &lt;發明欲解決之課題&gt; 電子零件,尤其半導髀曰 狀之形狀’且如前述,安,二二,2具各面為長方形的箱 之電路圖案之連接端子部ί :二【撓性電路板 性電路板之間隙,通常會注人巧nf之半導體晶片與撓 而固定。又,該底層填;材主==== 膜的端部直接連接。 々战之、、、巴緣保濩 輸送膠帶封裝體逐年隨電路圖案之微細化 體晶片的電子零件變得微小,近 1 ·2ιηιη以下之極微小的半導體a 裝短邊長度為 二,底層填充材可充分邊 ===電子零件經安裝時’會發生電子零以 而輸送朦帶封裝體用撓性電路板 綠色或藍色。由於近年環境問題高漲,用= ,,性電路板之絕緣膜予以著色使用之顏料,要 含氯原子及溴原子之顏料。 使用不 又’近年來’輸送膠帶封裝體用撓性電路 ,微細間距(fme pitch)化一直在進展,但另一 =裝體用,電路板之製造步驟, 驟二 裝置進行製程檢查。 使用九子式自動才双查 但若使用鮮式自動檢查裝置進行製程檢杳 目視檢查不會認為是異;之絕緣“ 造成檢查效率低落的問題。電路間_ 以下的狹窄部分時’會有容易發生缺陷 封^ 之,目的在於提供—種輸送膠帶 封讀之製造方法,其能夠將如短邊長度為^麵以下之極 201230908 ,小半導體W的電子詩,以具有充分 牢固地安裝在輪送膠帶封裝體賴性電路=式: 接端子部分。 奴之電路圖案之連 本發明之㈣態樣,目的在於提供—㈣ 電路板之製造方法,其包含使用光學 心查裝造之輸送膠帶封制用撓性電路板之, 絕緣膜著色之顏料為不含氯原子及、、拿 驟且用於將 由於誤檢測所致檢查效率降低,能^ 且可抑制 &lt;解決課題之方式〉 ^科良率。 本發明之各態樣如下。 &lt;第1態樣(Α部分)&gt; Α1· —種輸送膠帶封裝體之製造方 包含以下步驟: 〃特徵為. 電路Ϊ備在絕緣膜上具有導電性金屬形狀電路圖案之撓性 變性少連接端子部以外的電路圖案面塗佈 膜、z 驗成物,其錢行加熱處理而形成硬化 接πΐί4!之輸送料縣體職性電路板之電路圖案之連 接ϋ分,安裝短邊長度為1.“以下之電子零件芊及連 之後進經安裝之電子零件之間隙注入底層填充材, 之後進仃加熱處理使底層填充材硬化· n絲胺憎_敝祕包含:至料緩基且酸 ‘(B)。〜mgK〇H/g之變性聚胺曱酸醋樹脂⑷;及硬化性樹 性聚二封敵製造方法’其中,將變 於環氧:處理而得之硬化膜,浸潰 孔树J3日Β守之尺寸變化率為6〇%以下。 A1或Α2之輸送膠帶封裝體之製造方法,其中, 田丈:交性聚胺曱酸賴脂組成物予以加減理而得之硬化 201230908 巧剝離已硬化的層填充材時,至少有部分硬化膜發生内聚破 壞。 、A4.如A1〜A3中任一項之輸送膠帶封裝體之製造方 法,其中,變性聚胺甲酸酯樹脂組成物包含:酸價為 16〜40mgKOH/g之變性聚胺甲酸酯樹脂(A)及硬化性樹脂 巧’該=胺μ賴雖)健彡m㈣化合物 酸&amp;醇或聚丁二烯二醇之多元醇化合物 ()/、八羧基之—超基化合物(a3)反應而獲得。 A5.如A4之輸送膠帶封裝體之製造方法,1 二里 虱酸醋化合物㈣係具脂環結構之二異氰酸酿化&amp;物。一,、 士6上如A1〜AS中任-項之輸送膠帶封裝體之製造方 、/、中,A性聚胺曱酸酯樹脂(A)係主鏈中jLg &amp; # s % 性聚胺曱酸酉旨樹脂。 硬甲』亞月女%之變 法,2如f〜Α6中任—項之輸送膠帶封裝體之製造方 二、中’硬化性樹脂(Β)係選自於由環氧樹脂、胺美樹月匕 端化的多官能異氰酸醋、氰酸賴脂構成的群“二 至少1基樹脂組成物,其特徵為包含: (A);與硬^性樹脂⑻。mgKC&gt;H/g之、祕聚胺甲酸§旨樹脂 安之變性聚胺甲_樹脂組成物,轉使用在 文,短邊長度為1.2mm以下之雪早愛 ,、你便用在 &lt;第2態樣(B部分)&gt; 屯子$件的輸郝帶封裝體。 B1. —種輸送膠帶封裝體用撓 特徵為: 衣版用獍性電路板之製造方法,其 包含以下步驟: 準備在絕緣膜上具有導電性今眉报士、夕带 電路板、 屯性金屬形成之電路圖案之撓性 料性電路板之至少連接端子部以外的電制安而冷分 更化性絕緣膜用樹脂組成物,其次使硬化而=== 201230908 將獲得之輸送膠帶封裝體用撓性電路板於光學式自動檢 查裝置進行檢查; 前述硬化性絕緣膜用樹脂組成物係包含顏料(A)而著 色,該顏料(A)至少包含不含氣原子及溴原子之體質顏料(al) 與不含氯原子及漠原子之顏料(a2)。 B2.如B1之輸送膠帶封裝體用撓性電路板之製造方 法,其中,硬化性絕緣膜用樹脂組成物係含有顏料(A)而著色 為綠色,該顏料(A)包含不含氯原子及溴原子之體質顏料 (al)、不含氯原子及溴原子之藍色顏料(a3)、及不含氯原子及 溴原子之黃色顏料(a4)。 B3.如B2之輸送膠帶封裝體用撓性電路板之製造方 法,其中,不含氯原子及溴原子之體質顏料(al)之中位徑為1 OOnm〜lOOOnm ’不含氯原子及溴原子之藍色顏料(a3)之中位 徑為50nm〜500nm,不含氯原子及溴原子之黃色顏料(a4)之中 位徑為50nm〜500nm。 B4.如B1〜B3中任一項之輸送膠帶封裝體用撓性電路 板之製造方法,其中,硬化性絕緣膜用樹脂組成物含有變性 聚胺曱酸醋樹脂(B) ’該變性聚胺曱酸酯樹脂〈B)係至少將二 異氰酸醋化合物(bl)與含聚碳酸酯二醇或聚丁二烯二醇之多 元醇化合物(b2)與含羧基之二醇化合物(b3)反應而獲得。 B5.如B4之輸送膠帶封裝體用撓性電路板之製造方 法,其中’不含氯原子及溴原子之體質顏料(al)為硫酸鋇, 且 斤硬,性絕緣膜用樹脂組成物中,不含氯原子及溴原子之 體質顏料(al)相對於變性聚胺曱酸酯樹脂(B)固體成分1〇〇質 量份含量為10質量份以上。 、B6.如34或35之輸送膠帶封裝體用撓性電路板之製造 方法’其中’二異氰酸酯化合物(bl)為具脂環結構之二里氰 B7.如B4〜:b6中任一項之輸送膠帶封裝體用撓性電路 201230908 板之製造方法,其中,變性聚胺曱酸酯樹脂(B)在主 亞胺環結構。 〃 B8.如B1〜B7中任-項之輸送膠帶封裂體用挽性電路 板之製造方法,其中,撓性電路板具有含電路間隔為15 以下之部分的電路圖案。 B9. —種輸送膠帶封裝體用撓性電路板用之硬化性 膜用樹脂組成物,其特徵為:包含顏料(A)與變性聚胺酸酽 樹脂(B)而著色,該顏料(A)至少包含不含氯原子及溴 ^ 體質顏料(al)與不含氯原子及漠原子之顏料(a2),該變性 工係異娜旨化合物(bl)與含聚碳酸 或I 丁一烯一醇之夕70醇化合物(b2)與含羧基之二醇 化合物(b3)反應而獲得。 π ^Λ10.如B9之輸送膠帶封裝體用撓性電路板用之硬化性 用樹脂組成物’其包含顏料㈧而著色為、綠色,該顏料 溴t子3^含原子及漠原子之體質顏料⑷)、不含氯原子及 if色歸㈣、料含㈣子及_子之黃色顏料 &lt;發明之效果&gt; 製造日月之1樣之―,能提供—種輸送膠帶封裝體之 體晶片的電mm以下之極為微小的半導 輸送膠強度的方式,牢固地安褒於 如針、+、裳體用撓性电路板之電路圖案之連接端子部分。 以=¾送:开帶之製造方法中,底層填^使用與 絲使㈣定者,亦即使用包含至少具 化性樹脂(B) 6線1^ — H g之變性聚胺甲酸酯樹脂(A)與硬 短邊長;Λ,,交性女〒酸醋樹腊組成物,藉此,即使實施 &amp; ’’、、.2mm以下之極為微小之電子零件之安裝時,也 201230908 能以習知的底i填充财_定使具有足夠關離強度。並 且’雖使㈣疋之硬恤樹驗成物形絲緣賴 =、印,、口電絕緣性、撓性、低硬化收祕、她曲性更 n耐^性、焊料耐熱性等耐熱性、與 黏著護膜通常要求之各特性不會^ 垆性樣,能提供一種輸送膠帶刪用 “制造之ί &amp;其包含使用光學式自動檢查裝置檢 體用撓性電路板之步驟,其中用於 制由效率低落,而能減少檢查不良i 5亥輸祕讀I體賴性電路板 ϊϊίί^Ι^ 高生產性經濟的製造輸送料縣電ii i故能以 【實施方式】 &lt;實施發明之形態&gt; 成A與^樣(以下記載單記為發明)分 係指該部分中記載之,:本,一般 分記載之發明。但,依上丁;要不矛盾,也可意指其他部 的來看與其他部分之㈣ 從該部分記載之發明之目 明。又,A部分與B部分 2,係意指該部分記載之發 «Α部分》 记載之發明,只要不矛盾也可組合。 製造方法,提供—讀_帶封裝體之 導體晶片般的電子零件以以下之極為微小之半 裝於輸送膠帶封裝體用撓度之方式,牢固地安 分。 铌性電路板之電路圖案之連接端子部 201230908 、 .P刀揭示之%明係關於一種輸送膠帶封裝體之製造方 法’ 、 包含以下步驟: ^準備在絕緣膜上具有導電性金屬形成之電路圖案之撓性 電路板、 〃 於撓性電路板之至少連接端子部以外的電路圖案面塗佈 k性聚胺旨麟喊物,其錢行加熱處理*形成硬化 膜、 於獲得之輸送膠帶封裝體用撓性電路板之電路圖幸之連 接端子部分安裝短邊長度為1.2mm以下之電子零件/及 之德ί絕ίίί經安裝之電子零件之間隙注人“填充材, 之设進仃加熱處理而使底層填充材硬化; 其特徵為: ’ #太性聚胺甲酸醋樹脂組成物包含:至少具幾基且酸 ϋ gK〇Wg之變性聚胺甲酸醋樹脂⑷;與硬化性樹 τ牲ί方ΐ中,絕緣膜只要是具撓性之絕緣性之耐熱性膜即 =特別限疋,通常宜使用5〜8〇μιη厚之聚醯亞胺膜。踗 =適當地將絕緣膜與如鑛或㈣之導電性金翻二 無黏著劑而疊層而成的疊層體之導電性金屬/利^ 脂等之峰等去除既定圖案而形成 時’銅镇可為壓延銅箱也可為電解銅落k 吊電路圖案之厚度為約2〜8〇 , 5〜5〇〇_者為理想。 ㈣寬為約 v从ii有如此種電路圖案之撓性電路板之至少連接妒;加 路圖案面塗佈變性聚胺甲酸酯樹脂組成物 成硬化膜(絕緣保護臈)。於獲得之輸以 封裝體職性電路板之電關案之連 勝▼ ,晶片般之電子零件以公知方法,例如使用人J半導 子零件(半導 ⑧ 201230908 隙注入底層填充材,之後進行加熱處理 以製造輸娜帶聽體。 填充材硬化, 本方法中,係安裝如短邊長度為l 2mm以下,較 2 綠奸零件在輸送膠帶封震ί Ξίΐί板處於裝之狀_,電子零件之連接面ίϊ 性電路板之電路圖案連接之面)當中最小的尺寸 ,且,徑)。通常電子零件之連接面之形狀為具短邊與長j 之長方形,因此,在麟指「短邊長度」係其短邊長度。又, 電子零件處於絲㈣、時,與電路面騎行之顧i201230908 VI. Description of the Invention: [Technical Field of the Invention] One aspect of the present invention relates to a method of manufacturing a transport tape package and to a flexible tape package (more specifically, a flexible tape package) The denatured polyurethane resin composition used for the insulating film of the circuit board). In particular, it is a method for manufacturing a transfer tape package in which an electronic component such as a micro semiconductor wafer having a short side length of 1.2 mm or less can be ideally mounted, and is suitable for use as an insulating film as a transfer tape package in such a manufacturing method. A denatured polyamine phthalate ester composition. Another aspect of the invention is a flexible circuit board for transporting a tape package, and a resin composition for a curable insulating film which is suitable as a flexible circuit board for a transfer tape package. In particular, the method for manufacturing a secondary circuit board includes a manufacturing process, and a flexible circuit board for inspection by an optical automatic inspection device: an insulating film coloring pigment system It does not contain a chlorine atom or a bromine; it is a resin composition for a hardenable insulating film for a transfer tape package circuit board in which the inspection method is used to reduce the efficiency of inspection by the rate measurement and to reduce the flexible circuit for the inspection body. First, as a technology, a package made of a heterogeneous metal-structured tape package, an I-age, wide-flex flexible circuit board (also called a conveyor belt for transporting ΤΑΒ cof). A circuit diagram of a metal structure is formed by forming a resin composition for a film such as a semiconductor wafer on a surface of a connecting terminal portion of a conductive sub-assembly, and a plurality of circuit pattern surfaces are coated on the insulating film. /, 夂 hardened to form an insulating film (insulation protective film) 201230908 With a seal can be expected to be in the New Zealand step and make #, that is, the power ίίί 上上 with a guide _ red circuit pattern will t彳t Circuit board At least the circuit pattern surface other than the terminal portion is coated with a smear-like tree test object, and the phase is heated at the hardened film (insulating film), and the silicon is transferred to the sturdy circuit board. In the connection of the circuit pattern, the electronic component such as a semiconductor wafer, and the gap injection layer filler of the 'infrared film mounted electronic component and the conductor wafer are hardened to fix the electronic component. Low Patent Documents 1 to 4 describe the use of denatured poly A curable resin composition of a urethane film, a second one of which is a polylactic acid ester of the genus, which is the above-mentioned denatured polyurea: formazan vinegar resin, and two patent documents 5: the use of polyaniline The oxygen hyacinth composition is used as a curable resin group for forming the above-mentioned insulating protective film. The reason why the denatured polyurethane resin composition or the quinone imine is known to be a composition is: hardenability, Insulation protective films such as electrical insulation, ship, low-hardening shrinkage, low (four), low-viscosity, chemical resistance, solder heat resistance, and adhesion to the underfill material are generally required to have excellent properties. 1<(1) [PRIOR ART DOCUMENT] [Patent Document 1] JP-A-2006-104462 [Patent Document 2] Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. [Patent Document 4] Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. In particular, the shape of the semi-conductive shape is as follows, and as described above, the connection terminal portion of the circuit pattern of the box having a rectangular shape on each side is ί : 2 [the gap of the flexible circuit board, usually will be noted The semiconductor wafer of the human NF is fixed by scratching. Further, the underfill is filled; the main part of the material ==== The ends of the film are directly connected. 々 之 , , , , , , , , , , , , , , , , , , , 逐 濩 濩 逐 逐 逐 逐 逐 逐 逐 逐 逐 逐 逐 逐 逐 逐 逐 逐 逐 逐 逐 逐 逐 逐 逐 逐 逐 逐 逐 逐 逐 逐 逐 逐 逐 逐 逐 逐 逐 逐 逐 逐 逐 逐The material can be fully edged === When the electronic component is installed, the electronic zero will occur and the flexible circuit board for the tape package will be green or blue. Due to the high environmental problems in recent years, the pigment used for coloring the insulating film of the circuit board is a pigment containing chlorine atoms and bromine atoms. The use of a flexible circuit for transporting tape packages in recent years has been progressing in fine pitch (fme pitch), but another = mounting, circuit board manufacturing steps, and second steps are required for process inspection. Use the nine-child automatic double check, but if you use the fresh automatic inspection device for process inspection, the visual inspection will not be considered to be different; the insulation "causes the problem of low inspection efficiency. The circuit between the following narrow parts will be easy" A defect sealing method is provided for the purpose of providing a manufacturing method for conveying tape sealing, which is capable of mounting an electronic poem such as a short side of a length of 201230908 or a small semiconductor W to be fully and securely mounted on a turn. Tape package body circuit = type: terminal part. The slave circuit pattern is connected to the (fourth) aspect of the present invention, and the object is to provide a method for manufacturing a circuit board, which comprises using an optical core inspection and packaging tape. In the case of a flexible circuit board, the pigment colored by the insulating film is free of chlorine atoms, and is used for reducing the inspection efficiency due to erroneous detection, and can suppress &lt;solving the problem> ^Keliang The various aspects of the present invention are as follows: &lt;First Aspect (Α)&gt; Α1· The manufacture of a transport tape package includes the following steps: 〃Characteristics: Circuitry is insulated The circuit of the conductive metal-shaped circuit pattern on the film is less flexible and less connected to the circuit pattern surface coating film other than the terminal portion, and the z-inspection product, and the heat treatment is performed to form a hardened πΐί4! The connection of the circuit pattern of the board is divided into two parts. The length of the short side of the board is 1. "The following electronic parts are connected to the underlying filler material after the gap between the mounted electronic parts, and then the heat treatment is performed to harden the underlying material.丝 憎 敝 敝 敝 contains: to the slow base and acid '(B). ~mgK〇H/g denatured polyamine phthalic acid vinegar resin (4); and method for producing curable tree-shaped poly-encapsulated enantiomers, in which it will be changed to epoxy: treated hardened film, impregnated with hole tree J3 The dimensional change rate of the guard is less than 6〇%. A method for manufacturing a transport tape package of A1 or Α2, wherein the tianzhang: accommodating polyamine lanthanum lysate composition is added and reduced to obtain a hardening 201230908. When the hardened layer filler is peeled off, at least partially cured film Cohesive failure occurred. The method for producing a transfer tape package according to any one of the above-mentioned items, wherein the denatured polyurethane resin composition comprises a denatured polyurethane resin having an acid value of 16 to 40 mgKOH/g ( A) and a curable resin, which is a compound of an acid/alcohol or a polybutadiene diol, and a octacarboxy-super compound (a3) obtain. A5. A method for producing a transfer tape package such as A4, wherein the bismuth citrate compound (4) is a diisocyanate brewing & 1. In the manufacture of the conveyor tape package of the A-1 to AS, the A-type polyamine phthalate resin (A) is in the main chain, jLg &# s % Amino phthalic acid resin. The method of manufacturing the adhesive tape package of the hard armor of the month of the month, 2, such as f~Α6, the manufacture of the transfer tape package, the middle of the 'curing resin (Β) is selected from the epoxy resin, the amine tree A group of two at least one base resin composed of a terminally-packed polyfunctional isocyanuric acid or cyanic acid lanthanum, which is characterized by comprising: (A); and a hard resin (8). mgKC> H/g, secret Polyurethane § The resin is a denatured polyamine A resin composition, which is used in the text, the short side length is 1.2mm or less, and you use it in &lt;2nd aspect (Part B)&gt; B1. The transmission tape package is characterized by: a manufacturing method for a conductive circuit board for a plate, comprising the following steps: preparing a conductive film on the insulating film A flexible resin circuit board having a circuit pattern formed of a sturdy metal, a circuit board formed of an inert metal, and at least a resin composition other than the terminal portion except the terminal portion, and a resin composition for a cold-separating insulating film, which is hardened by the second step === = 201230908 The flexible circuit board for the conveyor tape package will be inspected by an optical automatic inspection device. The resin composition for a curable insulating film contains a pigment (A) and is colored, and the pigment (A) contains at least an extender pigment (al) containing no gas atom and a bromine atom, and a pigment containing no chlorine atom and a desert atom ( A2) A method for producing a flexible wiring board for a transfer tape package according to B1, wherein the resin composition for a curable insulating film contains a pigment (A) and is colored green, and the pigment (A) contains no An organic pigment (al) of a chlorine atom and a bromine atom, a blue pigment (a3) not containing a chlorine atom and a bromine atom, and a yellow pigment (a4) not containing a chlorine atom and a bromine atom. B3. A transfer tape package such as B2 A method for producing a flexible circuit board, wherein a bulk pigment having a chlorine atom and a bromine atom (al) has a diameter of from 100 nm to 100 nm, and a blue pigment (a3) containing no chlorine atom or bromine atom The median diameter is 50 nm to 500 nm, and the yellow pigment (a4) which does not contain a chlorine atom and a bromine atom has a range of 50 nm to 500 nm. B4. A flexible circuit board for a transfer tape package according to any one of B1 to B3 The manufacturing method of the resin composition for a curable insulating film, comprising a denatured polyamine phthalic acid resin (B) 'The denatured polyamine phthalate resin <B) is at least a diisocyanate compound (bl) and a polyol compound (b2) containing a polycarbonate diol or a polybutadiene diol and a carboxyl group-containing The diol compound (b3) is obtained by a reaction. B5. A method for producing a flexible circuit board for a transfer tape package according to B4, wherein 'the body pigment (al) containing no chlorine atom and bromine atom is barium sulfate, and the pound is hard. In the resin composition for an insulating film, the content of the extender pigment (al) containing no chlorine atom or bromine atom is 10 parts by mass or more based on 1 part by mass of the solid content of the denatured polyamine phthalate resin (B). B6. A method for producing a flexible circuit board for a transfer tape package such as 34 or 35, wherein the 'diisocyanate compound (bl) is an alicyclic C7 having an alicyclic structure. For example, any one of B4 to: b6 A method for producing a flexible circuit 201230908 sheet for a transfer tape package, wherein the denatured polyamine phthalate resin (B) is in a main imine ring structure. The method for manufacturing a conductive tape for a transfer tape sealing body according to any one of the items B1 to B7, wherein the flexible circuit board has a circuit pattern including a portion having a circuit interval of 15 or less. B9. A resin composition for a curable film for a flexible wiring board for a transfer tape package, characterized in that the pigment (A) and the denatured polyurethane resin (B) are colored, and the pigment (A) Containing at least a chlorine atom and a bromine-based pigment (al) and a pigment (a2) containing no chlorine atom and a desert atom, the modified process is a compound (bl) and a polycarbonate or a butylene monool The 70th alcohol compound (b2) is obtained by reacting with a carboxyl group-containing diol compound (b3). π Λ . . . . . . . . . . . . . . 输送 输送 输送 输送 输送 输送 输送 输送 输送 输送 输送 输送 输送 输送 输送 输送 输送 输送 输送 . . 输送 . . . . . . . . . . . . . . . . . . (4)), containing no chlorine atom and if color (4), material containing (four) and _ sub-yellow pigment &lt; effect of invention &gt; manufacturing day and month - ", can provide a kind of body wafer for transport tape package The method of the extremely small semi-conductive adhesive strength below the electric mm is firmly mounted on the connecting terminal portion of the circuit pattern such as the needle, the +, and the flexible circuit board for the body. In the manufacturing method of the open tape: in the manufacturing method of the open tape, the underlying layer is filled with the wire (4), that is, the denatured polyurethane resin containing at least the chemical resin (B) 6-line 1 ^ - H g is used. (A) It is long with a hard short side; Λ,, a fragrant vinegar vinegar tree wax composition, by which, even if the installation of extremely small electronic parts of &amp; '', .2mm or less is implemented, 201230908 can Filling with the conventional bottom i has a sufficient separation strength. And 'Although (four) 硬 硬 硬 硬 硬 验 验 验 验 验 验 验 验 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 And the characteristics that are usually required for the adhesive film are not sturdy, and can provide a transfer tape for "manufacturing ί &amp;; it includes a step of using a flexible circuit board for optical automatic inspection device, wherein The system is low in efficiency, and can reduce inspection defects. 5 ί ί 高 高 高 高 高 高 高 高 高 高 高 高 高 高 高 高 高 高 高 高 高 高 高 高 高 高 高 高 高 高 高 高 高 高 高 高 高 高 高 高 高 高 高 高 高The form of the form A and the sample (hereinafter referred to as the invention) refer to the part described in the section: the present invention is generally described in the following. However, depending on the case, it may mean other (4) The inventions described in this section and the other parts (4) The inventions described in this section. In addition, Part A and Part B 2 refer to the inventions described in the section «ΑParts", as long as they are not contradictory. Combination. Manufacturing method, providing - reading - electronic wafer-like electrons with a package The following is a very small half mounted on the conveyor tape package for the purpose of the deflection. The connection pattern of the circuit pattern of the flexible circuit board 201230908, .P knife revealed that the transmission tape package The manufacturing method includes the following steps: preparing a flexible circuit board having a circuit pattern formed of a conductive metal on an insulating film, and coating a circuit pattern on at least a connection terminal portion of the flexible circuit board The amine is called a singer, and the money is heated to form a hardened film. The circuit diagram of the flexible circuit board for the transfer tape package is obtained. For the connection terminal part, an electronic component having a short side length of 1.2 mm or less is attached.绝 ί 经 经 经 经 安装 安装 安装 安装 经 经 经 经 经 经 经 经 经 经 经 经 经 经 经 经 经 经 电子 电子 电子 电子 电子 电子 电子 电子 电子 电子 电子 电子 电子 电子 电子 电子 电子 电子 电子 电子 电子 电子 电子 电子 电子变性 ϋ gK 〇 Wg denatured polyurethane resin (4); and the hardening tree τ ί ί , , 绝缘 绝缘 绝缘 绝缘 绝缘 绝缘 绝缘 绝缘 绝缘 绝缘 绝缘 绝缘 绝缘 绝缘 绝缘 绝缘 绝缘 绝缘 绝缘 绝缘 绝缘 绝缘 绝缘 绝缘 绝缘 绝缘 绝缘 绝缘 绝缘 绝缘 绝缘It is generally preferable to use a thickness of the polyimide film 5~8〇μιη.踗=When the insulating film is appropriately formed by removing a predetermined pattern such as a peak of a conductive metal such as a laminate or a conductive gold-plated adhesive which is laminated with a non-adhesive agent such as ore or (4), the copper is formed. The town can be a rolled copper box or an electrolytic copper drop. The thickness of the circuit pattern is about 2~8〇, 5~5〇〇_ ideal. (4) The width is about v. At least the connection of the flexible circuit board having such a circuit pattern from ii; the addition of the patterned surface coating denatured polyurethane resin composition into a cured film (insulation protection 臈). In order to obtain the winning streak of the electrical circuit of the package body board, the wafer-like electronic parts are heated by a known method, for example, using a human J semi-conductor part (semiconductor 8 201230908 gap injection of the underfill material, followed by heating Processing to manufacture the body of the belt. The filler is hardened. In this method, the length of the short-side installation is l 2mm or less, and the 2 green placard parts are sealed in the conveyor belt. ί Ξ ΐ ΐ 板 板 , ,, electronic parts The smallest dimension and the diameter of the connection surface of the circuit board. Usually, the shape of the connecting surface of the electronic component is a rectangle having a short side and a long length j. Therefore, the short side length of the lining refers to the short side length. Also, the electronic parts are in the wire (four), when, and the circuit surface rides

夺’例如為橢圓形時’在此所#「短邊長度」係指A 底層填充材以往係使用液狀或膜狀之環氧樹脂系底層填 ,才^·,但,方法中,也可適當使用環氧樹脂系底層填充材。 環氧樹脂系底層填充材不限定,例如可列舉namic 司製CHIPCOAT系列、日立化成(股)公司製液狀密封材A CEL-C系列、曰立化成(股)公司製底層填充用膜UF系列。 尤其,於COF用途,較佳為黏度或其他特性經最適化者,例 如宜為 NAMICS(股)公司製 CHIPCOAT8462-2卜 8462-96、 8462-220A卜日立化成(股)公司製液狀密封材cm·。 底層填充材通常係注入(插入)形成有電路圖案之絕緣膜 與經女1之电子零件之間隙,之後於例如約6〇〜2〇〇。〇之溫度 進行加熱處理而硬化。 本方法中,用以在撓性電路板之至少連接端子部以外的 電路圖案上形成硬化膜(絕緣保護膜)所用之樹脂組成物,為 變性聚胺曱酸醋樹脂組成物,其包含:至少具缓基且酸價為 16〜40mgKOH/g之變性聚胺曱酸酯樹脂(A);與硬化性樹脂 (B)。變性聚胺甲酸酯樹脂(a),尤佳為酸價22〜34mgKOH/g, 更佳為25〜30mgKOH/g者。 至少具叛基且酸價為16〜40mgKOH/g之變性聚胺曱酸酯 13 201230908 樹脂(A),可藉由對於具有胺甲酸酯鍵之主鏈中的側鏈或主鏈 之末端部,以如專利文獻1〜4所記載之公知方法導入羧基而 理想地製造。其酸價於製造變性聚胺甲酸酯樹脂(A)時,可藉 由改變導入羧基所使用之成分(通常為含羧基之成分)之使用 比率而可輕易調節。 該羧基可以與變性聚胺甲酸酯樹脂組成物中含有之硬化 性樹脂(B)進行交聯反應,因此該變性聚胺曱酸酯樹脂組成物 具良好的硬化性且可形成具優異特性之硬化膜。 本方法使用之至少具羧基且酸價為16〜4〇rngK〇H/g,較 佳為22〜34mgKOH/g ’更佳為25〜30mgKOH/g之變性聚胺甲 酸酯樹脂(A) ’較佳為將至少二異氰酸酯化合物(al)、與含聚 碳酸酯二醇或聚丁二烯二醇之多元醇化合物(a2)、與具鲮基 之二羥基化合物(a3)反應而得。 土 t二異氰酸酯化合物(a 1)可理想地使用通常製造聚胺甲酸 酯時使用者。亦即,i分子中具2個異氰酸酯基者均可,較 佳者可舉例如:脂肪族、脂環族或芳香族之聚異氰酸酯,例如 2,4-曱伸苯基二異氰酸酯、2,6_甲伸苯基二異氰酸酯、異 ,二異氰酸酯、1,6-六亞曱基二異氰酸酯、三亞甲基二異. 氰酸酯、1,4-四亞甲基二異氰酸酯、2,2,4_三甲基六亞甲基^ 異^酸,、2,4,4-三甲基六亞曱基二異氰酸酯、19-壬烷亞甲 基二異氰酸酯、1,1〇_十亞曱基二異氰酸酯、丨,^環己烷二異 氰酸酯、2,2,-二乙醚二異氰酸酯、二苯基曱烷-4,4,_二異^ 酯、鄰二甲苯二異氰酸酯、間二甲苯二異氰酸酯、對二甲苯 二異氰酸,、亞甲基雙(環己基異氰酸酯)、環己烷二亞 甲基^異氰酸酯、環己烷-1,4-二亞甲基二異氰酸酯、萘 二異氰酸酯、對伸苯基二異氰酸酯、3,3,_亞甲基二甲伸笨£ =,4’-二異氰酸酯、4,4,_二苯醚二異氰酸酯、四氯伸苯基二^ ,酸酯、降莰烷二異氰酸酯、氫化1,3-亞二甲苯二異氰酸醋二 氫化1,4-亞二甲苯二異氰酸酯等二異氰酸酯。該等可以 使用也可組合2種以上使用。 14 201230908 二異氰酸酯化合物(al)以對於严 充耐性良好之觀點,為具脂環結構之膨潤或底層填 佳,其中,異佛爾酮二異氰酸酯、^^一,氰酸酯化合物較 亞曱基雙(環己基異氰酸酯)尤佳。又,己烷二異氰酸酯、 活,也可使用封端化之二異氰酸醋。,為了防止水分導致失 含聚碳酸酯二醇或聚丁二烯二 _ &gt; 為含聚碳酸酯二醇或聚丁二烯二酸夕夕醇化合物(a2) ’ 也可為含有_等兩者之多元醇化人醇化合物,視需要 元醇化合物(a2)不含驗基之二經基化=本發明中,該多 聚碳酸S旨二醇只要是在主鏈^ Q ° 即不特別限定,可理想地使用以。51=二醇化合物 性經基末端之聚碳_二醇。舰學式⑴表不之2官能In the case of "for example, when the shape is elliptical", "the length of the short side" means that the underfill material of the bottom layer A is filled with a liquid or film-like epoxy resin underneath, but in the method, An epoxy resin underfill material is suitably used. The epoxy resin-based underfill material is not limited, and examples thereof include a CHIPCOAT series manufactured by Namic Co., Ltd., a liquid sealing material A CEL-C series manufactured by Hitachi Chemical Co., Ltd., and a UF series of an underlying filling film manufactured by Aoli Chemical Co., Ltd. . In particular, in the case of COF use, it is preferred that the viscosity or other characteristics are optimized, for example, it is preferably a liquid sealing material of CHIPCOAT 8462-2, 8462-96, 8462-220A, and a product of Nippon Chemical Co., Ltd. Cm·. The underfill material is usually injected (inserted) into the gap between the insulating film formed with the circuit pattern and the electronic component of the female 1, and thereafter, for example, about 6 〇 2 〇〇. The temperature of the crucible is hardened by heat treatment. In the method, a resin composition for forming a cured film (insulating protective film) on a circuit pattern other than at least a connection terminal portion of the flexible wiring board is a denatured polyamine vinegar resin composition, which comprises: at least A denatured polyamine phthalate resin (A) having a slow base and an acid value of 16 to 40 mgKOH/g; and a curable resin (B). The denatured polyurethane resin (a) is preferably an acid value of 22 to 34 mgKOH/g, more preferably 25 to 30 mgKOH/g. Denatured polyamine phthalate 13 201230908 resin (A) having at least a rebel base and having an acid value of 16 to 40 mg KOH/g, which can be obtained by a side chain or a terminal portion of a main chain in a main chain having a urethane bond It is ideally produced by introducing a carboxyl group by a known method described in Patent Documents 1 to 4. When the acid value is used to produce the denatured polyurethane resin (A), it can be easily adjusted by changing the use ratio of the component (usually a carboxyl group-containing component) used for introducing a carboxyl group. The carboxyl group can be cross-linked with the curable resin (B) contained in the denatured polyurethane resin composition, and thus the denatured polyamine phthalate resin composition has good hardenability and can be formed into excellent properties. Hardened film. The method uses at least a carboxyl group and has an acid value of 16 to 4 〇rng K 〇 H / g, preferably 22 to 34 mg KOH / g 'more preferably 25 to 30 mg KOH / g of denatured polyurethane resin (A) ' It is preferred to obtain at least a diisocyanate compound (al), a polyol compound (a2) containing a polycarbonate diol or a polybutadiene diol, and a dihydroxy compound (a3) having a mercapto group. The earth t diisocyanate compound (a 1) can be desirably used by a user when a polyurethane is usually produced. That is, it is possible to have two isocyanate groups in the i molecule, and preferably, for example, an aliphatic, alicyclic or aromatic polyisocyanate such as 2,4-indole phenyl diisocyanate, 2,6 _methylphenyl diisocyanate, iso-, diisocyanate, 1,6-hexamethylene diisocyanate, trimethylene diiso. Cyanate, 1,4-tetramethylene diisocyanate, 2, 2, 4 _Trimethylhexamethylene^isophthalic acid, 2,4,4-trimethylhexamethylene diisocyanate, 19-decane methylene diisocyanate, 1,1 〇 _ decyl fluorenyl Isocyanate, hydrazine, cyclohexane diisocyanate, 2,2,-diethyl ether diisocyanate, diphenyldecane-4,4,_diisophthalate, o-xylene diisocyanate, m-xylene diisocyanate, Xylene diisocyanate, methylene bis(cyclohexyl isocyanate), cyclohexane dimethylene isocyanate, cyclohexane-1,4-dimethylene diisocyanate, naphthalene diisocyanate, benzoic acid Diisocyanate, 3,3,-methylenedimethylexene = 4'-diisocyanate, 4,4,diphenyl ether diisocyanate, tetrachlorophenylene diester, acid ester, hail Diisocyanate, hydrogenated xylylene diisocyanate, 1,3-dihydro-1,4 vinegar diisocyanate, xylylene diisocyanate and the like. These may be used in combination of two or more kinds. 14 201230908 The diisocyanate compound (al) is preferably swelled or underfilled with an alicyclic structure from the viewpoint of good charge tolerance, wherein isophorone diisocyanate, phthalocyanate compound Bis(cyclohexyl isocyanate) is especially preferred. Further, as the hexane diisocyanate, it is also possible to use a blocked isocyanuric acid vinegar. In order to prevent moisture from causing loss of polycarbonate diol or polybutadiene _ &gt; is a polycarbonate diol or polybutadiene diacid compound (a2) ' may also contain _ etc. The polyolized human alcohol compound, if necessary, the diol compound (a2) does not contain a thiol group. In the present invention, the diol of the polyethylene carbonate is not particularly limited as long as it is in the main chain. It can be used ideally. 51 = diol compound A poly-carbon diol at the end of the base. Ship-style (1)

〇~0~〇士 化學式(1 取山攸π 如肪族或方香族煙基,n為1〜40之整數〇 曰一醇以數量平均分子量 〜^ 獲得理想的撓性,又;時,有時不易 ,, 右数里干均分子量超過10000,有時 II? 0 ^ ^〇~0~ gentleman chemical formula (1) Take the mountain 攸 π such as aliphatic or square fragrant smoke base, n is an integer of 1~40 〇曰 one alcohol with a number average molecular weight ~ ^ to obtain the desired flexibility, and; Sometimes it is not easy, the average number of molecules in the right number is more than 10,000, sometimes II? 0 ^ ^

UH “I 牛例如宇部興產(股)公司製ETERNAC0LL 化:工i:股UD系列、uc系列、UB系列、 ,工業知司製pLACCEL系列、可樂 列、旭化成化學(股)公司製㈣L系列等 ίΪ Ϊ,可以單獨使用,也可組合二種以上使用。 、!* -二0^1、一醇不限定,但以2官能性羥基末端之聚丁二 二^數量平均分子量為5QG〜則⑽者較佳, 轉理相的佳。數量平均分子量若小於500 ’有時不易 又 心、70性’又’若數量平均分子量超過10000,有時 15 201230908 耐熱性或财溶劑性會變差。又’聚丁二烯二醇可在分子内具 雙鍵,也可為將分子内之雙鍵虱化者,但分子内若殘留雙鍵, 會起交聯反應有時喪失撓性,故尤佳為分子内之静鍵纟Γ奇化 者。本發明使用之聚丁二烯二醇,具體而言,較佳者ϋ舉 曰本曹達(股)公司製G系列、GI系列、出光石油化學(股)公 司製Poly bd系列、Poly Φ系列、EPOL系列、KRASOL· 系列、三菱化學(股)公司製Poly tail Η系列等。砵辇哿丁-掄 二醇可以單獨使用也可組合二種以上使用Α 一 具缓基之二輕基化合物(a3) ’係具羧基為取代基之二經 基化合物,若使用如此的具缓基之二經基化合物,變性聚胺 曱酸酯樹脂會成為具羧基,能輕易與硬化性樹脂(B)反庳。亦 當將變性聚胺曱酸酯樹脂予以交聯時,能有效交聯,獲 得之硬化物的对熱性或耐溶劑性會增大。 具羧基之二羥基化合物(a3)不特別限定,宜為具羧基當 ,,代基之碳數為1〜30,又更佳為碳數為2〜2〇之二羥基化 2雔具,言’例如2,2_二羥甲基叫2,2·二羥甲基丁酸、 ^雙絲乙基甘紐、取_勉紅基丙舰等。此等可 種也可組合,種以上使用。其中,從對於溶劑 /合解又之觀點,2,2-二羥曱基丙酸、2,2_二羥曱基丁酸尤佳。 且^方法使狀魏驗? _触(Α),更佳為在主鏈中 胺環之變性聚胺曱酸輯脂。主射賊亞胺環之變 醇化合物㈣、與频基之二“化合物 、_羧@欠一酐或二敌酸一酐或例如下列化學式(2)夺示之醇 而if醯亞胺寡聚物’與二異氰酸酯化合物⑹反應 ⑧ 16 201230908 化學式0 (式中,&amp;表示2價之脂肪族或芳 數1〜10之2價之脂肪族或芳香族 、:基1乂仫為厌 以外的4價之基,Y代表二胺之胺酸之幾基 0〜20之整數。) 土卜勺2價之基,m為 藉由使用主鏈中具ϋ亞胺環胺 ⑷,由變性聚胺曱酸_脂組成物構成的硬化=== 度、耐熱性、絕緣可靠性等增大故為= 別述以化學式(2)表示之酸!^+ 临t %性羥基末端之醯亞胺寡聚 物’可由㈣酸成分、與二胺化合物 化合物構成的胺成分獲得。式中,m代表 ^為0〜10,更佳為0〜5。m若超過2〇 ,有時會變差。又,該醇性末 :弋」但例如可以依照曰本特開2007-238818號 A報專S己載之公知方法輕易獲得。 亦即’本方法適用的變性聚胺甲_旨樹脂(A),較佳為將 二異氰,化合物(al)、含聚碳酸醋二醇或聚(丁)二烯二 ϊΓ-匕:物(-:具羧基之二基化合物㈣、及視需要之四 之^胺絲鱗詩導人輕胺環之化合物成ί (a4)進行反應而獲得。 取刀 使用之二異氰酸g旨化合物(al)與其 =間又莫耳比[其他化合物(a2)、㈣、㈣之合^莫^)數/ 「異亂W曰化合物(al)之莫耳數],較佳$ 〇 5〜3 〇,更佳為 右ί二ί佳為〇.9〜2.0之範圍。前述莫耳比若過小,溶液 有時會增黏,前述莫耳比若過大,變性聚胺甲酸賴脂之分 17 201230908 子量會減低,有時耐熱性等會降低。 變性聚胺甲酸酯樹脂(A)之製備使用之具致基之二經基 化合物(a3)之量’可決定其使用比例使得獲得之聚胺甲酸醋 樹脂之酸價成為16〜40mgKOH/g,較佳為22〜34mgKOH/g, 更佳為25〜30mgKOH/g。 使用具叛基之二經基化合物(a3)與、含聚碳酸酯二醇或 聚丁二烯二醇之二醇化合物(a2)時,其莫耳比[具羧基之二羥 基化合物(a3)之莫耳數/含聚碳酸自旨二醇或聚丁二烯二醇之二 醇化合物(a2)之莫耳數]’大約為〇.2〜6,較佳為〇 5〜3之範圍。 使用具缘基之二輕基化合物(a3)、含聚碳酸酯二醇或聚 丁一烯一醇之二醇化合物(a2)、及四緩酸二酐、三魏酸一酐 或例如前述化學式(2)所表示之醇性羥基末端之醯亞胺寡聚 物4用於導入酿亞胺環之化合物成分(a4)時,其莫耳比[具緩 基^二羥^化合物(a3)之莫耳數/含聚碳酸酯二醇或聚丁 2烯 二醇之二醇化合物(a2)與用於導入醯亞胺環之化合物成分^ 之合計總莫耳數]’約為〇.2〜1〇,較佳為〇 5〜5之範圍。 變性聚胺甲酸酯樹脂(A)之製造,更具體而言,將二異氰 酸酯化合物(al)、與含聚碳酸酯二醇或聚丁二烯二醇之 化合物(a2)、具絲之二減化合物㈣、及視需要的四缓酸 一酐、二羧酸一酐或例如前述化學式(2)所表示之醇性_芙 寡聚物等祕導入酸亞胺環之化合物成分㈣等 =化^之反應,可以於無溶劑或溶於有機溶劑而進行。 通吊,,了防止二異氰酸酯化合物(al)失活, 人你=刀政均勻、洛解後,再添加二異氰酸酯化 &amp;物()^佳。又,為了改善溶解性等目的,可以改變詨添 加的順序。反應、;ra疮、s $炎。 m:〜i8〇t:,反應〜00c,較佳為 用公知的胺甲,為/j r又’觸媒可以使 柄_既定減之_,添加醇當做末端停止 (§) 18 201230908UH "I cattle such as Ube Industries Co., Ltd. ETERNAC0LL: I: UD series, uc series, UB series, industrial know-how pLACCEL series, Coke column, Asahi Kasei Chemicals Co., Ltd. (4) L series, etc. Ϊ, may be used singly or in combination of two or more. 、!* - 00^1, monool is not limited, but the number average molecular weight of the polyfunctional hydroxy terminal of the bifunctional hydroxyl group is 5QG~ (10) Preferably, the phase of the phase is good. If the number average molecular weight is less than 500 'times, it is not easy to be heart-hearted, 70-like' and if the number average molecular weight exceeds 10,000, sometimes 15 201230908 heat resistance or solvent solubility will deteriorate. The polybutadiene diol may have a double bond in the molecule or may be a bismuth in the molecule. However, if a double bond remains in the molecule, the crosslinking reaction sometimes loses flexibility, so it is particularly preferable. The static bond in the molecule is singularized. The polybutadiene diol used in the present invention is, in particular, preferably the G series, the GI series, the EIKO, and the chemistry of the company. )Company Poly bd series, Poly Φ series, EPOL series, KRASOL· series, three Poly tail Η series manufactured by Ryo Chemical Co., Ltd., etc.. Butadiene-nonanediol can be used alone or in combination of two or more. A light-based compound (a3) with a carboxyl group is substituted. The base di-based compound, if such a dibasic compound is used, the denatured polyamine phthalate resin will have a carboxyl group and can easily react with the curable resin (B). When the phthalic acid ester resin is crosslinked, it can be effectively crosslinked, and the heat resistance or solvent resistance of the obtained cured product increases. The dihydroxy compound (a3) having a carboxyl group is not particularly limited, and is preferably a carboxyl group. The carbon number of the base is from 1 to 30, and more preferably the dihydroxylated 2 cookware having a carbon number of 2 to 2 Å, such as 2,2_dimethylol is called 2,2·dimethylolbutanoic acid. , ^Double silk ethyl gan, take _ 勉 基 propyl propyl ship, etc. These can also be used in combination, more than one species. Among them, from the point of view of solvent / recombination, 2,2-dihydroxy fluorenyl Propionic acid, 2,2-dihydroxyindolyl butyric acid is especially preferred. And the method is used to test the shape of the test. _ touch (Α), more preferably the amine ring in the main chain of the polyamine tannic acid grease. An imine ring-alcoholic compound (IV), and a fluoro group "compound, _carboxy@ under-anhydride or diaster-acid mono-anhydride or an alcohol such as the following formula (2) and an oxime imine oligomer" Diisocyanate compound (6) reaction 8 16 201230908 Chemical formula 0 (wherein &amp; represents a divalent aliphatic or an aromatic or aromatic having a valence of 1 to 10, and a valence of 4 or more The base, Y represents an integer of 0 to 20 of the amino acid of the diamine.) The divalent base of the earthy spoon, m is a denatured polyamine tannic acid by using a quinone imine cyclic amine (4) in the main chain. The hardening of the composition of the fat composition === degree, heat resistance, insulation reliability, etc., so that it is an acid represented by the chemical formula (2)! ^+ t % 羟基 羟基 % % % It can be obtained from an (iv) acid component and an amine component composed of a diamine compound. In the formula, m represents ^ from 0 to 10, more preferably from 0 to 5. If m exceeds 2 〇, it sometimes becomes worse. Further, the term "alcoholic acid" is, for example, easily obtained in accordance with a known method of the Japanese Patent Application Laid-Open No. 2007-238818. That is, the denatured polyamine A to which the method is applied is a resin (A), preferably diisocyanate, compound (al), polycarbonate-containing diol or poly(butadiene) diterpene-quinone: (-: a dicarboxylic compound having a carboxyl group (IV), and, if necessary, a compound of a light amine ring, which is obtained by reacting a compound of a light amine ring into a ί (a4). (al) is the ratio between the other compounds (a2), (four), (four), and the number of moles of the compound (al), preferably $ 〇5~3 〇, preferably the right ί ί 佳 is the range of 〇.9~2.0. If the aforementioned molar ratio is too small, the solution sometimes becomes sticky, if the aforementioned molar ratio is too large, the denatured polyurethane lysate is divided into 17 201230908 The amount of the component may be lowered, and the heat resistance may be lowered. The amount of the dibasic compound (a3) used for the preparation of the denatured polyurethane resin (A) may be determined by the ratio of use thereof. The acid value of the urethane carboxylic acid resin is 16 to 40 mgKOH/g, preferably 22 to 34 mgKOH/g, more preferably 25 to 30 mgKOH/g. The use of the dithiol-based compound (a3) and polycarbonate-containing Glycol Polybutadiene diol diol compound (a2), molar ratio thereof [molar number of carboxyl group-containing dihydroxy compound (a3) / polycarboxylate-containing diol or polybutadiene diol The molar number of the alcohol compound (a2) is 'about 2. 2 to 6, preferably 〇 5 to 3. Using a light-based compound (a3) having a rim group, a polycarbonate-containing diol or a poly a diol compound (a2) of tetrabutenol, and a tetrabasic acid dianhydride, a tricarboxylic acid monohydride or an alcoholic hydroxyl terminated quinone imine oligomer 4 represented by the above chemical formula (2) for introduction In the case of the compound component (a4) of the imine ring, the molar ratio of the molar ratio of the compound (a3) of the compound (a3) to the diol compound of the polycarbonate diol or polybutadiene diol The total molar number of (a2) and the compound component for introducing the quinone ring is about 〇2 to 1 Torr, preferably 〇5 to 5. The denatured polyurethane resin ( A) production, more specifically, a diisocyanate compound (al), a compound (a2) containing a polycarbonate diol or a polybutadiene diol, a dioxin compound (4), and optionally Tetrahydrous acid anhydride The reaction of the acid monoanhydride or the compound component (IV) which is introduced into the acid imine ring, such as the alcoholic oligomer represented by the above chemical formula (2), can be carried out without a solvent or dissolved in an organic solvent. By hanging, to prevent the diisocyanate compound (al) from deactivating, you can change the diisocyanate &amp; (good) after the solution, and, in order to improve the solubility, etc., can be changed.詨Addition order.Reaction,;ra sore, s $ inflammation. m:~i8〇t:, reaction ~00c, preferably using a known amine A, /jr and 'catalyst can make the handle _ definitely reduced _, add alcohol as the end stop (§) 18 201230908

劑Z別t可使用含氮系溶劑例如 胺、二乙基曱醯胺、队曱基·2♦各㈣、f 味唾啶酮、N-甲基己内醯胺等;含硫原子溶劑例如:;= ,:二乙基亞颯、二甲基砜、二乙基砜 :甲土亞 含氧溶劑,例如_溶劑之”,、二曱_.二;^= 二乙二醇二甲喊、乙二醇二⑽、卡必::、 丙二醇甲輕乙酸醋、丙二醇⑽乙酸酯、二丙 酉曰、二乙二醇乙醚乙酸S旨、曱氧基丙酸甲醋、甲氧基 醋、乙氧基丙酸甲S旨、乙氧基丙酸乙g旨、三乙二醇 = 溶劑之丙酮、苯乙酮、苯丙酮、環己酮、 異,爾酮等;_溶劑之乙二醇、二。找、四氫钱等;内醋 糸^劑之γ·Τ_#。尤佳為使用γ·τ_、二乙二醇乙鍵 乙酸酯、三乙二醇二曱喊等。 旦本方法使用之變性聚胺曱酸酯樹脂(Α)之數量平均分子 里不限定,較佳為3000〜100000,更佳為5〇〇〇〜5〇〇〇〇。在此, ,量平均好量係以凝膠渗透層析(Gpc)敎㈣苯乙稀換 具之値。數量平均分子量若低於前述範圍,獲得之硬化膜之 伸長度、撓性及強度等機械的特性有時會減損,另一方面若 超過前述範圍,黏度會増加到必要以上,故有時用途受限。 本方法使用之變性聚胺曱酸酯樹脂組成物之必要成分即 硬化性樹脂(B) ’係與變性聚胺甲酸酯樹脂中之羧酸反應之化 σ物。硬化性樹脂⑼只要是會與變性聚胺曱酸酯樹脂中之趣 酸反應之化合物即不特別限定,宜為環氧樹脂、胺基樹脂、 封、化之多官能異氰酸酉旨、氰酸g旨樹脂。 環氧樹脂,可理想地使用例如雙酚A型環氧樹脂、氫化 雙酚A型環氧樹脂、溴化雙酚A型環氧樹脂、雙酚F型環氧 樹脂、酚醛樹脂型環氧樹脂、酚酚醛樹脂型環氧樹脂、曱酚 酚醛樹脂型環氧樹脂、脂環環氧樹脂、N_環氧丙基型環氧樹 19 201230908 月:、巧? A之_樹脂型環氧樹脂、螯合型環氧樹脂、乙二 二掠巧二含胺基之環氧樹脂、橡膠變性環氧樹脂、二 = 氧樹脂、矽酮變性環氧樹脂、&amp;己内酯變性 二氮;二ϋ*化聚丁二烯等—分子中具2個以上之環氧基 气二F=虛f。尤其Ν_環氧丙基型環氧樹脂、含胺基之環 ^ :烯的,且另一方面’脂環環氧樹脂或環氧化 t 貝少’絕緣可靠性良好,可以理想地使用。 難燃性’可使用在其結構中導人有氯、漠㈣ 素或磷等原子的環氧化合物。 亞胺:匕?、經曱基基型、亞胺基型、 ^脲才福她l。尤其苯胍胺樹脂由於絕.緣可靠性良好為較 g旨美基多官能異氰酸酯化合物的異氰酸 == 二環族或芳香族之多官能異 碳數為2〜30 :==匕匕者’較佳為不含異氰《基的 之異氰酸能基者脂:刪芳 異氰酸妒、Λ 者,但不限定,例如丨,4-四亞甲基二 ΐ、22:: 曱基二異氰酸酯、i,6-六亞曱基二異氰酸 醋、L異^“ ίff5甲基二^_、離胺酸二異氰酸 二異氰酸酉旨)、13:^里:^基¥己基異氮酸醋(異佛爾酮 甲烷二里着辦2 ΐ(異識甲基)_環己烷、4,4,-二環己基 異氰酸酉旨、Γ5曰关二異氰酸酯、4,4,-二苯基曱烷二 曱苯二異氰酸酉:孽:二^酿、❹苯胺二異氰酸酉1、亞二 關於h t日#/、齓馱酯基經封端化者。 或活性亞甲可理想地使用麵衍生物“比吐衍生物 衍生物或“亞匕;多官能異氰酸醋。尤其,經吡唑 性高,為較佳。土化5物封端的多官能異氰酸酯由於反應 ⑧ 20 201230908 本方法使用之變性聚胺曱酸酯樹脂組成物,可視需要理 想地含有顏料或填料。 顏料可以單獨使用藍色顏料、綠色顏料、黃色顏料等公 知的顏料,或將多種混合使用。其中’較佳為含有分子結構 中不含氣原子及漠原子之藍色顏料、及分子結構中不含氯原 子及溴原子之黃色顏料、及分子結構中不含氯原子及溴原子 之體質顏料(亦即,無彩色顏料)且使變性聚胺曱酸酯樹脂組 成物呈綠色較佳。當組成物中含有在分子結構中含氯原子及 溴原子之化合物時’使用其之製品在焚燒時可能會產生有害 物質故為不佳。 分子結構中不含氯原子及溴原子之藍色顏料,可列舉銅 酉大花青藍(C.I.顏料藍15)、無金屬献花青藍(C.I.顏料藍16)、 鈦敝花青藍、鐵献花青藍、鎳酞花青藍、鋁酞花青藍、錫酞 花青藍、鹼性藍(C.I.顏料藍1、2、3、10、14、18、19、24、 56、57、61)、颯化CuPc(C.I.顏料藍17)、紺青(C.I.顏料藍 27)、群青(C_I.顏料藍29)、鈷藍(C.I.顏料藍28)、天藍(C.I. 顏料藍35) ' Co(A卜Cr)204(C.I.顏料藍36)、雙偶氮(C.I.顏 料藍 25,26)、陰丹酮(Indanthrone)(C.I.顏料藍 60)、靛青(C.I. 顏料藍63、66)、鈷酞花青(C.I·顏料藍75)等但不特別限定。 其中’從成本面以銅酞花青藍為較佳。 分子結構中不含氯原子及溴原子之黃色顏料,例如單偶 氣育(C.I.顏料黃 1,4,5,9,65,74)、苯并p米唾酮(Benzimidazolone) 黃(C.I.顏料黃 120,151,154,175,180,181,194)、黃士酮 (Flavanthrone)黃(C.I.顏料黃24)、偶氮甲基黃(C.I.顏料黃 m,i29)、蒽醌黃(c.i.顏料黃m,i47)、異吲哚滿黃(c丄顏料 黃139,185)、雙偶氮黃(c.I.顏料黃155)、縮合多環系(C,I. 顏料黃148,182,192)、氧化鐵(C.I.顏料黃42)、雙偶氮甲川 (C.I.顏料黃101)、偶氮沉澱(azo lake) (C.I.顏料黃 61,62,100,104,133,168,169)、金屬錯合物(C.I.顏料黃 150,153,17穴179)等,但不特別限定,從成本面及安全性.無 21 201230908 ^性方面,宜排除「有害性受到指摘之偶氮系顏料」。又, =子結構中含氟原子之黃色顏料時,由於分散性優異故為^ 分子結構中不含氯原子及溴原子之體質顏料,例如硫於 ,(^丄顏料白21,22)、碳酸鈣(C.I.顏料白18)等,但無特^別^ 變性聚胺甲酸酯樹脂組成物使用之上述顏料之構成比, 只要變性聚胺曱酸酯樹脂組成物能著色為綠色即無妨,立 2減J於絲式自動檢錄置的誤㈣,考慮*穿透心 4 ,八改善可理想地使用體質顏料。藍色顏料、黃乂 相對於變性聚胺甲酸酯樹脂100質量份各為0.01〜5質^份淤 佳,0.05〜1質量份更佳,體質顏料相對於變 脂削質量份,為1〇質量份以上較佳,10〜2〇〇^^;樹 、填料可使用公知者。例如:二氧化砍、氧化鈦、滑石、姑 ^、石英粉等無機微粒、環氧樹脂粉末、三聚 ^ 末'聚醯胺樹脂粉末、聚醯亞胺樹脂粉末、橡膠早、 若等^微粒。其粒徑(平均粒徑)為_加較 ㈣’容易於自動檢查裝置發生誤檢測。又, Γ酸咖旨(A)1GG質量份,通“ ζυυ貝里伤’較佳為5〜100質量份。 门 本方法使用之變牲聚胺曱酸醋樹月旨組成物中,妹甘 二言’也可摻合㈣氧烧、氟變性聚々氧燒、^ ,基化合物、聚乙烯基化合物等消泡劑 ,丙 ίΓί;义二受阻盼系化合物、㈣化合物、受:t胺匕 口物,氧化劑、齡樹脂等公知的各種添加劑。妝糸化 本發明中,變性聚胺曱酸酯樹脂組成物 甲酸醋樹脂均勻溶解於有機溶劑之溶液性聚胺 有機溶劑不_限定,可使用。 乙醯胺、N N _ 7 ^ J幻舉3虱糸各劑,例如N,N-二曱基 ,乙基乙醯胺、n,n-二曱基曱醯胺、N,N_二乙 22 ⑧ 201230908 基:知胺、N-:基各烧酮、u·二曱基如米啥綱 甲土 ^内酿胺等;含硫原子溶劑例如二甲基亞石風、二乙、 ?、二曱基颯、二乙基钱、六甲基續酿胺等含 ς 系二甲紛等;二甘二甲醚系溶劑例 一甲醚(chglyme)、三乙二醇二甲醚, 丁内酉旨等。尤其,較佳為①甲飞基杨各烧西例如: 甲基甲酸胺、n,n-二乙基甲酿胺、ΐ i 又胺,丁内醋、三乙二醇二甲—, 溶劑。接细在^成變性聚胺甲酸_脂時使用之有機 變性聚胺〒_旨樹驗成物 網版印刷形成圖案時,為 勘2咖,辄圍。以 細的填料以辭觸變性較彳卜β ’宜添加二a化石夕等微 網版ΐίιϋ佈旨樹脂組成物利用例如 圖案之表面形至,接端子部以外的電路 Γ〇〜=3,=為於⑽〜職進行5 ==時^ 1 時更佳為15分鐘〜2小時以熱風或红外線 =應理使 贼聯密敍良好㈣者。膜由於具 23 201230908 亦即,本方法使用之將使用了酸僧 f性聚胺甲酸醋樹脂的變性聚胺f旨,^40,K〇H/g之 處理而得之硬化膜,當浸潰於JU成物予以加熱 做底層填充材之主成分的雙^二,言多用為當 較佳為齡。以下,更佳為15%〜6^乳又=時的尺❶寸變化率 對於環氧樹賴雖優異。魏社 佳4 25%〜53% ’ 時,可以充八 :二,膜之尺寸變化率為60%以下 :二充刀防止硬化膜與底層填充界二 ,再者,硬化膜之尺寸變化率為15%〜6()%日士 3 填充材之密合性,從變性聚胺甲酸 ^由於”底層 材剝離時,具有至少部分硬成 為全面内聚破⑧之特性,密合性特別優異皮展(幸乂佳 以不,甲酸酉1樹脂組成物構成的硬化膜,伟 2直接連接於如半導體晶片之電子零件而是 接觸之結構使用。底層填充材,係 7 -s真充材 2封,並且發揮將電子零件固定於輸“裝 。若欲剝離電子零件,則結構上應 =充材與硬化膜之附近會最先被破壞m - ^層填充材與硬化膜之黏著性會大大影響電子零剝離強 度。 明巾,藉由使用具如前述特性之變性聚胺曱酸醋樹 月^組成物而形成硬化膜,可以提高底層填充材與硬化膜之 著〖生,因此即使女裝短邊長度為1 2mm以下,較佳為 0.3mm〜1.2mm ’更佳為〇.4ιηπι〜1.1mm之微小電子烫株日丰, 也能牢㈣絲使得電子科财充分_強度,件$ «Β部分》 B部分揭示之發明其目的在於提供一種輸送膠帶封裝體 用撓性電路板之製造方法,包含使用光學式自動檢查裝置檢 查所製造之輸送膠帶封裝體用撓性電路板之步驟,其中用於 將絕緣膜著色所使用之顏料為不含氯原子及溴原子^顏料,' 且可抑制誤檢測所致檢查效率之低落而減低檢查不良率。 ⑧ 24 201230908 路板之製造方法之么明係關於一種輸送膠帶封裝體用橈性電 其包含以下步驟: 準備在絕緣膜卜呈 電路板;在撓性電路柘、¥电f金屬形成之電路圖案之撓性 塗佈硬化性絕緣膜少連接端子部以外的電路圖案面 及將獲得之輸送豚帶封成物’其次使硬化而形成絕緣臈; 裝置檢查;1帶封裝_祕電路_絲式自動檢查 其特徵為: 原不含氯 (a2)的顏料(A)而著色。 3軋原子及溴原子之顏料 不特別限定,通常性的絕緣性的*t熱性膜即 程=為理想。電路間隔有i5〜1〇,m 造成光學式自動檢查裝置光的微細散射等影響 送膠帶封裝體用撓性電路板方^特別適用本發明之輸 於具有如此的電路圖牵的掉} 以外的電路圖案面塗佈I :之至少連接端子部 硬化而形成絕緣膜。並且巧樹脂組成物’其次使 用撓性電路板係使用光學十得之輪送膠帶封裝體 (秦_綱自動麵置,触為報對親 本方法使用之硬化性絕緣膜用樹脂組成物,其特徵為至 25 201230908 土含s子巾不含氣原子及溴、原子之體質顏料(al)與分子中 不έ氣原子及溴原子之顏料㈣的顏料(A)而著色。 體質顏料(al)係指所謂無彩色顏料,例如製造晝具時摻 ^的無祕韻,係折料為小、與亞麻仁油等展色劑混合 時折射率幾乎無差異而為透明或半透明者。 又,顏料(a2)並非無彩色顏料,而是通常的彩色顏料。 ^本方法使用之體質顏料(al),例如可使用當做晝具之體 貝顏料者,且較佳為分子中不含氯原子及溴原子者。例如: 硫酸鋇、碳酸鈣、高嶺土等。體質顏料(al)較佳為從硫酸鋇(例 如C.I·顏料白21,22)、碳酸鈣(例如cu.顏料白18)選出的至 少1種體質顏料,更佳為硫酸鋇(例如c丄顏料白21,22)。 又,使用體質顏料(al),於調整所形成之硬化膜(絕緣膜) 之光特性,且抑制光學式自動檢查裝置之誤檢測所致檢查效 率降低,且改良獲得之硬化絕緣膜之黏性,能獲得較低黏性 (無黏性)之觀點亦為較佳。 雖不特別限定,但是體質顏料(al)之中位徑為 100nm~1000nm 較佳 ’ 400nm~800nm 更佳,500nm~700nm 尤 佳。體質顏料(al)之中位徑為i〇〇〇nm以下時,硬化膜之光學 均勻性會提高’能更減低光學式自動檢查裝置之誤檢測,於 lOOnm以上時,硬化絕緣膜之黏性能改善為更良好(無黏 性)。又’體質顏料(al)之中位徑為400nm〜800nm時,較易 分散且能分散到接近一次粒徑之粒度分布,可獲得光學均勻 性高之硬化膜。 本方法使用之硬化性絕緣膜用樹脂組成物,係由於顏料 (A)成分中之分子中不含氯原子及溴原子之顏料(a2)而著 色。該顏料(a2)只要是分子中不含氯原子及漠原子者即不特 別限定,可考慮分散性或經濟性而使用以往公知之顏料。例 如宜將紅色顏料、藍色顏料、黃色顏料、綠色顏料等彩色顏 料皁獨使用,或混合多種使用。 本方法中,硬化性絕緣膜用樹脂組成物宜含有顏料(A) 26 ⑧ 201230908 而著色為綠色’ s亥顏料(A)包含:分子中不含氯原子及漠原子 之體質顏料(al)、分子中不含氣原子及溴原子之藍色顏料 (a3)、及分子.中不含氣原子及溴原子之黃色顏料(a4)。 分子結構中不含氣原子及溴原子之藍色顏料(a3),例如 銅酿花青藍(C.I.顏料藍15)、無金屬欧花青藍(c.l.顏料藍 16)、鈦献花青藍、鐵欧花青藍、鎳献花青藍、銘酿花青藍、 錫駄花青藍、驗性藍(C.I.顏料藍 1,2,3,10,14,18,19,24,56,57,61)、石風化 CuPc(C.I.顏料藍 π)&quot;? 紺青(C.I.顏料藍2&lt;7)、群青(C.I·顏料藍29)、鈷藍(C.I.顏料藍 28)、天藍(C.I.顏料藍 35)、Co(AL· Cr)204(C.I.顏料藍 36)二 雙偶氮(C.I.顏料藍25,26)、陰丹酮pndanthrone) (C.I·顏料藍 60)、散青(C.I.顏料藍63,66)、鈷酞花青(C.I.顏料藍75)等, 但不特別限定。該等之中,從成本面的觀點,以銅酜花青藍 較佳。 雖不特別限定’但分子中不含氯原子及溴原子之藍色顏 料(&gt;3)之中位徑為50nm〜500nm較佳,50nm〜200nm更佳。 藍色顏料(a3)之中位徑為500nm以下時,硬化膜之光學均勻 性會提高,可更減低光學式自動檢查裝置之誤檢測。 分子結構中不含氯原子及漠原子之黃色顏料(a4),例如 單偶氮黃(C.I.顏料黃1、4、5、9、65、74)、苯并咪唑酮 (Benzimidazolone)黃(C.I.顏料黃 120、151、154、175、180、 181、194)、黃士酮(Flavanthrone) (C.I.顏料黃 24)、偶氮曱基 黃(C.I.顏料黃117、129)、蒽醌黃(C.I.顏料黃123、147)、異 吲哚滿黃((:.1.顏料黃139、185)、雙偶氮黃((:.1.顏料黃155)、 縮合多環系(C.I.顏料黃148、182、192)、氧化鐵(C.I.顏料黃 42)、雙偶氮曱川(C.I.顏料黃101)、偶氮沉澱(azolake)(C.I. 顏料黃 6卜 62、100、104、133、168、169)、金屬錯合物(C.I. 顏料黃150、153、177、179)等,但不特別限定,從成本面 及安全性•無害性方面之觀點,宜排除「有害性受指摘之偶-* 氮系顏料」。又,為分子結構含有氟原子之黃色顏料時,從分 27 201230908 散性優異之觀點為較佳。 雖不特別限定’但分子中不含氣原子及溴原子之黃色顏 料(a4)之中位徑為50nm〜500nm較佳,50nm〜35〇nm更佳二 黃色顏料(a4)之中位徑為500nm以下時,硬化臈之光學均勻 1&quot;生向’此更為減低光學式自動檢查裝置之誤檢測。 又’分子中不含氯原子及溴原子之藍色顏料(a3)、及分 子中不含氯原子及溴原子之黃色顏料(a4)等彩色顏料,視需 要使用公知之顏料分散劑等,以珠磨機、球磨機等預先分散 於溶劑,並使用該分散液製備硬化性絕緣膜用樹脂组成物較 佳。 硬化性絕緣膜用樹脂組成物中之顏料(A)之摻合比,係摻 合為使得硬化性絕緣膜用樹脂組成物能充分著色成目的^ 色,但為了減低於光學式自動檢查裝置之誤檢測,尤佳為考 慮光穿透性而決定。雖不限定,但例如:不含氯原子及溴原子 之體質顏料(al)相對於硬化性絕緣膜用樹脂組成物所含有之 樹脂之固體成分1〇〇質量份,為10質量份以上較佳,為2〇 質:ε份以上200質量份以下更佳,40質量份以上12〇質量份 以下尤佳,不含氣原子及溴原子之顏料(a2)相對於樹脂固體 成分100質量份,為〇.〇1〜5質量份較佳,0.05]質量份更佳。 本方法中用於形成絕緣膜而使用的硬化性絕緣膜用樹脂 組成物,可以理想地使用在習知絕緣膜用的熱硬化性或光硬 化性樹脂組成物中任一者,但較佳為如專利文獻!〜4記載之 含變性聚胺甲酸酯樹脂之熱硬化性樹脂組成物,或如專利文 獻5 §己載之含聚驢亞胺發氧烧樹脂之熱硬化性樹脂組成物。 本方法中,雖不特別限定,但宜使用變性聚胺甲酸酯樹 脂組成物當做硬化性絕緣膜用樹脂組成物。於此情形,不含 氯原子及溴原子之體質顏料(al)為硫酸鋇,且體.質顏料(al) 之含量相對於變性聚胺甲酸酯樹脂(B)固體成分1〇〇質量 份,其下限較佳為10質量份以上,更佳為2〇質量份以上, 尤佳為40質量份以上,其上限較佳為2〇〇質量份以下,更佳 28 201230908 為120質量份以下,尤佳為1〇〇質量份以下較佳。於該情形, 體質顏料(al)之含量相對於變性聚胺曱酸酯樹脂固體成/八 1〇〇質量份少於10質量份時,有時無黏性會不足。 刀 變性聚胺甲酸酯樹脂組成物通常含有變性聚胺曱酸酽 脂(B)與硬化性樹脂(c)當做必要成分。 曰 變性聚胺曱酸酯樹脂(B)較佳為例如使至少二異氰酸酉旨 化合物(bl)、與含聚碳酸酯二醇或聚丁二烯二醇之多元醇^ 合物(b2)、與含羧基之二醇化合物作3)反應而獲得之變性聚胺 曱酸S旨樹脂(B)。 二異氰酸酯化合物(bl)可以適當使用在製造通常之 甲酸醋時可使用者。亦即,只盎是i分子中具2個異氰酸g 基者即可,可為脂肪族、脂環族或芳香族聚異氰酸酯,= 者例如2,4-曱伸苯基二異氰酸酯、2,6_曱伸苯基二異氰酸 異佛爾=二異氰酸酯、丨,6_六亞甲基二異氰酸酯、丨,3_三亞曰 基二異氰酸酯、1,4-四亞甲基二異氰酸酯、2,2,4_三 =基二,氰酸巧'2,4,4_三曱基六亞曱基二異氰酸酯ϋ壬 '二亞甲,二異氰酸酯、u〇_+亞曱基二異氰酸酯、U一環 烧二,氰酸醋、2,2,_二乙域二異氛酸酷、二苯基甲燒γ 二異氰,S旨、鄰二甲苯二異氰酸g旨、間二甲苯二異氰酸心、· =甲苯二異氰酸@旨、亞甲基雙(環己基異氰酸自旨)、環^燒 H亞氛酸醋、環己燒-1,4_二亞曱基二異氰酸酉Γ、 二^&quot;V&quot;&quot;/、氰欠§曰、對伸苯基二異氰酸酯、3,3,_亞甲Λ二甲 伸本基-4,4’-二異氰酸酯、4,4,_二苯醚二異 萨、:二: 基二異氰酸§旨、降莰烧二異氰酸S旨、氫化1 3·^二曱^二^ 亞二甲苯二異氰酸酿等二異氰酸醋。 可以早獨使用也可組合2種以上使用。 此寻 一異氰α酸酯化合物(bl),從對於搢备± 層填充耐性良好之_點,^呈护氧树脂之膨潤’或底 亞甲基雙(虹基異紐旬尤佳。Λ 〇〇 201230908The solvent Z may be a nitrogen-containing solvent such as an amine, diethyl decylamine, a sulfonyl group, a 2 (4), a f-succinone, an N-methyl caprolactam or the like; :; = , : diethyl hydrazine, dimethyl sulfone, diethyl sulfone: a sulfuric acid solvent, such as _solvent", two 曱.. two; ^ = diethylene glycol dimethyl shout , ethylene glycol two (10), carbene::, propylene glycol methyl light acetic acid vinegar, propylene glycol (10) acetate, dipropylene oxime, diethylene glycol ethyl ether acetic acid S, methoxy methoxyacetic acid methyl vinegar, methoxy vinegar , ethoxypropionic acid A, ethoxypropionic acid, g-ethylene glycol = solvent acetone, acetophenone, phenylacetone, cyclohexanone, iso- ketone, etc.; Alcohol, II. Find, tetrahydrogen, etc.; γ·Τ_# of vinegar 糸^. It is especially good to use γ·τ_, diethylene glycol ethyl acetate, triethylene glycol, etc. The number average molecular weight of the denatured polyamine phthalate resin (Α) used in the method is not limited, and is preferably from 3,000 to 100,000, more preferably from 5 to 5 Å. Here, the average amount is good. The amount is changed by gel permeation chromatography (Gpc) 敎 (four) styrene If the number average molecular weight is less than the above range, the mechanical properties such as the elongation, flexibility, and strength of the cured film may be degraded. On the other hand, if it exceeds the above range, the viscosity may be added to the above. Sometimes the use is limited. The curable resin (B) which is an essential component of the denatured polyamine phthalate resin composition used in the method is a sigma compound which reacts with a carboxylic acid in a denatured polyurethane resin. The resin (9) is not particularly limited as long as it reacts with the acidity in the denatured polyamine phthalate resin, and is preferably an epoxy resin, an amine resin, a polyfunctional isocyanate, and a cyanic acid. g. Resin. Epoxy resin, for example, bisphenol A type epoxy resin, hydrogenated bisphenol A type epoxy resin, brominated bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol resin Epoxy resin, phenolic phenolic resin epoxy resin, phenolic phenolic resin epoxy resin, alicyclic epoxy resin, N_epoxypropyl epoxy tree 19 201230908 Month: Qiao? A _ resin type Epoxy resin, chelating epoxy resin, B2 Amino-based epoxy resin, rubber-modified epoxy resin, bis-oxygen resin, fluorenone-modified epoxy resin, &amp;caprolactone denatured dinitrogen; diterpene* polybutadiene, etc. 2 or more epoxy groups, F = imaginary f. In particular, Ν epoxide-based epoxy resin, amine-containing ring olefin : and on the other hand ' alicyclic epoxy resin or epoxidized t Bei Shao' has good insulation reliability and can be used ideally. Flame retardant can use epoxy compounds that lead to atoms such as chlorine, methane or phosphorus in its structure. Imine: 匕? Type, imine type, ^urea, she l. Especially benzoguanamine resin due to excellent reliability of the edge is more than the isocyanate polyisocyanate compound isocyanic acid == bicyclic or aromatic The functional heterocarbon number is 2 to 30: == The latter is preferably an isocyanate-free group which does not contain an isocyanate group: a aryl isocyanate or a hydrazine, but is not limited, for example, hydrazine , 4-tetramethylene dihydrazide, 22:: mercapto diisocyanate, i,6-hexamethylene diisocyanate, L iso^" ίff5 methyl di^, lysine diisocyanate Diisocyanate ), 13: ^ Li: ^ base ¥ hexyl isophthalic acid vinegar (isophorone methane two to do 2 ΐ (different methyl) _ cyclohexane, 4,4,-dicyclohexyl isocyanate旨 Γ 曰 二 二 异 异 异 二 4 4 4 4 异 异 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 二 二 二 二 二 二 二 二 二 二 二 二 二The oxime ester group is blocked. Or the active methylene can be desirably used as a surface derivative "ratio derivative derivative" or "AZ; polyfunctional isocyanuric acid. In particular, it is preferred because of its high pyrazole property. Geochemical 5-blocked polyfunctional isocyanate due to the reaction 8 20 201230908 The denatured polyamine phthalate resin composition used in the method may optionally contain a pigment or a filler. As the pigment, a known pigment such as a blue pigment, a green pigment, or a yellow pigment may be used alone or in combination of plural kinds. Among them, 'preferably contains a blue pigment which does not contain a gas atom and a desert atom in a molecular structure, a yellow pigment which does not contain a chlorine atom and a bromine atom in a molecular structure, and an extender pigment which does not contain a chlorine atom and a bromine atom in a molecular structure. (i.e., an achromatic pigment) and the denatured polyamine phthalate resin composition is preferably green. When the composition contains a compound containing a chlorine atom and a bromine atom in the molecular structure, the product used therein may be harmful when it is incinerated, which is not preferable. A blue pigment which does not contain a chlorine atom or a bromine atom in the molecular structure, and may be exemplified by a copper scorpion large blue (CI pigment blue 15), a metal-free blue (CI pigment blue 16), a titanium phthalocyanine blue, and an iron flower. Blue blue, nickel phthalocyanine blue, aluminum phthalocyanine blue, tin phthalocyanine blue, alkaline blue (CI pigment blue 1, 2, 3, 10, 14, 18, 19, 24, 56, 57, 61) , deuterated CuPc (CI Pigment Blue 17), indigo (CI Pigment Blue 27), Ultramarine (C_I. Pigment Blue 29), Cobalt Blue (CI Pigment Blue 28), Sky Blue (CI Pigment Blue 35) 'Co (A Bu Cr ) 204 (CI Pigment Blue 36), bisazo (CI Pigment Blue 25, 26), Indanthrone (CI Pigment Blue 60), Indigo (CI Pigment Blue 63, 66), Cobalt Cyanine (CI) - Pigment Blue 75), etc., but is not particularly limited. Among them, it is preferable to use copper phthalocyanine blue from the cost side. A yellow pigment that does not contain a chlorine atom or a bromine atom in the molecular structure, such as monobutual gas (CI pigment yellow 1, 4, 5, 9, 65, 74), benzopyridinone (Benzimidazolone) yellow (CI pigment yellow 120, 151, 154, 175, 180, 181, 194), Flavanthrone yellow (CI Pigment Yellow 24), azomethyl yellow (CI pigment yellow m, i29), 蒽醌 yellow (ci pigment yellow) m, i47), isoindole full yellow (c丄 pigment yellow 139, 185), disazo yellow (cI pigment yellow 155), condensed polycyclic system (C, I. pigment yellow 148, 182, 192), oxidation Iron (CI Pigment Yellow 42), bisazomethine (CI Pigment Yellow 101), azo lake (CI Pigment Yellow 61, 62, 100, 104, 133, 168, 169), metal complex ( CI pigment yellow 150, 153, 17 holes 179), etc., but not particularly limited, from the cost side and safety. No 21 201230908 ^ sex, should be excluded "harmful azo pigments." Further, when the yellow pigment of the fluorine atom in the substructure is excellent in dispersibility, it is an extender pigment which does not contain a chlorine atom and a bromine atom in the molecular structure, for example, sulfur, (^丄 pigment white 21, 22), carbonic acid Calcium (CI Pigment White 18), etc., but the composition ratio of the above-mentioned pigments used in the denatured polyurethane resin composition is as long as the denatured polyamine phthalate resin composition can be colored in green, 2 minus J in the silk automatic inspection record error (four), consider * penetrating heart 4, eight improvement can ideally use body pigments. The blue pigment and the xanthine are preferably 0.01 to 5 mass parts per 100 parts by mass of the denatured polyurethane resin, more preferably 0.05 to 1 part by mass, and the body pigment is 1 part by mass relative to the fat-reduced mass part. It is preferably 10 parts by mass or more, and a known one is used for the tree or the filler. For example: oxidized chopped, titanium oxide, talc, guar, quartz powder and other inorganic particles, epoxy resin powder, tri-poly-polyamide resin powder, polyimine resin powder, rubber early, if etc. . The particle size (average particle diameter) is _plus (4)' and is easily detected by the automatic inspection device. Further, the citric acid coffee (A) is 1 GG parts by mass, and the "mussel injury" is preferably 5 to 100 parts by mass. The door method is used to change the polyamine vinegar vinegar tree composition. The second word 'can also be blended with (4) oxy-fired, fluorine-denatured polyoxymethane, ^, base compound, polyvinyl compound and other antifoaming agents, propyl Γ ;; yishen hindered compounds, (d) compounds, by: t amine 匕Various known additives such as a mouthpiece, an oxidizing agent, an ageing resin, etc. In the present invention, a denatured polyamine phthalate resin composition, a formic acid vinegar resin, is uniformly dissolved in an organic solvent, and the solution polyamine organic solvent is not limited, and can be used. Acetamine, NN _ 7 ^ J Magic 3 虱糸 each agent, such as N, N-dimercapto, ethyl acetamide, n, n-didecyl decylamine, N, N 2 22 8 201230908 基: Known amine, N-: ketone ketone, u·dimercapto group such as rice sulphate, sulphate, etc.; sulfur atomic solvent such as dimethyl sapphire, diethylene, 、, Dimethyl hydrazine, diethyl hydrazine, hexamethyl continuation amine, etc., containing hydrazine; dimethyl dimethyl ether solvent, monomethyl ether (chglyme), triethylene glycol dimethyl ether, In particular, it is preferred that each of the ketones of the ketones is, for example, methyl formate, n, n-diethyl amide, oxime, butyl vinegar, triethylene glycol A-, solvent. The organic denatured polyamine oxime used in the process of densifying poly- urethane _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ The derogation of the rhythm is better than that of the rhythm. It is preferable to add a fossil of the aa fossil and the like. The composition of the resin is used for example, the surface shape of the pattern is used, and the circuit other than the terminal portion is Γ〇~=3, = (10) 5 == when ^ 1 is better for 15 minutes ~ 2 hours with hot air or infrared = ought to make the thief joint good (4). Membrane with 23 201230908, that is, the method will use the acid 僧 f The denatured polyamine f of the urethane resin is a cured film obtained by the treatment of ^40, K〇H/g, and is immersed in the JU composition to be heated to make the main component of the underfill material. It is better to use it for better age. Below, more preferably 15%~6^milk=when the change rate of the inch size is excellent for epoxy tree Lai. Wei Shejia 4 25%~53% ' At the time, it can be charged eight: two, the dimensional change rate of the film is less than 60%: the two-filled knife prevents the hardened film from filling the bottom layer, and the dimensional change rate of the cured film is 15%~6()%. The adhesion of the filler, from the denatured polyamine formic acid, due to the peeling of the backing material, has at least partially hardened to become a fully cohesive broken 8 characteristic, and the adhesion is particularly excellent in skin spreading (fortunately, the product is not, formic acid 酉1) A cured film composed of a resin composition, which is directly connected to an electronic component such as a semiconductor wafer, but is in contact with a structure. The underfill material is a 7-s true filler, and functions to fix the electronic component to the "package". . If the electronic parts are to be stripped, the structure should be the first to be destroyed near the filler and the cured film. The adhesion of the m-^ layer filler to the cured film will greatly affect the zero-peel strength of the electron. The towel can be formed by using a denatured polyamine vinegar vinegar tree composition having the above characteristics, thereby improving the underlying filler and the cured film, so even if the short side length of the women's wear is 12 mm In the following, it is preferably 0.3 mm to 1.2 mm, which is more preferably 〇.4ιηπι~1.1mm, which is a tiny electronic scalding machine, and it is also able to make the electronic sufficiency _ strength, the piece of material «$Β part" B part reveals It is an object of the invention to provide a method for manufacturing a flexible circuit board for a transfer tape package, comprising the step of inspecting a manufactured flexible circuit board for a transfer tape package using an optical automatic inspection device, wherein the insulating film is colored The pigment used is such that it does not contain a chlorine atom or a bromine atom, and it can suppress the deterioration of the inspection efficiency caused by erroneous detection and reduce the inspection failure rate. 8 24 201230908 The manufacturing method of the road board is related to a conductive electric tape package. The method includes the following steps: preparing a circuit board in an insulating film; forming a circuit pattern in a flexible circuit The flexible coating-curable insulating film is less connected to the circuit pattern surface other than the terminal portion and the obtained gutta-performed article is formed to be hardened to form an insulating crucible; device inspection; 1 tape package _ secret circuit _ wire type automatic The characteristics of the inspection were as follows: The original pigment (A) containing no chlorine (a2) was colored. The pigment of 3 rolled atoms and bromine atoms is not particularly limited, and a general insulating *t thermal film is preferably =. The circuit interval is i5 to 1 〇, m causes the optical automatic inspection device to have fine scattering of light, etc., and affects the flexible circuit board for the tape package. The circuit of the present invention is particularly suitable for use in circuits having such a circuit diagram. Pattern surface coating I: at least the connection terminal portion is cured to form an insulating film. And the resin composition's second use of the flexible circuit board is the use of the optical wheel to send the tape package (Qin _ _ automatic surface, touched the resin composition for the hardenable insulating film used by the parent method) It is characterized by the coloring of pigments (A) which are characterized by up to 25 201230908 soil-containing sag, which does not contain air atoms and bromine, atomic pigments (al) and pigments (A) which are not helium atoms and bromine atoms in the molecule. Refers to the so-called achromatic pigments, such as the non-secret rhyme blended when making cookware, which is small in composition and is transparent or translucent when the refractive index is almost the same when mixed with a varnish oil developer. The pigment (a2) is not an achromatic pigment, but a usual color pigment. ^ The extender pigment (al) used in the method, for example, can be used as a shell pigment of a cookware, and preferably contains no chlorine atom in the molecule and a bromine atom, for example: barium sulfate, calcium carbonate, kaolin, etc. The extender pigment (al) is preferably at least selected from barium sulfate (for example, CI·Pigment White 21, 22) and calcium carbonate (for example, cu. Pigment White 18). One type of body pigment, more preferably barium sulfate (for example, c丄 pigment white 21, 22) Further, the use of the extender pigment (al) adjusts the light characteristics of the formed cured film (insulating film), suppresses the detection efficiency of the optical automatic inspection apparatus from being erroneously detected, and improves the adhesion of the obtained hardened insulating film. The viewpoint of obtaining a lower viscosity (non-stickiness) is also preferable. Although not particularly limited, the positional diameter of the extender pigment (al) is 100 nm to 1000 nm, preferably '400 nm to 800 nm, more preferably 500 nm~ 700nm is especially good. When the median pigment (al) has a position below i〇〇〇nm, the optical uniformity of the cured film will be improved, which can reduce the false detection of the optical automatic inspection device. When it is above 100 nm, it hardens the insulation. The adhesive property of the film is improved to be better (non-stickiness). When the median diameter of the bulk pigment (al) is 400 nm to 800 nm, it is easier to disperse and can be dispersed to a particle size distribution close to the primary particle size, and optical uniformity can be obtained. The resin composition for a curable insulating film used in the method is colored by a pigment (a2) containing no chlorine atom or bromine atom in the molecule of the pigment (A). The pigment (a2) As long as it is chlorine-free and desert The present invention is not particularly limited, and conventionally known pigments can be used in consideration of dispersibility or economy. For example, color pigment soaps such as red pigments, blue pigments, yellow pigments, and green pigments should be used alone or in combination. The resin composition for a hardenable insulating film preferably contains a pigment (A) 26 8 201230908 and is colored green. The pigment (A) contains: an organic pigment (al) containing no chlorine atom and a desert atom in the molecule, and a molecule. a blue pigment (a3) which does not contain a gas atom and a bromine atom, and a yellow pigment (a4) which does not contain a gas atom and a bromine atom in a molecule. A blue pigment which does not contain a gas atom and a bromine atom in a molecular structure (a3) For example, copper-brown blue (CI pigment blue 15), metal-free blue-green (cl pigment blue 16), titanium-flowered blue, iron-orange blue, nickel-flowered blue, mint blue, tin Indigo blue, blue (CI pigment blue 1,2,3,10,14,18,19,24,56,57,61), stone weathered CuPc (CI pigment blue π)&quot;? Pigment Blue 2 &lt;7), Ultramarine (CI·Pigment Blue 29), Cobalt Blue (CI Pigment Blue 28), Sky Blue (CI Pigment Blue 35), Co(AL·Cr) 2 04 (CI Pigment Blue 36) Di-bisazo (CI Pigment Blue 25, 26), Indanthrone pndanthrone) (CI·Pigment Blue 60), Disperse Blue (CI Pigment Blue 63, 66), Cobalt Cyanine (CI) Pigment blue 75) or the like, but is not particularly limited. Among these, from the viewpoint of the cost side, it is preferable to use a copper sapphire blue. The blue pigment (&gt;3) which does not contain a chlorine atom and a bromine atom in the molecule is preferably in the range of 50 nm to 500 nm, more preferably 50 nm to 200 nm. When the position of the blue pigment (a3) is 500 nm or less, the optical uniformity of the cured film is improved, and the erroneous detection of the optical automatic inspection device can be further reduced. A yellow pigment (a4) which does not contain chlorine atoms and desert atoms in the molecular structure, such as monoazo yellow (CI pigment yellow 1, 4, 5, 9, 65, 74), benzimidazolone yellow (CI pigment) Yellow 120, 151, 154, 175, 180, 181, 194), Flavanthrone (CI Pigment Yellow 24), Azoyl Yellow (CI Pigment Yellow 117, 129), Yellow (CI Pigment Yellow) 123, 147), different sputum full yellow ((: 1. pigment yellow 139, 185), bisazo yellow ((: 1. pigment yellow 155), condensed polycyclic system (CI pigment yellow 148, 182, 192), iron oxide (CI Pigment Yellow 42), bisazo azokawa (CI Pigment Yellow 101), azolake (azo pigment 6 6 62, 100, 104, 133, 168, 169), metal The complex compound (CI Pigment Yellow 150, 153, 177, 179), etc., is not particularly limited, and it is preferable to exclude the "harmful-expressed even-* nitrogen-based pigment" from the viewpoints of cost, safety, and harmlessness. Further, when it is a yellow pigment containing a fluorine atom in its molecular structure, it is preferable from the viewpoint that the dispersibility is excellent in 27 201230908. Although it is not particularly limited, the yellow pigment which does not contain a gas atom and a bromine atom in the molecule is not particularly limited. (a4) The median diameter is preferably 50 nm to 500 nm, and more preferably 50 nm to 35 〇 nm. When the position of the di-yellow pigment (a4) is 500 nm or less, the optical uniformity of the hardened yttrium is 1&quot; Incorrect detection of the optical automatic inspection device. Also, the blue pigment (a3) containing no chlorine atom or bromine atom in the molecule, and the yellow pigment (a4) containing no chlorine atom or bromine atom in the molecule, as needed. It is preferable to prepare a resin composition for a curable insulating film by using a known pigment dispersant or the like in a bead mill, a ball mill or the like, and to prepare a resin composition for a curable insulating film. The blending ratio is such that the resin composition for the curable insulating film can be sufficiently colored to a desired color, but in order to reduce the false detection of the optical automatic inspection device, it is particularly preferable to consider the light transmittance. For example, the solid pigment (al) containing no chlorine atom or bromine atom is used in an amount of 10 parts by mass or more based on 1 part by mass of the solid content of the resin contained in the resin composition for a curable insulating film. Good, for 2 enamel: ε or more 2 More preferably, it is 00 parts by mass or less, more preferably 40 parts by mass or more and 12 parts by mass or less, and the pigment (a2) containing no gas atom or bromine atom is 100 parts by mass relative to the solid content of the resin, and is 1 to 5 parts by mass. Preferably, the resin composition for a curable insulating film used for forming an insulating film in the method is preferably a thermosetting or photocurable resin composition for a conventional insulating film. Any of them, but preferably as a patent document! The thermosetting resin composition containing the denatured polyurethane resin as described in ~4, or the thermosetting resin composition containing the polyfluorene oxyalkylene resin as described in Patent Document 5 §. In the method, the denatured polyurethane resin composition is preferably used as a resin composition for a curable insulating film, although it is not particularly limited. In this case, the extender (al) containing no chlorine atom and bromine atom is barium sulfate, and the content of the bulk pigment (al) is 1 part by mass relative to the solid content of the denatured polyurethane resin (B). The lower limit thereof is preferably 10 parts by mass or more, more preferably 2 parts by mass or more, still more preferably 40 parts by mass or more, and the upper limit thereof is preferably 2 parts by mass or less, more preferably 28 201230908 is 120 parts by mass or less. It is preferably 1 part by mass or less. In this case, when the content of the extender pigment (al) is less than 10 parts by mass relative to the denatured polyamine phthalate resin solids, the non-stickiness may be insufficient. The knife-denatured polyurethane resin composition usually contains a denatured polyamine phthalate (B) and a curable resin (c) as essential components. The hydrazine-denatured polyamine phthalate resin (B) is preferably, for example, at least a diisocyanate compound (bl), and a polycarbonate diol or a polybutadiene diol-containing polyol compound (b2) And a denatured polyamine phthalic acid S obtained by reacting with a carboxyl group-containing diol compound as 3) resin (B). The diisocyanate compound (b1) can be suitably used in the production of a conventional formic acid vinegar. That is, only one of the i molecules may have two isocyanate g groups, and may be an aliphatic, alicyclic or aromatic polyisocyanate, such as 2,4-indole phenyl diisocyanate, 2 , 6_曱 phenyl diisocyanate isophor = diisocyanate, hydrazine, 6-hexamethylene diisocyanate, hydrazine, 3 - tridecyl diisocyanate, 1,4-tetramethylene diisocyanate, 2,2,4_three=base two, cyanate, '2,4,4-tridecylhexamethylene diisocyanate ϋ壬' dimethylene, diisocyanate, u〇_+ fluorenylene diisocyanate, U-ring-burning two, cyanic acid vinegar, 2,2, _ two-domain diiso-acid cool, diphenyl-methyl γ-diisocyanide, S-, o-xylene diisocyanate g, m-xylene Isocyanate, · = toluene diisocyanate @, methylene bis (cyclohexyl isocyanate from the purpose), ring ^ burning H sub-acid vinegar, cyclohexane -1,4 - di-indenylene Bismuth diisocyanate, di-&quot;V&quot;&quot;/, cyanide § 对, p-phenylene diisocyanate, 3,3,_methylene dimethyl hydrazino-4,4'-diisocyanate 4,4,_diphenyl ether diisosa, : 2: bis-isocyanate §, 莰 莰 二 diisocyanate S, hydrogenation 1 3·^二曱^2^ Dimethylene diisocyanate and other diisocyanate. It can be used alone or in combination of two or more. This isocyanate-like acid ester compound (bl), from the point of good resistance to the filling of the layer, the swelling of the oxygen-protecting resin or the bottom methylene double (the rainbow-based 〇〇201230908

活’也可使用經封端化的二異氰酸酷D 含聚碳酸酯二醇或聚丁二烯二醇之多元醇化合物(b2), 為含聚碳酸酯二醇或聚丁二烯二醇之多元醇化合物,且視需 要也可為含有此等兩者之多元醇化合物。又,本發明中,該 多元醇化合物(b2)不包含具羧基之二經基化合物。 聚碳酸酯二醇只要是主鏈中具碳酸酯鍵之二醇化合物即 不特別限定,T以理想地使用下列化學式⑴表示之2官能性 羥基末端之聚碳酸酯二醇。 化擧式⑴ (式中’ R!代表2價之脂肪族或芳香族烴基,較佳為碳 數2〜2〇,價一之?肪族或芳香族烴基,n為1〜4〇之整數。) 聚碳酸醋二醇為數量平均分子量5〇〇〜1〇〇〇 更佳。數量平均分子量若小於谓,有時不易 性’又’ ^數量平均分子量超過麵0,則有 或性會變差。本發明使用之聚碳酸醋二醇, = 例如宇部興產(股)公司製eternac〇ll UD系列、uc系列、UB系列、驗1 化學工業(月又)公司製PLACCEL系列、可It is also possible to use a blocked polyol of diisocyanate, a polyol compound containing a polycarbonate diol or a polybutadiene diol (b2), which is a polycarbonate diol or a polybutadiene. A polyol compound of an alcohol, and if necessary, a polyol compound containing both of them. Further, in the present invention, the polyol compound (b2) does not contain a di-based compound having a carboxyl group. The polycarbonate diol is not particularly limited as long as it is a diol compound having a carbonate bond in the main chain, and T is preferably a bifunctional hydroxy terminal polycarbonate diol represented by the following chemical formula (1). Formula (1) (wherein R! represents a divalent aliphatic or aromatic hydrocarbon group, preferably a carbon number of 2 to 2 Å, a valence of one or a aliphatic or aromatic hydrocarbon group, and n is an integer of 1 to 4 Å. .) Polycarbonate diol is preferably a number average molecular weight of 5 〇〇 to 1 〇〇〇. If the number average molecular weight is smaller than the above, sometimes the degree of difficulty is 'or'. If the number average molecular weight exceeds the surface 0, the degree may be deteriorated. Polycarbonate diol used in the present invention, for example, eternac〇ll UD series, uc series, UB series, and 1 chemical industry (monthly) company PLACEL series manufactured by Ube Industries Co., Ltd.

t PCDL 使::”;合,’用。 二烯二醇較佳,且數量平〜&amp; ^*性祕末端之聚丁 麵〜獅者更佳。〜lQ_者較佳、 獲得理想的撓性,且若小於500 ’有時不易 熱性或•劑性會變;數;!^子,過1〇_,有時耐 鍵,或分子内之雙鍵㈣化者*丁1稀醇可為分子内具雙 會起交聯反應而有由於若分子内殘留雙鍵時 亍艾侍/又有撓性,因此尤佳為分子内之雙 201230908 鍵經氫化者。本發明使用之聚丁二烯二醇,具體而今,較佳 為例如曰本曹達(股)公司製G系列、GI系列、出光^油化學 (股)公司製Poly bd系列、Poly ip系列、Ep〇L系列、 KRAS_OL系列、三菱化學(股)公司製p〇lytaim系列等。該等 聚丁二烯二醇可以單獨使用也可組合二種以上使用。。 具羧基之二羥基化合物(b3),係具羧基為取代基之二羥 基化合物,若使用如此的具羧基之二羥基化合物,變性聚胺 甲酸_脂會絲錢基,能㈣與硬化性_(c)反應。亦 =‘將’史性聚胺甲酸酯樹脂予以交聯時,能有效交聯,獲 得之硬化物的耐熱性或耐溶劑性會增大。 &amp; 具羧基之二羥基化合物(b3)不特別限定,宜為具羧基當 做取代基之碳數為,又更佳為碳數為2〜2()之^基^匕 合物。具體而言,例如2,2-二羥曱基丙酉| N,N-雙羥基乙基甘胺酸、n,N-雙經基乙 以單獨使用1種也可組合2種以上使用 之溶解度之觀點,2,2-二羥甲某而鹼、〇 ^ 例如2,2-一說曱基丙酸、2,2_二經甲基丁酸、 種以上使用。其中,從對於溶劑 、N,N-雙羥基乙基丙胺酸等。此等可 ¥ 2種以上你田。甘士 . 也丨丄λ1,t PCDL makes:: "; combined, 'use. Diene diol is preferred, and the amount is flat ~ &amp; ^ * secret end of the polybutyl surface ~ lion is better. ~ lQ_ is better, get the ideal Flexibility, and if less than 500 'times, it is not easy to heat or the agent will change; number; !^, over 1〇_, sometimes resistant to bonds, or intramolecular double bonds (four) can be * Ding 1 dilute alcohol It has a double cross-linking reaction in the molecule, and it is especially suitable for the double 201230908 bond in the molecule if the double bond is left in the molecule. The olefinic diol is specifically, for example, the G series, the GI series, the epoch oil company (Poly bd series, the Poly ip series, the Ep 〇 L series, the KRAS_OL series) manufactured by Sakamoto Soda Co., Ltd. The p〇lytaim series manufactured by Mitsubishi Chemical Corporation, etc. These polybutadiene diols may be used singly or in combination of two or more. The hydroxy group-containing dihydroxy compound (b3) having a carboxyl group as a substituent Dihydroxy compound, if such a hydroxy group-containing dihydroxy compound is used, the denatured polyamine formic acid _ lipid will be a sulphur group, energy (4) and hardenability _ (c) Reaction = also 'When the historical polyurethane resin is crosslinked, it can be effectively crosslinked, and the heat resistance or solvent resistance of the obtained cured product will increase. &amp; The dihydroxy compound having a carboxyl group (b3) is not In particular, it is preferably a carbon compound having a carboxyl group as a substituent, and more preferably a carbon number of 2 to 2 (). Specifically, for example, 2,2-dihydroxymethyl propyl hydrazine N,N-dihydroxyethylglycine, n,N-di-diyl-ethyl phthalate can be used alone or in combination of two or more kinds of solubility, 2,2-dihydroxymethyl, alkali, hydrazine ^ For example, 2,2-one says mercaptopropionic acid, 2,2_di-methylbutyric acid, or more than one species. Among them, from solvent, N,N-dihydroxyethylalanine, etc. More than 2 kinds of your field. Ganshi. Also 丨丄λ1,

合,(b2)、與具羧基之二羥基化合物(b3)一起 或三羧酸一酐或例如下列化學式(2)表示之g St亞胺寡聚物,.與二異着.酩^ 表示之醇‘隨基末i之 0 μ久峨曰日一籽取眾丁二烯二醇之多元醇化 、與具羧基之二羥基化合物(b3)—起’與四羧酸二酐 與一異氰酸酯化合物(bi)反應而輕易獲得。(b2), together with a dihydroxy compound (b3) having a carboxyl group or a tricarboxylic acid monoanhydride or a g-stylene oligomer represented by, for example, the following chemical formula (2), and two different meanings. The alcohol 'with the end of the base of 0 μ long, the seed of the butadiene diol is polyolized, and the hydroxy group-containing dihydroxy compound (b3) - with the tetracarboxylic dianhydride and the monoisocyanate compound ( Bi) The reaction is easily obtained.

201230908 0〜20之整數。) 聚胺it I酸醋樹脂⑻於主鍵中具酿亞胺環時,由變性 ,機械強度,性、 物,可由表不之醇性羥基末端之醯亞胺寡聚 化合物構成二?二=合物及具1個羥基之單元胺 酸醋樹脂之溶解超t0,則獲得之變性聚胺甲 胺〜有夺g紇差。又,遠醇性羥基末端之醯亞 報等纪裁·^八但可依例如日本特開2007-238818號公 報寺5己載之公知方法輕易獲得。 物㈤聚胺甲酸醋樹脂⑼較佳為將二異氰酸醋化合 具幾基之二物%聚醇f二醇化合物_、 妒一,匕口物b3)、及視需要的四羧酸二酐、三羧 田以剛述化學式⑺表示之醇性經基末端之酿亞 ΐ絲物相於導人酿亞胺環之化合物成分㈣反應而獲 .付0 使用之二異氰酸酯化合物(bl)與其他化合物(b2)、(b3)、 ϋ之^的ί耳比[其他化合物(b2)、(b3)、(Μ)之合計總莫耳 一/、鼠駄酯化合物(bl)之莫耳數],較佳為05〜30,更佳 二0.^2士5 ’又更佳為0·9〜2.0之範圍。前述莫耳比若過小, ;谷液k曰4黏’若别述莫耳比過大,變性聚胺甲酸醋樹脂 之分子量會減低,有時耐熱性等會降低。 變性聚胺f酸酯樹脂(B)之製備使用之具羧基之二_具 化合物_之料限定,但錢定制比織得獲得之匕 曱酸酯樹脂之酸價成為16〜4〇mgK〇H/g。 &gt;此時’ f用具敌基之二經基化合物(b3)、與含聚碳酸酯 二醇或聚丁二烯二醇之二醇化合物(b2)時,其莫耳比[具羧基 之二羥基化合物(b3)之莫耳數/含聚碳酸酯二醇或聚丁二烯二 醇之二醇化合物(b2)之莫耳數],约為〇2〜6,較佳為〇 5〜3 ⑧ 32 201230908 之範圍。 使用具魏基之一經基化合物φ3)、含聚碳酸酯二醇或聚 丁一稀一醇之二醇化合物(b2)、及四竣酸二酐、三羧酸一酐 或例如前述化學式(2)表示之醇性羥基末端之醯亞胺寡聚物 等用於導入醢亞胺環之化合物成分(b4)時,其莫耳比[具叛基 之二羥基化合物(b3)之莫耳數/含聚碳酸酯二醇或聚丁二烯二 醇之二醇化合物(b2)與用於導入醯亞胺環之化合物成分作句 的合rh總莫耳數],約為0.2〜10 ’較佳為0.5〜5之範圍。 變性聚胺甲酸S旨樹脂⑼之製造,更具體而言,可於益溶 劑或溶解於有機溶劑而實施二異氰酸酯化合物 盥 碳酸醋二醇或聚丁二烯二醇之二醇化合物(b 乂 ^ 經J化合物(b3)、及視需要之四缓酸二奸、三叛‘一 $或5 化ΐ式(2)所表示之醇性經基末端之驢亞胺寡聚物等 胺環之化合物成分(Μ)等其他化合物之反應。 入反應容器,使分散均勺、唆鲑始 打,、他化口物裝 v :勾解後’再添加二異氰酸醋化合 物(M)較佳。又,為了改善溶解性等目的,也可改 順序。反應溫度通常為3〇。〇〜2〇〇。 酸酯化艏搵。is 時 觸媒可以使用公知之胺曱 5級應為了防止異氰_旨因為水分導致失活, 於氮氣氛1S下進行較佳。又,我 刀㈣天右 !又為了调整黏度,可於反應混合 點添加醇當做末端停止劑。 反應使用之㈣不特職定 二甲基乙酿胺、Ν ^ =用3氛系公劑例如 胺、Ν,Ν-二乙基甲醒,胺、Ν,Ν二甲基甲酿 咪唑啶酮、Ν-甲::基咯烷酮、U_二甲基'2· 亞石風、—乙&amp;胺等、含硫原子溶劑、例如二甲基 含氧溶劑,例如_溶娜,、甲基〜_專; 系溶劑之二乙之巧二酚、二甲紛等;二甘二甲鱗 丙一私甲齡乙酸醋、丙二醇乙轉乙酸醋、二丙二_ 33 201230908 酉曰、一乙一醇乙_乙酸醋、甲氧基丙酸甲醋、甲氧基丙酸乙 酉曰、乙氧基丙酸甲@旨、乙氧基丙酸乙醋、三乙二醇二甲_、 四甘二曱趟等;酮系溶劑之丙酮、苯乙酮、苯丙酮、環己酮、 異佛爾酮等、醚系溶劑之乙二醇、二嘮烷、四氫呋喃等、内 醋系溶劑之γ-丁内酯等。尤其,宜使用γ_丁内酯、二乙二醇 乙驗乙酸醋、三乙二醇二f趟等。 變性聚胺甲酸g旨樹脂(B)之數量平均分子量不限定,但較 佳為3000〜looooo,更佳為5〇〇〇〜5〇〇〇〇。在此,數量平均分 子量係以凝膠滲透層析(GPC)測定之聚苯乙烯換算値。數量 平均刀子里若低於前述範圍,獲得之硬化膜之伸長度、撓性 及強度等機械的特性有時會減損,另一方面若超過前述範 圍,黏度會增加為必要以上,有時用途會受限。 嶔性聚胺曱酸酯樹脂組成物使用之硬化性樹脂係$ 樹脂中之㈣反應之化合物。硬化性樹月I /、f疋/、變性聚胺甲酸酯樹脂中之羧酸反應之化合物艮 官能ρΐΓΓ氰樹脂、胺基樹脂、經封端化之1 鮮環樹脂’例如細A型環氧樹脂、氫化雙紛A型環| 脂』3^氧酚if 樹脂、雙酚F型環氧樹脂、酚醛相 氧樹:Ϊ;環鑛 =之二=性縣樹脂、二環戊二稀嚷201230908 0 to 20 integer. The polyamine it I acid vinegar resin (8) is composed of denatured, mechanical strength, sex, and substance, which can be composed of an alcoholic hydroxyl terminated quinone imine oligomer compound in the primary bond. The dissolution of the substance and the monoamine vinegar resin having one hydroxyl group exceeds t0, and the denatured polyamine methylamine obtained is obtained. Further, it is easy to obtain, for example, a well-known method such as the Japanese Patent Publication No. 2007-238818. (5) Polyurethane vinegar resin (9) is preferably a diisocyanate vinegar with a few bases of the second alcohol polyf-fdiol compound _, 妒, 匕 mouth b3), and optionally tetracarboxylic acid The anhydride and the tricarboxylate are obtained by reacting the alkaloid phase of the alcoholic terminal group represented by the chemical formula (7) with the compound component (IV) of the artificially brewed imine ring. The diisocyanate compound (bl) and the 0 used are The molar ratio of the other compounds (b2), (b3), ϋ ^ ^ [the total of other compounds (b2), (b3), (Μ), the molar amount of the total molars /, the oxime ester compound (bl) ], preferably from 05 to 30, more preferably two. 0. ^ 2 ± 5 ' and more preferably in the range of 0 · 9 to 2.0. If the molar ratio is too small, the gluten solution k 曰 4 is viscous. If the molar ratio is too large, the molecular weight of the denatured polyurethane resin may be lowered, and heat resistance may be lowered. The modified polyamine f-ester resin (B) is prepared by using a compound having a carboxyl group as a compound, but the acid value of the phthalate resin obtained by the woven fabric is 16~4 〇mgK〇H. /g. &gt; At this time, the molar ratio of the di-based compound (b3) to the diol compound (b2) containing the polycarbonate diol or the polybutadiene diol (the second one with a carboxyl group) The molar number of the hydroxy compound (b3) / the molar number of the diol compound (b2) containing the polycarbonate diol or the polybutadiene diol, is about 〜2 to 6, preferably 〇5 to 3 8 32 The scope of 201230908. Using a diol compound (b2) having a thiol-based compound φ3), a polycarbonate diol or a polybutanol, and a tetracarboxylic dianhydride, a tricarboxylic acid monohydride or, for example, the aforementioned chemical formula (2) The molar ratio of the alcoholic hydroxyl terminated quinone imine oligomer or the like to the compound component (b4) of the quinone ring, and the molar ratio of the dihydroxy compound (b3) The diol compound (b2) containing a polycarbonate diol or a polybutadiene diol and the compound component for introducing a ruthenium ring are a total molar number of rhR, which is preferably about 0.2 to 10'. It is in the range of 0.5 to 5. The modified polyamine formic acid S is a resin (9), more specifically, a diol compound of a diisocyanate compound 盥carbonic acid diol or a polybutadiene diol which can be used in a solvent or dissolved in an organic solvent (b 乂 ^ a compound of an amine ring such as an amine ring of an alcoholic terminal group represented by a J compound (b3) and, if necessary, a serotonic acid, a scorpion, or a sulphuric acid (2) Reaction of other compounds such as components (Μ) into the reaction vessel, so that the dispersion is scooped, the crucible is started, and the stomatous material is loaded with v: after the hooking, it is preferable to add the diisocyanate compound (M). Further, in order to improve the solubility and the like, the order may be changed. The reaction temperature is usually 3 Torr. 〇 〜 2 〇〇. The acid ester can be used as a catalyst. A known amine amide grade 5 should be used to prevent isocyanide. _The purpose is to deactivate the water, and it is better to use it under nitrogen atmosphere 1S. In addition, I knife (4) Tianyou! In order to adjust the viscosity, alcohol can be added as a terminal stopper at the reaction mixing point. (4) No special duties Dimethyl ethanoamine, Ν ^ = with 3 atmospheres such as amine, hydrazine, hydrazine-diethyl ketone, amine , hydrazine, dimethyl ketone imidazolidinone, fluorene-methyl:: pyrrolidone, U_ dimethyl '2 · sapphire, - ethyl salt, amine, etc., sulfur atom solvent, such as dimethyl Oxygen-containing solvent, such as _ 娜 Na, methyl _ _ special; solvent of dimethena bisphenol, dimethyl sulphate; di glycerin butyl acetonide a private age-old acetate vinegar, propylene glycol ethyl acetate vinegar , 二丙二_ 33 201230908 酉曰, monoethyl alcohol B _ acetic acid vinegar, methoxy methoxyacetate, methoxy methoxyacetate, ethoxy propionate A, ethoxy propyl acetate , triethylene glycol dimethyl ketone, tetraglycol ruthenium, etc.; ketone solvent of acetone, acetophenone, phenylacetone, cyclohexanone, isophorone, etc., ether solvent, ethylene glycol, dioxane Γ-butyrolactone such as tetrahydrofuran or a vinegar-based solvent, etc. In particular, γ-butyrolactone, diethylene glycol ethyl acetate vinegar, triethylene glycol bis-fluorene or the like is preferably used. The number average molecular weight of the resin (B) is not limited, but is preferably 3000 to looooo, more preferably 5 to 5 Torr. Here, the number average molecular weight is determined by gel permeation chromatography (GPC). Polystyrene If the number average knife is lower than the above range, the mechanical properties such as elongation, flexibility, and strength of the cured film may be degraded. On the other hand, if it exceeds the above range, the viscosity will increase more than necessary. The use is limited. The curable resin used in the composition of the oxime polyamine phthalate resin is the compound of the (4) reaction in the resin. The sclerosing tree I /, f 疋 /, denatured polyurethane resin The carboxylic acid-reacting compound 艮 functional ΐΓΓ ΐΓΓ cyanide resin, amine-based resin, blocked 1 fresh ring resin 'such as fine A-type epoxy resin, hydrogenated double-type A ring|lipid 3 oxyphenol phenol resin, Bisphenol F type epoxy resin, phenolic phase oxygen tree: bismuth; ring ore = two = sex county resin, dicyclopentane bismuth

化聚丁 4;::;=曰二己内s赚環氧樹脂、環孽 尤其,N-環氧丙美型产Γ冉個以上裱氧基之環氧化合物等。 良,且另面以、含胺基之環氧樹脂反細I ί使用於結構中導人有氣、漠等4或化ί ⑧. 34 201230908 π ^ί,柄^曰較佳為使用例如完全烧基化型、 型、亞胺基/經甲基型三聚氰胺細、尿素=基^ 脂等。尤其,苯脈胺樹脂從絕緣可靠“ ,封端化之多官能異氰酸酉旨,可以適當使用 k S上異氣酸醋基之多官能異氰酸§旨化合物之異ί納妒 ίΠ匕者。例如:脂肪族、脂環族或芳香族之多; =異纖基經封端者,較佳為不含異 二= 五亞以 f萘二異氰_、聯甲苯胺二異氰_旨、;ιΐί —異氰I酯等之異氰酸酯基經封端者。 —肀本 =於封端,例如可理祕使用、赌触物、 觸多官能異氰酸η其,= 性高合物封端的多官能純_旨由於反應 變性聚胺曱酸酯樹脂組成物,可進一步 2或其他添加_等通常絕緣膜用樹‘仏 填料(D)可適當使用公知者。例如:二氧化石夕、氧化紹、 石、玻璃粉、石英粉等無機餘、環氧樹脂粉末、 二2樹腊粉末、尿素樹脂粉末、三聚氰二胺(gamine) =秦末、聚醋樹脂粉末、聚醯胺樹脂粉末、聚醯亞胺樹脂 =、橡膠粒子、石夕酮粉末等有機微粒。其粒徑(中位徑)為 0.001〜1,較佳,_5〜〇.5μηι更佳,〇 〇1〜〇 1μηι尤佳。粒Polybutylene 4;::;=曰二己内 earned epoxy resin, ring 孽 In particular, N-epoxy propyl-type epoxy resin produced by more than one oxime. Good, and the other side, the amine-containing epoxy resin anti-fine I ί is used in the structure to guide people to be mad, indifferent, etc. 4. 34 201230908 π ^ί, the handle is better to use, for example, complete The alkylation type, the type, the imine group / the methyl type melamine fine, the urea = the base resin, and the like. In particular, the benzophenone resin is reliable from the insulation, and the blocked polyfunctional isocyanic acid is used. The polyfunctional isocyanate of the sulphuric acid sulphate on the k S can be suitably used. For example: aliphatic, alicyclic or aromatic; = heterofibrous end capped, preferably free of iso-di = fya f-naphthalene diisocyanate, tolidine diisocyanide ΐ ; ; 异 异 — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — The blocked polyfunctional pure product is a reaction-denatured polyamine phthalate resin composition, and may be further used in addition to other or other additives such as a tree insulating material (D). For example, a corrosive stone is used. , oxidized Shao, stone, glass powder, quartz powder and other inorganic residues, epoxy resin powder, Er 2 tree wax powder, urea resin powder, melamine (gamine) = Qin end, polyester resin powder, polyamine Organic fine particles such as resin powder, polyimine resin = rubber particles, and iron ketone powder. The particle diameter (median diameter) is 0.001. ~1, preferably, _5~〇.5μηι is better, 〇 〇1~〇 1μηι尤佳.

勺C 201230908 其摻ί ί彳1 目式自動檢錄置容易發生誤檢測。又, ;欠'I胺甲酸酉旨樹脂出)100質量份,通常&gt;7 1〜200質量份,較佳為5〜⑽質量份。^里伤通吊為 而言又也樹脂組成物中’就其他添加劑⑹ 物、聚匕、氟變性聚彻、聚丙烯酸化合 媒、受阻“化I物也肖泡劑L貞或3級胺類等硬化觸 ^又_糸化合物、嶙系化合 化劑、_脂等公知的各種添加劑。 °物仏乳 «樹/旨二容^ S 曱酸酯樹脂組成物宜以變性聚胺曱 胺、N,N-二乙基乙二甲基乙酿 醯胺、N-甲基·2-吡丄N,N--甲基甲醯胺,二乙基甲 己内醯胺等.含^、U二甲基-2__唾咬嗣、N-曱基 甲基石風、ί,乙谷劑例如二曱基亞颯、二乙基亞颯、二 劑,例如甲盼r^、:、¥甲;?酿胺等;含氧溶劑例如紛系溶 醇二甲醚(diglyme)、~:甲,寻;二甘二甲_溶劑例如二乙二 甲醚等調孕溶·如:醇二甲_glyme)、四乙二醇二 佛爾酮丙Γ苯^、笨丙飼、環己酉同、異 丁内酿等。四虱。夫喃等系溶劑例如γ- 二乙基ί = 基甲醯胺、Ν,Ν-二甲基乙_、耶_ 可吉接伯田内酯、三乙二醇二曱醚等較佳。又,也 變性4甲ϊί聚胺甲酸關脂時使用的有機溶劑。 的印imH樹脂組成物之溶液黏度,為了獲得理想 sec〜5_a · se、c,車^旋轉黏度計之黏度通常為他· 季又佳為25Pa · sec〜200Pa · sec之筋圚。以 i的形成圖案時’為了抑制滲出’宜添加二氧化石夕等微 細的填料而辭觸魏。 7寻被 絕緣ff聚胺甲酸§1樹脂組成物為代表之硬化性 '、緣、_&amp;組成物’可藉由在撓性電路板之至少連接端子 ⑧ 201230908 部以外的電路蘭电 膜使硬化膜案之表面,利用例如網版印刷等塗佈形成塗 以加熱處1之厚度為約3〜60陴,並於低溫去除溶劑,其次 100〜130。(:,、^於60〜2〇〇°C,較佳為80〜15〇ϊ,更佳為 更佳為30八拉行5分鐘〜5小時,較佳為10分鐘〜3小時, 如變性臂脸刀田里Γ2小時以熱風或紅外線的加熱處理以進行例 獲得硬化崎邮)與硬錄獅(Q的交聯反應,而 含至二,就硬化性絕緣膜用樹脂組成物而言,使用包 脂與硬G性二i酸價為16〜4〇mgKOH/g之變性聚胺甲酸酯樹 該變性:而得之變性聚胺曱酸酯樹脂組成物較佳。將 述?組成物加熱處理而得之硬化膜,如前 i充想控制’具足夠的交聯密度,因此具底層 底層填充間的且不會有過度較度,具理想的與 得之^/胺將°亥麦性聚胺曱酸酯樹脂組成物予以加熱處理而 以下s 1具有浸潰於環氧樹脂時尺寸變化率較佳為6 0 % 密合性,環氧樹脂的耐性,而且於與底層填充材之 埴二姑田性聚胺甲酸酯樹脂組成物之硬化膜剝離底層 破壞)性少硬化膜會部分㈣破壞(較佳為全面内聚 硬化ί,ΐΐϊί之至少連接端子部以外的電路圖案面塗佈 造矜送ΐ概抖脂組成物,其次使硬化而形成絕緣膜並製 體‘撓敗Γ f撓性電路_ ’將獲得之輪送膠帶封裝 述包含至查。藉由使用如前 氯眉早芬、自氣原子及溴原子之體質顏料(al)與不含 膜用樹脂&amp;物之著色之硬化性絕緣 =子不之含:^ 絕緣 _=·==== 201230908 以古甚ί 率降低’能減低檢查不良率。其結果能 J f ΐ、,地獲得輸送膠帶縣體用撓性電路板。又, 獲t之輸送料縣翻撓性電路板,可理想地進行 狀硬化性絕緣朗樹脂組成物,由於獲得之硬 g緣狀絲性高、料含氯軒錢軒,故環境適合 本方法獲得之輸_帶職體賴性f路板,例如 由以凸塊等卫具安裝如半導體晶片般之電子^ 之連接端子部,再於經安裝之電子究杜 、電路圖案 充填底層填充材並進行加熱處理使硬化,朗 :、 而理想地獲得輸送料封裝體。又,在^ 形狀及尺柯制蚊。 令件之 [實施例] 又,本發明 以下舉實施例及比較例進一步說明本發明 不限於以下實施例。 x «Α部分之實施例》 以下之各例的評價依以下方法進行。 [溶液黏度] 之溶sri轉黏度計求出變性聚胺甲酸略樹脂溶液 [固體成分] 於铭製淺盤量取變性聚胺甲酸醋樹脂溶液Spoon C 201230908 Its automatic recording and recording is prone to false detection. Further, 100 parts by mass of the "I-carbamic acid-based resin" is used, and usually 7 1 to 200 parts by mass, preferably 5 to 10 parts by mass. ^In the case of resin damage, it is also a resin composition 'in terms of other additives (6), polyfluorene, fluorine depolymerization, polyacrylic acid compound, hindered "chemical I, also foaming agent L贞 or tertiary amines Other known additives such as hardening contact 又 又 compound, lanthanide compounding agent, _ lipid, etc. ° 仏 仏 树 树 树 树 树 树 树 树 树 树 树 S S S S S S S S S S S S S S S S , N-diethylethylenedimethylacetamide, N-methyl-2-pyridinium N, N-methylformamide, diethylmethylhexylamine, etc. Contains ^, U II Methyl-2__Salt, N-mercaptomethyl stone, ί, 乙谷剂, such as dimercaptoarrene, diethyl hydrazine, two agents, such as 甲盼r^,:, ¥甲; Oxygenated solvents, etc.; oxygen-containing solvents such as dimethyl dimethyl ether (diglyme), ~: A, hun; di-glyme _ solvent such as diethyl dimethyl ether, etc., such as: alcohol _glyme ), tetraethylene glycol diphorone acetophenone benzene ^, stupid propylene feed, cyclohexyl amide, isobutyl endogenous, etc. tetraterpenoids such as γ-diethyl ί = carbamide , Ν, Ν-dimethyl _ _, ye _ keji connected with Bertar lactone, triethylene glycol dioxime ether, etc. In addition, the organic solvent used in the modification of the 4 ϊ 聚 poly urethane is also used. The solution viscosity of the printed imH resin composition, in order to obtain the ideal sec~5_a · se, c, the viscosity of the car rotary viscometer is usually his · The season is preferably 25Pa · sec~200Pa · sec. When forming a pattern with i, 'to suppress the bleed out', it is advisable to add fine filler such as sulphur dioxide to the Wei. §1 Resin composition represented by the resin composition, rim, _&amp; composition' can be made on the surface of the cured film by using a circuit blue film other than the connection terminal 8 201230908 of the flexible circuit board. The coating is applied to form a coating having a thickness of about 3 to 60 Å, and the solvent is removed at a low temperature, followed by 100 to 130. (:, , ^ at 60 to 2 ° C, preferably 80 to 15〇ϊ, preferably more preferably 30 minutes for 5 minutes to 5 hours, preferably 10 minutes to 3 hours, such as denatured arm face knives for 2 hours with hot air or infrared heat treatment to obtain hardening崎邮) and hard lion (Q cross-linking reaction, and containing up to two, it is hardenability For the resin composition for the film, a denatured polyurethane resin having a fat content of 16 to 4 〇 mg KOH/g of a hard acid and a di-acid is used: the denatured polyamine phthalate resin is used. Preferably, the cured film obtained by heat-treating the composition has sufficient cross-linking density, so that it has a low-level underfill and does not have excessive degree, and is ideally The amine/polyamine phthalate resin composition is heat treated, and the following s 1 has a dimensional change rate of preferably 60% when impregnated with the epoxy resin, and the epoxy resin Resistant, and in the case of the underlying filler, the hardened film of the arsenic polyurethane resin composition is peeled off. The less hardened film will partially (4) break (preferably the full cohesive hardening, at least the connecting terminal) The circuit pattern surface coating other than the part is coated with the 抖 ΐ 抖 抖 抖 组成 , , , , 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 挠性 挠性 挠性 挠性 挠性 挠性 挠性By using the precursor pigment such as pre-chlorine, the self-gas atom and the bromine atom (al) and the hardening insulation without the film resin &amp; the inclusion of the film: ^ Insulation _=·== == 201230908 Lowering the rate of the ancients can reduce the rate of inspection failure. As a result, it is possible to obtain a flexible circuit board for the conveyance tape of the county body. Moreover, the flexible circuit board of the material material of the t-feeding material can be ideally formed into a hardening insulating resin composition, and the environment is suitable for the method because the hard g-like filament property is high and the material contains chlorine Xuan Xuan Xuan. Obtaining the _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ The heat treatment is performed to harden, and the carrier package is desirably obtained. Also, in the shape of the ^ and the ruler Ke mosquito. [Embodiment] Further, the present invention will be further described below by way of examples and comparative examples. The present invention is not limited to the following examples. Example of x «Α part The evaluation of each of the following examples was carried out in the following manner. [Solution viscosity] Solvent sri to viscometer to determine denatured polyamine formic acid solution [Solid composition] Derivatized polyamine formic acid resin solution

之熱風循環烘箱中加、熱2小時,除去固體 、C 從該殘留成分的質量求出變性聚胺甲酸^ j 7卜的成刀, 分(質量%)。 义酉曰樹脂溶液之固體成 [變性聚胺甲酸酯樹脂之酸價] 依照JIS K0070,以電位差滴定法求胺 樹脂之酸價。又,本發明之變性聚胺曱暖二 解性,故使用苯曱醇當做溶解之溶劑。-曰3、θ由於人缺溶The hot air circulating oven was heated and heated for 2 hours to remove solids, and C was obtained from the mass of the residual component to obtain a knives (mass%) of the denatured polyamine formic acid. The solid of the resin solution is [acid value of the denatured polyurethane resin] The acid value of the amine resin is determined by potentiometric titration according to JIS K0070. Further, since the denatured polyamine of the present invention is warm and divisible, phenylhydrin is used as a solvent for dissolution. -曰3, θ due to human deficiencies

酸價 A(mgKOH/g)=[Bxfx5.6U]/S 38 201230908 B:0.1N氫氧化鉀-乙醇溶液之使用量(ml) f:〇.IN氫氧化鉀-乙醇溶液之因子 S:變性聚胺曱酸酯樹脂之採取量(g) [晶片剝離強度] 、、在聚醯亞胺膜(宇部興產製UPILEX 35SGA)以網版印刷 塗佈變性聚胺曱酸酯樹脂組成物,於,80°C進行30分鐘、其 次於120。(:進行60分鐘加熱處理,形成約10μΓη厚之硬化膜。 在該聚醯亞胺膜基板上之硬化膜上載置短邊lmm至2mm之 模擬晶片,並於其附近滴加以雙酚F型環氧樹脂為主成分之 =售的C〇F用底層填充材,於150°C進行2.5小時加熱處理, 製作模擬晶片之接合面側由底層填充材密封成的試驗樣本。 一使用島津製作所製小型桌上試驗機Ez_s,將製作之剝離 j驗樣本其未與聚醯亞胺膜基板及模擬晶片接合之面固定於 f具(此時模擬晶片之短邊側係朝會先被破壞的方向固 具夾持聚醯亞賴基板,以與模擬晶片之接合面 分的速度拉提。模擬晶片於短邊侧剥離 期之硬化膜與底層填充材產生破壞之最大 足)二、、、以上者評為〇(良好)’小於3Ν者評為χ(強度不 [對於環氧樹脂之耐性(尺寸變化率)] 後严_樹脂組成物流延於玻璃板上,使硬化 fo 於8G°C進行3G分鐘、其次於1贼進行 切ΐ ’形成硬倾。將該硬化膜從玻璃板剝離, 後,浸潰於環氧樹脂(JAPAN ΕΡΟχΥ 邊:長度硬化臈,央洲^ 變化率,均求^浸频錢潰後之尺寸 浸清德徂姓對於裱氧樹脂之耐性(尺寸變化率)。又,當 ίίi ff更化膜之形狀時,評為X。 尺寸交化率(°〇(la-Lb)/LbX100 39 201230908 LA:浸潰後樣本4邊長度之平均値 lb:浸潰前樣本4邊長度之平均値 [對於底層填充材之耐性(外觀)] 以網版印刷於聚醯亞胺膜(宇部興產製Uhlex 35SG ,佈變性。聚胺甲酸酯樹脂組成物,於80°C進行30分鐘、其 次f 12〇°C進行60分鐘加熱處理,形成約ΙΟμπι厚之硬化膜、。 在ΐ硬化膜上薄薄地塗佈以雙酚F型環氧樹脂為主成分之市 售環氧樹脂系底層填充劑,於15(TC使進行2小時加熱硬化。 試驗片,無異常時評為。、發現膨起或皺紋 [與底層填充材之密合性(剝離樣式)] 以網版印刷在聚醯亞胺膜(宇部興產製UHLEX 35SGA) 主佈變性聚胺曱酸酯樹脂組成物,於8〇。〇進行1 =120C進行60 *鐘加熱處理,形成約1〇_厚之硬化膜 上使用機械式吸量管,滴加以雙紛F型環氧樹脂 二 成刀之市售裱氧樹脂系底層填充材3pL,於15〇。〇進 硬化。將經硬化之底層填充材從硬化膜剝離’ 為2 樣式。剝離樣式為硬化膜有内聚破壞時評 有硬倾之㈣破壞以及硬化膜與底層填充 [焊料财熱性] 樹脂更之光Γΐ佈變性聚胺甲酸酉1 上塗佈松香tit丨成卿厚之硬化膜。在該硬化膜Acid value A (mgKOH/g)=[Bxfx5.6U]/S 38 201230908 B: 0.1N potassium hydroxide-ethanol solution (ml) f: 〇.IN potassium hydroxide-ethanol solution factor S: denaturation The amount of the polyamine phthalate resin (g) [wafer peel strength], and the composition of the denatured polyamine phthalate resin coated by screen printing on a polyimine film (UPILEX 35SGA manufactured by Ube Industries, Ltd.) It was carried out at 80 ° C for 30 minutes, followed by 120. (: A heat treatment film of about 10 μm thick was formed by heat treatment for 60 minutes. A dummy wafer having a short side of 1 mm to 2 mm was placed on the cured film on the polyimide film substrate, and a bisphenol F ring was dropped in the vicinity thereof. Oxygen resin as a main component = sold as a C〇F underfill material, and heat-treated at 150 ° C for 2.5 hours to prepare a test sample in which the underlying filler was sealed on the joint surface side of the dummy wafer. The table tester Ez_s is used to fix the sample which is not bonded to the polyimide film substrate and the dummy wafer, and the surface of the dummy wafer is fixed in the direction of the first side. The substrate is clamped to the surface of the mating surface of the dummy wafer, and the maximum thickness of the hardened film and the underfill material in the short-side peeling period of the simulated wafer is as follows. It is rated as χ (strength) less than 3 χ (strength is not [resistant to epoxy resin (size change rate)] 严 _ resin composition flow extends on the glass plate, so that hardening fo at 8G ° C for 3G minutes Second, followed by a thief The hardened film is peeled off from the glass plate, and then impregnated in the epoxy resin (JAPAN ΕΡΟχΥ side: length hardened 臈, Yangzhou ^ change rate, both seek for the size of the dip smashed after the money immersed in the German surname For the resistance of the epoxy resin (dimension change rate). Also, when ίίi ff is used to change the shape of the film, it is rated as X. Size cross-linking rate (°〇(la-Lb)/LbX100 39 201230908 LA: sample after impregnation Average length of 4 sides 値 lb: Average length of 4 sides of the sample before impregnation [resistance to the underfill (appearance)] Screen printing on polyimine film (Uhlex 35SG, Ubex 35SG, cloth denaturation). The polyurethane resin composition was heat-treated at 80 ° C for 30 minutes and then f 12 ° C for 60 minutes to form a cured film of about ΙΟμπι thick. The bisphenol was thinly coated on the tantalum cured film. A commercially available epoxy resin-based underfill agent containing F-type epoxy resin as a main component, which was heat-cured at 15 (TC for 2 hours). The test piece was evaluated without any abnormality. It was found to be swollen or wrinkled [with underfill material Adhesion (peeling pattern)] Screen printing on polyimine film (UHLEX 35SGA) The cloth denatured polyamine phthalate resin composition was subjected to heat treatment at 80 ° C for 1 = 120 C to form a cured film of about 1 〇 thick, using a mechanical pipette, and dripping with a double F type. Epoxy resin 20% knife commercially available epoxy resin based underfill material 3pL, at 15 〇. Indentation hardening. The hardened underfill material is peeled from the cured film '2 style. The peeling pattern is cohesive for the cured film. When the damage is judged, there is a hard tilt (four) damage and the hardened film and the underfill [solder heat] resin and the lighter cloth denatured polyurethane 酉1 coated with rosin titer into a thick and hardened film. In the cured film

,二和化學工業公司製:SUNFLUX 以日 '目二t 260°c的焊料浴使接觸硬化膜10秒。之後, 異錢並㈣。無異常_。、發生膨起等 [低翹曲性] 於水齙亞胺膜(宇部興產製UPILEX 35SGA)塗佈變性聚 ⑧ 201230908 月女曱酸醋樹脂組成物,於80°C進行30分鐘、其次於12〇。〇進 行60分鐘加熱處理,形成約ι〇μιη厚之硬化膜。將該聚醯亞 胺膜與硬化膜之豐層體切成5cm&gt;&lt;5cm,以硬化膜朝上之狀態 乘載於水平的台座,求取4個角落距水平面之高度(聚醯亞&amp; 膜底面)。平均高度低於2mm時評為以上、低於3mm 時評為〇、3mm以上時評為X。 [彎曲性] 以網版印刷於聚醯亞胺膜(宇部興產製35SGA) 塗佈變性聚胺曱酸酯樹脂組成物,於80°C進行30分鐘、其 次於120°C進行60分鐘加熱處理,形成約10μπ1厚之硬化膜。 將該聚醯亞胺膜與硬化膜之疊層體切成長度2cmx寬度 lcm’於長度方向之中央彎曲,在彎曲部上載置5〇吆之砝碼, 並靜置1分鐘。將彎曲部以顯微鏡觀察,無異常時評為〇、 發現到裂痕·白化等時評為X。 [無黏性] 以網版印刷在聚醯亞胺膜(宇部興產製UPILEX 35SGA) 塗佈變性聚胺甲酸酯樹脂組成物,於8〇°c進行3〇分鐘、其 次於120 C進行60分鐘加熱處理,形成約ι〇μιη厚之硬化膜。 將該聚酿亞胺膜與硬化膜之疊層體切成寬度2 5cni、長度 5cm。,製作試樣。將該試樣以塗膜面朝上放置於已加熱為 160°C之熱板,於其上載置SUS製錘(底面積2cmx5cm、重量 500g)30秒’於提起時未貼附之情形評為◎,於16〇它時會貼 附但於M〇C未貼附時評為〇,於140〇C會貼附時評為X。 [外觀觀察] 使用網版印刷機(網版版SUS 150mesh),將變性聚胺 曱酸醋樹脂組成物印刷在聚醯亞胺膜(宇部興產製upiLEX 35SGA)上’於8〇ϊ進行3〇分鐘、其次於12〇t:進行6〇分鐘 加熱處理’形成硬化膜。將該硬化膜使用Nikon(股)公司製正 立,微鏡ECLIPSE (CCD攝像頭DS2Mv),以反射光觀察 外觀。無異常時評為0、硬化膜中確認有最大長度5μιη以上 201230908 =異=ΐΐ=、相分離結構或空隙(, 更化膜中之些〗政减集結構或相分離結構、空隙的大d、 射等(最大長)大於_時’光學=丄杳 展置…、法區为真正的異物或缺陷,故容易誤檢測。 〜 [對於自動檢查裝置之對應] # ^網版印刷機(網版聚芳醋220meSh),將變性聚賤 ^欠酉日納曰組成物印刷在形成有電路最小間隔為15叫之^ 路圖案的住友金屬礦山(股)公司製ESPERFLEX上進行 熱處理,製作成輸送膠帶封裝體用撓性電路板。使用下列 學式檢查裝置評價該輸送膠帶封裝體用撓性電路板。 攝像機:DALSA製Piranha2攝像機線剞CCD里白 8000畫素 、 …曰 解析能力:6μιη/晝素 光源:金屬鹵化物180W光源 以相同光量拍攝相同部位,由輝度直方圖之峰部形狀, 比較線/間隔交界部之對比度,當輝度直方圖之峰部寬度窄且 對比鮮明時評為〇、輝度直方圖之峰部寬度寬且對比鮮 時以X表示。 以下各例使用之化合物如下。 [二異氰酸酯化合物], manufactured by Erhe Chemical Industry Co., Ltd.: SUNFLUX is contacted with a hardened film for 10 seconds with a solder bath of the same day. After that, the money is different (four). No abnormality_. , bulging, etc. [low warpage] The composition of the scorpion vinegar resin was applied to the scorpion imine film (UPILEX 35SGA), which was carried out at 80 ° C for 30 minutes, followed by 12〇. The heat treatment was carried out for 60 minutes to form a cured film of about ι〇μηη thick. The polyimine film and the cured layer of the cured film were cut into 5 cm&gt;&lt;5 cm, and the hardened film was loaded upward on the horizontal pedestal to obtain the height of the four corners from the horizontal plane (Juyia &; the bottom of the membrane). When the average height is less than 2 mm, it is rated as above, when it is less than 3 mm, it is rated as 〇, and when it is 3 mm or more, it is rated as X. [Flexibility] The denatured polyamine phthalate resin composition was applied by screen printing on a polyimide film (35SGA manufactured by Ube Industries, Ltd.), and heated at 80 ° C for 30 minutes, followed by heating at 120 ° C for 60 minutes. The treatment forms a cured film of about 10 μπ thick. The laminate of the polyimide film and the cured film was cut into a length of 2 cm x width lcm' and bent at the center in the longitudinal direction, and a weight of 5 Å was placed on the bent portion, and allowed to stand for 1 minute. The bent portion was observed by a microscope, and when it was found to be flawless when no abnormality was observed, it was evaluated as X when it was found to be cracked and whitened. [Non-adhesive] The composition of the denatured polyurethane resin was coated on a polyimide film (UPILEX 35SGA manufactured by Ube Industries, Ltd.) by screen printing at 8 ° C for 3 〇 minutes, followed by 120 C. Heat treatment for 60 minutes to form a hardened film of about ι〇μηη thick. The laminate of the polyimide and the cured film was cut into a width of 2 5 cni and a length of 5 cm. , making samples. The sample was placed on a hot plate heated to 160 ° C with the coating film facing up, and a SUS hammer (bottom area 2 cm x 5 cm, weight 500 g) was placed thereon for 30 seconds, which was evaluated as unattached at the time of lifting. ◎, it will be attached at 16〇, but it will be rated as 〇 when M〇C is not attached, and will be rated as X when it is attached at 140〇C. [Appearance observation] Using a screen printing machine (screen version SUS 150mesh), the denatured polyamine phthalic acid resin composition was printed on a polyimine film (Utsumatsu-made upiLEX 35SGA) on the 8th floor. 〇 minute, followed by 12〇t: heat treatment for 6 minutes to form a cured film. The cured film was an erect, Nikon ECLIPSE (CCD camera DS2Mv) manufactured by Nikon Co., Ltd., and the appearance was observed with reflected light. When there is no abnormality, it is rated as 0, and the maximum length of the cured film is confirmed to be 5 μιη or more. 201230908 = different = ΐΐ =, phase separation structure or void (the gradual reduction structure or phase separation structure, large gap of the gap, When the shot (maximum length) is greater than _, 'optical=丄杳展..., the legal area is a real foreign object or defect, so it is easy to detect by mistake. ~ [For the automatic inspection device] # ^ Screen printing machine (screen version) Polyurethane vinegar 220meSh), the denatured poly 贱 酉 酉 酉 酉 曰 曰 曰 曰 曰 曰 曰 ES ES ES ES ES ES ES ES ES ES ES ES ES ES ES ES ES ES ES ES ES ES ES ES ES ES ES ES ES ES ES ES ES ES ES ES Flexible circuit board for package. The flexible circuit board for the transfer tape package was evaluated using the following inspection device. Camera: Piranha2 camera line made by DALSA 剞 8000 white 8000 pixels, ... 曰 Analytical ability: 6μιη / 昼素Light source: The metal halide 180W light source shoots the same part with the same amount of light, and the peak shape of the luminance histogram compares the contrast of the line/space boundary. When the peak width of the luminance histogram is narrow and contrasting Represents a square, a luminance histogram of the peak portion and a wide width when fresh contrast to X-. The following compounds were used in each Example are as follows. [Diisocyanate compound]

Desmodur W(HMDI):亞曱基雙(環己基異氰酸酯)住化 拜耳URETHANE(股)公司製 IPDI:異佛爾酮二異氰酸g旨Degussa Japan「股)公司 製 [聚碳酸醋二醇] UH-200:1,6-己炫二醇基礎的聚碳酸酯二醇宇部興產 (股)公司製 ETETNACOLL 羥基價 57.2mgKOH/g C-1065N:1,9-壬二醇、2-甲基-1,8-辛烷二醇基礎的聚碳酸 酯二醇(股)公司可樂麗製Kuraraypolyol 羥基價 42 201230908 112mgKOH/g [含缓基之二醇化合物]Desmodur W (HMDI): yttrium bis(cyclohexyl isocyanate) sulphate Bayer URETHANE Co., Ltd. IPDI: isophorone diisocyanate g Degussa Japan "shares" company [polycarbonate diol] UH-200: 1,6-hexahydrodiol-based polycarbonate diol UBE Xingsheng Co., Ltd. ETETNACOLL hydroxyvalence 57.2mgKOH/g C-1065N: 1,9-nonanediol, 2-methyl -1,8-octanediol-based polycarbonate diol (stock) company Kuraraypolyol hydroxy valence 42 201230908 112 mg KOH / g [glycol-containing diol compound]

Bis-MPA:2,2-雙(羥基曱基)丙酸廣榮PERSTORP (股) 公司製 DMBA:2,2-二羥甲基丁酸日本化成(股)公司製 [醇] l-Pentanol:l-戊醇和光純藥(股)公司製 [溶劑] ΒΙΧ)··γ-丁内酯三菱化學(股)公司製 CA:二乙醇乙鱗乙酸g旨和光純藥(股)公司製 [環氧樹脂] YH434:東都化成(股)公司製EPOTOTE、環氧當量121 [胺基樹脂]Bis-MPA: 2,2-bis(hydroxyindenyl)propanoic acid, Glory PERSTORP (shares) DMBA: 2,2-dimethylolbutanoic acid, manufactured by Nippon Kasei Co., Ltd. [Alcohol] l-Pentanol: L-Pentanol and Wako Pure Chemicals Co., Ltd. [Solvent] ΒΙΧ)··γ-butyrolactone Mitsubishi Chemical Co., Ltd. CA: Diethanol acetoacetate g and Wako Pure Chemical Co., Ltd. [Epoxy] Resin] YH434: EPOTOTE, Epoxy Equivalent 121 [Ethyl Resin] manufactured by Dongdu Chemical Co., Ltd.

M136:苯胍胺樹脂日本CYTEC INDUSTRIES(股)公司 製 MYCOATM136: benzoguanamine resin Japan CYTEC INDUSTRIES Co., Ltd. MYCOAT

[分子結構中不含氣原子及溴原子之藍色顏料] P.B.15:3:C. Y.顏料藍15:3銅酜花青β型献花青藍 G(NC)於雷射繞射/散射式粒度分布測定中之中位徑140 nm (使用預先添加當做溶劑之BLO、分散劑,以珠磨機分 散者。) [分子結構中不含氯原子及溴原子之黃色顏料] P.Y.180.C.Y.顏料頁180縮合偶氮Novoperm黃 P-HG ’ 雷射繞射/散射式粒度分布測定之中位徑470nm (使用預先添加當做溶劑之BLO、分散劑,以珠磨機分 散者。) [分子結構中不含氯原子及溴原子之體質顏料] P.W.21:C.Y.顏料白21沉降性硫酸鋇BARIFINE B-54以雷射繞射/散射式粒度分布測定之中位徑64〇nm 43 201230908 (使用預先添加當做溶劑之BL0、分散劑,以珠磨機分 散者。) [填料][Blue pigment containing no gas atom and bromine atom in the molecular structure] PB15:3:CY pigment blue 15:3 copper phthalocyanine β-type flower blue blue G (NC) in laser diffraction/scattering particle size distribution In the measurement, the median diameter is 140 nm (using a BLO and a dispersant previously added as a solvent, and dispersed in a bead mill.) [Yellow pigment containing no chlorine atom and bromine atom in the molecular structure] PY180.CY Pigment Page 180 Condensed azo Novoperm yellow P-HG 'The laser diffraction/scattering particle size distribution is determined by a median diameter of 470 nm (using a BLO, a dispersant previously added as a solvent, and dispersed in a bead mill.) [Molecular structure does not contain Physicochemicals of chlorine and bromine atoms] PW21: CY pigment white 21 Settling barium sulphate BARIFINE B-54 with laser diffraction/scattering particle size distribution Determination of median diameter 64 〇 nm 43 201230908 (Use pre-added as solvent BL0, dispersant, disperser in the bead mill.) [Filler]

Aerosil50:一氧化石夕日本Aerosil公司製平均一次粒 徑 30nm [其他添加劑] FA600:氟變性聚矽氧烷信越化學工業(股)公司製Aerosil50: Japan's Aerosil Corporation's average primary particle diameter 30nm [Other additives] FA600: Fluorine-denatured polyoxane Shin-Etsu Chemical Co., Ltd.

P410EF:聚乙烯基類化合物搞本化成工業(股)公司製 DISPAR0N HF-1:酚樹脂明和化成(股)公司製 [醯亞胺寡聚物二醇溶液之製造] 於配備氮氣導入管、Dean_Stark接受器、冷卻管之容量 5公升的玻璃製可分離燒瓶中,添加2,3,3,,4,-聯苯四叛酸二P410EF: Polyurethane-based compound DISPAR0N HF-1: phenol resin Minghe Chemical Co., Ltd. [Manufacture of sulphide oligomer diol solution] with nitrogen inlet tube, Dean_Stark Adding 2,3,3,,4,-biphenyltetrahydro acid to the 5 liter glass separable flask with the capacity of the receiver and cooling tube

酐1471g、乙醇507g及γ_ 丁内酯2〇92g,於氮氣氛圍下於9(TC 攪拌1小時。其次添加3-胺基丙醇376g、異佛爾酮二胺426g, 於氮氣氛圍下,於120°C加熱2小時、於180°C加熱2小時, 將醯亞胺化反應所產生之水藉由對於反應液中吹入氮氣而去 除。該酿亞胺寡聚物二醇溶液的固體成分為52.3%。 [參考例A1][變性聚胺甲酸酯樹脂(PU_A1)之製造] 於配備擾拌機、溫度計、氮氣導入管之玻璃製反應容器 中,添加聚碳酸醋二醇ETERNACOLL UH-200 60.0g、溶 劑γ-丁内酯(BLO) 17〇.5g、含叛基之二醇Bis-MPA 10. lg、於前述製造方法合成之醯亞胺寡聚物二醇溶液 48.0g,於90°C溶解後,添加二異氰酸酯化合物Desmodur W 33.7g。於90°C攪拌1小時後,升溫到110¾,於黏度成為 120〜150Pa · s之時點添加1-戊醇,再於13〇。〇攪拌2小時。 獲得固體成分40.5%、黏度97Pa · s、變性聚胺甲酸酯樹 脂固體成分之酸價為33mgKOH/g之變性聚胺曱酸酯樹脂 (PU-A1)溶液。 [參考例A2〜A7][變性聚胺曱酸醋樹脂(PU-A2〜A7)之製造] 44 201230908 使用表A1所不之原料,除此以外與參考例A1同樣進 行,獲得變性聚胺曱酸酯樹脂(PU_A2〜A7)溶液。表A1顯示 固體成分、黏度、變性聚胺曱固體成分之酸價。 [麥考例A8][變性聚胺曱酸酯樹脂(pu_A8)之製造] 於配備授拌機、溫度計、I氣導入管之玻璃製反應容器 中,添加 1¼酸酯一醇 Kuraraypoly〇lC-l〇651Si 83 90g、含 叛基之二醇麵A 15.85g、溶劑二乙二醇^ ^酸酉旨 150.15g,於9GC麟1小時。之後冷卻到贼後,添加二 異氰酸酯化合物Desmodur W 52.5g,攪拌丨小時後,於8〇。(: 攪拌1小時、於100°C攪拌2小時。獲得固體成分5〇·5%、 黏度151Pa· s、變性聚胺曱酸酯樹脂固體成分之酸價為 41mgKOH/g之變性聚胺曱酸酯樹脂(piJ_A8)溶液。 [實施例A1][組成物之製備、及硬化膜] 於參考例A1獲得之(A)變性聚胺曱酸酯樹脂(pu_A1)溶 液中’相對於樹脂固體成分100質量份,添加表A2記載之 (B)熱硬化性樹脂及(E)其他添加劑。均勻攪拌•混合。其次, 添加(C)顏料、(D)填料並混合後,使用3輥混練。以丫_丁内 吏物之黏度成為20〜60Pa·s,獲得變性聚胺曱酸 酯樹脂組成物。 針對該受性聚胺曱酸酉旨樹脂組成物之硬化滕,焊僧晶片 剝離強度、對於環氧樹紅雜(尺寸變化率)、、底層^充财 ί(外底層填充密合性(剝離樣式)、焊料耐熱性:低輕曲 t it無黏性、外觀觀察、對於光學式自動檢查裝置 之對應。該荨評價結果如表A2。 [實施例A2〜A7、比較例A1〜A2][組成物之製備、及硬化物] 奸所記載摻合,除此以外與實施例A1同樣進行, 二;女曱酸醋樹脂組成物。針對該變性聚胺曱酸醋樹 ϊ'ϊΐί物之硬化膜,與實施例A1同樣進行評價。此 寻之結果如表A2。 45 201230908 【Ιν·&lt;】 PU-A8 52.5 83.9 15.9 τ~Η 50.5 1—^ PU-A7 22.5 60.0 _1 〇 — 48.0 148 40.9 PU-A6 28.6 60.0 r &lt; Ο Τ-Η 1 48.0 r-H 40.3 芝 PU-A5 30.0 60.0 〇6 48.0 (N 〇〇 40.1 00 (N PU-A4 31.9 60.0 10.1 36.0 (N 1—H 40.7 cn PU-A3 26.2 60.0 ο 1 48.0 CN m r—H 40.5 &lt;N (N PU-A2 30.0 60.0 ο 00 48.0 o 寸 40.2 PU-A1 33.7 60.0 10.1 48.0 s; 40.5 m m 變性聚胺曱酸酯樹脂(A) 二異氰酸酯化合物(al) HMDI IPDI 聚碳酸酯二醇(a2) UH-200 C-1065N 具羧基之二羥基化合 物(a3) Bis-MPA DMBA 饍7 4姨 澍蕃 铝Ί 嫿荽 溶液黏度(Pa*s) 固體成分(質量%) 酸價(mgKOH/g) 46 ⑧ 201230908 【(Nv^】 比較例A2 〇 〇 寸 0\ 〇 〇 s «λ (N 〇 X 〇 &lt;1 Ο ◎ 〇 ◎ 〇 比較例A1 100 Vi d 〇 2 ο cs CO ίΝ 〇 X X X ◎ Ο ◎ 〇 ◎ 〇 1 實施例A7 〇 rt ΓΛ 00 〇 ο § s m Ό - 〇 〇 Os 〇 〇 Ο ◎ 〇 ◎ 〇 1 實施例A6 100 00 &lt;Ν Ό a ο 寸 ο S ο rs cn V&gt; &lt;s 〇 〇 5 〇 ◎ Ο ◎ 〇 ◎ 〇 1 實施例A5 100 Ό 〇〇 寸 ο 寸 ο S S ίΛ w*&gt; &lt;s 〇 〇 〇 ◎ Ο ◎ 〇 ◎ 〇 1 實施例A4 100 (Ν &lt;Ν 甘 ο 々 ο o s ΓΛ *Ti (N 〇 〇 »r&gt; 〇 ◎ Ο ◎ 〇 ◎ 〇 1 實施例A3 〇 〇 &lt;s Ό w&gt; 兮 ο 寸 ο s o rs r^j (S 〇 〇 &lt;s 〇 ◎ 〇 ◎ 〇 ◎ 〇 1 實施例A2 100 r- &lt;s σ\ 兮 ο ο o v〇 o fS m Vi &lt;N 〇 0 〇 ◎ 〇 ◎ 〇 ◎ 〇 0 實施例A1 100 cn ts 寸 c&gt; 甘 ο § ro ir&gt; oi 〇 〇 00 m 〇 ◎ 〇 ◎ 0 ◎ 〇 〇 一 雄 婆 谐 δ- Φί PU-A1 PU-A2 PU-A3 PU-A4 PU-A5 PU-A6 PU-A7 PU-A8 5 K o bo B 祭 谐 δ- 铤 ΥΗ434 ! M136 P.B,15:3 Ρ.Υ. 180 P.W. 21 Aerosil 50 J-4PY FA600 P410EF 丄 X ε &lt;N $ 〇§ 截 吨 π &lt; 想 Mi m 苕 3C &lt; 對於環氧樹脂的财性(尺寸變化率%) S' 实 钵 /«—S 錄 δ &lt;〇 案 t$D 埃 焊料耐熱性 低勉曲性 弩曲性 無黏性 外觀觀察 對於光學式自動外觀檢査裝置的對應 參考例Α1 參考例Α2 參考例A3 參考例Α4 參考例Α5 參考例Α6 參考例Α7 參考例Α8 環氧樹脂 胺基樹脂 藍色顏料 黃色顏料 體質顏料 二氧化矽 丙烯酸填料 氟變性聚矽氧烷 聚乙烯基類化合物 i酚樹脂 (Α)變性胺甲酸 酯樹脂 (B)熱硬化性樹脂 1 (c)顏料 (D)填料 (E)其他添加劑 評償結果 s 47 201230908 樹浐知,本發明之變性聚胺甲酸醋 樹月曰硬化性組成物,其硬化物具良好的料耐執性 ,、%,曲性、無黏性、均勻性(為光學上均勻的硬化膜)-也對 i於ί學式自動檢查裝置之光特性良好(抑制誤檢測所致檢 查效率降低,且可減低檢查不良率),並且,即使對於短 度1.2mm以下之晶片仍有足夠的晶片剝離強度。、 乂1471 g of anhydride, 507 g of ethanol and 92 g of γ-butyrolactone were stirred at 9 (TC for 1 hour) under a nitrogen atmosphere. Next, 376 g of 3-aminopropanol and 426 g of isophoronediamine were added under a nitrogen atmosphere. The mixture was heated at 120 ° C for 2 hours and heated at 180 ° C for 2 hours, and the water produced by the hydrazine imidization reaction was removed by blowing nitrogen gas into the reaction solution. The solid content of the brewing imine oligomer diol solution 52.3% [Reference Example A1] [Manufacture of denatured polyurethane resin (PU_A1)] Polycarbonate diol ETERNACOLL UH- was added to a glass reaction vessel equipped with a scrambler, a thermometer, and a nitrogen introduction tube. 200 60.0g, solvent γ-butyrolactone (BLO) 17〇.5g, thiol-containing diol Bis-MPA 10. lg, 48.0g of ruthenium oligodiol diol solution synthesized in the above production method, After dissolving at 90 ° C, 33.7 g of a diisocyanate compound Desmodur W was added, and after stirring at 90 ° C for 1 hour, the temperature was raised to 1103⁄4, and 1-pentanol was added at a viscosity of 120 to 150 Pa · s, and then 13 Torr. Stir for 2 hours. Obtain a solid content of 40.5%, a viscosity of 97 Pa · s, and an acid value of 33 mg of the solid content of the denatured polyurethane resin. KOH/g denatured polyamine phthalate resin (PU-A1) solution [Reference Example A2 to A7] [Manufacture of denatured polyamine phthalic acid vinegar resin (PU-A2 to A7)] 44 201230908 Using Table A1 In the same manner as in Reference Example A1, a solution of a denatured polyamine phthalate resin (PU_A2 to A7) was obtained. Table A1 shows the acid value of the solid content, viscosity, and denatured polyamine quinone solid content. A8] [Manufacture of denatured polyamine phthalate resin (pu_A8)] In a glass reaction vessel equipped with a mixer, a thermometer, and a gas introduction tube, 11⁄4 acid ester alcohol Kuraraypoly〇lC-l〇651Si 83 90g was added. Resin-containing diol surface A 15.85g, solvent diethylene glycol ^ ^ acid 酉 150.15g, 9GC Lin 1 hour. After cooling to the thief, add diisocyanate compound Desmodur W 52.5g, stir for a few hours (8: stirring for 1 hour, stirring at 100 ° C for 2 hours. Obtaining a solid content of 5 〇 · 5%, a viscosity of 151 Pa·s, and an acid value of a solid content of the denatured polyamine phthalate resin of 41 mgKOH/g. Denatured polyamine phthalate resin (piJ_A8) solution [Example A1] [Preparation of composition and cured film] Obtained in Reference Example A1 Of (A) a solution of denatured polyamine Yue ester resin (pu_A1) in 'with respect to the resin solid content 100 parts by mass, adding Table A2 described in the (B) thermosetting resin and (E) other additives. Stir • mixing. Next, (C) pigment and (D) filler were added and mixed, and then kneaded using a 3-roller. The composition of the denatured polyamine phthalate resin was obtained by setting the viscosity of the mash to 20 to 60 Pa·s. For the hardening of the resin composition of the acceptor polyamine phthalate, the peel strength of the solder wafer, the epoxy resin red (dimension change rate), and the bottom layer filling (external underfill adhesion (peeling) Pattern), solder heat resistance: low lightness t it non-stickiness, appearance observation, correspondence with an optical automatic inspection device. The evaluation results of this 如 are shown in Table A2. [Examples A2 to A7, Comparative Examples A1 to A2] [ The composition of the composition and the hardened material were mixed as described in Example A1, and the composition of the female vinegar resin was applied to the denatured polyamine vinegar vinegar. The film was evaluated in the same manner as in Example A1. The results are shown in Table A2. 45 201230908 [Ιν·&lt;] PU-A8 52.5 83.9 15.9 τ~Η 50.5 1—^ PU-A7 22.5 60.0 _1 〇 — 48.0 148 40.9 PU-A6 28.6 60.0 r &lt; Ο Τ-Η 1 48.0 rH 40.3 芝 PU-A5 30.0 60.0 〇6 48.0 (N 〇〇40.1 00 (N PU-A4 31.9 60.0 10.1 36.0 (N 1—H 40.7 cn PU-A3 26.2 60.0 ο 1 48.0 CN mr—H 40.5 &lt;N (N PU-A2 30.0 60.0 ο 00 48.0 o inch 40.2 PU-A1 33.7 60.0 10.1 48.0 s; 40.5 mm denatured polyamine phthalate resin (A) diisocyanate compound (al) HMDI IPDI polycarbonate diol (a2) UH-200 C-1065N with carboxyl group Dihydroxy compound (a3) Bis-MPA DMBA Diet 7 4 姨澍 Ί Ί 婳荽 Solution viscosity (Pa*s) Solid content (% by mass) Acid value (mgKOH/g) 46 8 201230908 [(Nv^] Comparison Example A2 0 inch 0\ 〇〇s «λ (N 〇X 〇&lt;1 Ο ◎ 〇 ◎ 〇 Comparative Example A1 100 Vi d 〇2 ο cs CO Ν 〇 XXX ◎ Ο ◎ 〇 ◎ 〇 1 Example A7 〇 Rt ΓΛ 00 〇ο § sm Ό - 〇〇Os 〇〇Ο ◎ 〇 ◎ 〇 1 Example A6 100 00 &lt;Ν Ό a ο inchο S ο rs cn V&gt;&lt;s 〇〇5 〇◎ Ο ◎ 〇 ◎ 〇 1 Example A5 100 Ό ο ο ο ο SS Λ * & SS Ο ◎ ◎ ◎ 〇 1 Example A4 100 (Ν &lt;Ν甘ο 々ο os ΓΛ *Ti (N 〇〇»r&gt; 〇◎ Ο ◎ 〇◎ 〇1 Example A3 〇〇 &lt;s Ό w&gt; 兮ο inchο so rs r^j (S 〇〇&lt;s 〇◎ 〇◎ 〇◎ 〇1 Example A2 100 r- &lt;s σ\ 兮ο ο ov〇o fS m Vi &lt;N 〇0 〇◎ 〇◎ 〇◎ 〇0 Example A1 100 cn ts inch c&gt; Ganο § ro ir&gt; oi 〇〇00 m 〇◎ 〇◎ 0 ◎ 〇〇一雄婆婆 harmonic δ- Φί PU- A1 PU-A2 PU-A3 PU-A4 PU-A5 PU-A6 PU-A7 PU-A8 5 K o bo B Harmony δ- 铤ΥΗ434 ! M136 PB,15:3 Ρ.Υ. 180 PW 21 Aerosil 50 J -4PY FA600 P410EF 丄X ε &lt;N $ 〇§ truncated π &lt; think Mi m 苕3C &lt; for epoxy resin (size change rate %) S' 实钵/«-S δ &lt; t t t 焊料 焊料 solder heat resistance low flexibility 弩 弩 无 无 外观 对于 对于 对于 对于 1 Reference example Α 2 Reference example A3 Reference example 参考 4 Reference example Α 5 Reference example Α 6 Reference example Α7 Reference Example 8 Epoxy Resin Amine Resin Blue Pigment Yellow Pigment Body Pigment Ceria Acrylate Filler Fluorine Modified Polyoxane Polyethylene Group i phenol resin (Α) denatured urethane resin (B) thermosetting resin 1 (c) pigment (D) filler (E) other additives evaluation result s 47 201230908 Shu Shu, the denatured polyamine formic acid of the present invention A sclerosing composition of vinegar tree, which has a good material resistance, %, curvature, non-stickiness, uniformity (as an optically uniform hardened film) - also true to i The optical characteristics of the inspection device are good (the inspection efficiency is reduced due to erroneous detection, and the inspection failure rate can be reduced), and sufficient wafer peel strength is maintained even for wafers having a shortness of 1.2 mm or less.乂

«Β部分之實施例》 X 以下各例的評價依以下方法進行。 [溶液黏度]、[固體成分]、[變性聚胺甲酸酯樹脂之酸 價]、[焊料耐熱性]、[低翹曲性]、[彎曲性]、[盖黏性]、[外觀 觀察[對於自動檢查裝置之因應]、[與底層填充材之密合 性]’係以如A部分之實施例説明過的方法評價。 [無鹵素] ' 將變性聚胺曱酸酯樹脂組成物流延在玻璃板上,使硬化 後之厚度成為約50μιη,於80°C進行30分鐘、其次於i2〇°C 進行60分鐘加熱處理,形成硬化膜。使用自動函素·硫分析 系統(YANACO 製 SQ-1/HSU-35 + DIONEX ICS-2000),定量 硬化膜中之氣、溴。硬化膜中之氣、溴之各含量低於3〇〇ppm 時評為◎、為300ppm以上、低於900ppm時評為〇、900ppm 以上時評為X。 以下各例使用之化合物如下。 [二異氰酸酯化合物]«Example of the Β part" X The evaluation of each of the following examples was carried out in the following manner. [Solid viscosity], [solid content], [acid value of denatured polyurethane resin], [solder heat resistance], [low warpage], [bending property], [cover viscosity], [appearance observation [Response to the automatic inspection device], [Adhesion to the underfill material]' was evaluated by the method described in the example of Part A. [No halogen] 'The denatured polyamine phthalate resin composition was spread on a glass plate to a thickness of about 50 μm after hardening, 30 minutes at 80 ° C, and then heat treated at i2 ° C for 60 minutes. A cured film is formed. The gas and bromine in the cured film were quantified using an automatic elemental sulfur analysis system (SQ-1/HSU-35 + DIONEX ICS-2000 manufactured by YANACO). When the content of the gas and bromine in the cured film is less than 3 〇〇 ppm, it is evaluated as ◎, and when it is 300 ppm or more, when it is less than 900 ppm, it is evaluated as 〇, and when it is 900 ppm or more, it is evaluated as X. The compounds used in the following examples are as follows. [diisocyanate compound]

Desmodur W(HMDI):亞曱基雙(環己基異氰酸酯)住化 拜耳URETHANE (股)公司製 IPDI:異佛爾嗣二異氰酸酯 DegussaJapan (股)公司 製 [聚碳酸酯二醇] UH-200:1,6-己烷二醇基礎的聚碳酸酯二醇宇部興產 (股)公司製 ETETNACOLL 羥基價 57.2mgKOH/g C-1065N:1,9-壬二醇,2-曱基-1,8-辛烷二醇基礎的聚碳酸 48 ⑧ 201230908 酉旨二醇可樂蓐(股)公司製Kuraraypolyol羥基價 112mgKOH/g [含緩基之二醇化合物]Desmodur W (HMDI): yttrium bis(cyclohexyl isocyanate) sulphate Bayer URETHANE Co., Ltd. IPDI: Isophoric diisocyanate Degussa Japan (polycarbonate diol) UH-200:1 , 6-hexanediol-based polycarbonate diol, Utopia COLL, manufactured by Ube Industries, Ltd., hydroxyl price 57.2 mgKOH/g C-1065N: 1,9-nonanediol, 2-mercapto-1,8- Octanediol-based polycarbonate 48 8 201230908 K diol cola cola Co., Ltd. Kuraraypolyol hydroxyl valence 112 mg KOH / g [glycol-containing diol compound]

Bis_MPA:2,2-雙(羥基曱基)丙酸廣榮PERSTORP (股) 公司製 DMBA:2,2-二羥曱基丁酸日本化成(股)公司製 [醇] l-Pentanol:l-戊醇和光純藥(股)公司製 [溶劑] ΒΙΧ):γ-丁内酯三菱化學(股)公司製 CA:二乙二醇乙醚乙酸酯和光純藥(股)公司製 [環氧樹脂] ΥΗ434:東都化成(股)公司製ΕΡΟΤΟΤΕ、環氧當量121 [胺基樹脂]Bis_MPA: 2,2-bis(hydroxyindenyl)propanoic acid, Glory PERSTORP (shares) DMBA: 2,2-dihydroxymercaptobutyric acid, manufactured by Nippon Kasei Co., Ltd. [Alcohol] l-Pentanol: l-戊-butyrolactone (M) Co., Ltd. [solvent] ΒΙΧ): γ-butyrolactone Mitsubishi Chemical Co., Ltd. CA: Diethylene glycol ethyl ether acetate and Kokon Pure Chemical Co., Ltd. [Epoxy resin] ΥΗ434: Dongdu Chemical Co., Ltd. Co., Ltd., epoxy equivalent 121 [Amine Resin]

Μ136:苯胍胺樹脂日本CYTEC INDUSTRIES (股)公司 製 MYCOATΜ136: phenyl hydrazine resin Japan CYTEC INDUSTRIES (shares) company MYCOAT

[分子結構中不含氯原子及溴原子之藍色顏料] P.B.15.3.C. Y.顏料皇15:3銅欧花青β型敝化青藍 G(NC)於雷射繞射/散射式粒度分布測定之中位徑為I40nm (使用預先添加當做溶劑之BLO、分散劑,以珠磨機分 散者。) [分子結構中不含氯原子及溴原子之黃色顏料][Blue pigment containing no chlorine atom and bromine atom in molecular structure] PB15.3.CY Pigment 15:3 Copper Ou Huaqing β-type sputum blue G (NC) in laser diffraction/scattering particle size distribution measurement The median diameter is I40nm (using BLO, a dispersant that is pre-added as a solvent, and dispersing it in a bead mill.) [Yellow pigment containing no chlorine or bromine atoms in the molecular structure]

P.Y.180:C.Y.顏料黃180 縮合偶氮 Novoperm黃 P-HG 雷射繞射/散射式粒度分布測定的中位徑為470nm (使用預先添加當做溶劑之BLO、分散劑,以珠磨機分 散者。) P.Y.154:C.Y·顏料黃 154 苯并咪唾酮(Benzimidazolone) 苯并咪唑酮(B enzimidazolone)黃H3 G於雷射繞射/散射式 粒度分布測定之中位徑為320nm 49 201230908 (使用預先添加當做溶劑之BLO、分散劑,以珠磨機分 散者。) [分子結構中不含氯原子及溴原子之體質顏料] RW.21:C.Y.顏料白21沉降性硫酸鋇BARIFINE B-54於雷射繞射/散射式粒度分布測定之中位徑為64〇nm [填料]PY180: CY Pigment Yellow 180 Condensed Azo Novoperm Yellow P-HG Laser diffraction/scattering particle size distribution has a median diameter of 470 nm (using a BLO, a dispersant previously added as a solvent, and a bead mill disperser). PY154: CY·Pigment Yellow 154 Benimidazolone Benzimidazolone Yellow H3 G The laser has a 320mm diameter in the laser diffraction/scattering particle size distribution. Add BLO as a solvent, dispersant, and disperse in a bead mill.) [External pigments containing no chlorine and bromine atoms in the molecular structure] RW.21: CY Pigment White 21 Settling Barium Sulfate BARIFINE B-54 The diffraction diameter of the diffraction/scattering particle size distribution is 64 〇nm [filler]

Aerosil 50:二氧化矽日本Aerosil公司製平均一次粒 徑 30nmAerosil 50: cerium oxide Japan Aerosil Corporation average primary particle diameter 30nm

Art Pearl J-4PY:壓克力珠粒根上(股)公司於雷射 繞射/散射式粒度分布測定之中位徑為2.2μιη [其他添加劑] FA600:氟變性聚矽氧烷信越化學工業(股)公司製Art Pearl J-4PY: Acrylic Beads on the Radar Diffraction/Scattering Particle Size Distribution Determination of 2.2μηη [Other Additives] FA600: Fluorine-denatured Polyoxane Shin-Etsu Chemical Industry ( Company system

P410EF··聚乙烯基類化合物楠本化成工業(股)公司製 DISPARON HF-1:酚樹脂明和化成(股)公司製 [醯亞胺寡聚物二醇溶液之製造]P410EF··Polyvinyl compound, manufactured by Nanben Chemical Co., Ltd. DISPARON HF-1: phenol resin Minghe Chemical Co., Ltd. [Manufacture of yttrium oligodiol solution]

於配備氮氣導入管、Dean-Stark接受器、冷卻管之容量 5公升的玻璃製可分離燒瓶中,添加2,3,3,,4,-聯苯四羧酸二 酐1471g、乙醇5〇7g及γ-丁内酯2092g,於氮氣氛圍下於90°C 授拌1小時。其次’添加3_胺基丙醇376g、異佛爾酮二胺· 426g ’於氮氣氛圍下於U(rc加熱2小時、於i8(rc加熱2 卞,’並將由於醯亞胺化反應產生的水藉由對於反應液吹入 氮氣而去除。該醯亞胺寡聚物二醇溶液的固體成分為52 3%。 [參考例B1][變性聚胺甲酸酯樹脂(PU-B1)之製造] 於配備授拌機、溫度計、氮氣導入管之玻璃製反應容器 中’添加聚碳酸酯二醇ETERNACOLL UH-200 60_0g、溶 劑γ- 丁内酯(BLO) 170.5g、含羧基之二醇 Bis-MPA 1〇.ig、於前述製造方法合成之醯亞胺寡聚物二醇溶液 48.0g ’ 於 9〇°c 溶解後,添加 Desm〇dur w 33 7g。於 9〇。〇攪 摔1小時後,升溫至11(rc,於黏度成為12〇〜15〇Pa· s之時 ⑧ 50 201230908 點’添加1-戊醇,再於13(rc攪拌2小時趨得固體成分40.5%、 黏度97Pa · s、變性聚胺甲酸酯樹脂固體成分之酸價為 33mgKOH/g之變性聚胺曱酸酯樹脂(FU_B1)溶液。 [參考例B2〜B6][變性聚胺曱酸酯樹脂(pu_B2〜B6)之製造] 使用表B1所示之原料,除此以外與參考例B1同樣進 行,獲得變性聚胺甲酸酯樹脂(PU-B2〜B6)溶液。表B1顯示 固體成分、黏度、變性聚胺曱酸酯固體成分之酸價。 [參考例B 7][變性聚胺曱酸酯樹脂(pu-B 7)之製造] 於配備攪拌機、溫度計、氮氣導入管之玻璃製反應容器 中,添加 KuraraypolyolC-1065N 83.90g &gt; DMBA 15.85g、 二乙二醇乙醚乙酸酯150.15g,於90°C攪拌1小時。之後冷 卻至70°C後’添加Desmodur W 52.5g,並擾拌1小時後,於 80 C擾拌1小時’於100°C擾拌2小時。獲得固體成分50.5%、 黏度151Pa· s、變性聚胺曱酸酯樹脂固體成分之酸價為 41mgKOH/g之變性聚胺甲酸酯樹脂(PU-B7)溶液。 [實施例B1][組成物之製備、及硬化膜] 於參考例B1獲得之(A)變性聚胺曱酸酯樹脂(PU_B1)溶 液中’相對於樹脂固體成分100質量份添加表記載之/硬 化性樹脂及其他添加劑,均勻擾拌•混合。其次,添加顏料、 填料並混合後’使用3輥混練。以γ-丁内酯稀釋使組成物之 黏度為20〜60Pa · s,獲得變性聚胺曱酸酯樹脂組成物。 針對該變性聚胺甲酸酯樹脂組成物之硬化膜,評價谭料 耐熱性、低翹曲性、彎曲性、無黏性、外觀觀察、對二^風 式自動檢查裝置之對應、底層填充密合性(剝離樣式)、無^ 素。該等評價結果如表B2。 工、…' [實施例B2〜B12、比較例B1〜B2][組成物之製備、及硬化 依照表B2之記載摻合,除此以外與實施例Bl同费·1 行’獲得變性聚胺曱酸酯樹脂組成物。針對該變性聚胺K甲酸 酯樹脂硬化性組成物之硬化膜,與實施例Β1同樣價#。兮&amp; 等之結果如表B2。 °貝〇Λ 51 201230908 1 PU-B7 1 | 52.5 | 83.9 15.9 r-H 50.5 T—Μ 1 PU-B6 | 28.6 | | 60.0 1 Li〇j__1 48.0 τ-Η 40.3 芝 PU-B5 30.0 | 60.0 1 〇ό 48.0 &lt;N 00 40.1 00 CN PU-B4 丨31.9 | 60.0 1 lo.i 1 36.0 126 40.7 &lt;η CO PU-A3 | 26.2 | 60.0 | ο vd 48.0 132 40.5 CN CN PU-B2 | 30.0 60.0 ο 〇〇 48.0 140 40.2 PU-B1 | 33.7 60.0 10.1 48.0 ON 40.5 cn m 奄 am 键 B- 绪 二異氰酸酯化合物(al) HMDI IPDI Ί 遛 UH-200 C-1065N 具羧基之二羥基化合物(a3) Bis-MPA DMBA ν_^ 姨 荽 楚 •Κ- *ΠΤΝ 醯亞胺寡聚物二醇溶液A _ cd P-l, ♦1 φ 韜 画 酸價(mgKOH/g) 原料之化學組成(g) 特性 ⑧ 201230908 【s &lt;〕 比較例 B2 100 卜 〇\ τί· 〇 寸 〇 s cn ΚΓ&gt; &lt;Ν 〇 ◎ 〇 X 〇 1 t ◎ 比較例 B1 100 卜 〇\ xr 〇 ο ο &lt;s ο cn (Ν 〇 ◎ 〇 ◎ X X 1 ◎ 實施例 B12 100 卜 &lt;N Os τί* ο 寸 ο 100 ο cn CS 〇 〇 〇 ◎ 〇 1 1 ◎ 實施例 B11 100 Ο ο 寸 ο ο s m V-) CN 〇 ◎ 〇 ◎ 〇 1 1 ◎ 實施例 B10 1〇〇 ! 〇\ 寸 ο 呀 ο ο .\〇 s ro f-H m 〇i O ◎ 〇 ◎ 〇 1 &lt;1 ◎ 實施例 B9 100 勺· 00 rf Ο ττ ο S s m V) cs 〇 ◎ 〇 ◎ 〇 1 ◎ ◎ 實施例 B8 100 1 〇〇 &lt;N Ό ο 寸 ο ο Ό o cs •n cs 〇 ◎ 〇 ◎ 〇 1 ◎ ◎ 實施例 B7 〇 〇 r〇 00 τΤ ο 寸 ό § s m 的 (N o ◎ 〇 ◎ 〇 ! ◎ ◎ 實施例 B6 〇 CS (N m 寸 ο 寸 ο S s m *r&gt; 〇 ◎ 〇 ◎ 〇 1 ◎ ◎ 實施例 B5 〇 〇 〇\ ο 寸 ο ο o vn fS 〇 ◎ 〇 〇 〇 1 ◎ ◎ 實施例 B4 100 r- fS ο 寸 ο ο \〇 o &lt;N m νΊ 〇 ◎ 〇 ◎ 〇 1 ◎ ◎ 實施例 B3 100 r- (N 寸 ο 寸· ο ο ν〇 o N m VI cs 〇 ◎ 〇 ◎ 〇 1 ◎ ◎ 實施例 B2 100 卜 &lt;N 〇 寸 ο 寸 ο S o cs CO (N 〇 ◎ 〇 ◎ 〇 〇 ◎ ◎ 實施例 B1 100 ro CN 对 ο 寸 ο S m oi 〇 ◎ 〇 ◎ 〇 〇 ◎ 變性胺甲酸酯樹脂硬化性組成物之摻合(質量 份) PU-B1 PU-B2 PU-B3 PU-B4 PU-B5 PU-B6 PU-B7 I 5 K o 旦 5 溫 ±1 m YH434 M136 Ρ.Β.15:3 Ρ.Υ. 180 Ρ.Υ. 154 P.W. 21 Aerosil 50 J-4PY FA600 P410EF d, P: 焊料耐熱性 低组曲性 彎曲性 無黏性 外觀觀察 對於光學式自動外觀檢查裝 置的對應 與底層填料的密合性(剝離樣 式) 無鹵素 參考例B1 參考例B2 參考例B3 參考例B4 參考例B5 參考例B6 參考例B7 環氧樹脂 胺基樹脂 藍色顏料 黃色顏料 體質顏料 二氧化矽 丙烯酸填料 氟變性聚矽氧 烷 聚乙烯基類化 合物 酚樹脂 (B)變性胺甲酸 酯樹脂 (C)熱硬化性樹 (Α)顏料 (D)填料 (E)其他添加劑 評價結果 53 201230908 [產業利用性] 法,其能之製造方 低龜曲性、健性、耐藥。^'緣性、撓性、低硬化收縮性、 充材之黏著罐生等耐舰、與底層填 將如短邊長奴縣之各雜降低,而可 件,牢固地安裝在輸送膠帶^1^\半導體晶片般的電子零 接端子部分,使具㈣的剝離^用撓性電路板之電路圖案之連 電路不=使仏;^ 之輸_帶封裝體用撓裝置檢查所製造 ;色之顏料係不含氯原子及漠原子二其 檢查效率降低而能減低檢查不良率。 可抑制误檢測所致 【圖式簡單說明】 【主要元件符號說明】2,3,3,4,4-biphenyltetracarboxylic dianhydride 1471 g, ethanol 5〇7 g were added to a glass separable flask equipped with a nitrogen gas introduction tube, a Dean-Stark receiver, and a cooling tube with a capacity of 5 liters. 2092 g of γ-butyrolactone was stirred at 90 ° C for 1 hour under a nitrogen atmosphere. Next, 'add 3_aminopropanol 376g, isophoronediamine·426g' in U (rc heating for 2 hours, i8 (rc heating 2 卞, ' and will be produced by hydrazine imidization reaction) The water was removed by blowing nitrogen gas into the reaction solution. The solid content of the quinone imine oligomer diol solution was 52 3%. [Reference Example B1] [Denaturing Polyurethane Resin (PU-B1) Manufacture] Adding polycarbonate diol ETERNACOLL UH-200 60_0g, solvent γ-butyrolactone (BLO) 170.5g, carboxyl group-containing diol Bis in a glass reaction vessel equipped with a mixer, thermometer, and nitrogen inlet tube -MPA 1 〇.ig, 48.0 g of the quinone imine oligomer diol solution synthesized in the above production method was dissolved at 9 ° C, and then Desm〇dur w 33 7 g was added. At 9 〇. After that, the temperature was raised to 11 (rc, when the viscosity became 12〇15〇Pa·s, 8 50 201230908 points, '1-pentanol was added, and then 13 (rc was stirred for 2 hours, the solid content was 40.5%, and the viscosity was 97 Pa. s, a denatured polyamine phthalate resin (FU_B1) solution having a solid content of a denatured polyurethane resin having an acid value of 33 mgKOH/g [Reference Example B2 to B6] [Deformation The production of the aminic phthalate resin (PU_B2 to B6) was carried out in the same manner as in Reference Example B1 except that the raw materials shown in Table B1 were used, and a denatured polyurethane resin (PU-B2 to B6) solution was obtained. The solid content, viscosity, and acid value of the denatured polyamine phthalate solid component are shown. [Reference Example B 7] [Manufacture of denatured polyamine phthalate resin (pu-B 7)] equipped with a stirrer, a thermometer, a nitrogen introduction tube In a glass reaction vessel, Kuraraypolyol C-1065N 83.90 g &gt; DMBA 15.85 g, and diethylene glycol diethyl ether acetate 150.15 g were added, and the mixture was stirred at 90 ° C for 1 hour, and then cooled to 70 ° C after adding 'Desmodur W 52.5 g, and after 1 hour of scramble, mix at 80 C for 1 hour and stir at 2 °C for 2 hours. Obtain a solid content of 50.5%, a viscosity of 151 Pa·s, and the acid value of the solid content of the denatured polyamine phthalate resin is 41 mg KOH/g of denatured polyurethane resin (PU-B7) solution [Example B1] [Preparation of composition, and cured film] (A) Denatured polyamine phthalate resin obtained in Reference Example B1 ( In the PU_B1) solution, 'the curable resin and other additives described in the table are added to 100 parts by mass of the resin solid content, After the addition of the pigment, the filler, and the mixing, the mixture is mixed using a 3-roller. The viscosity of the composition is 20 to 60 Pa·s by diluting with γ-butyrolactone to obtain a denatured polyamine phthalate resin composition. . For the cured film of the denatured polyurethane resin composition, evaluation of heat resistance, low warpage, bending property, non-stick property, appearance observation, correspondence of the two-wind automatic inspection device, and underfill filling Synthetic (peeling style), no substance. The results of these evaluations are shown in Table B2. [Examples B2 to B12, Comparative Examples B1 to B2] [Preparation and hardening of the composition were carried out in accordance with the description of Table B2, except that the same procedure as in Example B1 was carried out. A phthalate resin composition. The cured film of the denatured composition of the denatured polyamine K-formate resin was the same as that of Example #1. The results of 兮 & etc. are shown in Table B2. °贝〇Λ 51 201230908 1 PU-B7 1 | 52.5 | 83.9 15.9 rH 50.5 T—Μ 1 PU-B6 | 28.6 | | 60.0 1 Li〇j__1 48.0 τ-Η 40.3 芝 PU-B5 30.0 | 60.0 1 〇ό 48.0 &lt;N 00 40.1 00 CN PU-B4 丨31.9 | 60.0 1 lo.i 1 36.0 126 40.7 &lt;η CO PU-A3 | 26.2 | 60.0 | ο vd 48.0 132 40.5 CN CN PU-B2 | 30.0 60.0 ο 〇〇 48.0 140 40.2 PU-B1 | 33.7 60.0 10.1 48.0 ON 40.5 cn m 奄am key B- diisocyanate compound (al) HMDI IPDI Ί 遛UH-200 C-1065N Dihydroxy compound with carboxyl group (a3) Bis-MPA DMBA Ν_^ 姨荽楚•Κ- *ΠΤΝ 醯imino oligomer diol solution A _ cd Pl, ♦1 φ 韬 酸 acid value (mgKOH / g) chemical composition of raw materials (g) characteristics 8 201230908 [s &lt; 〕Comparative example B2 100 〇 〇 〇 〇 〇 〇 & & & & B 〇 〇 〇 〇 t B B B B B B B B B B B B B B B B B B B B B B B B 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 XX 1 ◎ Example B12 100 卜&lt;N Os τί* ο inchο 100 ο cn CS 〇〇 ◎ 〇 1 1 ◎ Example B11 100 Ο ο ο ο s sm V-) CN 〇 ◎ 〇 ◎ 〇 1 1 ◎ Example B10 1 〇〇! 〇 ο ο ο 〇 ro ro ro ro ro ro ro ro ro ro ro ro ro ro ro O ◎ 〇 ◎ 〇 1 &lt; 1 ◎ Example B9 100 scoops · 00 rf Ο ττ ο S sm V) cs 〇 ◎ 〇 ◎ 〇 1 ◎ ◎ Example B8 100 1 〇〇 &lt;N Ό ο ο ο ο Ό o cs • n cs 〇 ◎ 〇 ◎ 〇 1 ◎ ◎ Example B7 〇〇r〇00 τΤ ο ό § sm (N o ◎ 〇 ◎ 〇! ◎ ◎ Example B6 〇 CS (N m inch ο inch ο S sm *r&gt; 〇 ◎ 〇 ◎ 〇 1 ◎ ◎ Example B5 〇〇〇 ο 寸 ο ο o vn fS 〇 ◎ 〇〇〇 1 ◎ ◎ Example B4 100 r- fS ο inch ο ο \〇o &lt N m ν Ί 〇 ◎ 〇 ◎ 〇 1 ◎ ◎ Example B3 100 r- (N inch ο inch · ο ο ν〇o N m VI cs 〇 ◎ 〇 ◎ 〇 1 ◎ ◎ Example B2 100 卜 &lt; N 〇 Inch ο ο S o cs CO (N 〇 ◎ 〇 ◎ 〇〇 ◎ Example B1 100 ro CN vs. ο ο S m oi 〇 ◎ 〇 ◎ ◎ ◎ Deformation of the sclerosing urethane resin hardening composition (parts by mass) PU-B1 PU-B2 PU-B3 PU-B4 PU -B5 PU-B6 PU-B7 I 5 K o Dan 5 Temperature ±1 m YH434 M136 Ρ.Β.15:3 Ρ.Υ. 180 Ρ.Υ. 154 PW 21 Aerosil 50 J-4PY FA600 P410EF d, P: Solder heat resistance low composition bending flexibility non-adhesive appearance observation Correspondence to the underfill of the optical automatic visual inspection device (peeling pattern) Halogen-free reference example B1 Reference example B2 Reference example B3 Reference example B4 Reference example B5 Reference Example B6 Reference Example B7 Epoxy Resin Amine Resin Blue Pigment Yellow Pigment Body Pigment Ceria Acrylate Filler Fluorine Modified Polyoxane Polyvinyl Compound Phenol Resin (B) Denatured Urethane Resin (C) Heat Curing tree (Α) pigment (D) filler (E) Evaluation results of other additives 53 201230908 [Industrial use] method, which can produce low tortuosity, robustness, and resistance. ^ 'Boundary, flexible, low-hardening shrinkage, filling the tank and other resistant ships, and the bottom layer will be reduced as the short side of the long slave county, and can be securely installed on the conveyor tape ^1 ^\Semiconductor wafer-like electronic zero-connect terminal part, so that the circuit of the strip circuit with the flexible circuit board is not used for the wiring of the circuit board of the flexible circuit board; The pigment is free of chlorine atoms and desert atoms. The inspection efficiency is lowered and the inspection failure rate can be reduced. Can suppress false detection [Simplified illustration] [Main component symbol description]

Claims (1)

201230908 七、申清專利範圍: 1. 一種輸送膠帶封裝體之製造方法, 其特徵為: 包含以下步驟: 準備在絕緣膜上具有導電性金屬形成之電路圖案的撓性電路 後加======叙贿臥絲材,且之 該變性聚胺甲酸酯樹脂組成物包含 4〇mgK〇H/g之變性聚胺甲酸醋樹脂⑷;及硬化為Μ〜 2.如申請專利細第丨項之輸娜帶縣體之製造方法, 該變性聚胺甲義旨樹驗成物進行加熱處理轉之硬化膜、,告读 潰於環氧樹脂時之尺寸變化率為6〇%以下。 田义 3.如申請專利範圍第1或2項之輸送膠帶封裝體之製造方法,其 中^攸將5亥逢性1月女曱酸醋樹脂組成物進行加熱處理而得之硬 化膜剝離已硬化之底層填充材時,至少部分硬化膜會發生内聚破 壞。 4.如申請專利範圍第1至3項中任一項之輸送膠帶封裝體之製造方 法’其中’該變性聚胺曱酸酯樹脂組成物包含酸價為l6〜4〇mgKO H/g之變性聚胺曱酸g旨樹脂(A)及硬化性樹脂⑻;該變性聚胺曱酸 酯樹脂(A)係至少將二異氰酸酯化合物(al)與含聚碳酸酯二醇或聚 丁一細一醇之多元醇化合物(a2)及具缓基之二經基化合物(a3)反應 而獲得。. .55 201230908 5.如^請專利範圍第4項之輸送勝帶封褒體之製造方法,詨 -異亂酸酯化合物(al)健脂環結構之二異㈣自旨化合物,。、^ ^如2專利細第丨至5項巾任—項之輸送膠 ί性胺甲^樹脂⑷係在主鏈中具有醯亞胺環之 7木如專難圍第1至6項中任—項之輪送膠帶封裝體之f造方 :匕其中’該硬化性樹脂⑼係選自於由環氧樹脂、 仏化之多官能異氰酸酯、1酸酯樹脂構成的群組中工土種以曰上] 種變性聚胺甲酸酯樹脂組成物,其 16,_g之_料_脂⑷,^=旨 項之變性謝酸輸§_,其係使用 在文指敍度為Umnm下之好料的輸郷帶封裝體。 種輸送科職體職性板之製造方法,係包含以下步 板;準備在絕緣膜上具有導電性金屬形成之電路圖案之撓性電路 置檢查獲什之㈣膠讀裝體甩撓性電路板以光學式自動檢查裝 其特徵在於: ㈧至峨綱⑷瑜,該顏料 漠原子之顧'仅财麵㈣财錢原子及 56 201230908 U j請 =細第1G項之輸送舞體雌性電路板之!y 及漠原子之藍色顏綱、及不含氯= 12ΐΓ=咖第11項之輸_帶龍體職性電路板之製 二'中,该不含祕子及漠原子之體f顏料⑻之中位徑為 Οηη^ Ι,不含錢子及顧子之藍色 = 55=:=:不含氯原子及謝之黃色顏綱之中位^ 第// 3項巾—項之輸送釋細用撓性 j板之錢方法’其中鍵化性絕緣顧樹驗成物包 性聚胺甲自―旨樹脂(B) ’該變性聚胺曱酸自旨_旨⑻係將至少二 酸醋化合物(bl)與含聚碳酸醋二醇或聚丁二稀二醇之多元醇化人 物(b2)與含羧基之二醇化合物¢3)反應而獲得。 ° 14.如申請專難圍第13項之輸送膠帶封裝體賴性電路板之製 ^方法’其中’該不含氯原子及溴、原子之體f顏料⑻為硫酸鎖, 该硬化性轉顧麟喊物巾,相對於聚胺f_樹脂 分1〇°質量份’含有不含氯原子及演原子之體質顏料⑻)」 貝夏份以上。 15·ί、申請專利範_ 13气M項之輸送膠帶封裝體麟性電路板 ^製造方法’其中,該二異氰酸目旨化合物㈣倍、具脂環結構之二異 氰酸醋化合物。 16.如申請專利範圍第13至15項中任一項之輪送膠帶封裝體用換 性電路板之製造方法,其中,該變性聚胺曱酸酯樹脂(B)於主鏈中 57 9 201230908 具醯亞胺環結構。 1G至16項中任—項之輸送膠帶封裝體用挽 !·生電路板之t造方法,其巾,該齡電路板具有含電路 15μιη以下之部分的電路圖案。 18·—種輸送膠帶封裝體用撓性電路板用之硬化性絕緣膜用樹脂組 成物’其特徵為:包含顏料(Α)與變性聚胺甲酸酯樹脂(Β)而著色;、、 該顏料(Α)至少包含不含氣原子及溴原子之體質顏料盘 含氯原子及溴原子之顏料(a2); 該變性聚胺甲酸酯樹脂(B)係至少將二異氰酸酯化合物(b 含聚碳酸酯二醇或聚丁二烯二醇之多元醇化合物(b2)及含羧美^ 二醇化合物(b3)反應而獲得。 土 19.如申請專利範圍第18項之輸送膠帶封裝體用撓性電路板用之 硬化性絕緣膜用樹脂組成物’係包含顏料(A)而著色為綠色·該 (A)包含不含氯原子及溴原子之體質顏料(al)、不含氣原子及^原 子之藍色顏料(a3)、及不含氯原子及溴原子之黃色顏料(a4)。、” 58 m m 广(S&gt;201230908 VII. Shenqing Patent Range: 1. A manufacturing method of a conveyor tape package, comprising: the following steps: preparing a flexible circuit having a circuit pattern formed of a conductive metal on an insulating film, and then adding ==== == 〗 〖Blind silk, and the denatured polyurethane resin composition contains 4 〇 mg K 〇 H / g of denatured polyurethane urethane resin (4); and hardened to Μ ~ 2. As applied for fine 丨The method for producing the genus of the genus of the genus of the genus, the denatured polyamine, the sap of the sapphire, and the cured film which is subjected to heat treatment, and the dimensional change rate when the epoxy resin is smashed is 6 〇% or less. The method for manufacturing a transport tape package according to claim 1 or 2, wherein the hardened film peeling hardened by heat-treating the composition of the 5 亥 性 1 曱 曱 曱 曱 树脂 resin At least a portion of the cured film undergoes cohesive failure when the underfill is applied. 4. The method for producing a transfer tape package according to any one of claims 1 to 3, wherein the denatured polyamine phthalate resin composition comprises a denaturation of an acid value of from 16 to 4 〇 mg KO H/g. Polyamine niobic acid g resin (A) and curable resin (8); the denatured polyamine phthalate resin (A) is at least a diisocyanate compound (al) and a polycarbonate-containing diol or polybutanol The polyol compound (a2) and the dibasic compound (a3) having a slow group are obtained by a reaction. .55 201230908 5. The manufacturing method of the conveyor belt sealing body of the fourth paragraph of the patent scope, 詨 - the heterogeneous acid ester compound (al), the alicyclic structure of the alicyclic ring (4). ^ ^ ^ 2 专利 专利 专利 专利 专利 专利 专利 专利 专利 专利 专利 专利 专利 专利 专利 专利 专利 专利 专利 专利 专利 专利 专利 专利 专利 专利 专利 专利 专利 专利 专利 专利 专利 专利 专利 专利 专利 专利 专利 专利 专利 专利 专利 专利 专利 专利 专利 专利 专利 专利- The product of the wheel-feeding tape package: 匕 where the hardening resin (9) is selected from the group consisting of epoxy resin, polyfunctional isocyanate, and acid ester resin.曰上] A kind of denatured polyurethane resin composition, which is 16, _g___(4), ^= denaturing decanoic acid § _, which is used in the text of the Umnm The material of the belt is packaged. The manufacturing method of the transportation body occupational board includes the following step board; the flexible circuit for preparing the circuit pattern formed of the conductive metal on the insulating film is inspected and obtained (4) the plastic reading body 甩 flexible circuit board The optical automatic inspection device is characterized by: (8) to the 峨 ( (4) Yu, the pigment indifferent to the atom 'only financial face (four) financial atom and 56 201230908 U j please = fine 1G item of the dance body female circuit board ! y and the blue atom of the desert atom, and the chlorine-free = 12 ΐΓ = the eleventh item of the _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ The median diameter is Οηη^ Ι, without the money and the blue of the child = 55=:=: does not contain the chlorine atom and the yellow of the Xie, the middle of the ^ ^ / / 3 items of the towel - the delivery of the item The method of finely using the flexible j-board method, in which the bonding property is inspected by the tree-like polyaluminium-based resin (B), the denatured polyamine tannic acid is intended to be at least two acid vinegar. The compound (b1) is obtained by reacting a polyolized person (b2) containing a polycarbonate or a polybutylene glycol with a carboxyl group-containing diol compound (3). ° 14. For the application of the special method of the 13th article of the transmission tape package circuit board method ^ which 'the chlorine atom and bromine, atomic body f pigment (8) is sulfuric acid lock, the hardening turn Lin shouts a towel, which is divided into 1 part by mass with respect to the polyamine f_resin, and contains a body pigment (8) which does not contain a chlorine atom and an atom. 15. ί, 专利 专利 专利 专利 专利 专利 专利 专利 专利 专利 专利 专利 专利 专利 专利 专利 专利 专利 专利 专利 专利 专利 专利 专利 专利 专利 专利 专利 专利 专利 专利 专利 专利 专利 专利 专利 专利 专利 专利 专利 专利 专利 专利 专利 专利 专利 专利 专利The method for producing a flexible circuit board for a tape transfer package according to any one of claims 13 to 15, wherein the denatured polyamine phthalate resin (B) is in the main chain 57 9 201230908 It has a quinone ring structure. The transport tape package of any one of the items 1 to 16 is a method for manufacturing a circuit board, and the circuit board of the same age has a circuit pattern including a portion of a circuit of 15 μm or less. a resin composition for a curable insulating film for a flexible wiring board for a transport tape package, characterized in that it comprises a pigment (Α) and a denatured polyurethane resin (著) and is colored; The pigment (Α) contains at least a pigment (a2) containing a chlorine atom and a bromine atom in an organic pigment disk containing no gas atom and a bromine atom; the denatured polyurethane resin (B) is at least a diisocyanate compound (b contains poly A polyol compound (b2) of a carbonate diol or a polybutadiene diol and a carboxy-containing diol compound (b3) are obtained by reacting. 19. The transfer tape package of claim 18 is scratched. The resin composition for a curable insulating film for a circuit board contains a pigment (A) and is colored green. (A) contains an extender (al) containing no chlorine atom and a bromine atom, and contains no gas atom and ^ Atomic blue pigment (a3), and yellow pigment (a4) containing no chlorine or bromine atoms.," 58 mm wide (S&gt;
TW100135535A 2010-09-30 2011-09-30 Method for producing tape carrier package and method for producing flexible circuit board for tape carrier package TW201230908A (en)

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JP5841570B2 (en) * 2012-10-19 2016-01-13 太陽インキ製造株式会社 Curable resin composition, curable resin composition for forming solder resist, cured coating film and printed wiring board
JP6769425B2 (en) * 2017-11-21 2020-10-14 三菱マテリアル株式会社 Manufacturing method of resin for forming insulating film, varnish, electrodeposition liquid, insulating conductor

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JP4523679B2 (en) * 1998-06-22 2010-08-11 太陽インキ製造株式会社 Green resist ink composition for printed wiring board using halogen-free color pigment
JP3821426B2 (en) * 2000-08-31 2006-09-13 三井金属鉱業株式会社 Electronic component mounting board
JP2009088375A (en) * 2007-10-02 2009-04-23 Nippon Avionics Co Ltd Tape carrier holding device
US8674017B2 (en) * 2009-01-20 2014-03-18 Showa Denko K.K. (Poly)carbonate polyol and carboxyl group-containing polyurethane obtained from the (poly)carbonate polyol

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