TW201207059A - Resin composition for adhesive agent, adhesive agent containing thereof, adhesive sheet and printed wire board containing the same as adhesive layer - Google Patents

Resin composition for adhesive agent, adhesive agent containing thereof, adhesive sheet and printed wire board containing the same as adhesive layer Download PDF

Info

Publication number
TW201207059A
TW201207059A TW100112720A TW100112720A TW201207059A TW 201207059 A TW201207059 A TW 201207059A TW 100112720 A TW100112720 A TW 100112720A TW 100112720 A TW100112720 A TW 100112720A TW 201207059 A TW201207059 A TW 201207059A
Authority
TW
Taiwan
Prior art keywords
resin
mass
thermoplastic resin
adhesive
parts
Prior art date
Application number
TW100112720A
Other languages
Chinese (zh)
Other versions
TWI487762B (en
Inventor
Shintaro Nanbara
Hiroko Asada
Takeshi Ito
Original Assignee
Toyo Boseki
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Toyo Boseki filed Critical Toyo Boseki
Publication of TW201207059A publication Critical patent/TW201207059A/en
Application granted granted Critical
Publication of TWI487762B publication Critical patent/TWI487762B/en

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/0804—Manufacture of polymers containing ionic or ionogenic groups
    • C08G18/0819—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups
    • C08G18/0823—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups containing carboxylate salt groups or groups forming them
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
    • C08G18/6633—Compounds of group C08G18/42
    • C08G18/6659—Compounds of group C08G18/42 with compounds of group C08G18/34
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
    • C08G59/32—Epoxy compounds containing three or more epoxy groups
    • C08G59/3218—Carbocyclic compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J167/00—Adhesives based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Adhesives based on derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
    • C09J175/04—Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/38—Improvement of the adhesion between the insulating substrate and the metal
    • H05K3/386—Improvement of the adhesion between the insulating substrate and the metal by the use of an organic polymeric bonding layer, e.g. adhesive
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
    • C08K3/013—Fillers, pigments or reinforcing additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
    • C08L2666/02—Organic macromolecular compounds, natural resins, waxes or and bituminous materials
    • C08L2666/14—Macromolecular compounds according to C08L59/00 - C08L87/00; Derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • C08L63/08—Epoxidised polymerised polyenes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
    • C08L75/04—Polyurethanes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/0001—Technical content checked by a classifier
    • H01L2924/0002—Not covered by any one of groups H01L24/00, H01L24/00 and H01L2224/00
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
    • H05K2201/01—Dielectrics
    • H05K2201/0104—Properties and characteristics in general
    • H05K2201/0129—Thermoplastic polymer, e.g. auto-adhesive layer; Shaping of thermoplastic polymer
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
    • H05K2201/01—Dielectrics
    • H05K2201/0137—Materials
    • H05K2201/0154—Polyimide
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
    • H05K2201/02—Fillers; Particles; Fibers; Reinforcement materials
    • H05K2201/0203—Fillers and particles
    • H05K2201/0206—Materials
    • H05K2201/0209—Inorganic, non-metallic particles

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Manufacturing & Machinery (AREA)
  • Health & Medical Sciences (AREA)
  • Polymers & Plastics (AREA)
  • Medicinal Chemistry (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Laminated Bodies (AREA)
  • Adhesive Tapes (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

The present invention is a resin composition for adhesive agent, which contains thermoplastic resin (A1), thermoplastic resin (A2), inorganic filling material (B), epoxy resin having dicyclopentadiene backbone (D), wherein the thermoplastic resin (A1) is consisting of polyester resin or polyurethane resin, acid value (unit: eq/10<SP>6</SP>g) is not less than 100 and not more than 1000, glass transition temperature is not lower than 30 DEG C and not higher than 80 DEG C, number average molecular weight is not less than 5.0*10<SP>3</SP> and not more than 1.0*10<SP>5</SP>, the thermoplastic resin (A2) is consisting of polyester resin or polyurethane resin, glass transition temperature is lower than 0 DEG C, number average molecular weight is not less than 5.0*10<SP>3</SP> and not more than 1.0*10<SP>5</SP>, as well as in a cured coating film obtained from drying for 3 minutes at 130 DEG C and subsequently performing heat treatment for 4 hours at 140 DEG C, it is the least that at least a part of a thermoplastic resin (A1) and a thermoplastic resin (A2) adopts phase separated structure.

Description

201207059 相對於該等之課題，在例如特開平11- 1 1 693 0號公報（ 專利文獻1)、特開2008 -2 0 5 3 7 0號公報（專利文獻2)、特開 2007-204715號公報（專利文獻3)等提案有以特定的聚酯·聚 胺甲酸酯與環氧樹脂作爲主成分之黏著劑用樹脂組成物。 然而’示於專利文獻1之組成物雖可提升薄片壽命、在高 溫下及高濕度下之黏著性，但並非充分地滿足在更高溫下 之黏著強度保持力、將SUS等各種金屬用於加強板時之耐 加濕焊接性者。此外，示於專利文獻2之組成物雖可提高 在高溫下及高濕度下之黏著性 '將塑膠薄膜用於加強板時 之耐加濕焊接性，但並非充分地滿足將金屬用於加強板時 之耐加濕焊接性者。此外，示於專利文獻2之組成物係將 黏著性薄片在常溫及40°C、80%加濕環境下保管後之耐加 濕焊接性、黏著性顯著降低者，無法確保穩定的薄片壽命 。此外，在專利文獻3係在提升聚胺甲酸酯樹脂之玻璃轉 移溫度、改善在高溫下之黏著性、薄片壽命上獲得成功。 然而，提升玻璃轉移溫度必然伴隨柔軟性的降低，在撓性 印刷配線板之製造步驟中，有在將黏著性薄片進行裁剪· 打孔時、以及由脫模薄膜剝離時於黏著性薄片產生裂痕、 剝落，並且加工適性降低這樣的缺點。 另一方面，摻合玻璃轉移溫度不同的兩種聚酯樹脂之 黏著劑組成物係被揭示於特開2 0 0 8 - 0 1 9 3 7 5號公報（專利文 獻4)、特開2009-084348號公報（專利文獻5)。該等係藉由 摻合玻璃轉移溫度高之樹脂與玻璃轉移溫度低之樹脂而使 201207059 在室溫下之加工適性改善，但在一般的黏著性薄片之保管 溫度5 °C以下之條件則柔軟性低、並非滿足對於在低溫下 之加工性者。此外’該等係對PET薄膜、錫電鍍銅顯示優 異之黏者性且在抗黏連性（blocking resistance)亦優，尤其 因爲顯示作爲撓性扁平電纜用黏著劑的優異之特性但僅由 熱塑性樹脂所構成’故以撓性印刷配線板用黏著劑而言耐 熱性不足且並非充分滿足耐加濕焊接性者。 [先前技術文獻] [專利文獻] [專利文獻1]日本特開平11-116930號公報 [專利文獻2]日本特開2008-205370號公報 [專利文獻3]日本特開2007-204715號公報 [專利文獻4]日本特開2008-019375號公報 [專利文獻5]日本特開2009-084348號公報 【發明內容】 [發明所欲解決之課醴] 本發明之課題係在於改良該等以往的黏著劑所具有的 各問題點、提供在維持對於各種塑膠薄膜、銅、鋁、不鏽 鋼等金屬 '玻璃環氧樹脂之黏著性的同時亦可對應在高濕 度下之無鉛焊料的高度耐濕熱性、在高溫高濕度下之黏著 性優異、撓性印刷配線板製造時之加工適性優異之黏著劑 ’’進一步係在於提供由前述黏著劑.得到的黏著性薄片即使 在高溫高濕下流通後使用亦可維持良好的黏著特性之薄片 201207059 壽命良好的黏著劑薄片。此外，在於提供包含由前述黏著 劑或黏著性薄片所得之黏著劑層之印刷配線板。 [用於解決課題之手段] 本發明人等爲解決上述課題而致力硏究之結果，達至υ 完成本發明。亦即本發明係由以下構成所成。 本發明之黏著劑用樹脂組成物係含有：由聚酯樹脂或 聚胺甲酸酯樹脂所成且酸價（單位：當量/106g)爲1〇〇以上 1 000以下、玻璃轉移溫度爲30°C以上80°C以下、數量平均 分子量爲5_〇χ103以上Ι.ΟχΙΟ5以下之熱塑性樹脂（A1)，由 聚酯樹脂或聚胺甲酸酯樹脂所成且玻璃轉移溫度爲〇°C以 下、數量平均分子量爲5·〇χ103以上Ι.ΟχΙΟ5以下之熱塑性 樹脂（A2)，無機塡充材料（B)及具有二環戊二烯骨架之環 氧樹脂（D)，且在以130 °C乾燥3分鐘接著在140 °C熱處理4 小時而得之硬化塗膜中，至少前述熱塑性樹脂（A 1 )與前述 熱塑性樹脂（A2)之至少一部分係具有相分離結構。 本發明之黏著劑用樹脂組成物係藉由前述硬化塗膜之 在頻率10Hz、溫度上升速度4°C /分鐘之動態黏彈性的溫度 分散測定，而觀測到來自前述熱塑性樹脂（A 1 )之損失彈性 模數峰部及來自前述熱塑性樹脂（A2)之損失彈性模數峰部 ，且兩峰部之溫度差較佳爲40°C以上。。 本發明之黏著劑用樹脂組成物中，較佳爲前述熱塑性 樹脂（A1)係由聚酯樹脂所成、前述熱塑性樹脂（A2)係由聚 胺甲酸酯樹脂所成、或前述熱塑性樹脂（A 1 )係由聚胺甲酸 酯樹脂所成、前述熱塑性樹脂（A2)係由聚酯樹脂所成。 201207059 本發明之黏著劑用樹脂組成物中，相對於前述熱塑性 樹脂（A 1 )與前述熱塑性樹脂（A 2 )之合計1 〇 〇質量份，較佳 爲含有前述熱塑性樹脂（Al)55質量份以上80質量份以下。 本發明之黏著劑用樹脂組成物中，以前述黏著劑用樹 脂組成物中之含有比率計，由前述熱塑性樹脂（A 1 )、前述 熱塑性樹脂（A2)及無機塡充材料（B)之合計25質量份、甲乙 酮45質量份、甲苯30質量份而合計量爲1〇〇質量份所成之 分散液（α)在液溫2 5 °C之搖變度（T I値）較佳爲3以上6以下。 本發明之黏著劑用樹脂組成物，在將前述熱塑性樹脂 (A1)之酸價（單位：當量/ l〇6g)設爲AV(A1)、摻合量（單位：質 量份）設爲AW(A1)，將前述熱塑性樹脂（A2)之酸價設爲 AV(A2)、摻合量設爲AW(A2)，將前述環氧樹脂（D)之環氧 値（單位：當量/106g)設爲EV(D)、摻合量設爲EW(D)(單位： 質量份）時，較佳爲滿足下述式（1):0.7 $ {EV(D)xEW(D)}/{AV(Al)x AW(Al) + AV(A2)xAW(A2)} ^ 4.0。 本發明亦提供一種複數劑混合型之黏著劑用樹脂組成 物，其中樹脂組成物（β)含有：由聚酯樹脂或聚胺甲酸酯 樹脂所成且酸價（單位：當量/l〇6g)爲100以上1 000以下，玻 璃轉移溫度爲30°c以上8(TC以下，數量平均分子量爲 5.0 XI 03以上1.0 χΙΟ5以下之熱塑性樹脂（A1)，由聚酯樹脂 或聚胺甲酸酯樹脂所成且玻璃轉移溫度爲〇°C以下、數量 平均分子量爲5.〇χ103以上Ι.ΟχΙΟ5以下之熱塑性樹脂（A2) ，無機塡充材料（B)以及有機溶劑（C);樹脂組成物（γ)含有 201207059 環氧樹脂（D);將前述熱塑性樹脂（A1)之酸價（單位：當量 /l〇6g)設爲AV(A1)、摻合量（單位：質量份）設爲AW(A1)， 將前述熱塑性樹脂（A2)之酸價設爲AV(A2) '摻合量設爲 AW(A2)，將前述環氧樹脂（D)之環氧値（單位：當量/106g)設 爲EV(D)、摻合量設爲EW(D)(單位：質量份）時，以滿足下 述式（1):0.7 5 {EV(D)xEW(D)}/{AV(A1)xAW(A1) + AV(A2)x AW(A2)} S 4.0之摻合比摻合樹脂組成物（β)與樹目旨組成物 (γ) 〇 本發明又亦提供一種複數劑混合型之黏著劑用樹脂組 成物，其中樹脂組成物（δ)含有：由聚酯樹脂或聚胺甲酸 酯樹脂所成且酸價（單位：當量/106g)爲100以上1000以下、 玻璃轉移溫度爲3 0 °c以上8 0 °C以下、數量平均分子量爲 5.0xl03以上l.OxlO5以下之熱塑性樹脂（A1)，無機塡充材 料（B)以及有機溶劑（C);樹脂組成物（ε)含有：由聚酯樹脂 或聚胺甲酸酯樹脂所成且玻璃轉移溫度爲以下、數量 平均分子量爲5.0 χΙΟ3以上1.0 xlO5以下之熱塑性樹脂（A2) ’無機塡充材料（Β)以及有機溶劑（C);樹脂組成物（ζ)含有 環氧樹脂（D);將前述熱塑性樹脂（Α1)之酸價（單位：當量 /l〇6g)設爲AV(A1)、摻合量（單位：質量份）設爲AW(A1)， 將前述熱塑性樹脂（A2)之酸價設爲AV(A2)、摻合量設爲 AW(A2)，將前述環氧樹脂（D)之環氧値（單位：當量/106g)設 爲EV(D)、摻合量設爲EW(D)(單位：質量份）時，以滿足下 述式（1):〇.7S{EV(D)xEW(D)}/{AV(A1)xAW(A1) + AV(A2)x 201207059 AW(A2)} $ 4.0之摻合比摻合樹脂組成物（δ)與樹脂組成物 (ε)與樹脂組成物（ζ)。 本發明之黏著劑用樹脂組成物，較佳爲前述環氧樹脂 (D)占黏著劑用樹脂組成物所含之環氧樹脂整體的6 〇質量％ 以上9 9.9質量％以下。 本發明之黏著劑用樹脂組成物，較佳爲前述無機塡充 材料（Β)之摻合量相對於前述熱塑性樹脂（Α1)與前述熱塑 性樹脂（Α2)之合計100質量份爲10質量份以上50質量份以 下。 本發明之黏著劑用樹脂組成物，較佳爲前述溶劑（C) 之摻合量在將黏著劑用樹脂組成物設爲1 00質量份時爲60 質量份以上8 5質量份以下。 本發明之黏著劑用樹脂組成物較佳爲包含含有氮原子 之環氧樹脂。 本發明之黏著劑用樹脂組成物較佳爲前述含有氮原子 之環氧樹脂具有環氧丙基二胺結構。 本發明亦提供含有上述之本發明之黏著劑用樹脂組成 物之黏著劑。 本發明亦提供含有上述之本發明之黏著劑用樹脂組成 物所含有之前述熱塑性樹脂（Α1)、前述熱塑性樹脂（Α2)、 無機塡充材料（Β)、環氧樹脂（D)及來自此等之反應生成物 之黏著性薄片。 本發明亦提供包含使用上述之本發明之黏著劑或本發 明之黏著性薄片而成之黏著劑層的印刷配線板。 -10- 201207059 [發明的效果] 藉由本發明，可得到在對於各種塑膠薄膜及金屬之高 黏著性、亦可對應在高濕度下之無鉛焊料之高度耐濕熱性 、在高溫高濕度下之黏著性、FPC製造時之加工適性方面 . 優異之黏著劑，且可提供黏著性薄片即使在高溫高濕下流 通後使用亦可維持良好的黏著特性之薄片壽命良好的樹脂 組成物、含有其之黏著劑、黏著性薄片及含有其作爲黏著 劑層之印刷配線板。此外，本發明之較佳之實施態樣中， 亦可提供對於各種塑膠薄膜之黏著性、對於銅、鋁、不鏽 鋼等金屬之黏著性、對於玻璃環氧樹脂之黏著性亦優異之 樹脂組成物、含有其之黏著劑、黏著性薄片及含有其作爲 黏著劑層之印刷配線板。再者，本發明之較佳之實施態樣 中，尤其在對於鋁、不鏽鋼等金屬之黏著性、耐濕熱性優 異、將黏著物於高溫高濕環境下長期間放置後亦維持有高 剝離強度這方面，發揮更加優異之特性。 【實施方式】 [用以實施發明之形態] &lt;分散液（α)&gt; 本發明中，分散液（α)之搖變度（ΤI値）係成爲判斷本發 明之黏著劑用樹脂組成物中之熱塑性樹脂（A 1 )、熱塑性樹 脂（A2)、無機塡充材料（B)之組合及摻合比適當與否之指 針。分散液（α)之搖變度（TI値）爲3以上6以下，更佳爲3.5 以上5以下。分散液（α)所含有之無機塡充材料（Β)粒子間之 -11 - 201207059 相互作用、及/或熱塑性樹脂（Al)、熱塑性樹脂（A2)與無 機充塡劑（B)之相互作用若爲高則分散液（α)之搖變度有變 高之傾向。搖變度若少於3則無機塡充材料（Β)粒子間之相 互作用、及/或無機塡充材料（Β)與熱塑性樹脂（Α1)、熱塑 性樹脂（Α2)之相互作用降低且耐熱性有降低之傾向，此外 無機塡充材料容易沉降而有得不到穩定的適用期（pot life) 之傾向。搖變度若大於6則處理（handling)性降低且有變得 難以均勻地進行塗布之傾向。 分散液（〇〇，係以本發明之黏著劑用樹脂組成物中之 含有比率計，以熱塑性樹脂（A1)、熱塑性樹脂（A2)及無機 塡充材料（B)合計25質量份、甲乙酮45質量份、甲苯30質 量份之摻合比進行混合，進一步將直徑0.5毫米以上2毫米 以下之玻璃珠加入分散液（α)之體積的約1/3左右，使用塗 料搖動器（paint shaker)在室溫20°C以上25°C以下之室內使 其分散4小時後，除去玻璃珠而藉以調製。 分散液（α)之搖變度（TI値）係藉由以下之方法而求出。 將分散液（α)拿到容量225mL之玻璃製廣口瓶（通稱：美乃滋 瓶），以測定溫度25±1°C使用BL型黏度計（東機產業（股）製) 測定在旋轉數6rPm與60rpm之黏度（下文中有時各簡稱爲 BL(6)、BL(60)。單位：dPa.s)，BL(6)爲 100 以下時係藉由 下述式（2)而求出搖變度（TI値）。此外，在BL(6)大於100時 ’使用BH型黏度計（東機產業（股）製）以2rpm與2〇rpm測定 黏度（以下有時各簡稱爲BH(2)、BH(20)。單位：dPa.s)，藉 -12- 201207059 由下述式（3)而求出搖變度（ΤΙ値）。另外’利用BL型黏度 計及B Η型黏度計進行黏度測定時使用之轉子係依照各黏 度計之操作説明書的記載，選擇No. 2~4之任—者。 搖變度（TI値）= BL(6)/BL(60) (2) 搖變度（ΤΙ値）= BH(2)/BH(20) (3) &lt;樹脂組成物（β)&gt; 用於本發明之樹脂組成物（β)係藉由將熱塑性樹脂 (Α1)、熱塑性樹脂（Α2) '無機塡充材料（Β)、溶劑（C)、進 一步視需要之其他成分以前述之比例摻合，以輥磨機、混 合機、塗料搖動器等均勻地混合而得到，若爲可得充分的 分散之方法則在分散方法無特別限制。再者，樹脂組成物 (β)之固體成分濃度係較佳爲15質量％以上40質量％以下。 固體成分濃度若少於1 5質量％，則黏著劑之厚度變薄，耐 熱性、黏著強度降低，若變得比40質量％更大，則由於溶 液之黏度變得過高故有變得難以均勻地進行塗布之傾向。 &lt;樹脂組成物（γ)、樹脂組成物（ζ)&gt; 用於本發明之樹脂組成物（γ)及樹脂組成物（ζ)係亦可 僅由環氧樹脂（D)所構成，但較佳爲進一步含有溶劑（C)。 樹脂組成物（γ)及樹脂組成物（ζ)所含有之溶劑（C)係只要可 溶解樹脂組成物（γ)及樹脂組成物（ζ)中含有之成分者即可 ’無特別限制。此外，樹脂組成物（γ)及樹脂組成物（ζ)之 固體成分濃度係較佳爲1 5質量％以上8 0質量％以下。固體 成分濃度若少於1 5質量％，則溶劑揮發後之黏著劑的厚度 -13- 201207059 變薄，耐熱性、黏著強度有降低之傾向。固體成分濃度若 變得比80質量。/。更大，則由於黏著劑用樹脂組成物之黏度 變得過高，故有變得難以均勻地進行塗布之傾向。 &lt;樹脂組成物（δ ) &gt; 用於本發明樹脂組成物（δ)係藉由將熱塑性樹脂（Α1)、 無機塡充材料（Β)、溶劑（C)、進一步視需要之其他成分以 上述之比例摻合，以輥磨機、混合機、塗料搖動器等均勻 地混合而得到，若爲可得到充分的分散之方法則在分散方 法無特別限制。再者，樹脂組成物（δ)之固體成分濃度係 較佳爲I5質量％以上40質量％以下。固體成分濃度若少於 1 5質量。/。，則黏著劑之厚度變薄，耐熱性、黏著強度降低 ’若變得比40質量％更大，則由於溶液之黏度變得過高， 故有變得難以均勻地進行塗布之傾向。 &lt;樹脂組成物（ε)&gt; 本發明用於樹脂組成物（ε)係藉由將熱塑性樹脂（Α2)、 無機塡充材料（Β)、溶劑（C)、進一步視需要之其他成分以 前述之比例摻合，以輥磨機、混合機、塗料搖動器等均勻 地混合而得到，若爲可得到充分的分散之方法則在分散方 法無特別限制。再者，樹脂組成物（ε)之固體成分濃度係 較佳爲1 5質量％以上40質量％以下。固體成分濃度若少於 1 5質量％，則黏著劑之厚度變薄，耐熱性、黏著強度降低 ’若變得比40質量％更大，則由於溶液之黏度變得過高， 故有變得難以均勻地進行塗布之傾向。 -14 - 201207059 &lt;黏著劑用樹脂組成物&gt; 本發明之黏者劑用樹脂組成物係可爲含有熱塑性樹脂 (A1)、熱塑性樹脂（A2)、無機塡充材料（b)、環氧樹脂（D) 之一液型黏著劑用樹脂組成物’亦可爲分成複數劑而在使 用前進行混合之複數劑混合型黏著劑用樹脂組成物。藉由 作成複數劑混合型’有可長期保存之優點。另—方面，複 數劑混合型的情況’作爲黏著劑使用時須要將複數劑以正 確的摻合比且均勻地混合’劑數越是增加該步驟之困難度 亦變得越大。因此’複數劑混合型之中，較佳爲作爲二液 混合型或三液混合型。以二液混合型之較佳之例而言，可 舉出含有熱塑性樹脂（A〗）、熱塑性樹脂（A2)、無機塡充材 料（B)、溶劑（C)之樹脂組成物（β)、與含有環氧樹脂（D)之 樹脂組成物（γ)之當作二液之情形。以三液混合型之較佳 之例而言，可舉出含有熱塑性樹脂（Α1)、無機塡充材料 (Β)、溶劑（C)之樹脂組成物（δ)、含有熱塑性樹脂（Α2)、無 機塡充材料（Β)、溶劑（C)之樹脂組成物（ε)、與含有環氧’樹 脂（D)之樹脂組成物（ζ)之當作三液之情形。 本發明之黏著劑用樹脂組成物係較佳爲以熱塑性樹脂 (Α1)之酸價AV(A1)(單位：當量/106g)與摻合量AW(A1)(單位 :質量份）、熱塑性樹脂（A2)之酸價AV(A2)(單位：當量/ l〇6g) 與摻合量AW(A2)(單位：質量份）、環氧樹脂（D)之環氧値 EV(D)(單位：當量/ l〇6g)與摻合量EW(D)(單位：質量份）滿足 下述式（1).之摻合比來摻合熱塑性樹脂（A1)、熱塑性樹脂 (A2)、環氧樹脂（D)。 -15- 201207059 0.7^{EV(D)xEW(D)}/{AV(A1)xAW(A1) + AV(A2)x AW(A2) } ^4.0 (1) 上述摻合比若少於〇 · 7，則熱塑性樹脂（A 1 )、熱塑性 樹脂（A 2)與環氧樹脂之交聯變得不充分而有耐熱性降低之 傾向，上述摻合比若變得比4 · 0更大，則未反應的環氧樹 脂大量地殘存，有耐熱性、耐濕性降低之傾向。上述摻合 比係更佳爲〇 · 8以上3.5以下，進一步較佳爲〇 . 9以上3.0以 下。 &lt;熱塑性樹脂（A1)、熱塑性樹脂（A2)&gt; 本發明係含有：由聚酯樹脂或聚胺甲酸酯樹脂所成之 熱塑性樹脂（A 1 )、由聚酯樹脂或聚胺甲酸酯樹脂所成之熱 塑性樹脂（A2)、無機塡充材料（B)、環氧樹脂（D)之黏著劑 用樹脂組成物，在130°C乾燥3分鐘，接著在140。(：熱處理4 小時而得之硬化塗膜中，熱塑性樹脂（A 1 )與熱塑性樹脂 (A2)之至少一部分係具有分離之相分離結構。藉由具有相 分離結構，顯現由玻璃轉移溫度高的熱塑性樹脂（A 1 )所致 之在高溫或高溫高濕之黏著性、黏著強度保持力，且由玻 璃轉移溫度低的熱塑性樹脂（A2)，黏著性薄片之柔軟性增 加’在撓性印刷配線板製造時之加工步驟中，可抑制塗膜 之剝落或裂痕。 藉由使用作爲熱塑性樹脂（A 1 )與熱塑性樹脂（a 2 )相溶 性低之組合’可在硬化塗膜形成相分離結構。以相溶性低 之組合的例而言，可舉出將一者設爲聚酯樹脂而將另一者 -16- 201207059 設爲聚胺甲酸酯樹脂，或使熱塑性樹脂（A1)之溶解度參數 與熱塑性樹脂（A2)之溶解度參數之差增大。 本發明中，硬化塗膜是否有形成相分離結構係可藉由 例如動態黏彈性測定而確認。可藉由前述黏著劑用樹脂組 成物所成之硬化塗膜中，是否觀測到來自前述熱塑性樹脂 (A1)之損失彈性模數峰部或損失正切（tan5)峰部、以及來 自前述熱塑性樹脂（A2)之損失彈性模數峰部或損失正切 (tanS)峰部來判斷。在此所示之峰部，即使爲寬度廣而稍 微上凸亦無妨。此外，熱塑性樹脂（A1)及熱塑性樹脂（A2) 之損失彈性模數峰部之差較佳爲40°C以上。 用於本發明之熱塑性樹脂（A 1 )係相對於熱塑性樹脂 (A1)與熱塑性樹脂（A2)之合計1〇〇質量份，較佳爲55質量 份以上80質量份以下。熱塑性樹脂（A1)若相對於熱塑性樹 脂（A1)與熱塑性樹脂（A2)之合計1〇〇質量份少於55質量份 ，則在高溫及高溫高濕之黏著性、在高溫之黏著強度保持 力有降低之傾向，若變得比80質量份更大，則黏著性薄片 之柔軟性降低，在FPC製造時之加工步驟中由塗膜之裂痕 或剝落而致操作性降低，又有不良品率變高之傾向。較佳 爲熱塑性樹脂（A1)係相對於熱塑性樹脂（A1)與熱塑性樹脂 (A2)之合計1〇〇質量份之60質量份以上75質量份以下。 用於本發明之熱塑性樹脂（A1)及熱塑性樹脂（A2)之數 量平均分子量係5χ103以上lxlO5以下。熱塑性樹脂（A1)及 熱塑性樹脂（A 2)之數量平均分子量若少於5 X 1 〇3則剛塗布 -17- 201207059 後之密著性不足且操作性變差，數量平均分子量若大於 lxio5，則塗布時之溶液黏度過高，有時無法得到均勻的 塗膜。熱塑性樹脂（A1)及熱塑性樹脂（A2)之下限値係較佳 爲8xl〇3，進一步較佳爲lxl04。熱塑性樹脂（A1)及熱塑性 樹脂（A2)之上限値係較佳爲5χ104，進一步較佳爲3χ104。 用於本發明之熱塑性樹脂（A 1)之酸價AV(A1)(單位：當 量/l〇6g)係100以上1 000以下。熱塑性樹脂（A1)之酸價 AV(A1)若少於1〇〇當量/ i〇6g，則對於硬化後之金屬系基材 之密著性變得不足，又有交聯度低且耐熱性降低之傾向。 熱塑性樹脂（A1)之酸價AV(A1)若大於1 000當量/106g則溶 解於溶劑時之清漆的保存穩定性降低，又黏著性薄片之交 聯反應在常溫下容易進行，有無法得到穩定的薄片壽命這 樣的傾向。此外，亦預料會對酯鍵、胺甲酸酯鍵等之耐久 性產生不良影響。熱塑性樹脂（A 1 )之酸價AV( A 1 )的下限係 較佳爲2 5 0當量/l〇6g，更佳爲3 00當量/106g，進一步較佳 爲3 5 0當量/106g。熱塑性樹脂（A1)之酸價AV(A1)的上限係 較佳爲900當量/l〇6g，更佳爲800當量/106g，進一步較佳 爲700當量/106g。 用於本發明之熱塑性樹脂（A1)之玻璃轉移溫度係30°C 以上8 0 °C以下。熱塑性樹脂（A 1)之玻璃轉移溫度若少於3 0 °C ’則在高溫之黏著性有變得不足之傾向。熱塑性樹脂 (A 1)之玻璃轉移溫度若大於8 〇 eC，則產生與基材之密著性 之降低、在常溫之黏著性之降低、又黏著性薄片之柔軟性 -18- 201207059 之降低等，在FPC製造時之加工步驟中由塗膜之裂痕或剝 落而致有操作性降低之傾向。熱塑性樹脂（A 1 )之玻璃轉移 溫度的下限係較佳爲35°C，更佳爲40°C。熱塑性樹脂（A1) 之玻璃轉移溫度的上限係較佳爲75°C，更佳爲70°C。 用於本發明之熱塑性樹脂（A2)之酸價AV(A2)(單位·.當 量/106g)係1〇〇〇以下。酸價若大於1〇〇〇當量/l〇6g則溶解於 溶劑時之清漆的保存穩定性降低，又交聯反應在常溫下容 易進行，有無法得到穩定的薄片壽命這樣的傾向。此外， 有對於酯鍵或胺甲酸酯鍵等之耐久性產生不良影響之傾向 。熱塑性樹脂（A2)之酸價AV(A2)的上限係較佳爲900當量 /l〇6g’更佳爲8 00當量/l〇6g，進一步較佳爲700當量/106g。 用於本發明之熱塑性樹脂（A2)之玻璃轉移溫度係0°C 以下。玻璃轉移溫度若大於〇 t，則黏著性薄片有變得硬 且脆之傾向，在FPC製造時之加工步驟中由塗膜之裂痕、 彔IJ落而致有使操作性降低之傾向。此外黏著劑變硬，有黏 著性變得不足之傾向。熱塑性樹脂（A2)之下限係較佳爲_5 °C，更佳爲-1 (TC。 用於本：發明之聚酯樹脂，係將組成中之全部酸成分之 合計量設爲1〇〇莫耳％時，芳香族羧酸較佳爲60莫耳％以上 ’更佳爲8 5莫耳％以上，進—步較佳爲9 9莫耳％以上。芳 香族殘酸亦可佔1〇〇莫耳％。芳香族羧酸若少於6〇莫耳％時 ’ 聚力低弱，可看到對各種基材之黏著強度的降 低。 -19- 201207059 以芳香族羧酸之例而言，可例示對酞酸、異酞酸、鄰 酞酸、萘二甲酸、聯苯二甲酸、聯苯甲酸、5 -羥基異酞酸 等芳香族二羧酸。此外，可舉出磺基對酞酸、5 -磺基異酞 酸、4-磺基酞酸、4-磺基萘-2,7-二甲酸、5-(4-磺基苯氧基 )異酞酸等具有磺酸基之芳香族二羧酸、該等之金屬鹽、 銨鹽等具有磺酸鹽基之芳香族二羧酸、對羥基安息香酸、 對羥基苯基丙酸、對羥基苯基乙酸、6-羥基-2-萘甲酸、 4,4-雙（對羥基苯基）戊酸等芳香族羥基羧酸等。該等之中 ，在提升塗膜之內聚力方面特佳爲對酞酸、異酞酸、及其 混合物。 另外，以其他酸成分而言，可舉出1,4-環己烷二甲酸 、1,3-環己烷二甲酸、ι，2-環己烷二甲酸與其酸酐等脂環 族二甲酸、丁二酸、己二酸、壬二酸、癸二酸、十二烷二 酸、二體酸等脂肪族二甲酸。In the case of the above-mentioned problems, Japanese Patent Publication No. Hei 11- 1 693 0 (Patent Document 1), JP-A-2008-205-A (Patent Document 2), and JP-A-2007-204715 In the publication (Patent Document 3), there is proposed a resin composition for an adhesive having a specific polyester, polyurethane, and epoxy resin as a main component. However, the composition shown in Patent Document 1 can improve the life of the sheet, the adhesion at high temperatures and high humidity, but does not sufficiently satisfy the adhesion strength at a higher temperature, and uses various metals such as SUS for reinforcement. The board is resistant to humidification and soldering. Further, the composition shown in Patent Document 2 can improve the adhesion at high temperatures and high humidity, and the wet-weld resistance when the plastic film is used for the reinforcing plate, but does not sufficiently satisfy the use of the metal for the reinforcing plate. It is resistant to humidification and soldering. Further, the composition shown in Patent Document 2 is such that the adhesive sheet is stored at a normal temperature and 40 ° C in an 80% humidified environment, and the wet solderability and the adhesion are remarkably lowered, and stable sheet life cannot be ensured. Further, Patent Document 3 has succeeded in improving the glass transition temperature of the polyurethane resin, improving the adhesion at high temperatures, and the life of the sheet. However, it is inevitable that the glass transition temperature is accompanied by a decrease in flexibility. In the manufacturing process of the flexible printed wiring board, cracks are formed in the adhesive sheet when the adhesive sheet is cut and punched, and when the release film is peeled off. , peeling off, and the disadvantage of reduced processing suitability. On the other hand, an adhesive composition of two kinds of polyester resins having different transition temperatures of glass blending is disclosed in Japanese Patent Publication No. 2 0 0 8 - 0 1 9 3 7 5 (Patent Document 4), JP-A-2009- Japanese Patent Publication No. 084348 (Patent Document 5). These methods improve the processing suitability of 201207059 at room temperature by blending a resin having a high glass transition temperature and a resin having a low glass transition temperature, but are soft under the conditions of a storage temperature of 5 ° C or less for a general adhesive sheet. Low in character, not satisfactory for those who are processing at low temperatures. In addition, these systems exhibit excellent adhesion to PET film and tin-plated copper and are excellent in blocking resistance, especially because they are excellent as an adhesive for flexible flat cables but only thermoplastic. In the case of the resin, the adhesive for a flexible printed wiring board is insufficient in heat resistance and does not sufficiently satisfy the resistance to wet soldering. [Patent Document 1] [Patent Document 1] Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. 2008-205370 (Patent Document 3). [Patent Document 5] JP-A-2008-084348 [Patent Document 5] JP-A-2009-084348 SUMMARY OF INVENTION [Problem to be Solved by the Invention] The subject of the present invention is to improve such conventional adhesives. Each of the problems is provided to maintain the adhesion to various plastic films, copper, aluminum, stainless steel and other metal 'glass epoxy resins, and also to the high heat and humidity resistance of lead-free solder under high humidity, at high temperatures. The adhesive which is excellent in adhesiveness under high humidity and excellent in workability in the production of a flexible printed wiring board is further provided that the adhesive sheet obtained by the above-mentioned adhesive can be used even after being circulated under high temperature and high humidity. Good adhesion characteristics of the sheet 201207059 Good life adhesive sheet. Further, it is provided to provide a printed wiring board comprising an adhesive layer obtained from the above-mentioned adhesive or adhesive sheet. [Means for Solving the Problem] The present inventors have made efforts to solve the above problems and have achieved the present invention. That is, the present invention is constituted by the following constitution. The resin composition for an adhesive of the present invention comprises a polyester resin or a polyurethane resin and has an acid value (unit: equivalent/106 g) of 1 Å or more and 1,000 or less and a glass transition temperature of 30°. a thermoplastic resin (A1) having a C content of 80 ° C or less and a number average molecular weight of 5 〇χ 103 or more and ΟχΙΟ 5 or less is formed of a polyester resin or a polyurethane resin, and the glass transition temperature is 〇 ° C or less. a thermoplastic resin (A2) having a number average molecular weight of 5·〇χ103 or more and ΟχΙΟ5 or less, an inorganic chelating material (B) and an epoxy resin (D) having a dicyclopentadiene skeleton, and dried at 130 ° C In the hardened coating film obtained by heat-treating at 140 ° C for 4 hours for 3 minutes, at least a part of the thermoplastic resin (A 1 ) and the thermoplastic resin (A2) have a phase-separated structure. The resin composition for an adhesive of the present invention is measured by temperature dispersion of the above-mentioned cured coating film at a frequency of 10 Hz and a temperature increase rate of 4 ° C /min, and the thermoplastic resin (A 1 ) is observed. The loss elastic modulus peak portion and the loss elastic modulus peak portion from the thermoplastic resin (A2) are preferably 40 ° C or higher. . In the resin composition for an adhesive of the present invention, it is preferred that the thermoplastic resin (A1) is made of a polyester resin, the thermoplastic resin (A2) is made of a polyurethane resin, or the thermoplastic resin ( A 1 ) is made of a polyurethane resin, and the thermoplastic resin (A2) is made of a polyester resin. 201207059 The resin composition for an adhesive of the present invention preferably contains 55 parts by mass of the thermoplastic resin (Al) based on 1 part by mass of the total of the thermoplastic resin (A 1 ) and the thermoplastic resin (A 2 ). More than 80 parts by mass or less. In the resin composition for an adhesive according to the present invention, the total of the thermoplastic resin (A1), the thermoplastic resin (A2), and the inorganic filler (B) is based on the content ratio of the resin composition for the adhesive. 25 parts by mass, 45 parts by mass of methyl ethyl ketone, 30 parts by mass of toluene, and a total of 1 part by mass of the dispersion (α) is preferably 3 or more at a liquid temperature of 25 ° C. 6 or less. In the resin composition for an adhesive of the present invention, the acid value (unit: equivalent/l〇6g) of the thermoplastic resin (A1) is set to AV (A1), and the blending amount (unit: parts by mass) is AW ( A1), the acid value of the thermoplastic resin (A2) is AV (A2), the blending amount is AW (A2), and the epoxy resin (unit: equivalent/106 g) of the epoxy resin (D) is set. When EV (D) and the blending amount are EW (D) (unit: parts by mass), it is preferable to satisfy the following formula (1): 0.7 $ {EV(D)xEW(D)}/{AV( Al)x AW(Al) + AV(A2)xAW(A2)} ^ 4.0. The present invention also provides a resin composition for a multi-component mixed type adhesive, wherein the resin composition (β) contains: a polyester resin or a polyurethane resin and an acid value (unit: equivalent/l〇6g) a thermoplastic resin (A1) having a glass transition temperature of 30 ° C or more and a glass transition temperature of 30 ° C or more and 8 (TC or less, a number average molecular weight of 5.0 XI 03 or more and 1.0 χΙΟ 5 or less, or a polyester resin or a polyurethane resin) The thermoplastic resin (A2), the inorganic chelating material (B), and the organic solvent (C); the resin composition (the glass transition temperature is 〇 ° C or less, the number average molecular weight is 5. 〇χ 103 or more Ι ΟχΙΟ 5 or less; γ) contains 201207059 epoxy resin (D); the acid value (unit: equivalent/l〇6g) of the thermoplastic resin (A1) is set to AV (A1), and the blending amount (unit: parts by mass) is set to AW ( A1), the acid value of the thermoplastic resin (A2) is set to AV (A2)', the blending amount is AW (A2), and the epoxy resin (unit: equivalent/106 g) of the epoxy resin (D) is set. When EV (D) and the blending amount are set to EW (D) (unit: parts by mass), the following formula (1) is satisfied: 0.7 5 {EV(D)xEW(D) }/{AV(A1)xAW(A1) + AV(A2)x AW(A2)} S 4.0 blending ratio blending resin composition (β) and tree composition (γ) 〇 Provided is a resin composition for a multi-component mixing type adhesive, wherein the resin composition (δ) contains: a polyester resin or a polyurethane resin, and an acid value (unit: equivalent/106 g) is 100 or more and 1000 or more Hereinafter, the thermoplastic resin (A1), the inorganic chelating material (B), and the organic solvent (C); resin having a glass transition temperature of 30 ° C or more and 80 ° C or less, a number average molecular weight of 5.0×10 3 or more and 1.0××10 5 or less; The composition (ε) contains a thermoplastic resin (A2) which is made of a polyester resin or a polyurethane resin and has a glass transition temperature of less than or equal to a number average molecular weight of 5.0 χΙΟ 3 or more and 1.0 × 10 5 or less. And an organic solvent (C); the resin composition (ζ) contains an epoxy resin (D); the acid value (unit: equivalent/l〇6g) of the thermoplastic resin (Α1) is set to AV(A1), blending The amount (unit: parts by mass) is AW (A1), the acid value of the thermoplastic resin (A2) is AV (A2), and the blending amount is AW (A2). When the epoxy resin (unit: equivalent/106 g) of the epoxy resin (D) is EV (D) and the blending amount is EW (D) (unit: parts by mass), the following formula is satisfied ( 1): 〇.7S{EV(D)xEW(D)}/{AV(A1)xAW(A1) + AV(A2)x 201207059 AW(A2)} $4.0 blending ratio blending resin composition ( δ) and resin composition (ε) and resin composition (ζ). In the resin composition for an adhesive of the present invention, the epoxy resin (D) is preferably 6% by mass or more and 9.9 % by mass or less based on the total amount of the epoxy resin contained in the resin composition for the adhesive. In the resin composition for an adhesive of the present invention, the amount of the inorganic filler (Β) is preferably 10 parts by mass or more based on 100 parts by mass of the total of the thermoplastic resin (Α1) and the thermoplastic resin (Α2). 50 parts by mass or less. In the resin composition for an adhesive of the present invention, the amount of the solvent (C) is preferably 60 parts by mass or more and 805 parts by mass or less when the resin composition for an adhesive is 100 parts by mass. The resin composition for an adhesive of the present invention preferably contains an epoxy resin containing a nitrogen atom. In the resin composition for an adhesive of the present invention, it is preferred that the epoxy resin containing a nitrogen atom has a glycidyl propylene diamine structure. The present invention also provides an adhesive comprising the above-described resin composition for an adhesive of the present invention. The present invention also provides the thermoplastic resin (Α1), the thermoplastic resin (Α2), the inorganic chelating material (Β), the epoxy resin (D), and the like contained in the resin composition for an adhesive of the present invention. The adhesive sheet of the reaction product. The present invention also provides a printed wiring board comprising an adhesive layer using the above-described adhesive of the present invention or the adhesive sheet of the present invention. -10- 201207059 [Effects of the Invention] According to the present invention, high adhesion to various plastic films and metals, high heat resistance to lead-free solder at high humidity, and adhesion under high temperature and high humidity can be obtained. And the processing properties in the production of FPC. It is an excellent adhesive, and it can provide a resin composition which adheres to the adhesive sheet and maintains good adhesive properties even after being used under high temperature and high humidity. Agent, adhesive sheet and printed wiring board containing the same as an adhesive layer. Further, in a preferred embodiment of the present invention, it is also possible to provide a resin composition which is excellent in adhesion to various plastic films, adhesion to metals such as copper, aluminum, stainless steel, and adhesion to glass epoxy resins, An adhesive, an adhesive sheet, and a printed wiring board containing the same as an adhesive layer. Further, in a preferred embodiment of the present invention, the adhesion to the metal such as aluminum or stainless steel is excellent, and the heat and humidity resistance is excellent, and the adhesive is maintained in a high-temperature and high-humidity environment for a long period of time. In terms of aspects, we will play a more excellent role. [Embodiment] [Formation for Carrying Out the Invention] &lt;Dispersion Liquid (α)&gt; In the present invention, the degree of shaking of the dispersion liquid (α) is determined as a resin composition for determining the adhesive of the present invention. The combination of the thermoplastic resin (A 1 ), the thermoplastic resin (A2), the inorganic chelating material (B), and the blending ratio is appropriate. The degree of shaking (TI値) of the dispersion (α) is 3 or more and 6 or less, more preferably 3.5 or more and 5 or less. The interaction between the inorganic filler (Β) particles contained in the dispersion (α) -11 - 201207059 interaction, and / or thermoplastic resin (Al), thermoplastic resin (A2) and inorganic filler (B) If it is high, the degree of shaking of the dispersion (α) tends to be high. If the degree of shaking is less than 3, the interaction between the inorganic filler (Β) particles, and/or the interaction between the inorganic filler (Β) and the thermoplastic resin (Α1), the thermoplastic resin (Α2), and heat resistance There is a tendency to decrease, and the inorganic filler material is likely to settle and there is a tendency to obtain a stable pot life. When the degree of shaking is more than 6, the handling property is lowered and there is a tendency that it becomes difficult to apply uniformly. The dispersion (a total of 25 parts by mass of the thermoplastic resin (A1), the thermoplastic resin (A2), and the inorganic chelating material (B), and the methyl ethyl ketone 45, are contained in the resin composition for the adhesive of the present invention. The blending ratio of the mass parts and 30 parts by mass of toluene is mixed, and glass beads having a diameter of 0.5 mm or more and 2 mm or less are further added to about 1/3 of the volume of the dispersion (α), and a paint shaker is used. After dispersing for 4 hours in a room at room temperature of 20 ° C or more and 25 ° C or less, the glass beads were removed and prepared. The degree of shaking (TI 値) of the dispersion (α) was determined by the following method. The dispersion (α) was obtained in a glass jar made of 225 mL (commonly known as: Mina's bottle), and the measurement was carried out at a temperature of 25 ± 1 ° C using a BL type viscometer (manufactured by Toki Sangyo Co., Ltd.) at a rotation number of 6 rPm. The viscosity with 60 rpm (hereinafter sometimes referred to as BL (6), BL (60), unit: dPa.s), and when BL (6) is 100 or less, the shake is obtained by the following formula (2). Variation (TI値). In addition, when BL(6) is greater than 100, 'BH-type viscometer (made by Toki Sangyo Co., Ltd.) The viscosity was measured at 2 rpm and 2 rpm (hereinafter sometimes referred to as BH (2), BH (20). Unit: dPa.s), and the degree of shaking was determined by the following formula (3) by -12-201207059 ( ΤΙ値). In addition, the rotor used in the viscosity measurement using the BL type viscometer and the B Η type viscometer is selected according to the operation manual of each viscometer, and the choice of No. 2 to 4 is used. (TI値)= BL(6)/BL(60) (2) Shake degree (ΤΙ値) = BH(2)/BH(20) (3) &lt;Resin composition (β)&gt; The resin composition (β) of the invention is blended in the aforementioned ratio by a thermoplastic resin (Α1), a thermoplastic resin (Α2) 'inorganic chelating material (Β), a solvent (C), and other optional components as needed. It is obtained by uniformly mixing a roll mill, a mixer, a paint shaker, etc., and the dispersion method is not particularly limited as long as a method of sufficiently dispersing is obtained. Further, the solid content concentration of the resin composition (β) is more When the solid content concentration is less than 15% by mass, the thickness of the adhesive is reduced, and the heat resistance and the adhesive strength are lowered. When the 40% by mass is larger, the viscosity of the solution becomes too high, so that it tends to be difficult to apply uniformly. <Resin composition (γ), resin composition (ζ)&gt; Resin used in the present invention The composition (γ) and the resin composition (ζ) may be composed only of the epoxy resin (D), but preferably further contain a solvent (C). Resin composition (γ) and resin composition (ζ) The solvent (C) to be contained is not particularly limited as long as it can dissolve the components contained in the resin composition (γ) and the resin composition (ζ). Further, the solid content concentration of the resin composition (γ) and the resin composition (ζ) is preferably 15% by mass or more and 80% by mass or less. When the concentration of the solid component is less than 15% by mass, the thickness of the adhesive after the solvent is volatilized is -13-201207059, and the heat resistance and the adhesive strength tend to be lowered. The solid content concentration becomes more than 80 mass. /. When the viscosity of the resin composition for an adhesive is too high, it tends to be difficult to apply uniformly. &lt;Resin Composition (δ) &gt; The resin composition (δ) used in the present invention is obtained by using a thermoplastic resin (Α1), an inorganic chelating material (Β), a solvent (C), and other components as needed. The above ratio is blended and uniformly obtained by a roll mill, a mixer, a paint shaker, etc., and the dispersion method is not particularly limited as long as a method of sufficiently dispersing is obtained. Further, the solid content concentration of the resin composition (δ) is preferably from 15% by mass to 40% by mass. The solid content concentration is less than 15 mass. /. When the thickness of the adhesive is reduced, the heat resistance and the adhesive strength are lowered. If the viscosity is more than 40% by mass, the viscosity of the solution becomes too high, so that it tends to be difficult to apply uniformly. &lt;Resin Composition (ε)&gt; The resin composition (ε) of the present invention is obtained by using a thermoplastic resin (Α2), an inorganic chelating material (Β), a solvent (C), and other components as needed. The above ratio is blended and uniformly obtained by a roll mill, a mixer, a paint shaker, etc., and the dispersion method is not particularly limited as long as a method of sufficiently dispersing is obtained. Further, the solid content concentration of the resin composition (?) is preferably 15% by mass or more and 40% by mass or less. When the solid content concentration is less than 15% by mass, the thickness of the adhesive is reduced, and the heat resistance and the adhesive strength are lowered. If the viscosity is more than 40% by mass, the viscosity of the solution becomes too high, so that the viscosity becomes too high. It is difficult to uniformly apply the coating. -14 - 201207059 &lt;Resin Composition for Adhesives&gt; The resin composition for an adhesive of the present invention may contain a thermoplastic resin (A1), a thermoplastic resin (A2), an inorganic chelating material (b), and an epoxy resin. The resin composition for a liquid type adhesive of the resin (D)' may be a resin composition for a plurality of mixed type adhesives which are mixed into a plurality of agents and mixed before use. By making a mixture of plural agents, there is an advantage that it can be preserved for a long period of time. On the other hand, in the case of a mixed type of a plurality of agents, it is necessary to mix the plurality of agents at a proper blend ratio and uniformly mix as the adhesive. The more the number of the agents is increased, the more difficult the step is. Therefore, among the plural mixed type, it is preferably a two-liquid mixed type or a three-liquid mixed type. A preferred example of the two-liquid mixing type is a resin composition (β) containing a thermoplastic resin (A), a thermoplastic resin (A2), an inorganic chelating material (B), and a solvent (C), and The case where the resin composition (γ) containing the epoxy resin (D) is used as a two liquid. A preferred example of the three-liquid mixing type is a resin composition (δ) containing a thermoplastic resin (Α1), an inorganic chelating material (Β), a solvent (C), a thermoplastic resin (Α2), and an inorganic substance. The resin composition (ε), the resin composition (ε) of the solvent (C), and the resin composition (ζ) containing the epoxy resin (D) are used as the three liquids. The resin composition for an adhesive of the present invention is preferably an acid resin AV(A1) (unit: equivalent/106 g) and a blending amount AW (A1) (unit: parts by mass) of a thermoplastic resin (Α1), a thermoplastic resin. (A2) Acid value AV (A2) (unit: equivalent / l〇6g) and blending amount AW (A2) (unit: parts by mass), epoxy resin (D) epoxy 値 EV (D) (unit : Equivalent / l 〇 6g) and the blending amount EW (D) (unit: parts by mass) satisfying the blending ratio of the following formula (1). Blending thermoplastic resin (A1), thermoplastic resin (A2), epoxy Resin (D). -15- 201207059 0.7^{EV(D)xEW(D)}/{AV(A1)xAW(A1) + AV(A2)x AW(A2) } ^4.0 (1) If the above blending ratio is less than 〇 -7, the crosslinking between the thermoplastic resin (A1) and the thermoplastic resin (A2) and the epoxy resin is insufficient, and the heat resistance tends to be lowered. If the blending ratio becomes larger than 4·0, Then, the unreacted epoxy resin remains in a large amount, and the heat resistance and the moisture resistance tend to be lowered. The above blend ratio is more preferably 〇 8 or more and 3.5 or less, further preferably 〇 9 or more and 3.0 or less. &lt;Thermoplastic Resin (A1), Thermoplastic Resin (A2)&gt; The present invention contains a thermoplastic resin (A 1 ) made of a polyester resin or a polyurethane resin, and a polyester resin or a polyamic acid. The resin composition for the adhesive of the thermoplastic resin (A2), the inorganic chelating material (B), and the epoxy resin (D) made of the ester resin was dried at 130 ° C for 3 minutes, followed by 140. (In the hardened coating film obtained by heat treatment for 4 hours, at least a part of the thermoplastic resin (A 1 ) and the thermoplastic resin (A2) have a separated phase-separated structure. By having a phase-separated structure, the transition temperature from the glass is high. The thermoplastic resin (A 1 ) has high adhesion to high temperature, high temperature and high humidity, and adhesive strength retention, and the thermoplastic resin (A2) having a low glass transition temperature increases the flexibility of the adhesive sheet. In the processing step at the time of sheet production, peeling or cracking of the coating film can be suppressed. By using a combination of a thermoplastic resin (A 1 ) and a thermoplastic resin (a 2 ) having low compatibility, a phase separation structure can be formed in the cured coating film. In the case of a combination having a low compatibility, one of them may be a polyester resin, and the other may be a polyurethane resin or a solubility parameter of the thermoplastic resin (A1). The difference from the solubility parameter of the thermoplastic resin (A2) is increased. In the present invention, whether or not the cured coating film has a phase-separated structure can be confirmed by, for example, dynamic viscoelasticity measurement. Whether the loss elastic modulus peak portion or the loss tangent (tan5) peak portion from the thermoplastic resin (A1) and the loss elastic modulus from the aforementioned thermoplastic resin (A2) were observed in the cured coating film formed of the resin composition. The peak portion or the loss tangent (tanS) peak is judged. The peak portion shown here may be slightly convex even if it has a wide width. Further, the loss elastic modulus of the thermoplastic resin (A1) and the thermoplastic resin (A2) The difference between the peak portions is preferably 40 ° C or higher. The thermoplastic resin (A 1 ) used in the present invention is preferably 1 part by mass, preferably 55 parts by mass based on the total of the thermoplastic resin (A1) and the thermoplastic resin (A2). When the thermoplastic resin (A1) is less than 55 parts by mass based on 1 part by mass of the total of the thermoplastic resin (A1) and the thermoplastic resin (A2), the adhesiveness at high temperature and high temperature and high humidity is less than 80 parts by mass. The adhesive strength retention force at a high temperature tends to decrease, and if it becomes larger than 80 parts by mass, the flexibility of the adhesive sheet is lowered, and the coating film is cracked or peeled off during the processing step at the time of FPC production. Reduced sexuality The thermoplastic resin (A1) is preferably 60 parts by mass or more and 75 parts by mass or less based on 1 part by mass of the total of the thermoplastic resin (A1) and the thermoplastic resin (A2). The number average molecular weight of the thermoplastic resin (A1) and the thermoplastic resin (A2) is 5 χ 103 or more and 1 x 10 5 or less. The thermoplastic resin (A1) and the thermoplastic resin (A 2) have a number average molecular weight of less than 5 X 1 〇 3 and are just coated - 17-201207059 After the adhesion is insufficient and the workability is deteriorated, and the number average molecular weight is more than lxio5, the viscosity of the solution at the time of coating is too high, and a uniform coating film may not be obtained. Thermoplastic resin (A1) and thermoplastic resin (A2) The lower limit is preferably 8xl〇3, further preferably lxl04. The upper limit of the thermoplastic resin (A1) and the thermoplastic resin (A2) is preferably 5 χ 104, more preferably 3 χ 104. The acid value AV (A1) (unit: equivalent amount / l 〇 6 g) of the thermoplastic resin (A 1) used in the present invention is 100 or more and 1,000 or less. When the acid value AV (A1) of the thermoplastic resin (A1) is less than 1 〇〇 equivalent / i 〇 6 g, the adhesion to the metal substrate after curing becomes insufficient, and the degree of crosslinking is low and heat resistance is obtained. Reduce the tendency. When the acid value (A1) of the thermoplastic resin (A1) is more than 1,000 equivalents/106 g, the storage stability of the varnish is lowered when dissolved in a solvent, and the crosslinking reaction of the adhesive sheet is easy to proceed at normal temperature, and it is impossible to obtain stability. The tendency of the sheet life is such a tendency. Further, it is expected to have an adverse effect on the durability of the ester bond, the urethane bond or the like. The lower limit of the acid value AV (A 1 ) of the thermoplastic resin (A 1 ) is preferably 2,500 equivalents / 1 〇 6 g, more preferably 30,000 equivalents / 106 g, still more preferably 305 equivalents / 106 g. The upper limit of the acid value AV (A1) of the thermoplastic resin (A1) is preferably 900 equivalent / l 〇 6 g, more preferably 800 equivalent / 106 g, still more preferably 700 equivalent / 106 g. The glass transition temperature of the thermoplastic resin (A1) used in the present invention is 30 ° C or more and 80 ° C or less. When the glass transition temperature of the thermoplastic resin (A1) is less than 30 °C, the adhesion at high temperatures tends to be insufficient. When the glass transition temperature of the thermoplastic resin (A1) is more than 8 〇eC, the adhesion to the substrate is lowered, the adhesion at room temperature is lowered, and the softness of the adhesive sheet is lowered -18-201207059. In the processing step at the time of FPC production, there is a tendency that the workability is lowered by cracking or peeling of the coating film. The lower limit of the glass transition temperature of the thermoplastic resin (A 1 ) is preferably 35 ° C, more preferably 40 ° C. The upper limit of the glass transition temperature of the thermoplastic resin (A1) is preferably 75 ° C, more preferably 70 ° C. The acid value AV (A2) (unit: amount / 106 g) used in the thermoplastic resin (A2) of the present invention is 1 Torr or less. When the acid value is more than 1 〇〇〇 equivalent/l 〇 6 g, the storage stability of the varnish is lowered when it is dissolved in a solvent, and the crosslinking reaction tends to proceed at a normal temperature, and there is a tendency that a stable sheet life cannot be obtained. Further, there is a tendency to adversely affect the durability of an ester bond or a urethane bond or the like. The upper limit of the acid value AV (A2) of the thermoplastic resin (A2) is preferably 900 equivalent / l 〇 6g', more preferably 800 eq / l 〇 6g, still more preferably 700 equivalent / 106g. The glass transition temperature of the thermoplastic resin (A2) used in the present invention is 0 ° C or lower. When the glass transition temperature is larger than 〇t, the adhesive sheet tends to be hard and brittle, and the crack in the coating film and the 彔IJ fall in the processing step at the time of FPC production, which tends to lower the workability. In addition, the adhesive becomes hard and the adhesive tends to become insufficient. The lower limit of the thermoplastic resin (A2) is preferably _5 ° C, more preferably -1 (TC. For the present invention: the polyester resin of the invention is a combination of all the acid components in the composition is set to 1 〇〇. When the molar % is, the aromatic carboxylic acid is preferably 60 mol% or more, more preferably 85 mol% or more, and further preferably 9 9 mol% or more. The aromatic residual acid may also account for 1 〇. 〇 mol%. If the aromatic carboxylic acid is less than 6 〇 mol%, the cohesive strength is low, and the adhesion strength to various substrates can be seen. -19- 201207059 In the case of aromatic carboxylic acid An aromatic dicarboxylic acid such as citric acid, isophthalic acid, o-nonanoic acid, naphthalenedicarboxylic acid, diphenylic acid, dibenzoic acid or 5-hydroxyisophthalic acid can be exemplified. Acid, 5-sulfoisophthalic acid, 4-sulfodecanoic acid, 4-sulfonaphthalene-2,7-dicarboxylic acid, 5-(4-sulfophenoxy)isodecanoic acid, etc. having a sulfonic acid group An aromatic dicarboxylic acid having a sulfonate group such as an aromatic dicarboxylic acid, such a metal salt or an ammonium salt, p-hydroxybenzoic acid, p-hydroxyphenylpropionic acid, p-hydroxyphenylacetic acid or 6-hydroxy-2 -naphthoic acid, 4,4-bis(p-hydroxyl An aromatic hydroxycarboxylic acid such as phenyl)pentanoic acid, etc. Among them, citric acid, isononanoic acid, and a mixture thereof are particularly preferable in terms of enhancing the cohesive force of the coating film. Examples thereof include alicyclic dicarboxylic acid such as 1,4-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, iota, 2-cyclohexanedicarboxylic acid and an acid anhydride thereof, succinic acid, adipic acid, and hydrazine. An aliphatic dicarboxylic acid such as an acid, azelaic acid, dodecanedioic acid or a dimer acid.

另一方面，二醇成分係較佳爲由脂肪族二醇、脂環族 二醇、含芳香族之二醇、含醚鍵之二醇等而成，以脂肪族 二醇之例而言’可舉出乙二醇、1，2-丙二醇、1,3·丙二醇 、1，4-丁二醇、2-甲基-1,3-丙二醇、1，5-戊二醇、新戊二 醇、1,6-己二醇、3-甲基-1,5-戊二醇、1，9-壬二醇、2-乙 基-2-丁基-1,3-丙二醇、羥基三甲基·乙酸新戊二醇酯、二 羥甲基丁烷、2，2,4-三甲基-1，3-戊二醇等，以脂環族二醇 之例而言，可舉出1，4 -環己烷二醇、1，4 -環己烷二甲醇、 三環癸烷二醇、三環癸烷二羥甲基、螺二醇、氫化雙酚A -20· 201207059 、氫化雙酚A之氧化乙烯加成物及氧化丙烯加成物等。以 含醚鍵之二醇之例而言，可舉出二乙二醇、三乙二醇、二 丙二醇’進一步’聚乙二醇、聚丙二醇、聚四亞甲基二轉 、新戊二醇氧化乙烯加成物、新戊二醇氧化丙烯加成物等 。以含芳香族脂二醇之例而言，可例示對二甲苯二醇、間 二甲苯二醇、鄰二甲苯二醇、丨，4·苯二醇、1&gt;4•苯二醇之 氧化乙烯加成物、雙酚A、雙酚A之氧化乙烯加成物及氣 化丙烯加成物等於雙酚類的2個酚性羥基各加成氧化乙稀 或氧化丙烯1〜數莫耳所得到之二醇類等。 此外’在分子結構之中具有經基與竣基之經基竣酸化 合物亦可作爲聚酯原料使用，可例示5-羥基異酞酸、對羥 基安息香酸、對羥基苯乙基醇、對羥基苯基丙酸、對經基 苯基乙酸' 6-羥基-2-萘甲酸、4,4_雙（對羥基苯基）戊酸等。 在本發明所使用之聚酯樹脂中，視需要因導入分枝骨 架之目的’即使共聚合0.1莫耳％以上5莫耳％以下之3官能 以上之多羧酸類及/或多元醇類亦無妨。尤其使其與硬化 劑反應.而得到硬化塗膜時，藉由導入分枝骨架，樹脂之末 端基濃度（反應點）增加’交聯密度高，可得到有強度的塗 膜。以該情況下之3官能以上的多竣酸之例而言，可使用 苯偏三酸、苯均三酸、乙二醇雙（脫水苯偏三酸酯）、甘油 參（脫水苯偏三酸酯）、苯偏三酸酐、苯均四酸酐（PMDA)、 氧基二酞酸二酐（〇DPA)、3,3，，4,4，-二苯基酮四甲酸二酉干 (BTDA)、3，3’，4,4’-二苯基四甲酸二酐（bpda) 13,3^4,4,- •21- 201207059 二苯基磺基四甲酸二酐（DSDA)、4,4’-(六氟異亞丙基）二酞 酸二酐（6FDA)、2,2’ -雙[(二羧基苯氧基）苯基]丙烷二酐 (BS A A)等化合物等，另一方面，以3官能以上之多醇之例 而言，可使用甘油、三羥甲基乙烷、三羥甲基丙烷、新戊 四醇等。使用3官能以上之多羧酸及/或多元醇時’較佳爲 在相對於全部酸成分或全部二醇成分之0」莫耳％以上5莫 耳％以下，較佳爲〇.1莫耳％以上3莫耳％以下之範圍共聚合 爲較佳，若大於5莫耳％則有時會產生塗膜之斷裂點伸度 等力學物性的降低，又有在聚合中引起膠化之可能性。 以將酸價導入於本發明所使用之聚酯樹脂之方法而言 ，可舉出聚合後藉由酸加成而將羧酸導入於樹脂之方法。 若在酸加成使用單羧酸、二羧酸、多官能羧酸化合物，則 因酯交換而致有引起分子量之降低的可能性，較佳爲使用 至少具有一個羧酸酐之化合物。以酸酐而言，可使用丁二 酸酐、馬來酸酐、酞酸酐、2,5 -降莰烯二羧酸酐、四氫酞 酸酐、苯偏三酸酐、苯均四酸酐（PMDA)、氧基二酞酸二 酐（ODPA)、3,3’，4,4，-二苯基酮四甲酸二酐（BTDA)、 3,3’，4,4’-二苯基四甲酸二酐（bpda)、3,3，，4,4’-二苯基擴 基四甲酸二酐（DSDA)、4,4，-(六氟異亞丙基）二献酸二酐 (6FDA)、2,2’-雙[(二羧基苯氧基）苯基]丙烷二酐（BSAA)等 化合物等。將構成本發明所使用之聚酯系樹脂的全部酸成 分設爲1〇〇莫耳％時，若進行10莫耳％以上之酸加成，則有 時會引起膠化，又有時會引起聚酯之解聚合並降低樹脂分 •22- 201207059 子量。酸加成係有聚酯聚縮合後在成塊狀態（bulk state)直 接進行之方法、與將聚酯溶液化並加成之方法。在成塊狀 態之反應雖速度快，但若大量地加成則有時會引起膠化， 且因成爲在高溫之反應，故需要注意阻斷氧氣防止氧化等 。另一方面，在溶液狀態之加成雖反應慢，但可穩定地導 入大量羧基。 本發明所使用之聚酯樹脂係可共聚合β-丙內酯、γ-丁 內酯、δ-戊內酯、ε-己內酯等內酯單體。由原料之通用性 來看較佳爲ε -己內酯，以共聚合方法而言，較佳爲於聚縮 合後在成塊狀態投入內酯單體並於聚酯樹脂使其開環聚合 之方法。 用於本發明之聚胺甲酸酯樹脂係較佳爲使用聚酯多元 醇、聚異氰酸酯及鏈伸長劑作爲其原料。以導入酸價之方 法而言，有事先將酸價賦予構成聚胺甲酸酯樹脂之聚酯多 元醇之方法、或將含有羧酸之二醇使用於鏈伸長劑之方法 等。 述聚量若著甲之 前之子量黏胺醇 之述分子之聚元 料上均分下則多 原與平均濕，酯 的外量平高04聚 脂以數量溫XI。 樹量的數高[^5良 酯子醇之在 W 不 酸分元醇有 U 合 甲均多元高聚 胺平酯多變*起 聚量聚酯 Ρ 子引 之數之聚'«殳會 明了明 。&amp; 均時 發除發下!i平有 本爲本以駿量， 於佳於04申數低 用較用XI安，降 爲係。K5OI向性 作醇同U2!傾合 用元相2P10之聚 使多脂105X低之 酯樹5X於降酯 聚酯係少性酸 -23- 201207059 數里平均分子量之下限値係較佳爲8xi〇2，更佳爲ixl〇3。 聚醋多元醇之數量平均分子量之上限値係較佳爲3.5χ104 ’更佳爲2&gt;&lt;1〇4。 使用於製造用於本發明之聚胺甲酸酯樹脂之聚異氰酸 酯可爲二異氰酸酯、其二聚物（脲二酮）、其三聚物（異三聚 氰酸醋、三醇加成物、縮二脲）等之—種、或該等二種以 上之混合物。例如以二異氰酸酯成分而言，可舉出2，4_甲 苯二異氰酸酯、2,6-甲苯二異氰酸酯、對苯二異氰酸酯、 二苯基甲院二異氰酸酯、間苯二異氰酸酯、六亞甲基二異 氰酸酯、四亞甲基二異氰酸酯、3，3’-二甲氧基-4,4，-聯苯 二異氰酸酯、1，5-萘二異氰酸酯、2,6-萘二異氰酸酯、 4,4’-二異氰酸酯二苯醚、二甲苯二異氰酸酯、丨，3_二 異氰酸酯甲基環己烷、1，4-二異氰酸酯甲基環己烷、4，4’-二異氰酸酯環己烷' 4,4，-二異氰酸酯環己基甲烷、異佛酮 二異氰酸酯、二體酸二異氰酸酯、降莰烯二異氰酸酯等， 但從變黃性的問題來看，較佳爲脂肪族.脂環族之二異氰 酸酯。再因獲得容易度與經濟性的理由，特佳爲六亞甲基 二異氰酸酯、異佛酮二異氰酸酯》 在製造用於本發明之聚胺甲酸酯樹脂上，視需要亦可 使用鏈伸長劑。以鏈伸長劑而言，可舉出已記載作爲聚酯 多元醇之構成成分的低分子量二醇、二羥甲基丙酸、或二 羥甲基丁酸等具有一個羧酸與二個羥基的化合物等。其中 ，從酸價導入的容易度、與對於通用溶劑之溶解性來看較 -24- 201207059 佳爲二羥甲基丁酸。此外，以導入分枝的方法而言，使用 三羥甲基丙烷亦較佳。 以用於本發明之聚胺甲酸酯樹脂的製造方法而言，將 前述聚酯多元醇及前述聚異氰酸酯、視需要之鏈伸長劑一 次裝入反應容器亦可 '分開裝入亦可。進行任一者皆對於 系統內之聚酯多元醇、鏈伸長劑之羥基價的合計、聚異氰 酸酯之異氰酸酯基的合計，以異氰酸酯基/羥基之官能基 的比率在1以下而使其反應。又此反應係可藉由在對於異 氰酸酯基不活性的溶劑之存在下或非存在下使其反應而進 行。以該溶劑而言，可舉出酯系溶劑（乙酸乙酯、乙酸丁 酯、丁酸乙酯等）、醚系溶劑（二噚烷、四氫呋喃、二乙酸 等）、酮系溶劑（環己酮、甲乙酮、甲基異丁基酮等）、芳香 族烴系溶劑（苯、甲苯、二甲苯等）及該等之混合溶劑，但 性 燥 乾 及 性 用 通 之 上 業 Η 從 不 言 而 置 裝 應 反 以 0 苯 甲 或’ 酮罐 乙應 甲反 爲之 佳置 較裝 ’ 拌 看攪 來備 點具 觀於 的限 二酯 、 酸 機甲 合胺 捏進 用促 使爲 可 亦 合 混 的 類 之 機 出 擠 般 . 在 用 使 可 應 反 中 應 。 反 置醋 裝酸 合甲 捏胺 媒 觸 之 用 使 所 錫 甲 酸 桂 月 酸甲 桂二 月化 二氧 、 氫 錫二 甲 、 三錫 酸甲 桂三 月化 C 氧 媒氫 觸、 系 錫 如 例 錫 等 錫 亞 酸 辛 、 錫 胺 乙 三 Γ\ 媒 觸 系 胺 環。 雙媒 等 \|7 等 烯 、 吖觸 等一一系 ώ 、胺 罾烷爲 Β辛佳 基環較 乙雙看 2-吖來 、 二點 0 、 觀 酸啉的 (¾味性 媒、害 1胺有 系丁從 鉛三但 -25- 201207059 於本發明之黏著劑組成物，在不損及本發明之特性的 範圍內’即使摻合聚酯樹脂及聚胺甲酸酯樹脂以外之熱塑 性樹脂亦無妨。以熱塑性樹脂而言，可舉出苯乙烯系樹脂 、聚醯胺系樹脂、聚醯胺醯亞胺系樹脂、聚酯醯亞胺系樹 脂、聚碳酸酯系樹脂、聚氧化伸苯基系樹脂、乙烯基系樹 脂、烯烴系樹脂及丙烯酸系樹脂等，該等之熱塑性樹脂係 可使用單獨一種，倂用二種以上亦無妨。 &lt;無機塡充材料（B)&gt; 以用於本發明之無機塡充材料（B)而言雖無特別限制 ’但較佳爲可賦予分散液（α)搖變性者。以如此之無機塡 充材料而言，可使用例如氧化鋁 '氧化矽、二氧化鈦、氧 化鉅、氧化锆、氮化矽、鈦酸鋇、碳酸鋇、鈦酸鉛、鈦酸 銷酸錯、鈦酸鉻酸鑭鉛、氧化鎵、尖晶石、富鋁紅柱石、 堇青石、滑石、氫氧化鋁、氫氧化鎂、鈦酸鋁 '含氧化釔 之锆、矽酸鋇、氮化硼、碳酸鈣、硫酸鈣、氧化鋅、硼酸 鋅、欽酸鎂、硼酸鎂、硫酸鋇、有機膨土、碳等，該等係 可單獨使用，二種以上倂用亦無妨。從黏著劑用樹脂組成 物之透明性、機械特性、耐熱性、搖變性賦予的觀點來看 氧化砂較佳’尤其較佳爲具有三維網目結構之煙霧狀氧化 砂。此外’在賦予疏水性上較佳爲以單甲基三氯矽烷、二 甲基二氯矽烷、六甲基二矽氮烷、辛基矽烷、聚矽氧油等 進行過處理之疏水性氧化矽。使用煙霧狀氧化矽作爲無機 塡充材料（Β)時’一次粒子之平均徑較佳爲3〇nm以下，更 -26- 201207059 佳爲25nm以下。一次粒子之平均徑若大於30nm，則粒子 間或與樹脂之相互作用降低且有耐熱性降低之傾向。另外 ，在此所言之一次粒子之平均徑係從使用掃描型電子顯微 鏡而得之一次粒子影像隨機抽出之1〇〇個粒子的圓相等直 徑之平均値。 無機塡充材料（B)之摻合量相對於熱塑性樹脂（A1)與 熱塑性樹脂（A2)之合計1〇〇質量份係較佳爲10質量份以上 5〇質量份以下，更佳爲13質量份以上45質量份以下，進一 步較佳爲15質量份以上35質量份以下。無機塡充材料（B) 之摻合量若相對於熱塑性樹脂（A1)與熱塑性樹脂（A2)之合 計100質量份少於10質量份則耐熱性有不發揮使向上之效 果之情形，另一方面，若大於50質量份則氧化矽產生分散 不良且溶液黏度變得過高而在操作性上產生缺陷或有黏著 性降低之虞。 &lt;溶劑（C)&gt; 用於本發明之溶劑（C)可爲由單一成分所成者亦可爲 由2種以上之複數成分所成之混合溶劑。溶劑（(：）只要係可 溶解熱塑性樹脂（A 1 )、熱塑性樹脂（a 2 )及環氧樹脂（D )者 即無特別限制。以如此之溶劑而言，可舉出二甲基乙醯胺 、N -甲基-2 -吡咯啶酮等醯胺系溶劑、甲醇、乙醇 '異丙 醇等醇系溶劑、甲苯、二甲苯等芳香族系溶劑、丙酮、甲 乙酮、環己酮等酮系溶劑、乙酸乙酯等酯系溶劑等，從操 作性的觀點來看較佳係可舉出甲苯、二甲苯、甲乙酮、乙 -27- 201207059 酸乙酯，從乾燥容易性的觀點來看進一步較佳係可舉出甲 苯、甲乙酮、乙酸乙酯。該等之溶劑係可單獨1種使用， 倂用2種以上亦無妨。 &lt;環氧樹脂（D)&gt; 於本發明之黏著劑用樹脂組成物，係包含具有二環戊 二烯骨架之環氧樹脂（D)作爲必須成分。由具有剛直的二 環戊二烯骨架之環氧樹脂所成之硬化塗膜係吸濕率極小， 此外，由於可降低硬化塗膜之交聯密度、使剝離時之應力 緩和，故耐加濕焊接性提升。作爲環氧樹脂（D)之具體例 ，可舉出DIC製HP7200系列。 具有二環戊二烯骨架之環氧樹脂（D)之摻合量較佳爲 黏著劑用樹脂組成物所含之環氧樹脂整體的60質量％以上 ，更佳爲75質量％以上，進一步較佳爲90質量％以上。藉 由含有60質量％以上之具有二環戊二烯骨架之環氧樹脂（D) ，可展現更優異之耐加濕焊接性。 於本發明之黏著劑用樹脂組成物，若使其進一步含有 含氮原子之環氧樹脂作爲環氧樹脂，則可以較低的溫度、 短時間之加熱將黏著性薄片進行B階段化（半硬化狀態）’ 且有可抑制黏著性薄片之流動性、抑制加壓時之黏著劑之 擠出、流出、使操作性提升之傾向，又可期待抑制加壓時 之起泡的效果，爲較佳。以含有氮原子之環氧樹脂而言’ 可舉出例如四環氧丙基二胺基二苯基甲烷、三環氧丙基對 胺基苯酚、四環氧丙基雙胺基甲基環己酮、N，N，N’，N’-四 -28- 201207059 環氧丙基-間二甲苯二胺等環氧丙基胺系等。該 原子之環氧樹脂之摻合量較佳爲環氧樹脂整體的 以下。摻合量若變得比20質量％更多，則剛直性 高，黏著性有降低之傾向，交聯反應過度地進行 於被附著體之密著性降低之傾向。此外，黏著性 存中交聯反應容易進行，薄片壽命有降低之傾向 摻合量的上限係1 〇質量％，進一步較佳爲6質量％ 作爲用於本發明之環氧樹脂，亦可倂用其他 。可舉出例如雙酚A二環氧丙基醚、雙酚S二環氧 酚醛清漆環氧丙基醚、溴化雙酚A二環氧丙基醚等 醚型、六氫酞酸環氧丙基酯、二體酸環氧丙基酯 基酯型、三環氧丙基異三聚氰酸酯、或3,4-環氧基 基羧酸酯、環氧化聚丁二烯、環氧化大豆油等脂 肪族環氧化物等，可單獨一種使用亦可倂用二種公 在用於本發明之環氧樹脂的硬化反應中可使 媒。可舉出例如2 -甲基咪唑、1 , 2 -二甲基咪唑、 甲基咪唑或2 -苯基-4-甲基咪唑、1-氰乙基-2-乙； 咪唑等咪唑系化合物或三乙胺、三伸乙二胺、N (2-二甲胺基乙基）哌畊、1,8-二吖雙環（5,4,0)·十 1，5-二吖雙環（4,3,0)-壬烯-5、6-二 丁胺基-1,8-(5，·4,0)-十一烯-7等三級胺類及將該等之三級胺 、辛酸、四級化硼酸四苯醋鹽等作成胺鹽之化合 銻酸三烯丙锍或六氟銻酸二烯丙銚等陽離子觸媒 等含有氮 2 0質量％ 過度地變 而有使對 薄片在保 。更佳之 〇 環氧樹脂 丙基醚、 環氧丙基 等環氧丙 環己基甲 環族或脂 (上。 用硬化觸 2·乙基-4-基-4-甲基 甲基-Ν-—嫌-7、 二吖雙環 類以苯酚 物、六氟 -hf- -tf- 、二本基 -29- 201207059 膦等。該等之中以將1 ,8-二吖雙環（5,4,0)-十一烯-7、1，5-二吖雙環（4,3,0)-壬烯-5、6-二丁胺基-1，8-二吖雙環 (5,4,0)-十一烯_7等三級胺類及該等之三級胺類以苯酚、 辛酸、四級化硼酸四苯酯鹽等作成胺鹽之化合物在熱硬化 性及耐熱性、對金屬之黏著性、摻合後之保存穩定性方面 爲較佳。此時之摻合量係相對於熱塑性樹脂（A 1 )與熱塑性 樹脂（A2)之合計100質量份較佳爲〇.〇1質量份以上！.〇質量 份以下之摻合量’若在該範圍內則更增加對於熱塑性樹脂 (A1)及熱塑性樹脂（A2)與環氧樹脂之反應的觸媒效果，並 可得到強固的黏著性能。 &lt;其他添加劑&gt; 於本發明之黏著劑用樹脂組成物係視需要可適當摻合 溴系、磷系、氮系、氫氧化金屬化合物等阻燃劑、阻燃助劑 、熱穩定劑、抗氧化劑、.矽烷偶合劑、滑劑、調平劑、顏料 、染料等添加劑。此外，抗氧化劑之摻合係作爲在高溫及高 溫高濕之黏著性、黏著強度保持力的改善手段較佳。 以抗氧化劑而言，可舉出例如受阻酚系、磷系抗氧化 劑。具體而言，以受阻酚系而言可舉出1,3,5-參（3，5-二-三 級丁基·4-羥基苄基）異三聚氰酸酯、1，1，3-三（4-羥基-2-甲 基-5-三級丁基苯基）丁烷、丨，ι_雙（3 -三級丁基-6-甲基-4-羥基苯基）丁烷、3,5 -雙（1,1-二甲基乙基）-4-羥基-苯丙酸 、新戊四醇肆[3-(3,5-二-三級丁基-4-羥基苯基）丙酸酯、 3-(1，1-二甲基乙基）_4羥基-5-甲基-苯丙酸、3,9-雙[l，l-二 -30- 201207059 甲基- 2- [(3 -三級丁基-4-羥基-5-甲基苯基）丙醯氧基]乙基]-2,4,8，10-四氧螺[5.5]十一院、1，3,5-三甲基-2,4,6-參 (3，，5’-二-三級丁基-4’-羥基苄基）苯、十八烷基-3-(3,5-二-三級丁基-4 -羥基苯基）丙酸酯、2,5-二-三級丁基氫醌、 4,4，-亞丁基雙（3 -甲基-6-三級丁基苯酚）、1，1，3·參（2 -甲 基-4-羥基-5-三級丁基苯基）丁烷、1，3,5-參·甲基- 2,4,6-參 (3，5-二-三級丁基-4-羥基苄基）苯、參（3，5-二-三級丁基- 4-淫基苯基）異三聚氰酸酯等、或該等之衍生物’以磷系而 言，可舉出3,9-雙-(對壬基苯氧基）2,4,8，10-四氧-3,9-二磷 螺[5.5]十一烷、3,9-雙（十八烷氧基）-2,4,8，10-四氧-3,9-二 磷螺[5.5]十一烷、二乙基[[3,5·雙（1，卜二甲基乙基）-4-徑 基苯基]甲基]膦酸酯、三（單壬基苯基）亞磷酸酯、三苯氧 基膦、亞磷酸異癸酯、亞磷酸異癸基苯酯、二苯基-2-乙 基己基亞磷酸酯、二壬基苯基雙（壬基苯基）酯亞磷酸、 H3-參（2-甲基-4-二-十三烷亞磷酸酯-5-三級丁基苯基）丁 病、參（2,4_二-三級丁基苯基）亞磷酸酯、新戊四醇雙（2,4-二-三級丁基苯基亞磷酸酯）、2,2-亞甲基雙（4,6-二-三級丁 基苯基）-2_乙基己基亞磷酸酯、雙（2,6-二-三級丁基-4_甲 基苯基）新戊四醇二亞磷酸酯、或該等之衍生物，可將該 等單獨地、或複合而使用。抗氧化劑之添加量較佳爲5質 量％以下’若大於5質量％，則有可能會對黏著性產生不良 影響。 -31- 201207059 於本發明之黏著劑用樹脂組成物係視需要亦可摻合矽 烷偶合劑。藉由摻合矽烷偶合劑而提升對金屬之黏著性、 耐熱性之特性。作爲矽烷偶合劑係無特別限定，但可舉出 具有不飽和基者、具有環氧丙基者、具有胺基者等。以具 有不飽和基之矽烷偶合劑而言，可舉出乙烯基參（β-甲氧 基乙氧基）矽烷、乙烯基三乙氧基矽烷、乙烯基三甲氧基 矽烷等。以具有環氧丙基之矽烷偶合劑而言，可舉出γ-環 氧丙氧基丙基三甲氧基矽烷、β-(3,4-環氧基環己基）乙基 三甲氧基矽烷、β-(3,4-環氧基環己基）乙基三乙氧基矽烷 等。以具有胺基之矽烷偶合劑而言，可舉出Ν·β-(胺基乙 基）-γ-胺基丙基三甲氧基矽烷、Ν-β-(胺基乙基）·γ-胺基丙 基甲基二甲氧基矽烷、Ν-苯基-γ-胺基丙基三甲氧基矽烷 等。該等之中從耐熱性的觀點來看進一步較佳爲γ-環氧丙 氧基丙基三甲氧基矽烷、β-(3,4-環氧基環己基）乙基三甲 氧基矽烷、β-(3,4-環氧基環己基）乙基三乙氧基矽烷等具 有環氧丙基之矽烷偶合劑。矽烷偶合劑之摻合量係相對於 熱塑性樹脂（Α1)與熱塑性樹脂（Α2)之合計1〇〇質量份較佳 爲0.5質量份以上2〇質量份以下之摻合量。矽烷偶合劑之 摻合量若相對於熱塑性樹脂（Α1)與熱塑性樹脂（Α2)之合計 1 0 0質量份少於0 · 5質量份，則所得之黏著劑有可能變得耐 熱性不良，若大於20質量份則有可能變得耐熱性不良、黏 著性不良。 -32- 201207059 &lt;黏著性薄片&gt; 本發明中’所謂黏著性薄片係含有本發明之黏著劑 樹脂組成物所含有之前述熱塑性樹脂（A i )、前述熱塑性 脂（A 2)、前述無機塡充材料（B)、前述環氧樹脂（D)及來 此等之反應生成物者’將至少一部分經反應者稱爲B階 狀態（半硬化狀態）。F P C製造時之加壓步驟中，黏著性 片之流動性' 黏度係與加壓時之流出有關，流出多則牽 到製品的ig賴度之降低、或不良率之增加。黏著性薄片 較佳爲具有可抑制上述之流出之B階段狀態。本發明中 黏著性薄片係可爲由含有本發明之黏著劑用樹脂組成物 含有之前述熱塑性樹脂（A1)、前述熱塑性樹脂（A2)、前 無機塡充材料（B)、前述環氧樹脂（D)及來自此等之反應 成物的層單獨構成之薄片，或可爲由基材或脫模基材與 有本發明之黏著劑用樹脂組成物所含有之前述熱塑性樹 (A1)、前述熱塑性樹脂（A2)、前述無機塡充材料（B)、 述環氧樹脂（D)及來自此等之反應生成物的層所構成之 片’或可爲由基材或脫模基材與含有本發明之黏著劑用 脂組成物所含有之前述熱塑性樹脂（A 1 )、前述熱塑性樹 (A2)、前述無機塡充材料（B)、前述環氧樹脂（D)及來自 等之反應生成物的層與脫模基材所構成之薄片。含有本 明之黏著劑用樹脂組成物所含有之前述熱塑性樹脂（A】） 前述熱塑性樹脂（A2)、前述無機塡充材料（B)、前述環 樹脂（D)及來自此等之反應生成物的層係可形成於基材 用 樹 白 段 薄 連 係 之 所 述 生 含 脂 ^ * 刖 薄 樹 脂 此 發 、 氧 之 -33- 201207059 單面亦可形成於兩面。此外，於黏著性薄片係亦可含有微 量或少量之溶劑（C)。黏著性薄片係藉由黏著劑用樹脂組 成物而具有使基材黏著於被黏著材之功能。黏著性薄片之 基材係在黏著後作用爲被黏著材之保護層。又若使用脫模 基材作爲黏著性薄片之基材，則可將脫模基材進行脫模’ 再將黏著劑層轉印至另一被黏著材。 藉由將本發明之黏著劑用樹脂組成物依照常用方法塗 布於各種基材，並將溶劑之至少一部分除去並乾燥，可得 到本發明之黏著性薄片。又將溶劑之至少一部分除去並乾 燥後’若將脫模基材貼附於黏著劑層，則可不引起往基材 之內移而捲取並在操作性上優異，並且因黏著劑層被保護 故保存性優異’使用亦爲容易。又塗布於脫模基材、使其 乾燥後’視需要若貼附另一脫模基材，則亦可將黏著劑層 該者轉印至另一基材。 在此’以塗布本發明之黏著劑用樹脂組成物的基材而 言’雖並非特別受限者’但可舉出薄膜狀樹脂、金屬板、 金屬箔、紙類等。以薄膜狀樹脂而言，可例示聚酯樹脂、 聚醯胺樹脂、聚醯亞胺樹脂、聚醯胺醯亞胺樹脂、烯烴系 樹脂等。以金屬板及金屬箔之材料而言，可例示SUS、銅 、鋁、鐵 '鋅等各種金屬、及各自之合金、電鍍品等，以 紙類而W可例示良質紙、牛皮紙、紙捲、玻璃紙等。又以 複合材料而目’可例TF玻璃環氧樹脂等。從與黏著劑用樹 月曰組成物之黏著力、耐久性來看’以塗布本發明之黏著劑 -34- 201207059 用樹脂組成物的基材而言，較佳爲聚酯樹脂、聚醯胺樹脂 、聚醯亞胺樹脂、聚醯胺醯亞胺樹脂、SUS鋼板、銅箔、 鋁箔、玻璃環氧樹脂。 又以塗布本發明之黏著劑用樹脂組成物的脫模基材而 言，雖並非特別受限者，但可舉出例如於良質紙、牛皮紙 、紙捲、玻璃紙等紙的兩面設置黏土、聚乙烯、聚丙烯等 充塡劑的塗布層，再於該各塗布層上塗布聚矽氧系、氟系 、醇酸系之脫模劑者，以及將上述脫模劑塗布於聚乙烯、 聚丙烯、乙烯-α-烯烴共聚物、丙烯-α-烯烴共聚物等各種烯 烴薄膜上、聚酞酸乙二酯薄膜上者，但因與被塗布之黏著 劑層的脫模力、聚矽氧對電特性產生不良影響等理由，較 佳爲在良質紙之兩面進行聚丙烯充塡處理並於其上使用醇 酸系脫模劑者、在聚酞酸乙二酯上使用醇酸系脫模劑者。 另外，本發明中以將黏著劑用樹脂組成物塗布於基材 上之方法而言，雖並非特別受限，但可舉出缺角輪塗布機 (c 〇 m m a c 〇 a t e r)、逆輕塗布機（r e ν e r s e r ο 11 c 〇 a t e r)等。或 者，視需要亦可於印刷配線板構成材料之軋延銅箔、或聚 醯亞胺薄膜直接或以轉印法設置黏著劑層。乾燥後之黏著 劑層的厚度係可視需要適當變更，但較佳爲5微米以上200 微米以下之範圍。在黏著劑層的厚度少於5微米，係黏著 強度不足。黏著劑層之厚度大於200微米時，可舉出乾燥 不足且殘留溶劑變多、於印刷配線板製造的加壓時產生氣 泡這樣的問題點。乾燥條件係無特別限定，但乾燥後之殘 -35- 201207059 留溶劑率較佳爲4 %以下。乾燥後之殘留溶劑率若變得比 4 %更大，則可舉出於印刷配線板加壓時殘留溶劑起泡、 產生氣泡這樣的問題點。 &lt;印刷配線板&gt; 本發明中之印刷配線板係包含由形成導體電路的金屬 箔與樹脂層所形成之積層體作爲構成要素者。印刷配線板 係例如使用覆金屬積層體而藉由減除法等以往周知的方法 而製造。視需要將由金屬箔所形成之導體電路部分地、或 全面地使用上覆薄膜（cover film)或網版印刷印墨等來被 覆，總稱所謂撓性電路板（FPC)、扁平電纜、捲帶自動接 合（TAB)用之電路板等。 本發明之印刷配線板係可作成作爲印刷配線板可採用 之任意的積層構成。例如可作成由基材薄膜層、金屬箔層 、黏著劑層及上覆薄膜層之4層所構成的印刷配線板。此 外，例如可作成由基材薄膜層、黏著劑層、金屬箔層、黏 著劑層及上覆薄膜層之5層所構成之印刷配線板。印刷配 線板係視需要有時以加強材進行加強，該情況下加強材、 黏著劑層係設置於基材薄膜層之下。 再者，視需要亦可作成將上述之印刷配線板積層2個 或3個以上之構成。 本發明之黏著劑用樹脂組成物係可合適地使用於印刷 配線板之各黏著劑層。尤其若將本發明之黏著劑用樹脂組 成物用作爲黏著劑，則對於構成印刷配線板之基材具有高 -36- 201207059 黏著性’且具有對無鉛焊料亦可對應之高度的耐熱性，甚 至在商溫高濕度下亦可維持高黏著性。尤其在評價耐焊性 之高溫領域中’藉由跟樹脂與樹脂之化學交聯—起將樹脂 與無機塡充材料之物理交聯平衡良好地進行賦予，能夠沒 有因爲在加濕狀態之耐焊性測試中之水分蒸發所致之衝撃 而致氣泡或變形地緩和應力，適合於金屬箔層與上覆薄膜 層之間的黏著劑、及基材薄膜層與加強材層之間的黏著。 尤其，使用SUS板、鋁板之類的金屬加強材時，在加濕狀 態之焊接上時，因爲水分無法從加強材側蒸發，臨到基材 薄膜層與加強材層之間的黏著劑層之衝撃係尤其強大，作 爲用於那樣的情況之黏著的樹脂組成物係爲合適》 本發明之印刷配線板中，以基材薄膜而言，可使用自 以往作爲印刷配線板之基材一直被使用的任意之樹脂薄膜 。以基材薄膜之樹脂而言，可使用含鹵素之樹脂，亦可使 用不含鹵素之樹脂。從環境問題的觀點來看，較佳爲不含 鹵素之樹脂，但從阻燃性的觀點來看，亦可使用含鹵素之 樹脂。基材薄膜係較佳爲聚醯亞胺薄膜或聚醯胺醯亞胺薄 膜。 以用於本發明之金屬箔而言，可使用可用於電路基板 之任意的以往周知之導電性材料。以材質而言，可使用例 如銅箔、鋁箔、鋼箔、鎳箔等，亦可使用複合該等之複合 金屬箔、鋅、鉻化合物等以其他金屬處理過之金屬箔。較 佳爲銅箔。 -37- 201207059 關於金屬箔之厚度係無特別限定，但較佳爲i微 上’更佳爲3微米以上’進一步較佳爲1〇微米以上。 ’較佳爲50微米以下，更佳爲30微米以下，進一步較 2 0微米以下。於金屬箔之厚度過薄時，電路有可能會 得到足夠的電性能，另一方面，於金屬箔之厚度過厚 可能會降低電路製作時之加工效率等。 金屬箔係通常以輥狀之形態來提供。在製造本發 印刷配線板時所使用之金屬箔之形態係無特別限定。 輥狀形態的金屬箔時，其長度係無特別限定。此外， 度亦無特別限定，但較佳爲25 0毫米以上5 000毫米以 範圍內。 以上覆薄膜而言，可使用作爲印刷配線板用之絕 膜係以往周知之任意的絕緣薄膜。可使用例如由聚醯 、聚酯、聚苯硫醚、聚醚颯、聚醚醚酮、聚芳 (aramid)、聚碳酸酯、多芳基化合物（polyarylate)、 亞胺、聚醯胺醯亞胺等各種聚合物所製造之薄膜。更 聚醯亞胺薄膜或聚醯胺醯亞胺薄膜，進一步較佳爲聚 胺薄膜。 聚醯亞胺薄膜，以其樹脂成分而言將聚醯亞胺樹 作主成分。樹脂成分之中，較佳爲90質量％以上爲聚 胺，更佳爲95質量％以上爲聚醯亞胺，進一步較佳爲 量％以上爲聚醯亞胺，特佳爲99質量％以上爲聚醯亞 以聚醯亞胺樹脂而言，可使用以往周知之任意的樹脂 米以 此外 佳爲 難以 時有 明之 使用 其寬 下之 緣薄 亞胺 醯胺 聚醯 佳爲 醯亞 脂當 醯亞 98質 胺。 -38- 201207059 以上覆薄膜之材料樹脂而言，可使用含鹵素 亦可使用不含鹵素之樹脂。從環境問題的觀點來 爲不含鹵素之樹脂，但從阻燃性的觀點來看，亦 鹵素之樹脂。 以加強材而言，使用將SUS板、鋁板等金屬 亞胺薄膜、玻璃纖維以環氧樹脂硬化過之板（玻 脂板）等。尤其本發明之黏著劑用樹脂組成物係對 鋁板與聚醯亞胺薄膜之黏著發揮莫大的性能，其 耐熱性係顯示極優異之性能。 本發明之印刷配線板係除了使用上述之各層 外，可使用以往周知之任意之製程而進行製造。 在較佳之實施態樣，係製造將黏著劑層積層 膜層之半製品（以下稱爲「上覆薄膜側半製品J ) 面，製造將金屬箔層積層於基材薄膜層而形成期 圖案之半製品（以下稱爲「基材薄膜側2層半製占 黏著劑層積層於基材薄膜層並於其上積層金屬箔 期望的電路圖案之半製品（以下稱爲「基材薄膜{! 品j )(以下將基材薄膜側2層半製品與基材薄膜H 品合稱爲「基材薄膜側半製品」）。藉由貼合如 得之上覆薄膜側半製品、與基材薄膜側半製品， 層或5層之印刷配線板。進一步製造將黏著劑層 強材層之半製品（以下稱爲「加強材側半製品」） 要可貼合於印刷配線板之基材薄膜層進行加強。 之樹脂， 看，較佳 可使用含 板、聚醯 璃環氧樹 SUS 板、 黏著性、 的材料以 於上覆薄 。另一方 望的電路 匕J )或將 層而形成 PJ 3層半製 PJ 3層半製 此進行所 可得到4 積層於加 ，並視需 此外，亦 -39- 201207059 可將用於加強材與基材薄膜間之黏著劑塗布於脫模基材’ 並轉印至印刷配線板之基材薄膜背面’並與加強材貼合。 基材薄膜側半製品係藉由含例如 1) 將成爲基材薄膜之樹脂的溶液塗布於前述金屬 箔，將塗膜進行初期乾燥之步驟、 2) 將以1 )所得之金屬箔與初期乾燥塗膜之積層物進 行熱處理·乾燥之步驟（以下稱爲「熱處理·脫溶劑步驟」） 之製造法而得到。 金屬箔層中之電路之形成係可使用以往周知之方法。 可使用添加法，亦可使用減除法。較佳爲減除法。 所得之基材薄膜側半製品係亦可就原樣使用於與上覆 薄膜側半製品之貼合，此外，亦可在將脫模薄膜貼合並保 管後使用於與上覆薄膜側半製品之貼合。 上覆薄膜側半製品係例如將黏著劑塗布於上覆薄膜而 製造。視需要可進行所塗布之黏著劑中之交聯反應。在較 佳之實施態樣中，係使黏著劑層半硬化。 所得之上覆薄膜側半製品係可就原樣使用於與基材側 半製品之貼合，此外，亦可在將脫模薄膜貼合並保管後使 用於與基材薄膜側半製品之貼合。 所謂基材薄膜側半製品與上覆薄膜側半製品，係各自 在以例如輥之形態保管後，貼合，製造印刷配線板。以貼 合之方法而言，可使用任意之方法，可使用例如加壓或輥 等而貼合。此外’亦可藉由加熱加壓、或使用加熱輥裝置 等之方法一邊進行加熱一邊將兩者貼合。 •40- 201207059 加強材側半製品，在例如聚醯亞胺薄膜之類的柔軟且 可捲取之加強材的情況，將黏著劑塗布於加強材而製造係 爲合適。此外，在例如將s U S、鋁等金屬板、玻璃纖維以 環氧樹脂使其硬化之板等之類硬且無法捲取的加強板之情 況，藉由將預先塗布於脫模基材之黏著劑進行轉印塗布而 製造係爲合適。此外，視需要可進行所塗布之黏著劑中之 交聯反應。在較佳之實施態樣中，係使黏著劑層半硬化。 所得之加強材側半製品係可就原樣使用於與印刷配線 板背面之貼合，此外，亦可在將脫模薄膜貼合並保管後使 用於與基材薄膜側半製品之貼合。 本發明中，基材薄膜側半製品、上覆薄膜側半製品、 加強劑側半製品係皆在與被附著體貼合後以熱處理使其硬 化。熱處理之條件係無特別限定，但較佳爲130°c以上180 °C以下並且1小時以上5小時以下。 基材薄膜側半製品、上覆薄膜側半製品、加強劑側半 製品係皆爲本發明中之印刷配線板用積層體。 [實施例] 爲更加詳細地說明本發明而於以下舉出實施例，但本 發明係並非受限任何限制於實施例者。另外，於實施例中 單爲份者係表示質量份。此外，於無特別註記而記爲環氧 樹脂摻合率時，係當作指下述式（4)之値。 {EV(D)xEW(D)}/{AV(Al) χ A W (A 1) + AV (A 2) x A W (A 2)} -41 - (4) 201207059 (物性評價方法） (1) 熱塑性樹脂之組成 將熱塑性樹脂溶解於氘代氯仿，藉由iH-NMR分 出各成分之莫耳比。但該熱塑性樹脂不溶解於氘代氯 ，溶解於氘代二甲基亞颯而進行1 H-NMR分析。 (2) 數量平均分子量Μη 將試料溶解或稀釋於四氫呋喃使樹脂濃度成爲〇. 右’並將經以孔徑0.5微米之聚四氟化乙烯製膜濾器 者作爲測定用試料，將四氫呋喃當作移動相而將差示 計當作檢測器而藉由膠透層析術測定分子量。流速係 1 niL/分鐘、管柱溫度係設爲3 0 °C。管柱方面使用昭和 製KF-802、804L' 806L。分子量標準方面使用單分 苯乙烯。但是試料不溶解於四氫呋喃時，改變四氫呋 用N，N-二甲基甲醯胺。 (3 )玻璃轉移溫度 使用示差掃描熱卡計，將測定試料1 Omg放入鋁鍋 盡壓下密封，使用Seiko Instruments(股）製示差掃描 分析計（DSC)DSC-2〇0，以2〇t /分鐘之升溫速度測定 皮璃轉移溫度以下之基線的延長線與顯示遷移部中 Α彳頃斜之切線之交點即外插玻璃轉移起始溫度。 (4)酸價 將試料0.2g溶解於20ml氯仿，使用酚酞作爲指示 以0.1N氫氧化鉀乙醇溶液滴定，算出樹脂每1〇^之 (eq/io6g) 〇 析求 仿時 5 %左 過濾 折射 設爲 電工 散聚 喃使 ，將 熱量 ，求 之最 劑， 當量 -42- 201207059 (5)環氧値 依據JIS K 7236，使用過氯酸滴定法由所得之環氧當 量（含有1當量之環氧基的樹脂之質量）算出樹脂每l〇6g之當 量（eq/106g)。 (6)動態黏彈性測定 將黏著劑用樹脂組成物塗布於厚度50微米之聚丙烯薄 膜（東洋紡織股份有限公司製、PYLEN)，使乾燥後之厚度 成爲30微米以上40微米以下之範圍內，在130 t乾燥3分鐘 得到黏著性薄片。再在1 4 0。(：熱處理4小時得到硬化塗膜。 將硬化塗膜從聚丙烯薄膜使其剝離，製成寬4毫米長15毫 米之短籤狀試料。使用IT計測控制公司製動態黏彈性測定 裝置DVA-22〇 ’以頻率10Hz、4°C /分鐘之升溫速度進行前 述短籤狀試料的動態黏彈性之溫度分散測定，求出貯藏彈 性模數、損失彈性模數、損失正切（tan5)。另外，在表中 記載爲「-」者，係表示未測定。 (特性評價方法） (1 )耐焊性、剝離強度 (1 -1 )評價用樣品1作成方法 將後述之黏著劑組成物塗布於厚度2 5微米之聚醯亞胺 薄膜（kaneka股份有限公司製、APICAL)，使乾燥後之厚度 成爲3 0微米’在1 3 0 °C乾燥3分鐘。將如此進行而得之黏著 性薄片與18微米之軋延銅箔貼合時，使軋延銅箔之光澤面 與黏著劑相接而在160°C在35kgf/cm2之加壓下加壓30秒鐘 -43- 201207059 並黏著。接著在1 40 °C熱處理4小時使其硬化，得到耐焊性 及剝離強度評價用樣品1 (初期評價用）。 此外，將黏著性薄片在4 0 °C、8 0 %加濕下放置1 4天後’ 以上述條件與軋延銅箔加壓、進行熱處理使其硬化，得到 經時評價用之樣品1。 (1-2)評價用樣品2作成方法 將後述之黏著劑用樹脂組成物塗布於厚度50微米之聚 丙烯薄膜（東洋紡織股份有限公司製、P Y L EN)，使乾燥後 之厚度成爲30微米，在130 °C乾燥3分鐘得到黏著性薄片。 評價用基板係藉由將單面覆銅積層版（2 5微米聚醯亞胺薄 膜、18微米軋延銅箔）以一般的電路製作步驟（開孔、電鍍 、乾膜光阻（以下有時略稱爲DFR)積層、+曝光.顯影.蝕刻 、DFR剝離）進行製作、硬化而得到評價用基板。使如此進 行所得之評價用基板之聚醯亞胺薄膜面與前述黏著性薄片 之黏著劑用樹脂組成物塗布面相對而假壓著後，剝離聚丙 烯薄膜，並將5 00微米之SUS 3 04板在160°C在30kgf/cm2之 加壓下加壓1分鐘、並黏著作爲加強板。接著在140 °C熱處 理4小時使其硬化，得到耐焊性及剝離強度評價用樣品2( 初期評價用樣品）。 此外，將黏著性薄片在4〇°C、80%加濕下放置14天後 ’將評價用基板改變爲軋延銅箔此外係設相同之條件進行 加壓、熱處理使其硬化，得到經時評價用之樣品2。 各特性之評價係用以下之方法進行； -44- 201207059 •耐焊性（加濕） 將2 5毫米見方之樣品在4 〇 °C、相對濕度8 0 %加濕下放 置2天後，浮於經加熱之焊錫槽（solder bath)l分鐘，以1〇 °C間距測定不產生氣泡之上限溫度。此測試中，測定値高 者顯示具有良好的耐熱性，但有必要亦抑制各基材、黏著 劑層所含之水蒸氣的蒸發所致之衝撃，要求比乾燥狀態更 加嚴格之耐熱性。若考慮作爲FPC加強板之實用性，則較 佳爲2 5 0°C以上，更佳爲260°C以上。 •剝離強度 使用Toyo Baldwin公司製RTM100，在25°C環境下以拉 伸速度5〇毫米/分鐘測定剝離強度。另外，評價用樣品】係 進行90°剝離測試、評價用樣品2係進行丨80。剝離測試。此 測試係顯示在常溫之黏著強度者。若考慮作爲F P C加強板 之實用性’則較佳爲ΙΟΝ/cm以上，更佳爲i5N/cm以上。 (2)在高溫環境下之黏著強度保持力 使用上述之耐焊性及剝離強度評價用樣品2 (初期評價 及經時評價用），在高溫環境下懸掛2 〇 〇 g之秤錘，測定在 1 5分鐘間剝落之距離’並以丨0它間距測定剝落爲4毫米以 下即上限之溫度。另外’秤錘之懸掛方式係以剝離形態成 爲1 8 0。剝離地進行’樣品寬度係以丨〇毫米進行測試。此測 試中’測定値越高顯示具有在高溫下之良好的黏著強度及 黏著強度保持力。若考慮實用性能則較佳爲1 〇〇 r以上， 更佳爲150。(：以上，進一步較佳爲200 °C以上。 -45- 201207059 (3 )高溫高濕環境測試 將寬1 0毫米之前述耐焊性及剝離強度評價用樣品2 (初 期評價用.）放置於85 t、85%加濕環境下，測定經過500小 時後及經過1 000小時後之1 80°剝離強度。此測試係以確認 實際使用時之信賴度爲目的而評價在高溫且高濕環境下之 耐久性者，較佳爲5N/cm以上，更佳爲lON/cm以上。 (4)落錘衝撃測試 將後述之黏著劑用樹脂組成物塗布於厚度50微米之聚 丙烯薄膜（東洋紡織股份有限公司製、PYLEN)，使乾燥後 之厚度成爲30微米，在130°C乾燥3分鐘得到黏著性薄片。 在25t環境下將該黏著性薄片固定於鋼鐵製金屬板使黏著 劑用樹脂組成物之層在上，將前端爲直徑10毫米之半球狀 的鋼鐵製金屬冶具（jig)與該黏著劑組成物相接之面不滑動 地固定，使其接於該黏著劑用樹脂組成物之層之平面部分 。從50毫米至5 00毫米之高度爲止以50毫米間距，使76g之 金屬製秤錘落下於前述鋼鐵製金屬製冶具上部之平面部， 測定該於黏著性薄片不產生裂縫、龜裂、裂痕之上限高度 。測定値越高，則對於衝撃或變形越強固，在FPC製造時 之加工步驟中，裁剪、打孔 '狹縫加工時不易引起裂縫、 龜裂、裂痕，關連到操作性之提升、不良品率之降低。較 佳爲1〇〇毫米以上’更佳爲200毫米以上。 (判定） a: 2 0 0毫米以上、 -46- 201207059 b:100毫米以上少於200毫米、 c :少於1 0 0毫米。 (5)低溫彎曲測試 將後述之黏著劑用樹脂組成物塗布於厚度50微米之聚 丙烯薄膜（東洋紡織股份有限公司製、PYLEN)，使乾燥後 之厚度成爲30微米，在130°C乾燥3分鐘得到黏著性薄片。 將該黏著性薄片在5 °C環境下放置24小時以上後，就在5 °C 環境下使黏著劑用樹脂組成物之層成爲內側而彎曲1〇次確 認龜裂、裂痕的有無。沒有龜裂、裂痕者係即使在低溫下 在FPC製造時之裁剪、打孔、或狹縫加工時亦不易引起龜 裂、裂痕，可降低不良品率。 (判定） a:無龜裂、裂痕、 b:有龜裂、裂痕。 &lt;聚酯樹脂A之聚合例&gt; 於裝備攪拌器、溫度計、流出用冷卻器之反應罐內， 裝入對酞酸208份、異酞酸208份、2 -甲基-1，3 -丙二醇360 份、1,4_丁二醇90份、鈦酸四丁酯0·2份，花費4小時徐徐 地升溫至2 4 0 °C ’並一邊將餾出之水除去至系統外一邊進 行酯化反應。酯化反應結束後花費3〇分鐘減壓至1〇毫米汞 柱進行初期聚合並且將溫度升溫至250 °C ’再在1毫米汞柱 以下進行3 0分鐘後期聚合。其後’用氮回到常壓’投入苯 均四酸酐27份，藉由在180 °C使其15分鐘反應而得到聚酯 -47- 201207059 樹脂A。將如此進行所得之聚酯樹脂A之組成 '特性 於表1。各測定評價項目係依照上述之方法。 &lt;聚酯樹脂B之聚合例&gt; 於裝備攪拌器、溫度計、流出用冷卻器之反應罐 裝入對酞酸166份、異酞酸162.7份、苯偏三酸酐3_ 8份 甲基-1,3-丙二醇306份' 1,6-己二醇70.8份、鈦酸四 0.2份，花費4小時徐徐地升溫至24〇°C，並一邊將餾 水除去至系統外一邊進行酯化反應。酯化反應結束後 30分鐘減壓至10毫米汞柱進行初期聚合並且將溫度升 2 5 0 °C，再在1毫米汞柱以下進行1小時後期聚合。將 之樹脂1 〇〇份裝入具備攪拌器、溫度計、回流式冷卻 蒸餾管之反應容器，加入甲苯140份溶解後，使甲苯 蒸餾，藉由甲苯/水之共沸而將反應系統脫水。冷卻 °C後，藉由加入甲乙酮80份、3,3’，4,4’-二苯基酮四甲 酐7份、DMAP(二甲胺基吡啶）0.1份在70°C使其4小時 而得到聚酯樹脂B之溶液。將如此進行所得之聚酯楦 之組成、特性値示於表1。 &lt;聚酯樹脂C之聚合例&gt; 於裝備攪拌器、溫度計、流出用冷卻器之反應罐 裝入對酞酸203份、異酞酸203份、苯偏三酸酐9.6份 二醇158份、新戊二醇177份、鈦酸四丁酯〇.2份，花| 時徐徐地升溫至240 °C，並一邊將飽出之水除去至系 —邊進行酯化反應。酯化反應結束後花費30分鐘減壓On the other hand, the diol component is preferably an aliphatic diol, an alicyclic diol, an aromatic diol, an ether bond-containing diol, or the like, and in the case of an aliphatic diol. Examples thereof include ethylene glycol, 1,2-propylene glycol, 1,3·propylene glycol, 1,4-butanediol, 2-methyl-1,3-propanediol, 1,5-pentanediol, and neopentyl glycol. 1,6-hexanediol, 3-methyl-1,5-pentanediol, 1,9-nonanediol, 2-ethyl-2-butyl-1,3-propanediol, hydroxytrimethyl - neopentyl glycol acetate, dimethylol butane, 2,2,4-trimethyl-1,3-pentanediol, etc., and examples of the alicyclic diol include 1, 4-cyclohexanediol, 1,4-cyclohexanedimethanol, tricyclodecanediol, tricyclodecane dimethylol, spirodiol, hydrogenated bisphenol A -20· 201207059, hydrogenated bisphenol An ethylene oxide adduct of A and a propylene oxide adduct. Examples of the diol having an ether bond include diethylene glycol, triethylene glycol, and dipropylene glycol 'further' polyethylene glycol, polypropylene glycol, polytetramethylene di-trans, and neopentyl glycol. An ethylene oxide adduct, a neopentyl glycol propylene oxide adduct, and the like. In the case of the aromatic-containing aliphatic diol, ethylene oxide of p-xylene glycol, m-xylene glycol, o-xylene glycol, hydrazine, 4·benzenediol, and 1·4·benzenediol can be exemplified. The adduct, bisphenol A, ethylene oxide adduct of bisphenol A and vaporized propylene adduct are equal to the addition of two phenolic hydroxyl groups of bisphenol to each of ethylene oxide or propylene oxide 1 to several moles. Glycols and the like. Further, 'the phthalic acid compound having a trans group and a mercapto group in the molecular structure may also be used as a polyester raw material, and examples thereof include 5-hydroxyisodecanoic acid, p-hydroxybenzoic acid, p-hydroxyphenylethyl alcohol, and p-hydroxyl group. Phenylpropionic acid, p-phenylphenylacetic acid '6-hydroxy-2-naphthoic acid, 4,4-bis(p-hydroxyphenyl)pentanoic acid, and the like. In the polyester resin to be used in the present invention, it is possible to introduce a branched skeleton as needed, even if it is a copolymer of 0.1 mol% or more and 5 mol% or less of a trifunctional or higher polycarboxylic acid and/or a polyhydric alcohol. . In particular, when a hardened coating film is obtained, a branching skeleton is introduced, and the end group concentration (reaction point) of the resin is increased. The crosslinking density is high, and a coating film having strength is obtained. In the case of the trifunctional or higher polydecanoic acid in this case, trimellitic acid, trimesic acid, ethylene glycol bis(anhydrophthalate), glycerin (dehydrated trimellitic acid) can be used. Ester), trimellitic anhydride, pyromellitic anhydride (PMDA), oxydiphthalic acid dianhydride (〇DPA), 3,3,,4,4,-diphenyl ketone tetracarboxylic acid diterpene (BTDA) ,3,3',4,4'-diphenyltetracarboxylic dianhydride (bpda) 13,3^4,4,- •21- 201207059 Diphenylsulfotetracarboxylic dianhydride (DSDA), 4, 4 On the other hand, compounds such as '-(hexafluoroisopropylidene) dicarboxylic acid dianhydride (6FDA) and 2,2'-bis[(dicarboxyphenoxy)phenyl]propane dianhydride (BS AA) In the case of a trifunctional or higher polyhydric alcohol, glycerin, trimethylolethane, trimethylolpropane, neopentylol or the like can be used. When a trifunctional or higher polycarboxylic acid and/or a polyhydric alcohol is used, it is preferably at least 0 mol% or less, preferably 〇.1 mol, based on 0 or more of the total acid component or all of the diol component. % or more of the range of 3 mol% or less is preferably copolymerized, and if it is more than 5 mol%, the mechanical properties such as the elongation at break of the coating film may be lowered, and the possibility of gelation in the polymerization may occur. . In the method of introducing the acid value into the polyester resin used in the present invention, a method in which a carboxylic acid is introduced into the resin by acid addition after polymerization can be mentioned. When a monocarboxylic acid, a dicarboxylic acid or a polyfunctional carboxylic acid compound is used in the acid addition, the molecular weight may be lowered by transesterification, and a compound having at least one carboxylic anhydride is preferably used. As the acid anhydride, succinic anhydride, maleic anhydride, phthalic anhydride, 2,5-norbornene dicarboxylic anhydride, tetrahydrophthalic anhydride, trimellitic anhydride, pyromellitic anhydride (PMDA), oxydi Decanoic acid dianhydride (ODPA), 3,3',4,4,-diphenyl ketone tetracarboxylic dianhydride (BTDA), 3,3',4,4'-diphenyltetracarboxylic dianhydride (bpda) , 3,3,,4,4'-diphenylalkyltetracarboxylic dianhydride (DSDA), 4,4,-(hexafluoroisopropylidene) diacid dianhydride (6FDA), 2,2' a compound such as bis[(dicarboxyphenoxy)phenyl]propane dianhydride (BSAA). When the total acid component of the polyester-based resin used in the present invention is 1% by mole, if an acid addition of 10 mol% or more is performed, gelation may occur and sometimes it may cause Depolymerization of polyester and reduction of resin content • 22- 201207059. The acid addition is a method in which the polyester is polycondensed and then directly carried out in a bulk state, and a method in which the polyester is solutionized and added. Although the reaction in a bulk state is fast, if it is added in a large amount, gelation may occur, and since it reacts at a high temperature, it is necessary to block oxygen to prevent oxidation. On the other hand, although the addition in the solution state is slow, a large amount of carboxyl groups can be stably introduced. The polyester resin used in the present invention may copolymerize a lactone monomer such as ?-propiolactone, ?-butyrolactone, ?-valerolactone or ?-caprolactone. From the viewpoint of versatility of the raw materials, ε-caprolactone is preferred. In the case of the copolymerization method, it is preferred to introduce the lactone monomer in a bulk state after the polycondensation and to subject the polyester resin to ring-opening polymerization. method. The polyurethane resin used in the present invention is preferably a polyester polyol, a polyisocyanate or a chain extender as a raw material thereof. In the method of introducing an acid value, there is a method of imparting an acid value to a polyester polyol constituting a polyurethane resin in advance, or a method of using a diol containing a carboxylic acid in a chain extender. If the amount of the agglomerate is the amount of the molecule before the nail, the molecular weight of the molecule is divided into multiples and the average is wet. The external amount of the ester is higher than the amount of the polyester. The number of trees is high [^5 good esters of alcohols in W, non-acids, alcohols, U-methyl, multi-components, high-polyamines, polyesters, polyesters, polyesters, polyesters, Clearly understood. & Time is issued and released! i Ping has the original to the amount of Chun, Yu Jia in the 04 application number is lower than the use of XI An, down to the system. K5OI tropism as the same as U2! Tilting with the phase 2P10 to make the fat 105X low ester tree 5X in the ester-lowering polyester-based less acid -23- 201207059 The lower limit of the average molecular weight in the number is preferably 8xi〇 2, better for ixl〇3. The upper limit of the number average molecular weight of the polyglycol polyol is preferably 3.5 χ 104 ' more preferably 2 gt; &lt;1〇4. The polyisocyanate used in the manufacture of the polyurethane resin used in the present invention may be a diisocyanate, a dimer thereof (uretdione), a terpolymer thereof (iso-cyanuric acid vinegar, a triol adduct, a biuret or the like, or a mixture of the two or more. Examples of the diisocyanate component include 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, p-phenylene diisocyanate, diphenylmethyl diisocyanate, isophthalic diisocyanate, and hexamethylene diene. Isocyanate, tetramethylene diisocyanate, 3,3'-dimethoxy-4,4,-biphenyl diisocyanate, 1,5-naphthalene diisocyanate, 2,6-naphthalene diisocyanate, 4,4'- Diisocyanate diphenyl ether, xylene diisocyanate, hydrazine, 3 - diisocyanate methylcyclohexane, 1,4-diisocyanate methylcyclohexane, 4,4'-diisocyanate cyclohexane ' 4,4, - Diisocyanate cyclohexylmethane, isophorone diisocyanate, dimer acid diisocyanate, norbornene diisocyanate, etc., but from the viewpoint of yellowing property, an aliphatic alicyclic diisocyanate is preferred. Further, for reasons of easiness and economy, particularly preferred is hexamethylene diisocyanate or isophorone diisocyanate. In the production of the polyurethane resin used in the present invention, a chain extender may be used as needed. . Examples of the chain extender include a low molecular weight diol, a dimethylolpropionic acid, or a dimethylolbutyric acid having a carboxylic acid and two hydroxyl groups, which are constituent components of the polyester polyol. Compounds, etc. Among them, the ease of introduction from an acid value and the solubility in a general-purpose solvent are preferably -24-201207059 as dimethylolbutanoic acid. Further, in the method of introducing the branch, it is also preferred to use trimethylolpropane. In the method for producing a polyurethane resin to be used in the present invention, the polyester polyol and the polyisocyanate and optionally the chain extender may be separately charged into the reaction container. In any case, the total of the hydroxyl groups of the polyester polyol and the chain extender in the system and the isocyanate groups of the polyisocyanate are reacted at a ratio of the functional group of the isocyanate group/hydroxy group to 1 or less. Further, this reaction can be carried out by reacting it in the presence or absence of a solvent inactive to the isocyanate group. Examples of the solvent include ester solvents (ethyl acetate, butyl acetate, ethyl butyrate, etc.), ether solvents (dioxane, tetrahydrofuran, diacetic acid, etc.), and ketone solvents (cyclohexanone). , methyl ethyl ketone, methyl isobutyl ketone, etc.), aromatic hydrocarbon solvents (benzene, toluene, xylene, etc.) and these mixed solvents, but the dryness and sexual use of the industry Η from the stand The loading should be reversed to 0 benzo or 'ketone cans, and the ketone can be better than the one loaded. ' Look at the mixture and prepare the diester, and the acid methamine can be mixed. The machine of the class is like a crowd. The reverse vinegar is filled with acid and the kneading agent is used to make the tin succinic acid, lauric acid, sulphate, dioxane, hydrogen hydride, trisuccinic acid, sulphuric acid, oxy-hydrogen hydrogen, and tin. Tin, etc., tin bisulphate, tin amide, triterpenoid, medium contact amine ring. Double medium, etc. \|7 et al., oxime, etc., and amine decane are Β 佳 基 基 较 较 较 较 较 较 较 吖 吖 吖 吖 吖 吖 吖 吖 吖 吖 吖 吖 吖 吖 吖 吖 吖 吖 吖 吖 吖 胺 胺The adhesive composition of the present invention is not limited to the range of the present invention, even if the thermoplastic resin other than the polyester resin and the polyurethane resin is blended from the adhesive composition of the present invention. The thermoplastic resin may, for example, be a styrene resin, a polyamide resin, a polyamidoximine resin, a polyester quinone resin, a polycarbonate resin or a polyoxyphenylene group. The resin, the vinyl resin, the olefin resin, the acrylic resin, and the like may be used alone or in combination of two or more. &lt;Inorganic entanglement material (B)&gt; The inorganic ruthenium material (B) used in the present invention is not particularly limited, but is preferably a dispersion of the dispersion (α). In the case of such an inorganic chelating material, for example, alumina 'yttria, titanium dioxide, oxidized giant, zirconia, tantalum nitride, barium titanate, barium carbonate, lead titanate, titanic acid, and titanic acid can be used. Lead strontium chromate, gallium oxide, spinel, mullite, cordierite, talc, aluminum hydroxide, magnesium hydroxide, aluminum titanate, zirconium oxide containing cerium oxide, barium strontium silicate, boron nitride, calcium carbonate , calcium sulfate, zinc oxide, zinc borate, magnesium dibasate, magnesium borate, barium sulfate, organic bentonite, carbon, etc., these systems can be used alone, and two or more can be used. From the viewpoint of transparency, mechanical properties, heat resistance, and shake imparting property of the resin composition for an adhesive, it is preferable that the oxidized sand is particularly preferably a smoke-like oxidized sand having a three-dimensional network structure. Further, 'hydrophobic cerium oxide which is preferably treated with monomethyltrichlorodecane, dimethyldichlorodecane, hexamethyldiazepine, octyldecane, polyoxyxane or the like in imparting hydrophobicity . When aerosolized cerium oxide is used as the inorganic cerium (Β), the average diameter of the primary particles is preferably 3 〇 nm or less, and more preferably -26 to 201207059 is 25 nm or less. When the average diameter of the primary particles is more than 30 nm, the interaction between the particles or the resin is lowered and the heat resistance tends to be lowered. Further, the average diameter of the primary particles referred to herein is the average diameter of the circle equal to the diameter of one particle randomly extracted from the primary particle image obtained by using the scanning electron microscope. The blending amount of the inorganic filler (B) is preferably 10 parts by mass or more and 5 parts by mass or less, more preferably 13 parts by mass, based on 1 part by mass of the total of the thermoplastic resin (A1) and the thermoplastic resin (A2). The amount is 45 parts by mass or less, more preferably 15 parts by mass or more and 35 parts by mass or less. When the blending amount of the inorganic filler (B) is less than 10 parts by mass based on 100 parts by mass of the total of the thermoplastic resin (A1) and the thermoplastic resin (A2), the heat resistance may not be exerted to cause an upward effect. On the other hand, when it is more than 50 parts by mass, cerium oxide is poorly dispersed and the viscosity of the solution becomes too high to cause defects in workability or a decrease in adhesion. &lt;Solvent (C)&gt; The solvent (C) used in the present invention may be a single component or a mixed solvent of two or more plural components. The solvent ((:) is not particularly limited as long as it is a thermoplastic resin (A 1 ), a thermoplastic resin (a 2 ), and an epoxy resin (D). Examples of such a solvent include dimethyl acetamidine. A phthalamide solvent such as an amine or N-methyl-2-pyrrolidone; an alcohol solvent such as methanol or ethanol 'isopropyl alcohol; an aromatic solvent such as toluene or xylene; or a ketone system such as acetone, methyl ethyl ketone or cyclohexanone. The ester solvent such as a solvent or an ethyl acetate is preferably a toluene, xylene, methyl ethyl ketone or ethyl -27-201207059 acid ethyl ester from the viewpoint of workability, and is further improved from the viewpoint of easiness of drying. The solvent is preferably used in the form of toluene, methyl ethyl ketone or ethyl acetate. These solvents may be used alone or in combination of two or more. &lt;Epoxy Resin (D)&gt; The resin composition for an adhesive of the present invention contains an epoxy resin (D) having a dicyclopentadiene skeleton as an essential component. The hardened coating film formed of the epoxy resin having a rigid dicyclopentadiene skeleton has an extremely low moisture absorption rate, and further, since the crosslinking density of the cured coating film can be lowered and the stress at the time of peeling is relaxed, the humidification resistance is enhanced. Improved weldability. Specific examples of the epoxy resin (D) include the DIC HP7200 series. The blending amount of the epoxy resin (D) having a dicyclopentadiene skeleton is preferably 60% by mass or more, more preferably 75% by mass or more, based on the total amount of the epoxy resin contained in the resin composition for an adhesive. Good is 90% by mass or more. By containing 60% by mass or more of the epoxy resin (D) having a dicyclopentadiene skeleton, it is possible to exhibit more excellent wet solder resistance. When the resin composition for an adhesive of the present invention further contains an epoxy resin containing a nitrogen atom as an epoxy resin, the adhesive sheet can be B-staged (semi-hardened) by heating at a low temperature and for a short period of time. In addition, it is preferable to suppress the fluidity of the adhesive sheet, suppress the extrusion and discharge of the adhesive during pressurization, and improve the workability, and it is preferable to suppress the foaming effect at the time of pressurization. . In the case of an epoxy resin containing a nitrogen atom, for example, tetraepoxypropyldiaminediphenylmethane, triepoxypropyl-aminophenol, tetraepoxypropyldiaminomethylcyclohexane may be mentioned. Ketone, N, N, N', N'-tetra-28-201207059 Epoxypropylamine such as epoxypropyl-m-xylenediamine. The blending amount of the epoxy resin of the atom is preferably the following or less of the entire epoxy resin. When the blending amount is more than 20% by mass, the rigidity is high and the adhesiveness tends to be lowered, and the crosslinking reaction tends to excessively decrease the adhesion of the adherend. Further, the adhesive cross-linking reaction is easy to proceed, and the sheet life is lowered, and the upper limit of the blending amount is 1% by mass, more preferably 6% by mass, as the epoxy resin used in the present invention. other. Examples thereof include an ether type such as bisphenol A diglycidyl ether, bisphenol S diepoxy novolac epoxy propyl ether, brominated bisphenol A diglycidyl ether, and hexahydrophthalic acid propylene cyanide. Base ester, dimer acid glycidyl ester type, triepoxypropyl isocyanate, or 3,4-epoxy carboxylic acid ester, epoxidized polybutadiene, large epoxidation An aliphatic epoxide such as soybean oil may be used alone or in combination with two kinds of curing reactions which are used in the epoxy resin of the present invention. For example, an imidazole compound such as 2-methylimidazole, 1,2-dimethylimidazole, methylimidazole or 2-phenyl-4-methylimidazole, 1-cyanoethyl-2-ethyl or imidazole may be mentioned. Triethylamine, triethylenediamine, N(2-dimethylaminoethyl) piped, 1,8-dioxabicyclo(5,4,0)·d 1,5-diindole bicyclic (4, 3,0)-terpene-5,6-dibutylamino-1,8-(5,4,0)-undecene-7 and other tertiary amines and the tertiary amines, octanoic acid a tetrabasic boric acid tetraphenylacetate or the like as an amine salt, a cationic catalyst such as triallyl citrate or a bismuth hexafluoroantimonate or the like, containing 60% by mass of nitrogen, excessively changing, and having a pair of flakes Guarantee. More preferably, epoxy propyl ether, epoxy propyl, etc., propylene oxide, cyclohexylmethyl or aliphatic (top. with hardened 2, ethyl-4-yl-4-methylmethyl-hydrazine-- It is suspected that -7, bisbicyclic phenols, hexafluoro-hf--tf-, di-based -29-201207059 phosphine, etc.. Among these, 1 ,8-dioxinbicyclo (5,4,0 )-undecene-7,1,5-dioxabicyclo(4,3,0)-nonene-5,6-dibutylamino-1,8-diguanidine (5,4,0)- a compound of a tertiary amine such as undecene-7 and a tertiary amine such as phenol, octanoic acid or tetrabasic boronic acid tetrabasic ester, which is an amine salt, has thermosetting property, heat resistance, and adhesion to metal. In addition, it is preferable that the blending amount after blending is 100 parts by mass or more based on 100 parts by mass of the total of the thermoplastic resin (A 1 ) and the thermoplastic resin (A2). In the range of 〇 by mass, the blending amount of the thermoplastic resin (A1) and the thermoplastic resin (A2) and the epoxy resin is further increased, and strong adhesive properties can be obtained. &lt;Other Additives&gt; The resin composition for an adhesive of the present invention may be appropriately blended with a flame retardant such as a bromine-based, phosphorus-based, nitrogen-based or metal hydroxide compound, a flame retardant auxiliary, a heat stabilizer, or the like. Additives such as antioxidants, decane coupling agents, slip agents, leveling agents, pigments, dyes, and the like. Further, the blending of the antioxidant is preferable as a means for improving the adhesion at a high temperature, a high temperature, a high humidity, and the adhesion strength. The antioxidant is, for example, a hindered phenol-based or phosphorus-based antioxidant. Specifically, the hindered phenol type may, for example, be a 1,3,5-glycol (3,5-di-tri-butyl-4-hydroxybenzyl)isomeric cyanurate or 1,1,3. -Tris(4-hydroxy-2-methyl-5-tributylphenyl)butane, hydrazine, ι_bis(3-tributylbutyl-6-methyl-4-hydroxyphenyl)butane ,3,5-bis(1,1-dimethylethyl)-4-hydroxy-phenylpropionic acid, pentaerythritol 肆[3-(3,5-di-tertiary butyl-4-hydroxybenzene) Propionate, 3-(1,1-dimethylethyl)_4hydroxy-5-methyl-phenylpropionic acid, 3,9-bis[l,l-di-30- 201207059 methyl-2 - [(3 -Tributyl-4-hydroxy-5-methylphenyl)propanoxy]ethyl]-2,4,8,10-tetraoxaspiro[5.5] Eleven, 1, 3,5-trimethyl-2,4,6-paran (3,5'-di-tertiary butyl-4'-hydroxybenzyl)benzene, octadecyl-3-(3,5- Di-tertiary butyl-4-hydroxyphenyl)propionate, 2,5-di-tert-butylhydroquinone, 4,4,-butylene bis(3-methyl-6-tertiary butyl Phenol), 1,1,3·g (2-methyl-4-hydroxy-5-tributylphenyl)butane, 1,3,5-paraxyl-methyl-2,4,6-para (3,5-di-tri-butyl-4-hydroxybenzyl)benzene, ginseng (3,5-di-tertiary butyl-4- Benzylphenyl)isomeric cyanurate or the like, or such derivatives, in the case of phosphorus, 3,9-bis-(p-nonylphenoxy) 2,4,8,10 -tetraoxo-3,9-diphosphospiro[5.5]undecane, 3,9-bis(octadecyloxy)-2,4,8,10-tetraoxa-3,9-diphosphorane [ 5.5] undecane, diethyl [[3,5·bis(1,b-dimethylethyl)-4-diacylphenyl]methyl]phosphonate, tris(monodecylphenyl) Phosphate ester, triphenyloxyphosphine, isodecyl phosphite, isodecyl phenyl phosphite, diphenyl-2-ethylhexyl phosphite, dimercaptophenyl bis(nonylphenyl) ester Phosphoric acid, H3-sodium (2-methyl-4-di-tridecyl phosphite-5-tris-butylphenyl) butyl, ginseng (2,4-di-tertiary butylphenyl) Phosphate, neopentyl bis (2,4-di-tert-butylphenyl phosphite), 2,2-methylenebis(4,6-di-tert-butylphenyl)-2 _Ethylhexyl phosphite, bis(2,6-di-tert-butyl-4-methylphenyl)neopentitol diphosphite, or such derivatives, which may be separately Or use in combination. The amount of the antioxidant added is preferably 5% by mass or less. If it is more than 5% by mass, the adhesiveness may be adversely affected. -31-201207059 The resin composition for an adhesive of the present invention may be blended with a decane coupling agent as needed. The properties of adhesion to metal and heat resistance are enhanced by blending a decane coupling agent. The decane coupling agent is not particularly limited, and examples thereof include those having an unsaturated group, those having an epoxy group, and those having an amine group. Examples of the decane coupling agent having an unsaturated group include vinyl stilbene (β-methoxyethoxy) decane, vinyl triethoxy decane, vinyl trimethoxy decane, and the like. Examples of the decane coupling agent having a glycidyl group include γ-glycidoxypropyltrimethoxydecane and β-(3,4-epoxycyclohexyl)ethyltrimethoxydecane. --(3,4-epoxycyclohexyl)ethyltriethoxydecane, and the like. Examples of the decane coupling agent having an amine group include Ν·β-(aminoethyl)-γ-aminopropyltrimethoxydecane and Ν-β-(aminoethyl)·γ-amine. Propyl propyl dimethoxy decane, fluorenyl-phenyl-γ-aminopropyltrimethoxy decane, and the like. Among these, γ-glycidoxypropyltrimethoxydecane, β-(3,4-epoxycyclohexyl)ethyltrimethoxydecane, β is further preferable from the viewpoint of heat resistance. a decane coupling agent having a glycidyl group such as (3,4-epoxycyclohexyl)ethyltriethoxydecane. The blending amount of the decane coupling agent is preferably 0.5 parts by mass or more and 2 parts by mass or less based on 1 part by mass of the total of the thermoplastic resin (?1) and the thermoplastic resin (?2). When the blending amount of the decane coupling agent is less than 0.5 parts by mass based on 100 parts by mass of the total of the thermoplastic resin (Α1) and the thermoplastic resin (Α2), the resulting adhesive may become poor in heat resistance. When it is more than 20 parts by mass, the heat resistance may be poor and the adhesion may be poor. -32- 201207059 &lt;Adhesive sheet&gt; In the present invention, the term "adhesive sheet" includes the thermoplastic resin (A i ), the thermoplastic resin (A 2 ), and the inorganic filler (including the thermoplastic resin (A 2 )) contained in the adhesive resin composition of the present invention. B), the epoxy resin (D) and the reaction product of the above are referred to as at least a part of the responder as a B-stage state (semi-hardened state). In the pressurizing step in the production of F P C, the fluidity of the adhesive sheet 'viscosity is related to the outflow at the time of pressurization, and the excessive outflow leads to a decrease in the ig dependence of the product or an increase in the defective ratio. The adhesive sheet preferably has a B-stage state which suppresses the above-described outflow. In the present invention, the adhesive sheet may be the thermoplastic resin (A1), the thermoplastic resin (A2), the pre-inorganic chelating material (B), and the epoxy resin (including the thermoplastic resin (A2) contained in the resin composition for an adhesive of the present invention. D) and a sheet composed of a layer of the reaction product derived from the above, or the thermoplastic tree (A1) contained in the resin composition of the adhesive of the present invention, or the release base material, or the aforementioned The sheet composed of the thermoplastic resin (A2), the inorganic filler (B), the epoxy resin (D), and the layer derived from the reaction product may be formed of a substrate or a release substrate and The thermoplastic resin (A1), the thermoplastic tree (A2), the inorganic chelating material (B), the epoxy resin (D), and the reaction product derived from the same, which are contained in the fat composition for an adhesive of the present invention The layer and the sheet formed by the release substrate. The thermoplastic resin (A) contained in the resin composition for an adhesive of the present invention, the thermoplastic resin (A2), the inorganic chelating material (B), the ring resin (D), and a reaction product derived therefrom The layer system can be formed on the base material of the substrate by the thin layer of the raw fat containing resin. * The thin layer of the resin, the oxygen-33-201207059 can also be formed on both sides. Further, the adhesive sheet may contain a small amount or a small amount of a solvent (C). The adhesive sheet has a function of adhering the substrate to the adherend by the resin composition for the adhesive. The substrate of the adhesive sheet acts as a protective layer for the adhered material after adhesion. Further, if a release substrate is used as the substrate of the adhesive sheet, the release substrate can be released from the mold, and the adhesive layer can be transferred to the other adhesive. The adhesive sheet of the present invention can be obtained by applying the resin composition for an adhesive of the present invention to various substrates in accordance with a usual method, and removing at least a part of the solvent and drying. When at least a part of the solvent is removed and dried, 'If the release substrate is attached to the adhesive layer, it can be wound without being transferred to the substrate and is excellent in handleability, and is protected by the adhesive layer. Therefore, it is easy to use. Further, after application to the release substrate and drying, the adhesive layer may be transferred to another substrate if another release substrate is attached as needed. Here, the substrate to which the resin composition for an adhesive of the present invention is applied is not particularly limited, but a film-like resin, a metal plate, a metal foil, a paper, or the like can be given. The film-like resin may, for example, be a polyester resin, a polyamide resin, a polyimide resin, a polyamide amide resin or an olefin resin. Examples of the material of the metal plate and the metal foil include various metals such as SUS, copper, aluminum, and iron 'zinc, and alloys and plating products thereof. For the paper, W-paper, kraft paper, and paper roll can be exemplified. Cellophane, etc. Further, in the case of a composite material, a TF glass epoxy resin or the like can be exemplified. From the viewpoint of the adhesion and durability of the composition of the sapphire with the adhesive, it is preferred to apply the adhesive of the present invention-34-201207059. The substrate of the resin composition is preferably a polyester resin or a polyamide. Resin, polyimine resin, polyamidimide resin, SUS steel plate, copper foil, aluminum foil, glass epoxy resin. In addition, the release base material to which the resin composition for an adhesive of the present invention is applied is not particularly limited, and for example, clay is formed on both sides of paper such as a good quality paper, a kraft paper, a paper roll, or a cellophane. a coating layer of an admixture such as ethylene or polypropylene, and a polyfluorene-based, fluorine-based or alkyd-based release agent applied to the respective coating layers, and the release agent is applied to polyethylene or polypropylene. , ethylene-α-olefin copolymer, propylene-α-olefin copolymer and other olefin films, on the polyethylene phthalate film, but due to the release force of the coated adhesive layer, polyoxygen For the reason that the electrical properties are adversely affected, it is preferred to carry out the polypropylene charging treatment on both sides of the good paper, and to use the alkyd-based release agent thereon, and to use the alkyd-based release agent on the polyethylene terephthalate. By. Further, in the present invention, the method of applying the resin composition for an adhesive to a substrate is not particularly limited, and examples thereof include a chamfer coater (c 〇mmac 〇ater) and a reverse light coater. (re ν erser ο 11 c 〇ater) and so on. Alternatively, the pressure-sensitive adhesive layer may be provided directly or by a transfer method on the rolled copper foil or the polyimide film of the printed wiring board constituent material as needed. The thickness of the adhesive layer after drying may be appropriately changed as needed, but is preferably in the range of 5 μm or more and 200 μm or less. In the case where the thickness of the adhesive layer is less than 5 μm, the adhesive strength is insufficient. When the thickness of the pressure-sensitive adhesive layer is more than 200 μm, there is a problem that drying is insufficient and residual solvent is increased, and bubbles are generated during pressurization of the printed wiring board. The drying conditions are not particularly limited, but the residual solvent after drying -35 - 201207059 is preferably 4% or less. When the residual solvent ratio after drying becomes larger than 4%, there is a problem that bubbles are generated in the residual solvent when the printed wiring board is pressurized, and bubbles are generated. &lt;Printed wiring board&gt; The printed wiring board of the present invention includes a laminate formed of a metal foil forming a conductor circuit and a resin layer as a constituent element. The printed wiring board is produced by, for example, a conventional method known as a subtractive method using a metal-clad laminate. The conductor circuit formed of the metal foil is partially or completely covered with a cover film or a screen printing ink as needed, and is generally called a flexible circuit board (FPC), a flat cable, and a tape automatic. A board for bonding (TAB), etc. The printed wiring board of the present invention can be formed as any laminated layer which can be used as a printed wiring board. For example, a printed wiring board composed of four layers of a base film layer, a metal foil layer, an adhesive layer, and an overlying film layer can be used. Further, for example, a printed wiring board composed of five layers of a base film layer, an adhesive layer, a metal foil layer, an adhesive layer, and an overlying film layer can be used. The printed wiring board is sometimes reinforced with a reinforcing material as needed, in which case the reinforcing material and the adhesive layer are disposed under the substrate film layer. Further, it is also possible to form two or three or more layers of the above-mentioned printed wiring board as needed. The resin composition for an adhesive of the present invention can be suitably used for each adhesive layer of a printed wiring board. In particular, when the resin composition for an adhesive of the present invention is used as an adhesive, the substrate constituting the printed wiring board has a high-36-201207059 adhesive property and has a high heat resistance corresponding to lead-free solder, and even High adhesion can also be maintained at high temperatures and temperatures. In particular, in the high-temperature field in which solder resistance is evaluated, 'the chemical crosslinking of the resin and the resin is used to balance the physical crosslinking of the resin and the inorganic chelating material, and the soldering resistance can be prevented. It is suitable for the adhesion between the metal foil layer and the overlying film layer and the adhesion between the substrate film layer and the reinforcing layer by the evaporation caused by the evaporation of water during the test. In particular, when a metal reinforcing material such as a SUS plate or an aluminum plate is used, when it is welded in a humidified state, since the moisture cannot be evaporated from the reinforcing material side, the adhesive layer between the base film layer and the reinforcing layer is washed. In particular, it is suitable as a resin composition for adhesion in such a case. In the printed wiring board of the present invention, the base film can be used from a substrate which has been conventionally used as a printed wiring board. Any resin film. As the resin of the base film, a halogen-containing resin or a halogen-free resin can be used. From the viewpoint of environmental problems, a halogen-free resin is preferred, but a halogen-containing resin can also be used from the viewpoint of flame retardancy. The base film is preferably a polyimide film or a polyimide film. As the metal foil used in the present invention, any conventionally known conductive material which can be used for a circuit board can be used. For the material, for example, a copper foil, an aluminum foil, a steel foil, a nickel foil, or the like may be used, and a metal foil which is treated with other metals such as a composite metal foil, zinc or a chromium compound may be used. It is preferably copper foil. -37-201207059 The thickness of the metal foil is not particularly limited, but is preferably more preferably 3 μm or more and more preferably 1 μm or more. ' is preferably 50 μm or less, more preferably 30 μm or less, and further less than 20 μm. When the thickness of the metal foil is too thin, the circuit may have sufficient electrical properties. On the other hand, if the thickness of the metal foil is too thick, the processing efficiency during circuit fabrication may be lowered. The metal foil is usually provided in the form of a roll. The form of the metal foil used in the production of the printed wiring board of the present invention is not particularly limited. In the case of a metal foil in the form of a roll, the length thereof is not particularly limited. Further, the degree is not particularly limited, but is preferably in the range of from 25 mm to 5,000 mm. As the above-mentioned film, any insulating film which is conventionally known as a film for a printed wiring board can be used. For example, polyfluorene, polyester, polyphenylene sulfide, polyether oxime, polyetheretherketone, aramid, polycarbonate, polyarylate, imine, polyamidoxime can be used. A film made of various polymers such as amines. Further, a polyimide film or a polyimide film is further preferably a polyimide film. The polyimide film has a polyimine tree as a main component in terms of its resin component. Among the resin components, 90% by mass or more is preferably a polyamine, more preferably 95% by mass or more is a polyimine, and more preferably a polyvalent imine or more, and particularly preferably 99% by mass or more. In the case of a polyimine resin, any of the conventionally known resin rice can be used, and it is difficult to use it when it is difficult to use it. The thin imine amide is used as the bismuth linoleum. 98 amines. -38- 201207059 For the material of the film coated with a film, a halogen-containing resin or a halogen-free resin can be used. From the viewpoint of environmental problems, it is a halogen-free resin, but from the viewpoint of flame retardancy, it is also a halogen resin. For the reinforcing material, a metal imide film such as a SUS plate or an aluminum plate, or a plate (glass plate) obtained by curing glass fibers with an epoxy resin is used. In particular, the resin composition for an adhesive of the present invention exerts a great performance on the adhesion of an aluminum plate to a polyimide film, and its heat resistance shows extremely excellent performance. The printed wiring board of the present invention can be produced by using any of the above-described layers in addition to the above-described respective layers. In a preferred embodiment, a semi-finished product (hereinafter referred to as an "overcoat film side semi-product J" surface) is formed by laminating an adhesive layer, and a metal foil is laminated on the base film layer to form a pattern. A semi-finished product (hereinafter referred to as "substrate film side two-layer half-layer" is a semi-finished product in which a desired circuit pattern of a metal foil is laminated on a base film layer and a metal foil is laminated thereon (hereinafter referred to as "substrate film {! j) (hereinafter, the two-layered semi-finished product on the base film side is referred to as "substrate film-side semi-product"), and the film-side semi-finished product and the base film are laminated. A semi-finished product, a layer or a 5-layer printed wiring board. Further, a semi-finished product (hereinafter referred to as a "reinforcing material side semi-product") in which an adhesive layer is formed in a strong material layer can be attached to a base film layer of a printed wiring board. For the resin, it is preferable to use a plate, a glazed epoxy SUS plate, an adhesive, or a material to cover the film. The other circuit 匕J) or the layer to form PJ 3 Layer half PJ 3 layer half system can be obtained by adding 4 layers. Also depending on the need, can also be used -39-201207059 adhesive between the reinforcing member and the base film coated release substrate 'base film and transferred to the back surface of the printed wiring board "and bonded with the reinforcing member. The base film side semi-product is a step of applying a solution of a resin which becomes a base film to the metal foil, for example, to perform initial drying of the coating film, and 2) drying the metal foil obtained by 1) with initial drying. The laminate of the coating film is obtained by a method of heat treatment and drying (hereinafter referred to as "heat treatment and solvent removal step"). The formation of the circuit in the metal foil layer can be carried out by a conventionally known method. Addition methods can be used, and subtraction methods can also be used. Preferably, the subtraction method. The obtained base film side semi-finished product may be used as it is for bonding to the overcoat film side semi-finished product, or may be used for attaching and detaching the release film to the overlying film side semi-product. Hehe. The overcoat film side product is produced by, for example, applying an adhesive to an overlying film. The crosslinking reaction in the applied adhesive can be carried out as needed. In a preferred embodiment, the adhesive layer is semi-hardened. The obtained overcoat film side product can be used as it is for bonding to the substrate-side semi-finished product, or can be bonded to the substrate film-side semi-product after the release film is attached and stored. The base film side semi-product and the overcoat film side semi-product are each stored in the form of, for example, a roll, and bonded to each other to produce a printed wiring board. In the case of the bonding method, any method can be used, and it can be bonded by using, for example, a press or a roll. Further, the two may be bonded together by heating or pressurizing or by using a heating roll device or the like while heating. • 40- 201207059 The reinforcing material side semi-product is suitable for the production of an adhesive by applying the adhesive to a reinforcing material in the case of a soft and retractable reinforcing material such as a polyimide film. Further, for example, in the case of a hard plate which is hard and cannot be wound up, such as a metal plate such as s US or aluminum, a plate in which glass fibers are hardened with an epoxy resin, or the like, adhesion to a release substrate is previously applied. It is suitable if the agent is subjected to transfer coating. Further, a crosslinking reaction in the applied adhesive can be carried out as needed. In a preferred embodiment, the adhesive layer is semi-hardened. The obtained reinforcing material side semi-finished product can be used as it is for bonding to the back surface of the printed wiring board, or can be bonded to the base film side semi-product after the release film is attached and stored. In the present invention, the base film side semi-product, the overcoat film side semi-product, and the reinforcing agent side semi-product are bonded to the adherend and then hardened by heat treatment. The conditions of the heat treatment are not particularly limited, but are preferably 130 ° C or more and 180 ° C or less and 1 hour or more and 5 hours or less. The base film side semi-product, the overcoat film side semi-product, and the reinforcing agent side semi-product are all laminated bodies for the printed wiring board of the present invention. [Examples] The examples are described below in order to explain the present invention in more detail, but the present invention is not limited to the examples. Further, in the examples, the parts are all parts by mass. Further, when it is referred to as an epoxy resin blending ratio without special attention, it is referred to as the following formula (4). {EV(D)xEW(D)}/{AV(Al) χ AW (A 1) + AV (A 2) x AW (A 2)} -41 - (4) 201207059 (Physical evaluation method) (1) Composition of Thermoplastic Resin The thermoplastic resin was dissolved in deuterated chloroform, and the molar ratio of each component was separated by iH-NMR. However, the thermoplastic resin was not dissolved in deuterated chlorine and dissolved in deuterated dimethyl hydrazine to carry out 1 H-NMR analysis. (2) The number average molecular weight Μη The sample is dissolved or diluted in tetrahydrofuran to make the resin concentration 〇. Right' and the polytetrafluoroethylene membrane filter having a pore diameter of 0.5 μm is used as a sample for measurement, and tetrahydrofuran is used as a mobile phase. The molecular weight was determined by gel permeation chromatography using a differential meter as a detector. The flow rate was 1 niL/min and the column temperature was set to 30 °C. The column is made of Showa KF-802 and 804L' 806L. Single-part styrene is used in terms of molecular weight standards. However, when the sample was not dissolved in tetrahydrofuran, N,N-dimethylformamide was used for the tetrahydrofuran. (3) The glass transition temperature was measured by using a differential scanning calorimeter, and 1 mg of the measurement sample was placed in an aluminum pan under a pressure to be sealed, and a differential scanning analyzer (DSC) DSC-2〇0 manufactured by Seiko Instruments was used. The temperature rise rate of t/min is determined by the intersection of the extension line below the transition temperature of the glass transition and the tangent to the tangent line showing the inclination of the migration portion, that is, the transition temperature of the extrapolated glass transition. (4) Acid value 0.2 g of the sample was dissolved in 20 ml of chloroform, and phenolphthalein was used as an instruction to titrate with a 0.1 N potassium hydroxide ethanol solution, and the resin was calculated to be eq. (eq/io6g). Set to electrician to dissolve, to heat, to find the best, equivalent -42- 201207059 (5) epoxy oxime according to JIS K 7236, using perchloric acid titration method from the epoxy equivalent (containing 1 equivalent of ring The mass of the resin of the oxy group) was calculated to be equivalent to the equivalent of 6 g of the resin (eq/106 g). (6) Dynamic viscoelasticity measurement The resin composition for an adhesive is applied to a polypropylene film (PYLEN, manufactured by Toyobo Co., Ltd.) having a thickness of 50 μm, and the thickness after drying is in the range of 30 μm or more and 40 μm or less. The adhesive sheet was obtained by drying at 130 t for 3 minutes. Then at 1 4 0. (: The heat-treated coating film was obtained by heat treatment for 4 hours. The hardened coating film was peeled off from the polypropylene film to prepare a short-shaped sample having a width of 4 mm and a length of 15 mm. The dynamic viscoelasticity measuring device DVA-22 manufactured by IT Measurement and Control Co., Ltd. was used. 〇' The temperature dispersion measurement of the dynamic viscoelasticity of the short-stacked sample was carried out at a temperature increase rate of 10 Hz and 4 ° C /min, and the storage elastic modulus, the loss elastic modulus, and the loss tangent (tan5) were determined. In the table, it is described as "-", and it is not measured. (Characteristic evaluation method) (1) Solderability and peel strength (1 -1 ) Evaluation Sample 1 is prepared by applying the adhesive composition described later to the thickness of 2 A 5 micron polyimine film (APICAL, manufactured by Kaneka Co., Ltd.) was dried to a thickness of 30 μm and dried at 130 ° C for 3 minutes. The adhesive sheet thus obtained was 18 μm. When the rolled copper foil is bonded, the shiny side of the rolled copper foil is brought into contact with the adhesive and pressurized at 160 ° C under a pressure of 35 kgf / cm 2 for 30 seconds - 43 - 201207059 and adhered. Then in 1 Heat treatment at 40 °C for 4 hours to harden it to obtain solder resistance Sample 1 for peel strength evaluation (for initial evaluation). Further, after the adhesive sheet was left to stand at 40 ° C and 80% humidification for 14 days, the steel sheet was pressed under the above conditions and heat-treated. It was hardened, and the sample 1 for the evaluation of the time was obtained. (1-2) The sample 2 for evaluation was used, and the resin composition for adhesives mentioned later was apply|coated to the polypropylene film of the thickness of 50 micrometer (made by Toyobo Co., Ltd., PYL EN), the thickness after drying was 30 μm, and dried at 130 ° C for 3 minutes to obtain an adhesive sheet. The evaluation substrate was obtained by laminating a single-sided copper-clad laminate (25 μm polyimide film, 18 μm film) The copper-clad foil is produced and hardened by a general circuit fabrication step (opening, plating, dry film photoresist (hereinafter sometimes referred to as DFR), + exposure, development, etching, DFR peeling) to obtain an evaluation substrate. The polyimide film surface of the substrate for evaluation thus obtained is placed against the coated surface of the adhesive resin composition of the adhesive sheet, and then the polypropylene film is peeled off, and the SUS 3 of 500 μm is peeled off. 04 board at 160 ° C at 30kgf / After pressurizing for 1 minute under the pressure of cm2, the adhesive was applied as a reinforcing plate, and then heat-treated at 140 ° C for 4 hours to be cured, thereby obtaining sample 2 (sample for initial evaluation) for evaluation of solder resistance and peel strength. After the sheet was left to stand at 4 ° C and 80% humidification for 14 days, the substrate for evaluation was changed to a rolled copper foil, and the same conditions were applied to pressurize and heat-treat the sample to obtain a sample for evaluation by time. 2. The evaluation of each characteristic is carried out by the following method: -44- 201207059 • Solderability (Humidification) Place the sample of 25 mm square at 4 °C and humidification at 80% for 2 days. It floated in a heated solder bath for 1 minute, and the upper limit temperature at which no bubbles were generated was measured at a pitch of 1 °C. In this test, those having a high degree of measurement showed good heat resistance, but it is also necessary to suppress the evaporation caused by evaporation of water vapor contained in each substrate or the adhesive layer, and it is required to have stricter heat resistance than the dry state. When considering the practicality as an FPC reinforcing plate, it is preferably 250 ° C or higher, more preferably 260 ° C or higher. • Peel strength The peel strength was measured at a stretching speed of 5 mm/min at 25 ° C using RTM100 manufactured by Toyo Baldwin. Further, the sample for evaluation was subjected to a 90° peel test, and the sample for evaluation 2 was subjected to 丨80. Peel test. This test shows the adhesion strength at room temperature. The practicality of the F P C reinforcing plate is preferably ΙΟΝ/cm or more, and more preferably i5 N/cm or more. (2) Adhesive strength retention in a high-temperature environment Using the above-mentioned sample 2 for evaluation of solder resistance and peel strength (for initial evaluation and evaluation by time), a weight of 2 〇〇g was suspended in a high temperature environment, and the measurement was performed. The distance of peeling off during 1 to 5 minutes is measured by 间距0 at a distance of 4 mm or less, that is, the upper limit. In addition, the suspension method of the scale hammer was set to 180 in the peeling form. Peeling was performed. The sample width was tested in 丨〇 mm. The higher the measured enthalpy in this test, the better the adhesion strength and the adhesion strength retention at high temperatures. If practical performance is considered, it is preferably 1 〇〇 r or more, and more preferably 150. (: The above is more preferably 200 ° C or higher. -45- 201207059 (3) High-temperature and high-humidity environment test The sample 2 (for initial evaluation) with the above-mentioned solder resistance and peel strength evaluation of 10 mm width is placed. In the 85 t, 85% humidified environment, the peel strength of 1 80° after 500 hours and after 1 000 hours was measured. This test was evaluated in a high temperature and high humidity environment for the purpose of confirming the reliability in actual use. The durability is preferably 5 N/cm or more, more preferably 1 ON/cm or more. (4) Drop hammer punching test The resin composition for an adhesive described later is applied to a polypropylene film having a thickness of 50 μm (Toyo Textile Co., Ltd. Co., Ltd., PYLEN), the thickness after drying is 30 microns, and dried at 130 ° C for 3 minutes to obtain an adhesive sheet. The adhesive sheet is fixed to a steel plate in a 25 t environment to make a resin composition for the adhesive. The layer of the steel metal jig (jig) having a hemispherical shape of 10 mm in diameter at the front end is fixed to the surface of the adhesive composition without sliding, and is attached to the layer of the resin composition for the adhesive. Plane part. from 50 mm At a height of 500 mm, a 76 g metal scale was dropped on the flat portion of the upper portion of the steel metallizing tool at a pitch of 50 mm, and the upper limit height of cracks, cracks, and cracks in the adhesive sheet was measured. The higher the measurement, the stronger the punching or deformation. In the processing steps of FPC manufacturing, the cutting and punching 'slit processing is not easy to cause cracks, cracks, cracks, and is related to the improvement of the operability and the defective rate. It is preferably 1 mm or more and more preferably 200 mm or more. (Judgement) a: 200 mm or more, -46-201207059 b: 100 mm or more and less than 200 mm, c: less than 1 0 0 mm. (5) Low-temperature bending test A resin composition for an adhesive to be described later was applied to a polypropylene film (PYLEN, manufactured by Toyobo Co., Ltd.) having a thickness of 50 μm so that the thickness after drying became 30 μm at 130°. C. The adhesive sheet was dried for 3 minutes to obtain an adhesive sheet. After the adhesive sheet was allowed to stand at 5 ° C for 24 hours or more, the layer of the resin composition for the adhesive was bent inside at 5 ° C for 1 time. Crack The presence or absence of cracks. Cracks and cracks are not likely to cause cracks or cracks during cutting, punching, or slit processing at the time of FPC production, which can reduce the rate of defective products. (Judgement) a: None Cracks, cracks, b: cracks, cracks. &lt;Polymerization Example of Polyester Resin A&gt; In a reaction tank equipped with a stirrer, a thermometer, and a chiller for effluent, 208 parts of citric acid, 208 parts of isononanoic acid, and 2-methyl-1,3- 360 parts of propylene glycol, 90 parts of 1,4-butanediol, and 0.2 parts of tetrabutyl titanate, it took 4 hours to slowly raise the temperature to 240 ° C and removed the distilled water to the outside of the system. Esterification reaction. After the end of the esterification reaction, the pressure was reduced to 1 mmHg for 3 minutes to carry out initial polymerization and the temperature was raised to 250 °C and then 30 minutes of post-polymerization was carried out below 1 mmHg. Thereafter, 27 parts of pyromellitic anhydride was introduced by returning to normal pressure with nitrogen, and the mixture was reacted at 180 ° C for 15 minutes to obtain a polyester-47-201207059 resin A. The composition of the obtained polyester resin A thus obtained was shown in Table 1. Each measurement evaluation item is in accordance with the above method. &lt;Polymerization Example of Polyester Resin B&gt; In a reaction tank equipped with a stirrer, a thermometer, and a chiller for effluent, 166 parts of citric acid, 162.7 parts of isononanoic acid, and 3 to 8 parts of methyl-1 of phthalic anhydride were charged. 306 parts of 3-propanediol, 70.8 parts of 1,6-hexanediol, and 0.2 parts of titanic acid were used, and the temperature was gradually raised to 24 ° C for 4 hours, and the esterification reaction was carried out while removing the distilled water to the outside of the system. After the end of the esterification reaction, the pressure was reduced to 10 mmHg for 30 minutes to carry out initial polymerization and the temperature was raised to 250 ° C, and further polymerization was carried out for 1 hour under 1 mmHg. One part of the resin was placed in a reaction vessel equipped with a stirrer, a thermometer, and a reflux-type cooling distillation tube, and 140 parts of toluene was added thereto, and then toluene was distilled, and the reaction system was dehydrated by azeotropy of toluene/water. After cooling at ° C, by adding 80 parts of methyl ethyl ketone, 7 parts of 3,3',4,4'-diphenyl ketone tetracarboxylic anhydride, and 0.1 part of DMAP (dimethylaminopyridine) at 70 ° C for 4 hours. A solution of the polyester resin B was obtained. The composition and characteristics of the polyester crucible thus obtained are shown in Table 1. &lt;Polymerization Example of Polyester Resin C&gt; In a reaction tank equipped with a stirrer, a thermometer, and a chiller for effluent, 203 parts of citric acid, 203 parts of isononanoic acid, 9.6 parts of 1,3-tricarboxylic acid 1,3-partic acid were charged, 177 parts of neopentyl glycol and 2 parts of tetrabutyl titanate, and the temperature was slowly raised to 240 ° C, and the esterified reaction was carried out while removing the saturated water to the system. 30 minutes after the end of the esterification reaction

値示 內， 、2-丁酯 出之 花費 溫至 所得 管及 60份 至60 酸二 反應 f脂B 內， 、乙 t 4小 統外 至10 -48- 201207059 毫米汞柱進行初期聚合並且將溫度升溫至250 °C，再在1毫 米汞柱以下進行30分鐘後期聚合。其後，用氮回到常壓， 投入ε-己內酯3 99份，藉由在200 °C使其反應1小時而得到 聚酯樹脂C。將如此進行所得之聚酯樹脂C之組成、特性 値示於表1。各測定評價項目係依照上述之方法。 &lt;聚酯樹脂D之聚合例&gt; 於裝備攪拌器、溫度計、流出用冷卻器之反應罐內， 裝入對酞酸99.6份' 異酞酸99.3份、癸二酸161.6份、苯偏 三酸酐3.8份、2 -甲基-1,3 -丙二醇248.4份、1,4 -丁二醇 1 1 1 .6份、鈦酸四丁酯0.2份，花費4小時徐徐地升溫至240 °C，並一邊將餾出之水除去至系統外一邊進行酯化反應。 酯化反應結束後花費3 0分鐘減壓至1 0毫米汞柱進行初期聚 合並且將溫度升溫至250 °C，再在1毫米汞柱以下進行45分 鐘後期聚合。其後，用氮回到常壓，投入苯偏三酸酐3.8 份，藉由在22(TC使其30分鐘反應而得到聚酯樹脂D。將如 此進行所得之聚酯樹脂D之組成、特性値示於表1。各測定 評價項目係依照上述之方法。 &lt;聚酯樹脂E之聚合例&gt; 於裝備攪拌器、溫度計、流出用冷卻器之反應罐內， 裝入對酞酸203份、異酞酸2〇3份、苯偏三酸酐9.6份、乙 二醇Π0.7份、新戊二醇185.6份、鈦酸四丁酯0.2份，花費 4小時徐徐地升溫至240 °C，並一邊將餾出之水除去至系統 外一邊進行酯化反應。酯化反應結束後降溫至1 80 °C並裝 -49- 201207059 入數量平均分子量1 000之聚四亞甲基二醇（ptmg· 1 000)400 份’花費30分鐘減壓至10毫米录柱進行初期聚合並且將溫 度升溫至250 °C ’再在1毫米汞柱以下進行60分鐘後期聚合 。其後，用氮回到常壓’投入苯偏三酸酐9.6份’藉由在 220 °C使其30分鐘反應而得到聚酯樹脂E。將如此進行所得 之聚酯樹脂E之組成、特性値示於表1。各測定評價項目係 依照上述之方法。 &lt;聚醋樹脂Ρ,ϋ,Η,Ι，】之聚合例&gt; 與聚酯樹脂D之聚合例同樣地進行，此外溫度、時間 係適當地選擇並使用示於表1之原料，得到聚酯樹脂 F，G，H，I，J。將該樹脂之組成、特性値示於表1。 -50- 201207059 【I撇】 ^Τ) » — 00 m I 1 1 1 1 1 1 ο ο »·Η οο ►—» Ο vr^ 1 1 1 1 I I 1 1 1 1 ( ο ο CN Ο !?； (N 〇 1 1 Ο ΓΠ Ο 1 1 1 1 1 1 1 c ο Γ&lt;· § in (Ν X Ο m 1 00 in QJ 1 1 1 1 1 寸 1 1 ο ο 400 ο o 1 1 1 1 1 1 1 1 1 1 1 ο 1 ο 〇\ 1 t ΓΛ 00 卜 1 1 1 1 1 I 1 ο ιτ § ο w α σ&gt; 1 t CN I 1 1 VO 1 (Ν 1 I ο C CN Ο ν〇 Γ^* Q ο Γ^Ί On (N 1 ο σ\ m 1 \ 1 1 % 1 1 C 〇ς C&lt;· § σ\ 1 U σ； Os 1 1 &lt;N 1 • 1 1 〇 1-^ 1 1 1 ο C 0C Γ&lt; ο 1 CQ 沄 Os 1 1 ST) 00 1 Ό 1 1 1 &lt; 1 1 χη Ο C 600 &lt; ο ^Τ) 1 1 1 S 1 1 1 1 1 1 1 ο ο ιτ 500 聚酯樹脂 趑 異酞酸 己二酸 癸二酸 苯偏三酸酐 姊 )SL II Ε 11 卜 *4λ ***·Η 1,6-己二醇 乙二醇 新戊二醇 PTMG-1000 ε-己內酯 氍 in 擊 淋 苯均四酸酐 匾 m 擀H_ η 氍 ffi- 2 a 1 φ Φ Η- _ Μ Μ Ό ίί |ι 氍 ✓—ν Ρ m m s tzrn； 绝 s m 多元羧酸成分 多元醇成分 內酯類 加成酸 1 組成 莫耳 % 物性 (0001 ¥ff^^dz_ia)li-R 韜«iHa跋doo I-owHd (¾) s 201207059 &lt;聚胺甲酸酯樹脂A之聚合例&gt; 於具備溫度計、攪拌機、回流式冷卻管及蒸餾管之反 應容器中裝入並溶解聚酯樹脂F650份、甲苯650份後，餾 去甲苯4 1 3份，並藉由甲苯/水之共沸而將反應系統脫水❶ 冷卻至60°C後，加入2,2-二羥甲基丁酸（DMBA)29.3份、甲 乙酮237份。DMBA溶解後，加入六亞甲基二異氰酸酯 (HDI)30.6份、進一步加入二吖雙環_(--烯（DBU)0.03份作 爲反應觸媒’在80°C使其反應7小時後，投入甲乙酮444份 、甲苯148份而將固體成分濃度調整至4〇質量％，並得到聚 胺甲酸醋樹脂A溶液。使用經藉由將聚胺甲酸酯樹脂a之溶 液在1 2 0 °C乾燥1小時而除去溶劑之薄膜，依照前述之各測 定評價項目而測定。將聚胺甲酸酯樹脂之特性示於表2。 &lt;聚胺甲酸酯樹脂3，(；:，1：),£/,(3，1^,1之聚合例&gt; 與聚胺甲酸醋樹脂a之聚合例同樣地進行，使用示於 表2之原料’得到聚胺甲酸酯樹脂imFn〗。將特 性値不於表2 °各測定評價項目係依照上述之方法.。 -52- 201207059 【i】 l-H 1 1 1 1 〇 1 — 1 1 ¥ 1 21000 380 X 1 1 1 〇 1 f On 1 1 t 4500 670 VO o I 1 1 〇 1 S ro (N &lt; CO 1 22000 1100 〇 1 1 1 〇 1 1 1 Os 1 1 (N od ( 17000 650 CS w 1 〇 1 1 1 1 1 CN ΓΛ 1 寸_ 1 15000 g in Ό Q ο *-H 1 1 1 1 1 CS &lt;N i 1 oo 1 18000 1150 U 1 1 1 〇 1 § 1 v〇 &lt;N t 28000 ο PQ 1 〇 1 1 1 1 ON 1 1 (N 00 1 18000 650 VO &lt; 100 1 1 1 1 1 IT) — 1 1 x&gt;- 寸· 1 22000 380 ο 聚胺甲酸酯樹脂 [J-I 〇 ΗΗ OD-X-688 i DMBA 新戊二醇 1，6-己二醇 HDI ! MDI 數量平均分子量(Mn) τ〇 »W 氍 玻璃轉移點溫度fc) 聚酯樹脂 (聚酯多元醇） _ 鏈延長劑 二異氰酸酯 1 組成 質量份 特性 ^^S0S^S^,PO sw Γΰ-es- 201207059 &lt;實施例1&gt; 調整摻合70份聚酯樹脂A(僅固體成分之質量，以 同）作爲熱塑性樹脂（A1)、75份聚胺甲酸酯樹脂溶液 體成分3〇份）作爲熱塑性樹脂（A2)、25份R972[曰本 Aerosil(股）製疏水性煙霧狀氧化矽]作爲無機塡充材 )、198份甲乙酮、132份甲苯作爲溶劑（C)、固體成分 2 5 %之樹脂組成物（β )。接著，調整摻合1 6 · 0份環氧樹 大日本印墨化學工業（股）製 ΗΡ7200-Η(二環戊二烯型 樹脂）、環氧値= 3 5 4 0當量/106g]作爲環氧樹脂（D)、( 甲乙酮作爲溶劑（C )、固體成分濃度7 0 %之樹脂組成! 。藉由摻合所得之樹脂組成物（β)與樹脂組成物（γ)而 目的之黏著劑用樹脂組成物。環氧樹脂之摻合量係以 聚酯樹脂Α及聚胺甲酸酯樹脂C之酸價之總量的1 .6倍 氧基的方式來算出並決定。以上述之方法製作黏著評 料，並將評價之結果示於表3。初期評價、經時評價 示良好的結果。 &lt;實施例2 &gt; 與實施例1相同地，以表3所示之成分、摻合量製 脂組成物並評價特性。此外，在所有實施例中，樹脂 物（P)係以固體成分濃度25%、樹脂組成物（γ)係以固 分濃度70%來調製。 &lt;實施例3 &gt; 調整摻合1 62.5份聚胺甲酸酯樹脂溶液Α(固體成 下相 C(固 料（Β 濃度 脂Α[ 環氣 丨.9份 匆（γ) 得到 含有 之環 價試 皆顯 成樹 組成 體成 分6 5 -54- 201207059 份）作爲熱塑性樹脂（Al)、35份聚酯樹脂C作爲熱塑性樹脂 (A2)、25份R972作爲無機塡充材料（B)、159份甲乙酮、甲 苯1〗8份作爲溶劑（c )、固體成分濃度2 5 %之樹脂組成物（β ) 。接著’調整摻合10.5份環氧樹脂A、0.3份環氧樹脂Β作 爲環氧樹脂（D)、4.6份甲乙酮作爲溶劑（C) '固體成分濃度 70%之樹脂組成物（γ)。藉由摻合所得之樹脂組成物（β)與 樹脂組成物（γ)而得到目的之黏著劑用樹脂組成物。環氧 樹脂之摻合量係以含有聚胺甲酸酯樹脂Α及聚酯樹脂C之 酸價之總量的1.6倍之環氧基的方式來算出並決定。以上 述之方法製作黏著評價試料，並將評價之結果示於表3。 初期評價、經時評價皆顯示良好的結果。 &lt;實施例4〜1 4 &gt; 與實施例3相同地，以表3〜表5所示之成分、摻合量製 成黏著劑用樹脂組成物並評價特性。此外，在所有實施例 中，組成物（β)係以固體成分濃度25%、組成物（γ)係以固 體成分濃度7 0 %來調製。 以下記載各成分之明細。 •Aerosil R8200:日本Aerosil(股）製疏水性煙霧狀氧 化矽、 • REOLOSIL DM-10:TOKUYAMA(股）製疏水性煙霧 狀氧化矽、 • REOLOSIL HM-20L:TOKUYAMA(股）製疏水性煙霧 狀氧化矽、 -55- 201207059 •HIGILITE H-42M:昭和電工（股）製氫氧化鋁、 •環氧樹脂B:三菱瓦斯化學（股）製 TETRAD-X(N，N,N，， Ν’ -四環氧丙基-間二甲苯二胺）、環氧値=10000當量/1〇6g。 •環氧樹脂C:東都化成公司製 YDCN703(鄰甲酚酚醛 清漆型環氧樹脂）、環氧値=4 5 5 0當量/106£〇 環氧樹脂之摻合量係以含有熱塑性樹脂（A 1)與熱塑性 樹脂（A2)之酸價之總量的〇.8倍以上4.5倍以下之範圍內的 環氧基的方式來算出並決定。將評價之結果示於表3〜表5 。初期評價、經時評價皆顯示良好的結果。 -56- 201207059 [表3] 實施例 1 2 3 4 5 熱塑性樹 組成(聚酯樹脂） A Β - - - 脂 組成(聚胺甲酸酯樹脂） - - A A A (Α1) 質量份(固體成分） 70 70 65 70 70 熱塑性樹 組成(聚酯樹脂） - - C D E 脂 組成(聚胺甲酸酯樹脂） C C - - - 組成 (Α2) 質量份(固體成分） 30 30 35 30 30 物(β) R972 25 25 25 - - 無機塡充 R8200 - - - 25 - 組 材料 DM-10 - - - - 25 個體成分） HM-20L - - - - - Η-42Μ - - - - - 溶劑 E 3乙酮/甲苯 環氧 樹脂 Α質量份涸體成分） 16.0 14.3 10.5 9.9 19.8 組成 B質量份涸體成分） - 0.44 0.30 0.30 0.41 物(γ) C質量份(固體成分） - - - - - 溶劑 甲乙酮 {EV(y)xEW(y)}/{AV(p)xAW(p)} 1.60 1.30 1.60 1.30 2.50 組成物⑻搖變度(T聰） 3.5 3.5 3.7 4.0 3.7 損失彈性模數峰部(來自Α1) - - 44 44 - 損失彈性模數峰部(來 自A2) - - 0 -4 - 初期評價 剝離強度(N/cm) 12 12 16 11 13 樣品1 耐加濕焊接性(。〇 250 250 270 260 260 經時評價 剝離強度(N/cm) 11 12 16 10 12 耐加濕焊接性(。〇 250 250 260 260 250 剝離強度(N/cm) 18 15 &gt;25 &gt;25 &gt;25 特 初期評價 耐加濕焊接性(。〇 250 250 270 260 260 性 高溫環境黏著強度保持力（ 180 150 210 220 210 剝離強度(N/cm) 12 10 &gt;25 20 23 樣品2 經時評價 耐加濕焊接性(。〇 250 250 260 260 260 高溫環境黏著強度保持力（ 130 110 210 210 210 高溫高濕 經過500小時 15 9 20 18 15 環境測試 剝離強度 經過1000小時 10 6 15 7 11 落錘衝轚測試 判定 a a a a a 低溫彎曲測試 判定 a a a a a 環氧樹脂Λ··大日本油墨工業(股)製HP7200-H(二環戊二烯型環氧樹脂） 環氧樹脂Β :三菱瓦斯化學(股)製TETRAD-X(N，N，N’,N’-四環氧丙基-間二甲苯二胺) 環氧樹脂C :東都化成公司製YDCN703(鄰甲酚酚醛清漆型環氧樹脂） -57- 201207059 [表4] 實施例 6 7 8 9 10 熱塑性樹 組成(聚酯樹脂） - - - - - 脂 組成(聚胺甲酸酯樹脂） A A B A A (Α1) 質量份(固體成分） 80 55 65 65 65 熱塑性樹 組成(聚酯樹脂） C E C E C 脂 組成(聚胺甲酸酯樹脂） - - - - - 組成 (Α2) 質量份(固體成分） 20 45 35 35 35 物(β) R972 25 - 18.5 25 25 無機塡充 R8200 - - - - - 組 成 材料 DM-10 - - - - - (固體成分） HM-20L - 37.5 - - - H-42M - - - 25 - 溶劑 E 3乙酮/甲苯 環氧 樹脂 A質量份(固體成分） 8.6 10.6 14.4 9.5 8.5 組成 B質量份個體成分） 0.18 0.30 0.44 0.29 0.32 物(γ) C質量份(固體成分） - - - - 1.5 溶劑 甲乙酮 {EV(y)xEW(y)}/{AV(P)xAW(P)} 1.05 1.60 1.30 1.30 1.60 組成物(α)搖變度(ΤΙ値） 3.7 5.5 3.3 3.5 3.7 損失彈性模數峰部(來自Α1) 46 - - - 44 損失彈性模數峰部(來自Α2) 0 - - - 2 初期評價 剝離強度(N/cm) 14 17 18 10 13 樣口口 1 耐加濕焊接性rc) 260 250 260 250 260 經時評價 剝離強度(N/cm) 14 16 17 10 11 耐加濕焊接性(。〇 250 250 250 250 250 剝離強度(N/cm) 25 &gt;25 16 15 &gt;25 特 性 初期評價 耐加濕焊接性(。〇 260 250 260 260 260 高溫環境黏著強度保持力（ 220 110 200 170 200 剝離強度(N/cm) &gt;25 &gt;25 11 13 21 樣品2 經時評價 耐加濕焊接性ΓΟ 260 250 260 250 250 高溫環境黏著強度保持力（ 200 100 180 150 200 高溫高濕 經過500小時 10 17 13 18 16 環境測試 剝離強度 經過1000小時 6 13 11 10 11 落錘衝轚測試 判定 b a a b a 低溫-曲測試 判定 a a a a a 環氧樹脂A:大日本油墨工業(股)製HP7200-H(二環戊二烯型環氧樹脂） 環氧樹脂B :三菱瓦斯化學(股)製丁£丁]1^0((^凡?^；^-四環氧丙基-間二甲苯二胺) 環氧樹脂C :東都化成公司製YDCN703(鄰甲酚酚醛清漆型環氧樹脂） -58- 201207059 [表5] 實施例 11 12 13 14 組 成 組成物 (β) 熱塑性樹脂 (Α1) 組成(聚酯樹脂） - - - - 組成(聚胺甲酸酯樹脂） B A A A 質量份(固體成分） 65 65 65 65 熱塑性樹脂 (Α2) 組成(聚酯樹脂） E C C C 組成(聚胺甲酸酯樹脂） - - - - 質量份(固體成分） 35 35 35 35 無機塡充 材料 個體成分） R972 25 25 25 - R8200 - - - - DM-10 - - - 25 HM-20L - - - - H-42M - - - - 溶劑 甲乙酉 同/甲苯 組成物 (y) 環氧 樹脂 A質量份個體成分） 14.5 5.2 20.1 30.4 B質量份個體成分） - 0.18 0.41 0.51 C質量份(固體成分） 4.7 - - - 溶劑 甲乙酮 (EV(y)xEW(y)}/{AV(P)xAW(P)} 1.60 0.80 3.00 4.50 特 性 組成物(〇0搖變度(ΤΙ値） 4.5 3.7 3.7 3.5 損失彈性模數峰部(來自Λ1) - 44 . 44 44 損失彈性模數峰部(來自Α2) - -2 4 4 樣品1 初期評價 剝離強度(N/cm) 10 15 Π 13 耐加濕焊接性ΓΟ 250 260 270 250 經時評價 剝離強度(N/cm) 10 14 16 11 耐加濕焊接性(°c) 250 250 270 250 樣品2 初期評價 剝離強度(N/cm) 17 &gt;25 &gt;25 19 耐加濕焊接性fc) 260 260 280 250 高溫環境黏著強度保持力(°C) 210 200 210 170 經時評價 剝離強度(N/cm) 10 23 &gt;25 13 耐加濕焊接性rc) 260 250 280 250 高溫環境黏著強度保持力(°C) 210 200 200 170 高溫高濕環 境測試剝離 強度(N/cm) 經過500小時 10 6 14 7 經過1000小時 9 5 9 5 落錘衝撃測試 判定 a a a a 低漶蠻曲測試 判定 a a a a 環氧樹脂A:大日本油墨工業(股)製HP7200-H(二環戊二烯型環氧樹脂） 環氧樹脂B :三菱瓦斯化學(股)製丁£丁11^0((^况比,1^-四環氧丙基-間二甲苯二胺) 環氧樹脂C :東都化成公司製YDCN703(鄰甲酚酚醛清漆型環氧樹脂） -59- 201207059 &lt;實施例1 5 &gt; 調整摻合162.5份聚胺甲酸酯樹脂溶液八（固體成分6s 份）作爲熱塑性樹脂（A1)、16.3份R972作爲無機塡充材料（ B)、93.6份甲乙酮、52.7份甲苯作爲溶劑（〇、固體成分濃 度2 5 %之樹脂組成物（δ )。調整摻合3 5份聚酯樹脂C作爲熱 塑性樹脂（六2)、8.7份11972作爲無機塡充材料（8)、65.6份 甲乙酮、65.6份甲苯作爲溶劑（C)、固體成分濃度25 %之樹 脂組成物（ε)。接著，調整摻合1〇·5份環氧樹脂a、〇.3份環 氧樹脂B作爲環氧樹脂（D)、甲乙酮4.6份作爲溶劑（C)、固 體成分濃度7 0 %之樹脂組成物（ζ)。藉由摻合所得之樹脂組 成物（δ)與樹脂組成物（ε)與樹脂組成物（ζ)而得到目的之黏 著劑用樹脂組成物。環氧樹脂之摻合量係以含有聚胺甲酸 酯樹脂Α及聚酯樹脂C之酸價之總量的1.6倍之環氧基的方 式來算出並決定。將黏著評價試料以上述之方法製作，並 將評價之結果示於表6。初期評價、經時評價皆顯示良好 的結果。 &lt;實施例16〜21&gt; 與實施例15相同地，以表6所示之成分、摻合量製成 黏著劑用樹脂組成物並評價特性。此外，在所有實施例中 ’組成物（δ)、組成物（ε)係以固體成分濃度25%、組成物（ζ )係以固體成分濃度7 0 %來調製。 -60- 201207059 [表6] 實施例 15 16 17 18 19 20 21 組 成 組成 物(δ) 熱塑性樹脂 (Α1) 組成(聚酯樹脂） - - - - - - - 組成(聚胺甲酸醋樹脂） A A A A A A A 質量份(固體成分） 65 70 80 65 65 65 65 無機塡充材料 個體成分） R972 16.3 - 20 16.3 16.3 16.3 - R8200 - 17.5 - - - - - DM-10 - - - - - - 16.3 HM-20L - - - - - - - H-42M - - - - - - - 溶劑 甲乙酮/甲苯 組成 物⑻ 熱塑性樹脂 (Α2) 組成(聚酯樹脂） C D C C C C C 組成(聚胺甲酸酯樹脂） - - - - - - - 質量份(固體成分） 35 30 20 35 35 35 35 無機塡充材料 個體成分） R972 8.7 - 5 8.7 8.7 8.7 - R8200 - 7.5 - - - - - DM-10 - - - - - - 8.7 HM-20L - - - - - - - H-42M - - - - - - - 溶劑 甲乙酮/甲苯 組成 物(Q 環氧 樹脂 A質量份(固體成分） 10.5 9.9 8.6 8.5 5.2 20.1 30.4 B質量份(固體成分） 0.30 0.30 0.18 0.32 0.18 0.41 0.51 C質量份(固體成分） - - - 1.5 - - - 溶劑 甲乙酮 {EV(y)xEW(y)}/{AV(P)xAW(P)} 1.60 1.30 1.05 1.60 0.80 3.00 4.50 特 性 組成物⑷搖變度(ΤΙ値） 3.7 4.0 3.6 3.7 3.7 3.5 3.5 損失彈性模數峰部(來自Α1) 44 44 46 44 44 44 44 損失彈性模數峰部(來自Α2) 0 -4 0 2 -2 4 4 樣品1 初期評價 繊強©N/cm) 16 11 14 13 15 17 13 耐加濕焊接性ΓΟ 270 260 260 260 260 270 260 經時評價 剝離強度(N/cm) 15 10 14 12 14 16 10 耐加濕焊接性(°C) 260 250 250 260 250 270 250 樣品2 初期評價 剝離強度(N/cm) &gt;25 &gt;25 25 &gt;25 &gt;25 &gt;25 19 耐加濕焊接性(°C) 270 260 260 270 260 280 260 高溫環境黏著強度保持力 210 210 220 200 200 210 170 經時評價 剝離強度(N/cm) &gt;25 20 &gt;25 21 23 &gt;25 13 耐加濕焊接性(°C) 260 250 260 250 250 280 250 高溫環境黏著強度保持力 210 210 210 200 200 200 170 高溫高濕環境測 試 經過500小時 20 15 10 16 6 14 7 經過1000小時 15 7 6 11 5 9 5 落錘衝撃測試 判定 a a b a a a a 低溫彎曲測試 判定 a a a a a a a 環氧樹脂A:大曰本油墨工業(股)製HP7200-H(二環戊二烯型環氧樹脂） 環氧樹脂B :三菱瓦斯化學(股)製丁£丁11^0(〇^，^’-四環氧丙基-間二甲苯二胺) 環氧樹脂C :東都化成公司製YDCN703(鄰甲酚酚醛清漆型環氧樹脂） -61 - 201207059 &lt;比較例1 ~ 8 &gt; 與實施例1〜1 4同樣地進行，以表7〜表8所示之成分、 摻合量製作黏著劑用樹脂組成物，並評價特性。 -62- 201207059 [表7] 比較例 1 2 3 4 5 組 成 組成物 (β) 熱塑性樹脂1 組成(聚酯樹脂） F - - - - 組成(聚胺甲酸酯樹脂） - D E F A 質量份(固體成分） 65 65 65 65 65 熱塑性樹脂2 組成(聚酯樹脂） - C D C H 組成(聚胺甲酸酯樹脂） I - - - - 質量份(固體成分） 35 35 35 35 35 無機塡充材料 涸體成分） R972 25 25 25 25 25 R8200 - - - - - DM-10 - - - - - HM-20L - - - - - H-42M - - - - - 溶劑 甲乙酮/甲苯 組成物 (γ) 環氧 樹脂 a質量份涸體成分） 13.0 14.3 8.5 9.9 10.3 B質量份(固體成分） - 0.44 0.24 0.30 0.21 C質量份個體成分） - - - - - 溶劑 甲乙酮 {EV(y)xEW(y)}/{AV(P)xAW(P)} 1.30 1.30 1.30 1.30 1.30 特 性 組成物⑻搖變度(ΤΙ値） 4.0 4.0 3.3 3.7 3.7 損失彈性模數峰部(來自熱塑性樹脂1) - - - - - 損失彈性模數峰3 |5(來自熱塑性樹脂2) - - - - - 樣口口 1 初期評價 剝離強度(N/cm) 9 12 10 15 15 耐加濕焊接性(°c) 260 250 &lt;230 250 250 經時評價 剝離強度(N/cm) 3 4 9 10 12 耐加濕焊接性(°C) &lt;230 &lt;230 &lt;230 250 250 樣品2 初期評價 剝離強度(N/cm) 18 22 14 22 &gt;25 耐加濕焊接性rc) 260 260 &lt;230 250 260 高溫環境黏著強度保持力(°C) 150 200 80 70 220 經時評價 剝離強度(N/cm) 7 9 12 20 &gt;25 耐加濕焊接性ΓΟ &lt;230 &lt;230 &lt;230 250 260 高溫環境黏著強度保持力(°C) 80 70 80 60 210 高溫高濕環境測試 剝離強度(N/cm) 經過500小時 15 17 3 15 16 經過1000小時 10 11 1 9 9 落錘衝撃測試 判定 a a a a c 低溫彎曲測試 判定 a a a a b 環氧樹脂A:大曰本油墨工業(股)製HP7200-H(二環戊二烯型環氧樹脂） 環氧樹脂B :三菱瓦斯化學(股)製TETRAD-X(N,N,N’，N’-四環氧丙基-間二甲苯二胺) 環氧樹脂C :東都化成公司製YDCN703(鄰甲酚酚醛清漆型環氧樹脂） -63- 201207059 [表8] 比較例 6 7 8 9 組 成 組成物 (β) .熱塑性樹脂1 組成(聚酯樹脂） A - - ※ 組成(聚胺甲酸酯樹脂） - Η A 質量份(固體成分） 65 65 65 熱塑性樹脂2 組成(聚酯樹脂） - C - 組成(聚胺甲酸酯樹脂） G - I 質量份(固體成分） 35 35 35 無機塡充材料 個體成分） R972 25 25 25 R8200 - - - DM-10 - - - HM-20L - * - H-42M - - - 溶劑 E 3乙酮/甲苯 組成物 (γ) 環氧 樹脂 A質量份(固體成分） 10.6 8.6 9.5 B質量份(固體成分） 0.22 0.25 0.29 C質量份涸體成分） - - - 溶劑 甲乙酮 {EV(y)xEW(y)}/{AV(P)xAW(P)} 1.30 1.30 1.30 0 特 性 組成物⑹搖變度(Ή値） 4.0 3.5 3.8 &lt;2.0 損失彈性模數峰部(來自熱塑性樹脂1) - - 40 - 損失彈性模數峰S |5(來自熱塑性樹脂2) - - - 樣品1 初期評價 剝離強度(Ν/αη) 10 9 15 12 耐加濕焊接性(。〇 250 &lt;230 250 &lt;230 經時評價 剝離強度(N/cm) 7 3 12 9 耐加濕焊接性(。〇 230 &lt;230 250 &lt;230 樣品2 初期評價 剝離強度(N/cm) 16 20 23 8 耐加濕焊接性(°C) 250 &lt;230 260 &lt;230 高溫環境黏著強度保持力(°C) 170 80 140 90 經時評價. 剝離強度(N/cm) 11 18 19 5 耐加濕焊接性(。〇 230 &lt;230 250 &lt;230 高溫環境黏著強度保持力(°C) 150 80 90 90 高溫高濕環境測試 剝離強度(Ν/αη) 經過500小時 12 4 18 5 經過1000小時 6 2 13 3 落錘衝撃測試 判定 a c b b 低溫彎曲測試 判定 a b b b ※實施例9之配合組成係參照另外之記載 環氧樹脂A :大日本油墨工業(股)製HP7200-H(二環戊二烯型環氧樹脂） 環氧樹脂B :三菱瓦斯化學(股)製TETRAD-X(N,N，N’，N’-四環氧丙基-間二甲苯二胺) 環氧樹脂C :東都化成公司製YDCN703(鄰甲酚酚醛清漆型環氧樹脂） -64 - 201207059 比較例1中，聚酯樹脂F係因酸價低而並不相當於熱塑 性樹脂（A 1 )，因而爲本發明之範圍外。耐加濕焊接性、高 溫環境黏著強度保持力、在高溫高濕環境測試之剝離強度 低。硬化物之交聯變得不足，認爲係耐熱性降低者。 比較例2中，聚胺甲酸酯樹脂D係因酸價高而並不相當 於熱塑性樹脂（A1)，因而爲本發明之範圍外。黏著性薄片 之薄片壽命低、在經時評價之剝離強度、耐加濕焊接性、 高溫環境黏著強度保持力低。 比較例3中，聚胺甲酸酯樹脂E係因酸價低而並不相當 於熱塑性樹脂（A1)，因而爲本發明之範圍外。耐加濕焊接性 、高溫環境黏著強度保持力、在高溫高濕環境測試之剝離強 度低。硬化物之交聯變得不足，認爲係耐熱性降低者。 比較例4中，聚胺甲酸酯樹脂F係因玻璃轉.移溫度低而 並不相當於熱塑性樹脂（A1)，因而爲本發明之範圍外。耐 熱性低、高溫環境黏著強度保持力亦低。 比較例5中，聚酯樹脂Η係因玻璃轉移溫度高而並不相 當於熱塑性樹脂（Α2)，因而爲本發明之範圍外。黏著性薄 片之柔軟性低，不能達成落錘衝撃測試、低溫彎曲測試之 判定基準。 比較例6中，聚胺甲酸酯樹脂G係因酸價高而並不相當 於熱塑性樹脂（Α2)，因而爲本發明之範圍外。黏著性薄片 之薄片壽命低、在經時評價之耐加濕焊接性亦低。 -65- 201207059 比較例7中’聚胺甲酸酯樹脂η係因分子量低而並不相 當於熱塑性樹脂（Α1)’因而爲本發明之範圍外。由於黏著 劑爲脆、耐熱性亦低’認爲係剝離強度、耐加濕焊接性、 高溫環境黏著強度保持力、在高溫高濕環境測試之剝離強 度、落錘衝撃測試、低溫彎曲測試爲低者。 比較例8，雖然聚胺甲酸酯樹脂a係相當於熱塑性樹脂 (A1) ’聚胺甲酸酯樹脂ϊ係相當於熱塑性樹脂（A2)，但由 於聚胺甲酸酯樹脂A與聚胺甲酸酯樹脂〗相溶而不形成相分 離結構’故爲本發明之範圍外。黏著性薄片之柔軟性低， 尤其不能達成成爲在低溫下之塗膜柔軟性指標之低溫彎曲 測試的判定基準。 &lt;比較例9&gt; 與專利文獻4之合成例1 '合成例5同樣地進行，合成 聚酯樹脂1、聚酯樹脂2。使用所得之聚酯樹脂1、聚酯樹 脂2而與專利文獻4之實施例1同樣地進行得到分散溶液（黏 著劑）。 &lt;聚酯樹脂1之合成&gt; 於裝備攪拌器、溫度計、流出用冷卻機之反應罐內， 裝入對献酸83份、異献酸81份 '苯偏三酸酐2份、乙二醇 77份、新戊二醇79份，加壓下花費4小時徐徐地上升至23〇 °C，並一邊將餾出之水除去至系統外~邊進行醋化反應。 接著放入欽酸四丁酯0.08份作爲聚合觸媒，在常壓攪丨半1〇 分鐘後，花費1小時減壓至10毫米永柱進行初期聚合並且 -66- 201207059 將溫度上升至250°C ’再在1毫米汞柱以下進行30分鐘後期 聚合。其後，在氮環境下中，冷卻至200 °C後，裝入苯偏 三酸酐2份，進行3 0分鐘攪拌，得到聚酯樹脂1。將如此進 行所得之聚酯樹脂1之特性値示於以下。各測定評價項目 係依照前述之方法。 •數量平均分子量Μ4000、 •酸價：100當量/ i〇6g、 •玻璃轉移溫度：60°C、 •樹脂組成：對酞酸/異酞酸/苯偏三酸//乙二醇/新戊二 醇 ///苯偏三酸= 5 0/49/ 1 //5 0/5 0/// 1 (莫耳比）。 &lt;聚酯樹脂2之合成&gt; 於裝備攪拌器、溫度計、流出用冷卻機之反應罐內， 裝入對酞酸105份、異酞酸17份、癸二酸55份、乙二醇90 份、新戊二醇68份’花費4小時徐徐地上升至230 °C，並一 邊將餾出之水除去至系統外一邊進行酯化反應。接著放入 鈦酸四丁酯〇.〇8份作爲聚合觸媒，在常壓攪拌10分鐘後， 花費1小時減壓至1〇毫米汞柱進行初期聚合並且將溫度上 升250°C ’再在1毫米汞柱以下進行3〇分鐘後期聚合，得到 聚酯樹脂2。將如此進行所得之聚酯樹脂2之特性値示於以 下。各測定評價項目係依照前述之方法。 •數量平均分子量：30000、 •酸價：40當量/1 〇6g、値,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,, The temperature was raised to 250 ° C and then post-polymerization was carried out for 30 minutes below 1 mm Hg. Thereafter, nitrogen was returned to normal pressure, and 3,99 parts of ε-caprolactone was introduced, and the mixture was reacted at 200 ° C for 1 hour to obtain a polyester resin C. The composition and characteristics of the polyester resin C thus obtained are shown in Table 1. Each measurement evaluation item is in accordance with the above method. &lt;Polymerization Example of Polyester Resin D&gt; In a reaction tank equipped with a stirrer, a thermometer, and a chiller for effluent, 99.6 parts of citric acid, 99.3 parts of 'isodecanoic acid, 161.6 parts of sebacic acid, and benzotrim were charged. 3.8 parts of anhydride, 248.4 parts of 2-methyl-1,3-propanediol, 11.16 parts of 1,4-butanediol, and 0.2 parts of tetrabutyl titanate, and the temperature was gradually raised to 240 ° C in 4 hours. The esterification reaction is carried out while removing the distilled water to the outside of the system. After the end of the esterification reaction, it took 30 minutes to reduce the pressure to 10 mmHg for initial polymerization and the temperature was raised to 250 °C, and then polymerization was carried out for 45 minutes at a temperature of 1 mmHg or less. Thereafter, nitrogen was returned to normal pressure, and 3.8 parts of phthalic anhydride was charged, and the polyester resin D was obtained by reacting at 22 (TC for 30 minutes. The composition and characteristics of the obtained polyester resin D were thus obtained. The measurement and evaluation items are in accordance with the above-described method. <Polymerization Example of Polyester Resin E> In a reaction tank equipped with a stirrer, a thermometer, and a chiller for effluent, 203 parts of citric acid was charged. 2〇3 parts of isophthalic acid, 9.6 parts of trimellitic anhydride, 0.7 parts of ethylene glycol oxime, 185.6 parts of neopentyl glycol, and 0.2 parts of tetrabutyl titanate, it took 4 hours to slowly heat up to 240 °C, and The esterification reaction is carried out while removing the distilled water to the outside of the system. After the esterification reaction, the temperature is lowered to 180 ° C and charged with -49-201207059 into a polytetramethylene glycol having a number average molecular weight of 1,000 (ptmg· 1 000) 400 parts 'It takes 30 minutes to decompress to 10 mm column for initial polymerization and raise the temperature to 250 ° C' and then carry out 60 minutes of post-polymerization below 1 mm Hg. Thereafter, return to atmospheric pressure with nitrogen. 'Investing 9.6 parts of trimellitic anhydride' to obtain a polyester resin E by reacting at 220 ° C for 30 minutes The composition and characteristics of the polyester resin E thus obtained are shown in Table 1. Each measurement evaluation item was in accordance with the above method. <Polymeric resin Ρ, ϋ, Η, Ι, 】 Polymerization Example> The polymerization example of the ester resin D was carried out in the same manner, and the materials shown in Table 1 were appropriately selected and used in the temperature and time to obtain polyester resins F, G, H, I, and J. The composition and characteristics of the resin were shown. In Table 1. -50- 201207059 [I撇] ^Τ) » — 00 m I 1 1 1 1 1 1 ο ο »·Η οο ►-» Ο vr^ 1 1 1 1 II 1 1 1 1 ( ο ο CN Ο !?; (N 〇1 1 Ο ΓΠ Ο 1 1 1 1 1 1 1 c ο Γ&lt;· § in (Ν X Ο m 1 00 in QJ 1 1 1 1 1 inch 1 1 ο ο 400 ο o 1 1 1 1 1 1 1 1 1 1 1 ο 1 ο 〇\ 1 t ΓΛ 00 卜 1 1 1 1 1 I 1 ο ιτ § ο w α σ&gt; 1 t CN I 1 1 VO 1 (Ν 1 I ο C CN Ο ν〇Γ^* Q ο Γ^Ί On (N 1 ο σ\ m 1 \ 1 1 % 1 1 C 〇ς C&lt;· § σ\ 1 U σ; Os 1 1 &lt;N 1 • 1 1 〇 1-^ 1 1 1 ο C 0C Γ&lt; ο 1 CQ 沄Os 1 1 ST) 00 1 Ό 1 1 1 &lt; 1 1 χη Ο C 600 &lt; ο ^Τ) 1 1 1 S 1 1 1 1 1 1 1 ο ο ιτ 500 Polyester resin bismuthic acid adipic acid azelaic acid benzene trimellitic anhydride 姊) SL II Ε 11 Bu*4λ ***·Η 1,6- Hexanediol ethylene glycol neopentyl glycol PTMG-1000 ε-caprolactone 氍in shot pyromellitic anhydride 匾m 擀H_ η 氍ffi- 2 a 1 φ Φ Η- _ Μ Μ Ό ίί |ι 氍✓ —ν Ρ mms tzrn; sm polycarboxylic acid component polyol component lactone addition acid 1 composition mol % physical property (0001 ¥ff^^dz_ia)li-R 韬«iHa跋doo I-owHd (3⁄4) s 201207059 &lt;Polymerization Example of Polyurethane Resin A&gt; Into a reaction vessel equipped with a thermometer, a stirrer, a reflux cooling tube, and a distillation tube, 650 parts of a polyester resin and 650 parts of toluene are charged and dissolved, and then toluene is distilled off. 4 1 3 parts, and the reaction system was dehydrated by azeotropy of toluene/water. After cooling to 60 ° C, 29.3 parts of 2,2-dimethylolbutanoic acid (DMBA) and 237 parts of methyl ethyl ketone were added. After the DMBA was dissolved, 30.6 parts of hexamethylene diisocyanate (HDI) was added, and further, dioxobicyclo-(--ene (DBU) 0.03 parts was added as a reaction catalyst, and the reaction was carried out at 80 ° C for 7 hours, and then methyl ethyl ketone was introduced. 444 parts and 148 parts of toluene were adjusted to a solid concentration of 4% by mass, and a solution of the polyurethane resin A was obtained. The solution was dried at 120 ° C by using a solution of the polyurethane resin a. The film from which the solvent was removed was measured in accordance with each of the above-mentioned measurement evaluation items. The properties of the polyurethane resin are shown in Table 2. &lt;Polyurethane resin 3, (;:, 1:), £ / (Polymerization example of 3, 1^, 1) In the same manner as in the polymerization example of the polyurethane resin a, the raw material of the material shown in Table 2 was used to obtain the polyurethane resin imFn. The evaluation items in Table 2 ° are in accordance with the above method. -52- 201207059 [i] lH 1 1 1 1 〇1 — 1 1 ¥ 1 21000 380 X 1 1 1 〇1 f On 1 1 t 4500 670 VO o I 1 1 〇1 S ro (N &lt; CO 1 22000 1100 〇1 1 1 〇1 1 1 Os 1 1 (N od ( 17000 650 CS w 1 〇1 1 1 1 1 CN ΓΛ 1 inch _ 1 15000 g in Ό Q ο *-H 1 1 1 1 1 CS &lt;N i 1 oo 1 18000 1150 U 1 1 1 〇1 § 1 v〇&lt;N t 28000 ο PQ 1 〇1 1 1 1 ON 1 1 (N 00 1 18000 650 VO &lt; 100 1 1 1 1 1 IT) — 1 1 x&gt;- inch · 1 22000 380 ο Polyurethane resin [JI 〇ΗΗ OD-X-688 i DMBA neopentyl glycol 1,6-hexanediol HDI ! MDI number average molecular weight (Mn) τ〇»W 氍 glass transition point temperature fc) polyester resin (polyester polyol) _ chain extender diisocyanate 1 composition mass part characteristics ^^S0S ^S^, PO sw Γΰ-es- 201207059 &lt;Example 1&gt; Adjustment of blending 70 parts of polyester resin A (mass of only solid components, same) as thermoplastic resin (A1), 75 parts of polyurethane 3 parts by weight of the resin solution) as a thermoplastic resin (A2), 25 parts of R972 [hydrophobic fumed cerium oxide produced by Essence Aerosil] as an inorganic cerium material), 198 parts of methyl ethyl ketone, and 132 parts of toluene as a solvent ( C), a resin composition (β) having a solid content of 25%. Next, a blend of 1 6 · 0 parts of epoxy resin, Nippon Ink Chemical Industry Co., Ltd., 7200-Η (dicyclopentadiene type resin), epoxy oxime = 3 5 4 0 equivalent / 106 g] was adjusted as a ring. Oxygen resin (D), (methyl ethyl ketone as a solvent (C), a resin having a solid concentration of 70%! By the purpose of blending the obtained resin composition (β) with the resin composition (γ) for the purpose of the adhesive The resin composition is calculated and determined in such a manner that the blending amount of the epoxy resin is 1-6 times the total amount of the acid value of the polyester resin oxime and the polyurethane resin C. The evaluation was carried out, and the results of the evaluation are shown in Table 3. The initial evaluation and the evaluation by time showed good results. &lt;Example 2 &gt; In the same manner as in Example 1, the components and the amounts shown in Table 3 were blended. Further, in all the examples, the resin (P) was prepared at a solid concentration of 25% and a resin composition (γ) at a solid concentration of 70%. [Example 3] &gt; Adjust blending 1 62.5 parts of polyurethane resin solution Α (solid to lower phase C (solid material (Β concentration Α [ 环气丨.9匆 ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( Filling material (B), 159 parts of methyl ethyl ketone, toluene 1 8 parts as solvent (c), resin composition (β) having a solid concentration of 25%. Then 'adjusting blending 10.5 parts of epoxy resin A, 0.3 parts Epoxy resin Β as epoxy resin (D), 4.6 parts of methyl ethyl ketone as solvent (C) 'Resin composition (γ) having a solid concentration of 70%. Resin composition (β) and resin composition obtained by blending (γ), the desired resin composition for an adhesive is obtained. The blending amount of the epoxy resin is an epoxy group containing 1.6 times the total amount of the acid value of the polyurethane resin and the polyester resin C. The results were calculated and determined. The adhesion evaluation sample was prepared by the above method, and the results of the evaluation are shown in Table 3. Both the initial evaluation and the evaluation by time showed good results. <Examples 4 to 1 4 &gt; and Examples 3 Similarly, the composition and the amount shown in Table 3 to Table 5 are made to be adhered. In addition, in all the examples, the composition (β) was prepared at a solid concentration of 25%, and the composition (γ) was prepared at a solid concentration of 70%. • Aerosil R8200: Hydrophobic sulphur oxides produced by Japan Aerosil Co., Ltd., • REOLOSIL DM-10: Hydrophobic smog samarium made by TOKUYAMA, • REOLOSIL HM-20L: Hydrophobicity by TOKUYAMA Smoky yttrium oxide, -55- 201207059 •HIGILITE H-42M: aluminum hydroxide produced by Showa Denko (shares), epoxy resin B: TETRAD-X (N,N,N,,Ν made by Mitsubishi Gas Chemical Co., Ltd.) '-tetraepoxypropyl-m-xylylenediamine), epoxy oxime = 10,000 equivalents / 1 〇 6 g. • Epoxy resin C: YDCN703 (o-cresol novolak type epoxy resin) made by Dongdu Chemical Co., Ltd., epoxy 値 = 4 5 5 0 / 106 〇 epoxy resin blended with thermoplastic resin (A 1) The epoxy group in the range of 8 times or more and 4.5 times or less of the total amount of the acid value of the thermoplastic resin (A2) is calculated and determined. The results of the evaluation are shown in Tables 3 to 5. Both the initial evaluation and the evaluation by time showed good results. -56-201207059 [Table 3] Example 1 2 3 4 5 Thermoplastic tree composition (polyester resin) A Β - - - Lipid composition (polyurethane resin) - - AAA (Α1) Parts by mass (solid content) 70 70 65 70 70 Thermoplastic tree composition (polyester resin) - - CDE Lipid composition (polyurethane resin) CC - - - Composition (Α2) Parts by mass (solid content) 30 30 35 30 30 (β) R972 25 25 25 - - Inorganic RR8200 - - - 25 - Group material DM-10 - - - - 25 Individual ingredients) HM-20L - - - - - Η-42Μ - - - - - Solvent E 3 ethyl ketone / toluene Epoxy resin Α mass part carcass component) 16.0 14.3 10.5 9.9 19.8 Composition B mass part carcass component) - 0.44 0.30 0.30 0.41 substance (γ) C part by mass (solid content) - - - - - Solvent methyl ethyl ketone {EV (y )xEW(y)}/{AV(p)xAW(p)} 1.60 1.30 1.60 1.30 2.50 Composition (8) Shakeness (T Cong) 3.5 3.5 3.7 4.0 3.7 Loss modulus of elasticity peak (from Α1) - - 44 44 - Loss modulus of elasticity peak (from A2) - - 0 -4 - Initial evaluation peel strength (N/cm) 12 12 16 11 13 Sample 1 Resistance to humidification welding (.〇250 250 270 260 260 Evaluated peel strength (N/cm) over time 11 12 16 10 12 Humidity resistance (.250 250 260 260 250 Peel strength (N/cm) 18 15 &gt;25 &gt; 25 &gt;25 Special evaluation of resistance to wet solderability (. 250 250 270 260 260 high temperature environmental adhesion strength retention (180 150 210 220 210 peel strength (N / cm) 12 10 &gt; 25 20 23 sample 2 Evaluation of resistance to wet solderability (. 250 250 260 260 260 high temperature environmental adhesion strength retention (130 110 210 210 210 high temperature and high humidity after 500 hours 15 9 20 18 15 environmental test peel strength after 1000 hours 10 6 15 7 11 Drop hammer test to determine aaaaa low temperature bending test to determine aaaaa epoxy resin Λ··Japan ink industry (stock) HP7200-H (dicyclopentadiene epoxy resin) epoxy resin 三: Mitsubishi Gas Chemical ) TETRAD-X (N, N, N', N'-tetraepoxypropyl-m-xylenediamine) Epoxy Resin C: YDCN703 (o-cresol novolac type epoxy resin) manufactured by Dongdu Chemical Co., Ltd. - 57- 201207059 [Table 4] Example 6 7 8 9 10 Thermoplastic Composition (polyester resin) - - - - - Lipid composition (polyurethane resin) AABAA (Α1) Parts by mass (solid content) 80 55 65 65 65 Thermoplastic tree composition (polyester resin) CECEC Lipid composition (polyamine) Formate resin) - - - - - Composition (Α2) Parts by mass (solid content) 20 45 35 35 35 (β) R972 25 - 18.5 25 25 Inorganic RR8200 - - - - - Composition material DM-10 - - - - - (solid content) HM-20L - 37.5 - - - H-42M - - - 25 - Solvent E 3 Ethyl ketone / Toluene Epoxy Resin A part by mass (solid content) 8.6 10.6 14.4 9.5 8.5 Composition B parts by mass Individual composition) 0.18 0.30 0.44 0.29 0.32 (γ) C parts by mass (solid content) - - - - 1.5 Solvent methyl ethyl ketone {EV(y)xEW(y)}/{AV(P)xAW(P)} 1.05 1.60 1.30 1.30 1.60 Composition (α) rocking degree (ΤΙ値) 3.7 5.5 3.3 3.5 3.7 Loss modulus of elasticity peak (from Α1) 46 - - - 44 Loss modulus of elasticity peak (from Α 2) 0 - - - 2 Initial Evaluation of peel strength (N/cm) 14 17 18 10 13 Sample mouth 1 Humidification resistance rc) 260 250 260 250 260 Evaluation by time Delamination strength (N / cm) 14 16 17 10 11 moisture resistance weldability (. 〇250 250 250 250 250 Peel strength (N/cm) 25 &gt;25 16 15 &gt;25 Initial evaluation of resistance to wet solderability (. 〇260 250 260 260 260 High temperature environmental adhesion strength retention (220 110 200 170 200 Peel strength (N/cm) &gt;25 &gt;25 11 13 21 Sample 2 Evaluation of resistance to humidification and solderability 经 260 250 260 250 250 Adhesion strength retention in high temperature environment (200 100 180 150 200 High temperature and high humidity after 500 hours) 10 17 13 18 16 Environmental test Peel strength After 1000 hours 6 13 11 10 11 Drop hammer test to determine baaba Low temperature-curve test to determine aaaaa Epoxy resin A: Big Japan Ink Industry Co., Ltd. HP7200-H (dicyclopentane) Diene type epoxy resin) Epoxy resin B: Mitsubishi Gas Chemical Co., Ltd. 丁丁丁]1^0((^凡?^;^-tetraepoxypropyl-m-xylenediamine) Epoxy resin C: YDCN703 (o-cresol novolac type epoxy resin) manufactured by Tohto Kasei Co., Ltd. -58- 201207059 [Table 5] Example 11 12 13 14 Composition (β) Thermoplastic resin (Α1) Composition (polyester resin) - - - - Composition (polyurethane resin) BAAA parts by mass ( Body composition) 65 65 65 65 Thermoplastic resin (Α2) Composition (polyester resin) ECCC composition (polyurethane resin) - - - - Parts by mass (solid content) 35 35 35 35 Inorganic filling material individual component) R972 25 25 25 - R8200 - - - - DM-10 - - - 25 HM-20L - - - - H-42M - - - - Solvent methyl ethyl hydrazine / toluene composition (y) Epoxy resin A mass parts individual components) 14.5 5.2 20.1 30.4 B parts by mass) - 0.18 0.41 0.51 C parts by mass (solid content) 4.7 - - - Solvent methyl ethyl ketone (EV(y)xEW(y)}/{AV(P)xAW(P)} 1.60 0.80 3.00 4.50 Characteristic composition (〇0 yaw degree (ΤΙ値) 4.5 3.7 3.7 3.5 Loss modulus of elasticity peak (from Λ1) - 44 . 44 44 Loss modulus of elasticity peak (from Α 2) - -2 4 4 Sample 1 Initial evaluation Peel strength (N/cm) 10 15 Π 13 Resistance to wet solderability 250 260 270 250 Evaluation of peel strength (N/cm) over time 10 14 16 11 Humidity resistance (°c) 250 250 270 250 Sample 2 Initial evaluation Peel strength (N/cm) 17 &gt;25 &gt;25 19 Humidity resistance fc) 260 260 280 250 High temperature environmental adhesion strength retention (° C) 210 200 210 170 Penetration strength (N/cm) over time 10 23 &gt; 25 13 Humidification resistance rc) 260 250 280 250 Adhesion strength retention at high temperature (°C) 210 200 200 170 High temperature and high humidity Environmental test peel strength (N/cm) After 500 hours 10 6 14 7 After 1000 hours 9 5 9 5 Drop hammer test to determine aaaa Low 漶 漶 测试 test aaaa Epoxy resin A: Big Japan ink industry (stock) system HP7200 -H (dicyclopentadiene type epoxy resin) Epoxy resin B: Mitsubishi Gas Chemical Co., Ltd. 丁丁丁11^0(((^ ratio, 1^-tetraepoxypropyl-m-xylene II) Amine) Epoxy resin C: YDCN703 (o-cresol novolac type epoxy resin) manufactured by Tohto Kasei Co., Ltd. -59-201207059 &lt;Example 1 5 &gt; Adjustment of blending 162.5 parts of polyurethane resin solution VIII (solid 6 parts by weight of the resin composition (δ) as a thermoplastic resin (A1), 16.3 parts of R972 as an inorganic chelating material (B), 93.6 parts of methyl ethyl ketone, and 52.7 parts of toluene (〇, a solid content concentration of 25%). Adjusting 35 parts of polyester resin C as a thermoplastic resin (six 2), 8.7 parts of 11972 as an inorganic chelating material (8), 65.6 parts of methyl ethyl ketone, 65.6 parts of toluene as a solvent (C), a resin having a solid concentration of 25% Composition (ε). Next, a resin composition in which 1 〇·5 parts of epoxy resin a, 〇.3 parts of epoxy resin B was blended as epoxy resin (D), 4.6 parts of methyl ethyl ketone as a solvent (C), and a solid concentration of 70% was adjusted. (ζ). The resin composition for the adhesive of interest is obtained by blending the obtained resin composition (?) with the resin composition (?) and the resin composition (?). The blending amount of the epoxy resin was calculated and determined in such a manner that the epoxy group containing 1.6 times the total amount of the acid value of the polyurethane resin and the polyester resin C was used. The adhesion evaluation sample was prepared by the above method, and the results of the evaluation are shown in Table 6. Both initial evaluation and elapsed time evaluation showed good results. &lt;Examples 16 to 21&gt; In the same manner as in Example 15, the components and the amounts of the ingredients shown in Table 6 were used to prepare a resin composition for an adhesive, and the properties were evaluated. Further, in all the examples, the composition (δ) and the composition (ε) were prepared at a solid concentration of 25%, and the composition (ζ) was prepared at a solid concentration of 70%. -60-201207059 [Table 6] Example 15 16 17 18 19 20 21 Composition (δ) Thermoplastic resin (Α1) Composition (polyester resin) - - - - - - - Composition (polyurethane resin) AAAAAAA Parts by mass (solid content) 65 70 80 65 65 65 65 Inorganic filling materials Individual composition) R972 16.3 - 20 16.3 16.3 16.3 - R8200 - 17.5 - - - - - DM-10 - - - - - - 16.3 HM-20L - - - - - - - - H-42M - - - - - - - Solvent methyl ethyl ketone / toluene composition (8) Thermoplastic resin (Α 2) Composition (polyester resin) CDCCCCC Composition (polyurethane resin) - - - - - - - parts by mass (solid content) 35 30 20 35 35 35 35 Inorganic filling material individual composition) R972 8.7 - 5 8.7 8.7 8.7 - R8200 - 7.5 - - - - - DM-10 - - - - - - 8.7 HM-20L - - - - - - - H-42M - - - - - - - Solvent methyl ethyl ketone / toluene composition (Q epoxy resin A part by mass (solid content) 10.5 9.9 8.6 8.5 5.2 20.1 30.4 B parts by mass (solid content) 0.30 0.30 0.18 0.32 0.18 0.41 0.51 C parts by mass (solid content) - - - 1.5 - - - Solvent methyl ethyl ketone {EV(y)xEW(y)}/{AV(P)xAW(P) } 1.60 1.30 1.05 1.60 0.80 3.00 4.50 Characteristic composition (4) Shake degree (ΤΙ値) 3.7 4.0 3.6 3.7 3.7 3.5 3.5 Loss modulus of elasticity peak (from Α1) 44 44 46 44 44 44 44 Loss modulus of elasticity peak ( From Α2) 0 -4 0 2 -2 4 4 Sample 1 Initial evaluation bareness ©N/cm) 16 11 14 13 15 17 13 Humidity resistance ΓΟ 270 260 260 260 260 270 260 Peel strength evaluation over time (N /cm) 15 10 14 12 14 16 10 Humidity resistance (°C) 260 250 250 260 250 270 250 Sample 2 Initial evaluation peel strength (N/cm) &gt;25 &gt;25 25 &gt;25 &gt;25 &gt;25 19 Humidity resistance (°C) 270 260 260 270 260 280 260 Adhesion strength retention at high temperature 210 210 220 200 200 210 170 Peel strength (N/cm) over time &gt;25 20 &gt;25 21 23 &gt;25 13 Humidity resistance (°C) 260 250 260 250 250 280 250 Adhesion strength retention in high temperature environment 210 210 210 200 200 200 170 High temperature and high humidity environment test after 500 hours 20 15 10 16 6 14 7 After 1000 hours 15 7 6 11 5 9 5 drop hammer test to determine aabaaaa low temperature bending test to determine aaaaaaa epoxy Grease A: HP7200-H (dicyclopentadiene type epoxy resin) manufactured by Otsuka Ink Industry Co., Ltd. Epoxy resin B: Mitsubishi Gas Chemical Co., Ltd. 丁丁丁11^0(〇^,^' -tetraepoxypropyl-m-xylylenediamine) Epoxy resin C: YDCN703 (o-cresol novolac type epoxy resin) manufactured by Tohto Kasei Co., Ltd. -61 - 201207059 &lt;Comparative Examples 1 to 8 &gt; and Examples 1 to 1 4 were carried out in the same manner, and the resin composition for an adhesive was prepared from the components and the amounts shown in Tables 7 to 8, and the properties were evaluated. -62- 201207059 [Table 7] Comparative Example 1 2 3 4 5 Composition (β) Thermoplastic Resin 1 Composition (Polyester Resin) F - - - - Composition (Polyurethane Resin) - DEFA Parts by Mass (Solid Ingredient) 65 65 65 65 65 Thermoplastic Resin 2 Composition (Polyester Resin) - CDCH Composition (Polyurethane Resin) I - - - - Parts by mass (solid content) 35 35 35 35 35 Inorganic Filling Material R972 25 25 25 25 25 R8200 - - - - - DM-10 - - - - - HM-20L - - - - - H-42M - - - - - Solvent methyl ethyl ketone / toluene composition (γ) Epoxy resin a Mass parts carcass component) 13.0 14.3 8.5 9.9 10.3 B parts by mass (solid content) - 0.44 0.24 0.30 0.21 C parts by weight of individual components) - - - - - Solvent methyl ethyl ketone {EV(y)xEW(y)}/{AV( P)xAW(P)} 1.30 1.30 1.30 1.30 1.30 Characteristic composition (8) Shake degree (ΤΙ値) 4.0 4.0 3.3 3.7 3.7 Loss modulus of elasticity peak (from thermoplastic resin 1) - - - - - Loss modulus of elasticity peak 3 |5 (from thermoplastic resin 2) - - - - - Sample mouth 1 Initial evaluation Peel strength (N/cm) 9 12 10 15 15 Resistance to wet solderability (°c) 260 250 &lt;230 250 250 Peel strength (N/cm) over time 3 4 9 10 12 Humidity resistance (°C) &lt;230 &lt;230 &lt;230 &lt; 230 250 250 Sample 2 Initial evaluation peel strength (N/cm 18 22 14 22 &gt;25 Humidity resistance rc) 260 260 &lt; 230 250 260 Adhesion strength retention at high temperature (°C) 150 200 80 70 220 Peel strength (N/cm) over time 7 9 12 20 &gt;25 Moisture Resistance Weldability ΓΟ &lt;230 &lt;230 &lt;230 250 260 High Temperature Environmental Adhesion Strength Retention (°C) 80 70 80 60 210 High Temperature and High Humidity Environment Test Peel Strength (N/cm) After 500 Hours 15 17 3 15 16 After 1000 hours 10 11 1 9 9 Drop hammer test to determine aaaac Low temperature bending test to determine aaaab Epoxy resin A: HP7200-H (dicyclopentadiene ring) manufactured by Otsuka Ink Industry Co., Ltd. Oxygen resin) Epoxy resin B: TETRAD-X (N, N, N', N'-tetraepoxypropyl-m-xylene diamine) manufactured by Mitsubishi Gas Chemical Co., Ltd. Epoxy resin C: manufactured by Toho Chemical Co., Ltd. YDCN703 (o-cresol novolac type epoxy resin) -63- 201207059 [Table 8] Comparative Example 6 7 8 9 Composition (β). Thermoplastic Resin 1 Composition (Polyester Resin) ) A - - ※ Composition (polyurethane resin) - Η A parts by mass (solid content) 65 65 65 Thermoplastic resin 2 Composition (polyester resin) - C - Composition (polyurethane resin) G - I Parts by mass (solid content) 35 35 35 Inorganic filling material individual composition) R972 25 25 25 R8200 - - - DM-10 - - - HM-20L - * - H-42M - - - Solvent E 3 ethyl ketone / toluene composition (γ) Epoxy Resin A parts by mass (solid content) 10.6 8.6 9.5 B parts by mass (solid content) 0.22 0.25 0.29 C by mass of steroidal component) - - - Solvent methyl ethyl ketone {EV(y)xEW(y)}/ {AV(P)xAW(P)} 1.30 1.30 1.30 0 Characteristic composition (6) Shakeness (Ή値) 4.0 3.5 3.8 &lt;2.0 Loss modulus of elasticity peak (from thermoplastic resin 1) - - 40 - Loss elastic mode Number peak S | 5 (from thermoplastic resin 2) - - - Sample 1 Initial evaluation Peel strength (Ν / αη) 10 9 15 12 Resistance to wet solderability (. 〇250 &lt;230 250 &lt;230 Time-dependent evaluation of peel strength (N/cm) 7 3 12 9 Resistance to wet solderability (.230 230 &lt; 230 250 &lt; 230 Sample 2 Initial evaluation peel strength (N/cm) 16 20 23 8 Moisture resistance (°C) 250 &lt;230 260 &lt;230 Adhesion strength retention at high temperature (°C) 170 80 140 90 Elapsed evaluation. Peel strength (N/cm) 11 18 19 5 Moisture resistance (.〇230 &lt;230 250 &lt;230 High temperature environmental adhesion strength retention (°C) 150 80 90 90 High temperature and high humidity environment test peel strength (Ν/αη) After 500 hours 12 4 18 5 1000 hours 6 2 13 3 Falling hammer test to determine acbb Low-temperature bending test judgment abbb * The composition of Example 9 is based on the other description Epoxy resin A: HP7200-H (D2A) manufactured by Dainippon Ink Industrial Co., Ltd. Ethylene type epoxy resin) Epoxy resin B: TETRAD-X (N, N, N', N'-tetraepoxypropyl-m-xylene diamine) manufactured by Mitsubishi Gas Chemical Co., Ltd. Epoxy resin C: Dongdu YDCN703 (o-cresol novolac type epoxy resin) manufactured by Kasei Co., Ltd. -64 - 201207059 In Comparative Example 1, polyester resin F is not equivalent due to low acid value. The thermoplastic resin (A 1 ) is outside the scope of the present invention. The wet-resistant solderability, the high-temperature environment adhesive strength retention force, and the high-humidity environment test have low peel strength. The cross-linking of the cured product becomes insufficient. In Comparative Example 2, the polyurethane resin D is not in the range of the present invention because the acid value is high and does not correspond to the thermoplastic resin (A1). The sheet of the adhesive sheet has a low life. In the comparative example 3, the polyurethane resin E was low in acid value and did not correspond to the thermoplastic resin (A1). Therefore, it is outside the scope of the present invention. The wet heat resistance, the high-temperature environment adhesive strength retention force, and the high-humidity environment test have low peel strength. The cross-linking of the cured product is insufficient, and it is considered that the heat resistance is lowered. In Comparative Example 4, the polyurethane resin F was not in the range of the present invention because the glass transition temperature was low and did not correspond to the thermoplastic resin (A1), and the heat resistance was low, and the adhesion strength in the high-temperature environment was also maintained. Low. In Example 5, the polyester resin lanthanum is not in the range of the present invention because the glass transition temperature is high and does not correspond to the thermoplastic resin (Α2). The adhesive sheet has low flexibility and cannot be subjected to the drop hammer test and low temperature bending. Criteria for the test. In Comparative Example 6, the polyurethane resin G was not in the range of the present invention because the acid value was high and did not correspond to the thermoplastic resin (Α2). The sheet of the adhesive sheet has a low life and is low in resistance to humidification weldability. -65-201207059 In Comparative Example 7, the 'polyurethane resin η is not inferior to the thermoplastic resin (?1) because of its low molecular weight, and is outside the scope of the present invention. Because the adhesive is brittle and has low heat resistance, it is considered to be peel strength, wet solderability, high temperature environment adhesive strength retention, peel strength in high temperature and high humidity environment test, drop hammer punch test, low temperature bend test is low. By. In Comparative Example 8, although the polyurethane resin a corresponds to the thermoplastic resin (A1), the polyurethane resin corresponds to the thermoplastic resin (A2), but the polyurethane resin A and the polyamine It is outside the scope of the present invention that the acid ester resin is compatible without forming a phase separation structure. The adhesive sheet has low flexibility, and in particular, it cannot be used as a criterion for determining a low-temperature bending test which is an index of flexibility of a coating film at a low temperature. &lt;Comparative Example 9&gt; The polyester resin 1 and the polyester resin 2 were synthesized in the same manner as in Synthesis Example 1 of Synthesis Document 4, Synthesis Example 5. Using the obtained polyester resin 1 and polyester resin 2, a dispersion solution (adhesive) was obtained in the same manner as in Example 1 of Patent Document 4. &lt;Synthesis of Polyester Resin 1&gt; In a reaction tank equipped with a stirrer, a thermometer, and a chiller for effluent, 83 parts of acid donation, 81 parts of 'isophthalic acid', and 2 parts of phthalic anhydride were charged. 77 parts and 79 parts of neopentyl glycol were slowly raised to 23 ° C under a pressure of 4 hours, and the distilled water was removed to the outside of the system to carry out a acetification reaction. Next, 0.08 parts of tetrabutyl phthalate was added as a polymerization catalyst. After stirring for one and a half minutes at normal pressure, it took 1 hour to reduce the pressure to 10 mm for the initial polymerization and -66-201207059 to raise the temperature to 250 °. C' is then post-polymerized for 30 minutes at less than 1 mm Hg. Thereafter, the mixture was cooled to 200 ° C in a nitrogen atmosphere, and then charged with 2 parts of phthalic anhydride, and stirred for 30 minutes to obtain a polyester resin 1. The characteristics of the polyester resin 1 thus obtained are shown below. Each measurement evaluation item is in accordance with the aforementioned method. • number average molecular weight Μ 4000, • acid value: 100 equivalents / i 〇 6g, • glass transfer temperature: 60 ° C, • resin composition: citric acid / isophthalic acid / trimellitic acid / / ethylene glycol / new pentylene Glycol///trimellitic acid = 5 0/49/ 1 //5 0/5 0/// 1 (Morbi). &lt;Synthesis of Polyester Resin 2&gt; In a reaction tank equipped with a stirrer, a thermometer, and a chiller for effluent, 105 parts of citric acid, 17 parts of isononanoic acid, 55 parts of sebacic acid, and ethylene glycol 90 were charged. The fraction of 68 parts of neopentyl glycol was slowly raised to 230 ° C in 4 hours, and the esterified reaction was carried out while removing the distilled water to the outside of the system. Next, 8 parts of tetrabutyl titanate ruthenium ruthenium was added as a polymerization catalyst, and after stirring at normal pressure for 10 minutes, it took 1 hour to reduce pressure to 1 mmHg for initial polymerization and raise the temperature by 250 ° C. After 3 minutes of post-polymerization of 1 mmHg or less, a polyester resin 2 was obtained. The characteristics of the polyester resin 2 thus obtained are shown below. Each measurement evaluation item is in accordance with the aforementioned method. • Number average molecular weight: 30,000, • Acid value: 40 equivalents / 1 〇 6g,

.玻璃轉移溫度：1 0 °C •67· 201207059 .樹脂組成：對酞酸/異酞酸/癸二酸//乙二醇/新戊二醇 = 63/10/27//58/42(莫耳比）。 &lt;分散溶液（黏著劑）之製作&gt; 將所得之聚酯樹脂1及聚酯樹脂2各以甲乙酮/甲苯 = 1/4(質量比）溶解使固體成分濃度成爲30%。將該等經溶 解之聚酯樹脂以固體成分量計1〇〇份（聚酯樹脂W聚酯樹脂 2 = 2 8/72 [質量比])、十溴二苯醚50份、三氧化銻36份、二 氧化鈦14份、二氧化矽4份、玻璃珠1〇〇份，放入250ml美 乃滋瓶，以搖動器分散6小時，得到分散溶液。 &lt;分散溶液（黏著劑）之黏著劑特性評價&gt; 將所得之分散溶液依照上述之特性評價方法進行評.價。 比較例9係由於不含有環氧樹脂，故爲本發明之範圍 外。由於黏著性低、不具有交聯結構，故耐熱性降低且耐 加濕焊接性、高溫環境黏著強度保持力降低。此外，所摻 合之聚酯樹脂的玻璃轉移溫度高、低溫彎曲性亦降低。 [產業上之利用可能性] 藉由本發明，可提供可得到在對於各種塑膠薄膜及金 屬之高黏著性、亦可對應在高濕度之無鉛焊料的高度耐濕 熱性、在高溫高濕度下之黏著性優異之黏著劑，且黏著性 薄片爲即使在高溫高濕下流通後使用亦可維持良好的黏著 特性之薄片壽命良好的黏著劑用樹脂組成物、含有其之黏 著劑、黏著性薄片及含有其作爲黏著劑層之印刷配線板》 此外’在本發明之較佳之實施態樣中，係可提供在對各種 -68- 201207059 塑膠薄膜之黏著性、對銅、鋁、不鏽鋼等金屬之黏著性、 對玻璃環氧樹脂之黏著性亦優異之樹脂組成物、含有其之 黏著劑、黏著性薄片及含有其作爲黏著劑層之印刷配線板 。更甚者，在本發明之較佳之實施態樣中係尤其在對鋁、 不鏽鋼等金屬之黏著性、耐濕熱性優異、將黏著物長期間 放置於高溫高濕環境下後亦維持有高剝離強度這方面發揮 更加優異之特性。 【圖式簡單說明】 Ατττ 拂。 【主要元件符號說明】 4vrt 挑0 -69- 201207059 PD1117687(11) 發明專利說明書 (本說明書格式、順序，請勿任意更動，※記號部分請勿填寫；惟已有申請案號者請填寫） &gt;0 co^^/o^ (2006.01) ※申請案號：※申請日期：1心α ’今 ※工卩匸分類 一、發明名稱：（中文/英文） 黏著劑用樹脂組成物 及含有其作爲黏著劑層之印刷配線板 I αύ ί〇η 〇5σ/63/,〇(2006.01) Τ (67/β〇 (2006.01； C〇ST l7^/〇¥ (2006.01) co'jJ y/〇〇 (2006.01) H〇/u M/to (2006.01) 含有其之黏著劑、黏著性薄片Glass transition temperature: 10 °C • 67· 201207059 . Resin composition: citric acid / isophthalic acid / azelaic acid / / ethylene glycol / neopentyl glycol = 63/10/27 / / 58 / 42 ( Moerby). &lt;Production of Dispersion Solution (Adhesive)&gt; Each of the obtained polyester resin 1 and polyester resin 2 was dissolved in methyl ethyl ketone/toluene = 1/4 (mass ratio) to have a solid content concentration of 30%. The dissolved polyester resin is 1 part by weight of the solid content (polyester resin W polyester resin 2 = 2 8/72 [mass ratio]), decabromodiphenyl ether 50 parts, antimony trioxide 36 A portion, 14 parts of titanium dioxide, 4 parts of cerium oxide, and 1 part of glass beads were placed in a 250 ml merlot bottle and dispersed in a shaker for 6 hours to obtain a dispersion solution. &lt;Evaluation of Adhesive Properties of Dispersion Solution (Adhesive)&gt; The obtained dispersion solution was evaluated in accordance with the above-described characteristic evaluation method. Comparative Example 9 is outside the scope of the present invention because it does not contain an epoxy resin. Since the adhesiveness is low and there is no crosslinked structure, the heat resistance is lowered, and the wet solderability and the high temperature environment adhesive strength retention force are lowered. Further, the blended polyester resin has a high glass transition temperature and a low temperature bendability. [Industrial Applicability] According to the present invention, it is possible to provide high adhesion resistance to various plastic films and metals, high moisture resistance to high-humidity lead-free solder, and adhesion under high temperature and high humidity. An adhesive agent excellent in adhesion, and an adhesive sheet is a resin composition for an adhesive having a good adhesive life even after being used under high temperature and high humidity, and has an excellent adhesive life, an adhesive composition, an adhesive sheet, and the like. It is a printed wiring board as an adhesive layer. In addition, in the preferred embodiment of the present invention, adhesion to various -68-201207059 plastic films and adhesion to metals such as copper, aluminum, and stainless steel can be provided. A resin composition excellent in adhesion to a glass epoxy resin, an adhesive containing the same, an adhesive sheet, and a printed wiring board containing the same as an adhesive layer. Furthermore, in a preferred embodiment of the present invention, the adhesion to the metal such as aluminum or stainless steel is excellent, and the heat and humidity resistance is excellent, and the high adhesion is maintained after the adhesive is placed for a long period of time. The strength is more excellent in this respect. [Simple description of the diagram] Ατττ 拂. [Main component symbol description] 4vrt Pick 0 -69- 201207059 PD1117687(11) Invention patent specification (The format and order of this manual, please do not change it arbitrarily, please do not fill in the ※ part; please fill in the application number) &gt ;0 co^^/o^ (2006.01) ※Application number: ※Application date: 1 heart α 'Today ※Working class classification I. Invention name: (Chinese / English) Resin composition for adhesives and containing it Printed wiring board for adhesive layer I αύ 〇 〇 〇 5σ/63/, 〇 (2006.01) Τ (67/β〇(2006.01; C〇ST l7^/〇¥ (2006.01) co'jJ y/〇〇( 2006.01) H〇/u M/to (2006.01) Adhesives and adhesive sheets containing the same

RESIN COMPOSITION FOR ADHESIVE AGENT, ADHESIVE AGENT CONTAINING THEREOF, ADHESIVE SHEET AND PRINTED WIRERESIN COMPOSITION FOR ADHESIVE AGENT, ADHESIVE AGENT CONTAINING THEREOF, ADHESIVE SHEET AND PRINTED WIRE

BOARD CONTAINING THE SAME AS ADHESIVE LAYER o 二、中文發明摘要： 一種黏著劑用樹脂組成物，其係含有：由聚酯樹脂或 聚胺甲酸酯樹脂所成且酸價（單位：當量/I06g)爲100以上 1 000以下、玻璃轉移溫度爲30°c以上80°c以下，數量平 均分子量爲 5.0χ103以上Ι.ΟχΙΟ5以下之熱塑性樹脂 (A1)，由聚酯樹脂或聚胺甲酸酯樹脂所成且玻璃轉移溫度 爲以下、數量平均分子量爲5.0χ103以上、Ι.ΟχίΟ5以 下之熱塑性樹脂（A2) ’無機塡充材料（B)及具有二環戊二 烯骨架之環氧樹脂（D)’並在130 °C乾燥3分鐘接著140 °C 熱處理4小時而得到之硬化塗膜中，至少前述熱塑性樹脂 (A1 )與前述熱塑性樹脂（A2)之至少一部分係具有相分離結BOARD CONTAINING THE SAME AS ADHESIVE LAYER o II. Abstract of the Invention: A resin composition for an adhesive comprising: a polyester resin or a polyurethane resin and having an acid value (unit: equivalent/I06g) a thermoplastic resin (A1) having a number average molecular weight of 5.0 χ 103 or more and 以下 5 or less, which is composed of a polyester resin or a polyurethane resin, having a glass transition temperature of 30 or more and 1,000 or less and a glass transition temperature of 30° C. or more and 80° C. or less. And the glass transition temperature is below, the number average molecular weight is 5.0 χ 103 or more, and the thermoplastic resin (A2) 'inorganic chelating material (B) and the epoxy resin (D) having a dicyclopentadiene skeleton' In the hardened coating film obtained by drying at 130 ° C for 3 minutes and then heat treatment at 140 ° C for 4 hours, at least a part of the thermoplastic resin (A1) and the thermoplastic resin (A2) are phase-separated.

Claims (1)

201207059 5 .如申請專利範圍第1項之黏著劑用樹脂組成物，其中相 對於前述熱塑性樹脂（A1)與前述熱塑性樹脂（A2)之合計 1〇〇質量份而言，該組成物含有55質量份以上80質量份 以下之前述熱塑性樹脂（A1)。 6 ·如申請專利範圍第1項之黏著劑用樹脂組成物，其中以 在前述黏著劑用樹脂組成物中之含有比率計，由前述熱 塑性樹脂（A1)、前述熱塑性樹脂（A2)及無機塡充材料 (B)之合計25質量份、甲乙酮45質量份、甲苯30質量份 而合計量爲100質量份所成之分散液（α)的在液溫25 °C之 搖變度（TI値）爲3以上6以下。 7.如申請專利範圍第1項之黏著劑用樹脂組成物，其中將 前述熱塑性樹脂（A 1)之酸價（單位：當量/1 〇6g)設爲 AV(A1)、摻合量（單位：質量份）設爲AW(A1)，將前述熱 塑性樹脂（A2)之酸價設爲AV(A2)、摻合量設爲AW(A2) ，將前述環氧樹脂（D)之環氧値（單位：當量/ i〇6g)設爲 EV(D)、摻合量設爲EW(D)(單位··質量份）時，滿足下述 式（1 ) ’ 0.7^{EV(D)xEW(D)}/{AV(A1)xAW(A1) + AV(A2)x AW(A2)} ^4.0 (1) 。 8 . —種複數劑混合型之黏著劑用樹脂組成物，其係以滿足 下述式（1)之摻合比摻合樹脂組成物（β)與樹脂組成物（γ) 而成，其中樹脂組成物（β)含有：由聚酯樹脂或聚胺甲 酸酯樹脂所成且酸價（單位：當量/106g)爲100以上1000以 -71 - 201207059 下、玻璃轉移溫度爲3〇°C以上80°C以下、數量平均分子 量爲5.0χ103以上l.OxlO5以下之熱塑性樹脂（A1)，由聚 酯樹脂或聚胺甲酸酯樹脂所成且玻璃轉移溫度爲〇 °C以 下、數量平均分子量爲5.〇xl03以上Ι.ΟχΙΟ5以下之熱塑 性樹脂（A2)，無機塡充材料（B)以及有機溶劑（C); 樹脂組成物（γ)含有環氧樹脂（D); 且將前述熱塑性樹脂（Α1)之酸價（單位：當量/106g)設爲 AV(A1)、摻合量（單位：質量份）設爲AW(A1)，將前述熱 塑性樹脂（A2)之酸價設爲AV(A2)、摻合量設爲AW(A2) ，將前述環氧樹脂（D)之環氧値（單位：當量/ l〇6g)設爲 EV(D)、摻合量設爲EW(D)(單位：質量份）時，摻合比爲 滿足下述式（1): 0.7^{EV(D)xEW(D)}/{AV(Al)xAW(Al) + AV(A2)x AW(A2)} ^4.0 (1) 。 9 ·—種複數劑混合型之黏著劑用樹脂組成物，其係以滿足 下述式（1)之摻合比摻合樹脂組成物（δ)、樹脂組成物（ε) 、與樹脂組成物（ζ)而成，其中樹脂組成物（δ)含有：由 聚酯樹脂或聚胺甲酸酯樹脂所成且酸價（單位：當量 /l〇6g)爲100以上1000以下、玻璃轉移溫度爲30 t：以上80 °C以下、數量平均分子量爲5.〇χ103以上l.OxiO5以下之 熱塑性樹脂（A1) ’無機塡充材料（B)以及有機溶劑（c); 樹脂組成物（ε)含有：由聚酯樹脂或聚胺甲酸酯樹脂所 成且玻璃轉移溫度爲〇°C以下、數量平均分子量爲 -72- 201207059 5.〇χ103以上Ι.ΟχΙΟ5以下之熱塑性樹脂（A2)，無機塡充 材料（B)以及有機溶劑（C); 樹脂組成物（ζ)含有環氧樹脂（D); 且將前述熱塑性樹脂（Α1)之酸價（單位：當量/106g)設爲 AV(A1 )、摻合量（單位：質量份）設爲AW(A1)，將前述熱 塑性樹脂（A2)之酸價設爲AV(A2)、摻合量設爲AW(A2) ，將前述環氧樹脂（D)之環氧値（單位：當量/ l〇6g)設爲 EV(D)、摻合量設爲EW(D)(單位：質量份）時，摻合比爲 滿足下述式Π): 0.7^{EV(D)xEW(D)}/{AV(Al)xAW(Al) + AV(A2)x AW(A2)} ^ 4.0 (1) 。 1 0 ·如申請專利範圍第1項之黏著劑用樹脂組成物，其中前 述環氧樹脂（D)爲黏著劑用樹脂組成物所含之環氧樹脂 整體之6 0質量％以上9 9 · 9質量％以下。 1 1 ·如申請專利範圍第1 0項之黏著劑用樹脂組成物，其中 相對於前述熱塑性樹脂（A 1 )與前述熱塑性樹脂（A 2)之 合計1〇〇質量份而言，前述無機塡充材料（B)之摻合量 爲10質量份以上50質量份以下。 1 2 ·如申請專利範圍第1 1項之黏著劑用樹脂組成物，其中 將黏著劑用樹脂組成物當作1 〇 〇質量份時，前述溶劑 (C)之摻合量爲60質量份以上85質量份以下。 1 3 ·'如申請專利範圍第1 2項之黏著劑用樹脂組成物，其中 包含含有氮原子之環氧樹脂。 -73- 201207059 1 4 .如申請專利範圍第〗3項之黏著劑用樹脂組成物，其中 則述含有氮原子之環氧樹脂具有環氧丙基二胺結構。 15. —種黏著劑’其係含有如申請專利範圍第1至M項中任 一項之黏著劑用樹脂組成物。 16. —種黏著性薄片’其係含有如申請專利範圍第1至η項 中任一項之黏著劑用樹脂組成物中所含有之前述熱塑 性樹脂（Α1)、前述熱塑性樹脂（Α2)、無機塡充材料（Β) 、環氧樹脂（D)及來自此等之反應生成物。 1 7 . —種印刷配線板’其係包含使用如申請專利範圍第1 5 項之黏著劑或如申請專利範圍第1 6項之黏著性薄片而 成之黏著劑層。 -74- 201207059 四、指定代表圖： (一） 本案指定代表圖為：無。 (二） 本代表圖之元件代表符號簡單說明: μ。 y»\\ 五、本案若有化學式時，請揭示最能顯示發明特徵的化學式: 201207059 第100 1 1 2720號「黏著劑用樹脂組 'f ^ W物.: 修正本 杳有其之黏著劑、 黏著性薄片及含有其作爲黏著劑層之印刷配線板」專利案 (2011年8月12日修正） 七、申請專利範圍： 1 . 一種黏著劑用樹脂組成物，其係含有：熱塑性樹脂（A 1) 、熱塑性樹脂（A2)、無機塡充材料（B)及具有二環戊二 烯骨架之環氧樹脂（D);其中 〇 該熱塑性樹脂（A 1 )係由聚酯樹脂或聚胺甲酸酯樹脂所成 且酸價（單位：當量/106g)爲100以上1000以下、玻璃轉移 ’ 溫度爲30°C以上80°C以下、數量平均分子量爲5.〇xl〇3 以上1.0 X 1 05以下； 該熱塑性樹脂（A 2 )係由聚酯樹脂或聚胺甲酸酯樹脂所成 且玻璃轉移溫度爲〇°C以下、數量平均分子量爲5.〇χ103 以上1 . 0 X 1 0 5以下； Q 且在130°C乾燥3分鐘接著在140°C熱處理4小時而得到之 硬化塗膜中，至少前述熱塑性樹脂（A 1)與前述熱塑性樹 脂（A2)之至少一部分係具有相分離結構。 2 ·如申請專利範圍第1項之黏著劑用樹脂組_成物，其中藉由 前述硬化塗膜之在頻率10Hz、溫度上升速度4。(：/分鐘之 動態黏彈性的溫度分散測定，觀測到來自前述熱塑性樹 脂（A 1 )之損失彈性模數峰部及來自前述熱塑性樹脂（A2) 之損失彈性模數峰部，且兩峰部之溫度差爲40 °C以上。 修正本 201207059 3 .如申請專利範圍第1項之黏著劑用樹脂組成物’其中.前 述熱塑性樹脂（A 1 )係由聚醋樹脂所成’即述熱塑性樹月曰 (A2)係由聚胺甲酸酯樹脂所成。 4.如申請專利範圍第1項之黏著劑用樹脂組成物’其中前 述熱塑性樹脂（A1)係由聚胺甲酸酯樹脂所成’前述熱塑 性樹脂（A2)係由聚酯樹脂所成。 5 .如申請專利範圍第1項之黏著劑用樹脂組成物’其中相 對於前述熱塑性樹脂（A1)與前述熱塑性樹脂（A2)之合計 ❹ 100質量份而言，該組成物含有55質量份以上80質量份 以下之前述熱塑性樹脂（A 1 )。 6 .如申請專利範圍第1項之黏著劑用樹脂組成物’其中以 ' 在前述黏著劑用樹脂組成物中之含有比率計，由前述熱 塑性樹脂（A1)、前述熱塑性樹脂（A2)及無機塡充材料 (B)之合計25質量份、甲乙酮45質量份、甲苯30質量份 而合計量爲100質量份所成之分散液（α)的在液溫25 t之 Ο 搖變度（TI値）爲3以上6以下。 7 ·如申請專利範圍第1項之黏著劑用樹脂組成物，其中將 前述熱塑性樹脂（A1)之酸價（單位：當量/1 〇6g)設爲 AV ( A 1 )、摻合量（單位：質量份）設爲aW (A 1 )，將前述熱 塑性樹脂（A2)之酸價設爲AV(A2)、摻合量設爲AW(A2) ’將前述環氧樹脂（D)之環氧値（單位：當量/106g)設爲 EV(D)、摻合量設爲EW(D)(單位：質量份）時，滿足下述 式⑴， 修正本 201207059 0.7^{EV(D)xEW(D)}/{AV(Al)xAW(Al) + AV(A2)x AW(A2)} ^4.0 (1 ) 。 8.—種複數劑混合型之黏著劑用樹脂組成物，以滿足下述 式（1)之摻合比摻合樹脂組成物（β)與樹脂組成物（γ)而成 ;其中 該樹脂組成物（β)係含有：熱塑性樹脂（Α1)、熱塑性樹 脂（Α2)、無機塡充材料（Β)及有機溶劑（C)而成；該樹脂 組成物（γ)係含有環氧樹脂（D); 〇 該熱塑性樹脂（A 1 )係由聚酯樹脂或聚胺甲酸酯樹脂所成 且酸價（單位：當量/l〇6g)爲100以上1 000以下、玻璃轉移 溫度爲30°C以上80°C以下、數量平均分子量爲5.〇xl〇3 - 以上1 · 0 X 1 05以下； 該熱塑性樹脂（A2)係由聚酯樹脂或聚胺甲酸酯樹脂所成 且玻璃轉移溫度爲Ot以下、數量平均分子量爲5.〇xl〇3 以上1 · 0 X 1 0 5以下； Q 且將前述熱塑性樹脂（A1)之酸價（單位：當量/106g)設爲 AV(A1)、摻合量（單位：質量份）設爲AW(A1)，將前述熱 塑性樹脂（A2)之酸價設爲AV(A2)、摻合量設爲AW(A2) ，將前述環氧樹脂（D)之環氧値（單位：當量/106g)設爲 EV(D)、摻合量設爲EW(D)(單位：質量份）時，摻合比爲 滿足下述式（1): 〇.7^{EV(D)xEW(D)}/{AV(Al)xAW(Al) + AV(A2)x AW(A2)} ^4.0 (1) 。 修正本 201207059 9 . 一種複數劑混合型之黏著劑用樹脂組成物，其係以滿足 下述式（1)之摻合比摻合樹脂組成物（δ)、樹脂組成物（ε) 、與樹脂組成物（ζ)而成；其中 該樹脂組成物（δ)含有：熱塑性樹脂（Α1) '無機塡充材 料（Β)以及有機溶劑（C);該熱塑性樹脂（Α1)係由聚酯樹 脂或聚胺甲酸酯樹脂所成且酸價（單位：當量/l〇6g)爲1〇〇 以上1 00 0以下、玻璃轉移溫度爲30°C以上80°C以下、數 量平均分子量爲5·〇χ103以上Ι.ΟχΙΟ5以下； 該樹脂組成物（ε)含有：熱塑性樹脂（A2)、無機塡充材 料（Β)以及有機溶劑（C);該熱塑性樹脂（Α2)係由聚酯樹 脂或聚胺甲酸酯樹脂所成且玻璃轉移溫度爲以下、 數量平均分子量爲5·〇χ103以上Ι.ΟχΙΟ5以下； 該樹脂組成物（ζ)含有環氧樹脂（D); 且將前述熱塑性樹脂（Α1)之酸價（單位：當量/106g)設爲 AV (A1)、摻合量（單位：質量份）設爲AW(A1)，將前述熱 塑性樹脂（A2)之酸價設爲AV(A2)、摻合量設爲AW(A2) ，將前述環氧樹脂（D)之環氧値（單位：當量/106g)設爲 EV(D)、摻合量設爲EW(D)(單位：質量份）時，摻合比爲 滿足下述式（1): 0.7^{EV(D)xEW(D)}/{AV(Al)xAW(Al) + AV(A2)x AW(A2)} ^4.0 (1 ) 。 1 0 ·如申請專利範圍第1項之黏著劑用樹脂組成物，其中前 述環氧樹脂（D)爲黏著劑用樹脂組成物所含之環氧樹脂 整體之60質量％以上9 9.9質量％以下。 修正本 201207059 1 1 ‘如申請專利範圍第〗0項之黏著劑用樹脂組成物，其中 相對於前述熱塑性樹脂（A i)與前述熱塑性樹脂（Α2)之 合計質量份而言，前述無機塡充材料（B)之摻合量 爲1 〇質量份以上5 0質量份以下。 1 2 ·如申請專利範圍第1 1項之黏著劑用樹脂組成物，其中 將黏著劑用樹脂組成物當作1 〇 〇質量份時，前述溶劑 (C)之摻合量爲60質量份以上85質量份以下。 1 3 .如申請專利範圍第1 2項之黏著劑用樹脂組成物，其中 〇 包含含有氮原子之環氧樹脂。 1 4.如申請專利範圍第1 3項之黏著劑用樹脂組成物，其中 前述含有氮原子之環氧樹脂具有環氧丙基二胺結構。 ' 1 5 . 一種黏著劑’其係含有如申請專利範圍第1至1 4項中任 一項之黏著劑用樹脂組成物。 16.—種黏著性薄片，其係含有如申請專利範圍第1至14項 中任一項之黏著劑用樹脂組成物中所含有之前述熱塑 Q 性樹脂（A1)、前述熱塑性樹脂（A2)、無機塡充材料（B) 、環氧樹脂（D)及來自此等之反應生成物。 1 7. —種印刷配線板，其係包含使用如申請專利範圍第1 5 項之黏著劑或如申請專利範圍第1 6項之黏著性薄片而 成之黏著劑層。The resin composition for an adhesive according to the first aspect of the invention, wherein the composition contains 55 masses based on 1 part by mass of the total of the thermoplastic resin (A1) and the thermoplastic resin (A2). The above thermoplastic resin (A1) is 80 parts by mass or more. 6. The resin composition for an adhesive according to the first aspect of the invention, wherein the thermoplastic resin (A1), the thermoplastic resin (A2), and the inorganic cerium are contained in the resin composition of the adhesive. The degree of shaking at a liquid temperature of 25 ° C (TI値) of a dispersion (α) of a total of 25 parts by mass of the charged material (B), 45 parts by mass of methyl ethyl ketone, and 30 parts by mass of toluene in a total amount of 100 parts by mass. It is 3 or more and 6 or less. 7. The resin composition for an adhesive according to the first aspect of the invention, wherein the acid value (unit: equivalent/1 〇 6 g) of the thermoplastic resin (A 1) is set to AV (A1), blending amount (unit) : (parts by mass) is AW (A1), the acid value of the thermoplastic resin (A2) is AV (A2), the blending amount is AW (A2), and the epoxy resin of the epoxy resin (D) is 値(Unit: equivalent / i〇6g) When EV (D) is used and the blending amount is EW (D) (unit··mass), the following formula (1) '0.7^{EV(D)xEW is satisfied. (D)}/{AV(A1)xAW(A1) + AV(A2)x AW(A2)} ^4.0 (1) . 8. A resin composition for a multi-component mixed type adhesive which is obtained by blending a resin composition (β) and a resin composition (γ) in a blending ratio of the following formula (1), wherein the resin The composition (β) contains: a polyester resin or a polyurethane resin, and the acid value (unit: equivalent/106 g) is 100 or more and 1000 is -71 - 201207059, and the glass transition temperature is 3 〇 ° C or more. The thermoplastic resin (A1) having a number average molecular weight of 5.0 χ 103 or more and 1.0 OxlO 5 or less is formed of a polyester resin or a polyurethane resin, and has a glass transition temperature of 〇 ° C or less and a number average molecular weight of 80 ° C or less. 5. 热塑性xl03 or more ΟχΙΟ. ΟχΙΟ5 or less thermoplastic resin (A2), inorganic chelating material (B) and organic solvent (C); resin composition (γ) containing epoxy resin (D); and the aforementioned thermoplastic resin ( The acid value (unit: equivalent/106 g) of Α1) is set to AV (A1), the blending amount (unit: parts by mass) is AW (A1), and the acid value of the aforementioned thermoplastic resin (A2) is set to AV (A2). ), the blending amount is set to AW (A2), and the epoxy resin (unit: equivalent/l〇6g) of the epoxy resin (D) is set. When EV (D) and the blending amount are set to EW (D) (unit: parts by mass), the blending ratio satisfies the following formula (1): 0.7^{EV(D)xEW(D)}/{AV( Al)xAW(Al) + AV(A2)x AW(A2)} ^4.0 (1) . (9) A resin composition for a binder of a mixed type of a mixture which satisfies the blending ratio of the following formula (1), a resin composition (?), a resin composition (?), and a resin composition. (ζ), wherein the resin composition (δ) contains: a polyester resin or a polyurethane resin, and the acid value (unit: equivalent / l 〇 6g) is 100 or more and 1000 or less, and the glass transition temperature is 30 t: above 80 ° C, the number average molecular weight is 5. 〇χ 103 or more 1. OxiO5 or less thermoplastic resin (A1) 'Inorganic chelating material (B) and organic solvent (c); Resin composition (ε) contains : a thermoplastic resin (A2) made of a polyester resin or a polyurethane resin and having a glass transition temperature of 〇 ° C or less and a number average molecular weight of -72 to 201207059 5. 〇χ 103 or more Ι. ΟχΙΟ 5 or less, inorganic hydrazine a filling material (B) and an organic solvent (C); the resin composition (ζ) contains an epoxy resin (D); and the acid value (unit: equivalent/106 g) of the aforementioned thermoplastic resin (Α1) is set to AV (A1) The blending amount (unit: parts by mass) is set to AW (A1), and the acid of the aforementioned thermoplastic resin (A2) is used. It is assumed that AV (A2) and the blending amount are AW (A2), and the epoxy oxime (unit: equivalent / l 〇 6 g) of the epoxy resin (D) is EV (D), and the blending amount is set to When EW(D) (unit: parts by mass), the blending ratio satisfies the following formula: 0.7^{EV(D)xEW(D)}/{AV(Al)xAW(Al) + AV(A2) x AW(A2)} ^ 4.0 (1) . The resin composition for an adhesive according to the first aspect of the invention, wherein the epoxy resin (D) is 60% by mass or more of the entire epoxy resin contained in the resin composition for an adhesive; 9 9 · 9 Below mass%. The resin composition for an adhesive according to the invention of claim 10, wherein the inorganic cerium is the same as the total mass of the thermoplastic resin (A1) and the thermoplastic resin (A2) The blending amount of the filling material (B) is 10 parts by mass or more and 50 parts by mass or less. In the resin composition for an adhesive according to the first aspect of the invention, wherein the resin composition of the adhesive is used as 1 part by mass, the blending amount of the solvent (C) is 60 parts by mass or more. 85 parts by mass or less. 1 3 'A resin composition for an adhesive according to claim 12, which comprises an epoxy resin containing a nitrogen atom. -73-201207059 1 4. The resin composition for an adhesive according to the third aspect of the patent application, wherein the epoxy resin containing a nitrogen atom has a glycidyl propylamine structure. An adhesive composition which is a resin composition for an adhesive according to any one of claims 1 to M. The above-mentioned thermoplastic resin (Α1), the aforementioned thermoplastic resin (Α2), inorganic, which is contained in the resin composition for an adhesive according to any one of the first to seventh aspects of the invention. A charge material (Β), an epoxy resin (D), and a reaction product derived therefrom. A printed wiring board is an adhesive layer comprising an adhesive as disclosed in claim 15 or an adhesive sheet as disclosed in claim 16. -74- 201207059 IV. Designated representative map: (1) The representative representative of the case is: None. (2) The symbol of the representative figure of this representative figure is briefly described: μ. y»\\ V. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: 201207059 100 1 1 2720 "Resin group for adhesives" f ^ W.: Correction of adhesives , adhesive sheet and printed wiring board containing the same as the adhesive layer" (August 12, 2011 amendment) VII. Patent application scope: 1. A resin composition for adhesives, which contains: thermoplastic resin ( A 1), a thermoplastic resin (A2), an inorganic chelating material (B), and an epoxy resin (D) having a dicyclopentadiene skeleton; wherein the thermoplastic resin (A 1 ) is a polyester resin or a polyamine The acid value of the formic acid ester resin (unit: equivalent / 106 g) is 100 or more and 1000 or less, and the glass transition 'temperature is 30 ° C or more and 80 ° C or less, and the number average molecular weight is 5. 〇 xl 〇 3 or more 1.0 X 1 05 or less; The thermoplastic resin (A 2 ) is a polyester resin or a polyurethane resin and has a glass transition temperature of 〇 ° C or less and a number average molecular weight of 5. 〇χ 103 or more 1. 0 X 1 0 5 Following; Q and drying at 130 ° C for 3 minutes followed by heat treatment at 140 ° C 4 In the hardened coating film obtained in an hour, at least a part of the thermoplastic resin (A1) and the thermoplastic resin (A2) have a phase separation structure. 2. The resin group for an adhesive according to the first aspect of the invention, wherein the cured film is at a frequency of 10 Hz and a temperature rise rate of 4 by the hardening coating film. Temperature dispersion measurement of dynamic viscoelasticity of (:/min, the loss elastic modulus peak portion from the thermoplastic resin (A1) and the loss elastic modulus peak portion from the thermoplastic resin (A2) were observed, and the two peak portions were observed. The temperature difference is 40 ° C or more. Amendment 201207059 3. The resin composition for adhesives according to the first application of the patent scope of the invention, wherein the thermoplastic resin (A 1 ) is made of a polyester resin The ruthenium (A2) is a resin composition for an adhesive according to the first aspect of the invention, wherein the thermoplastic resin (A1) is made of a polyurethane resin. The thermoplastic resin (A2) is made of a polyester resin. 5. The resin composition for an adhesive according to the first aspect of the invention is the total of the thermoplastic resin (A1) and the thermoplastic resin (A2). In the case of 100 parts by mass, the composition contains 55 parts by mass or more and 80 parts by mass or less of the above-mentioned thermoplastic resin (A 1 ). 6. The resin composition for an adhesive according to claim 1 of the invention sticky The total content of the thermoplastic resin (A1), the thermoplastic resin (A2), and the inorganic chelating material (B) is 25 parts by mass, 45 parts by mass of methyl ethyl ketone, and 30 parts by mass of toluene. The total amount of the dispersion (α) is 100 parts by mass. The liquidity is 25 t. The degree of shaking (TI値) is 3 or more and 6 or less. 7 · The adhesive of the first application of the patent scope is composed of a resin. And the acid value (unit: equivalent/1 〇 6 g) of the thermoplastic resin (A1) is set to AV (A 1 ), and the blending amount (unit: parts by mass) is set to aW (A 1 ), and the aforementioned thermoplastic The acid value of the resin (A2) is AV (A2), and the blending amount is AW (A2). The epoxy oxime (unit: equivalent/106 g) of the epoxy resin (D) is EV (D). When the blending amount is EW (D) (unit: parts by mass), the following formula (1) is satisfied, and this 201207059 0.7^{EV(D)xEW(D)}/{AV(Al)xAW(Al) + AV is corrected. (A2) x AW(A2)} ^4.0 (1) 8. A resin composition for a multi-component mixed type adhesive to satisfy a blending ratio of the following formula (1) to blend a resin composition (β And a resin composition (γ); The resin composition (β) contains a thermoplastic resin (Α1), a thermoplastic resin (Α2), an inorganic chelating material (Β), and an organic solvent (C); the resin composition (γ) contains an epoxy resin. (D); 热塑性 The thermoplastic resin (A 1 ) is made of a polyester resin or a polyurethane resin and has an acid value (unit: equivalent/l 〇 6 g) of 100 or more and 1,000 or less, and a glass transition temperature of 30 °C or more and 80 ° C or less, the number average molecular weight is 5. 〇 xl 〇 3 - above 1 · 0 X 1 05 or less; the thermoplastic resin (A2) is made of polyester resin or polyurethane resin and glass The transfer temperature is below Ot, and the number average molecular weight is 5. 〇xl 〇 3 or more and 1 · 0 X 1 0 5 or less; Q and the acid value (unit: equivalent/106 g) of the thermoplastic resin (A1) is set to AV (A1) And the blending amount (unit: parts by mass) is AW (A1), the acid value of the thermoplastic resin (A2) is AV (A2), and the blending amount is AW (A2), and the epoxy resin is used. When the epoxy oxime (unit: equivalent: 106 g) of (D) is EV (D) and the blending amount is EW (D) (unit: parts by mass), the blending ratio satisfies the following formula (1) : 〇.7^{EV(D)xEW(D)}/{AV(Al)xAW(Al) + AV(A2)x AW(A2)} ^4.0 (1) . MODIFICATION 201207059 9. A resin composition for a multi-component mixed type adhesive which is blended to satisfy a blending ratio of the following formula (1): a resin composition (δ), a resin composition (ε), and a resin The composition (ζ) is obtained; wherein the resin composition (δ) contains: a thermoplastic resin (Α1) 'an inorganic filler (Β) and an organic solvent (C); the thermoplastic resin (Α1) is a polyester resin or The value of the acid value (unit: equivalent / l 〇 6g) is 1 〇〇 or more and 100 Å or less, the glass transition temperature is 30 ° C or more and 80 ° C or less, and the number average molecular weight is 5 〇. Χ103 or more ΟχΙΟ.5 or less; the resin composition (ε) contains: a thermoplastic resin (A2), an inorganic chelating material (Β), and an organic solvent (C); the thermoplastic resin (Α2) is a polyester resin or a polyamine a resinate resin having a glass transition temperature of the following, a number average molecular weight of 5·〇χ103 or more Ι.5 or less; the resin composition (ζ) containing an epoxy resin (D); and the aforementioned thermoplastic resin (Α1) Acid value (unit: equivalent / 106g) is set to AV (A1), blending amount (Unit: parts by mass) is AW (A1), the acid value of the thermoplastic resin (A2) is AV (A2), the blending amount is AW (A2), and the epoxy resin (D) is ring-shaped. When oxime (unit: equivalent/106 g) is EV (D) and the blending amount is EW (D) (unit: parts by mass), the blending ratio satisfies the following formula (1): 0.7^{EV( D) xEW(D)}/{AV(Al)xAW(Al) + AV(A2)x AW(A2)} ^4.0 (1). The resin composition for an adhesive according to the first aspect of the invention, wherein the epoxy resin (D) is 60% by mass or more and 99.9% by mass or less of the entire epoxy resin contained in the resin composition for an adhesive. . The resin composition for an adhesive according to the above Patent Application No. 00, wherein the inorganic filler is added to the total mass of the thermoplastic resin (A i) and the thermoplastic resin (Α2). The blending amount of the material (B) is 1 part by mass or more and 50 parts by mass or less. In the resin composition for an adhesive according to the first aspect of the invention, wherein the resin composition of the adhesive is used as 1 part by mass, the blending amount of the solvent (C) is 60 parts by mass or more. 85 parts by mass or less. A resin composition for an adhesive according to claim 12, wherein 〇 contains an epoxy resin containing a nitrogen atom. 1 . The resin composition for an adhesive according to claim 13 wherein the epoxy resin containing a nitrogen atom has a glycidyl propylene diamine structure. The adhesive composition for an adhesive according to any one of claims 1 to 14 of the patent application. The above-mentioned thermoplastic Q-resin (A1), the aforementioned thermoplastic resin (A2) contained in the resin composition for an adhesive according to any one of claims 1 to 14 of the invention. ), an inorganic chelating material (B), an epoxy resin (D), and a reaction product derived therefrom. 1 7. A printed wiring board comprising an adhesive layer formed using an adhesive as disclosed in claim 15 or an adhesive sheet as disclosed in claim 16.
TW100112720A 2010-04-14 2011-04-13 Resin composition for adhesive agent, adhesive agent containing thereof, adhesive sheet and printed wire board containing the same as adhesive layer TWI487762B (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP2010092938 2010-04-14

Publications (2)

Publication Number Publication Date
TW201207059A true TW201207059A (en) 2012-02-16
TWI487762B TWI487762B (en) 2015-06-11

Family

ID=44798654

Family Applications (1)

Application Number Title Priority Date Filing Date
TW100112720A TWI487762B (en) 2010-04-14 2011-04-13 Resin composition for adhesive agent, adhesive agent containing thereof, adhesive sheet and printed wire board containing the same as adhesive layer

Country Status (5)

Country Link
JP (1) JP4978753B2 (en)
KR (1) KR101660083B1 (en)
CN (1) CN102782074B (en)
TW (1) TWI487762B (en)
WO (1) WO2011129278A1 (en)

Families Citing this family (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5304152B2 (en) * 2008-09-30 2013-10-02 東洋紡株式会社 RESIN COMPOSITION FOR ADHESIVE, ADHESIVE CONTAINING THE SAME, ADHESIVE SHEET AND PRINTED WIRING BOARD CONTAINING THE SAME AS ADHESIVE LAYER
CN102822304B (en) 2010-04-14 2014-04-30 东洋纺织株式会社 Resin composition for adhesive agent, adhesive agent and adhesive sheet each comprising same, and printed circuit board comprising same as adhesive agent layer
WO2016013621A1 (en) * 2014-07-25 2016-01-28 横浜ゴム株式会社 Adhesive agent composition
JP5850103B1 (en) * 2014-07-25 2016-02-03 横浜ゴム株式会社 Adhesive composition
JP5924383B2 (en) * 2014-07-25 2016-05-25 横浜ゴム株式会社 Adhesive composition
JP5953391B1 (en) * 2015-03-30 2016-07-20 株式会社フジクラ Thermosetting adhesive composition, coverlay film, adhesive film, metal-clad laminate and flexible printed wiring board
JP6170211B1 (en) * 2016-07-15 2017-07-26 株式会社フジクラ Thermosetting adhesive composition, coverlay film, adhesive film, metal-clad laminate and flexible printed wiring board
JP7156267B2 (en) * 2017-03-28 2022-10-19 東洋紡株式会社 Carboxylic acid group-containing polyester adhesive composition
TWI779066B (en) * 2017-07-19 2022-10-01 日商東洋紡股份有限公司 adhesive composition
JP7098350B2 (en) * 2018-02-28 2022-07-11 キヤノン株式会社 Inkjet recording head using adhesive sheet and manufacturing method
CN108587508B (en) * 2018-03-29 2021-04-06 广东莱尔新材料科技股份有限公司 High-viscosity metal hot-melt adhesive film and preparation method thereof
CN116731500A (en) * 2023-06-20 2023-09-12 国网湖北省电力有限公司孝感供电公司 Cable line cladding material and preparation method thereof

Family Cites Families (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP3376133B2 (en) * 1994-10-21 2003-02-10 ダイセル化学工業株式会社 Adhesive composition
JP4423513B2 (en) 1997-10-20 2010-03-03 東洋紡績株式会社 Adhesive resin composition and adhesive film
JP4865157B2 (en) * 2001-07-19 2012-02-01 日東シンコー株式会社 Moist heat resistant hot melt adhesive composition
JP2005170999A (en) * 2003-12-09 2005-06-30 Toyobo Co Ltd Adhesive and polyester film laminated steel plate using the same
JP4946080B2 (en) * 2006-02-06 2012-06-06 東洋紡績株式会社 Adhesive composition and flexible copper-clad laminate using the same
JP5050429B2 (en) 2006-07-14 2012-10-17 東洋紡績株式会社 Polyester resin composition and adhesive containing the same
JP5286084B2 (en) * 2006-07-19 2013-09-11 積水化学工業株式会社 Dicing die bonding tape and semiconductor chip manufacturing method
JP2008205370A (en) 2007-02-22 2008-09-04 Sumitomo Bakelite Co Ltd Resin composition, adhesive with supporting base, and printed circuit board with reinforcing plate
JP2008260831A (en) * 2007-04-11 2008-10-30 Mitsubishi Plastics Ind Ltd Aqueous adhesive and resin sheet-covered metal plate
JP5181601B2 (en) * 2007-09-28 2013-04-10 東洋紡株式会社 Adhesive composition, laminate and flexible flat cable using solvent-soluble crystalline polyester resin
JP5304656B2 (en) * 2008-09-29 2013-10-02 東洋紡株式会社 Polyester resin composition, adhesive containing the same, adhesive tape and flexible flat cable
WO2010038733A1 (en) * 2008-09-30 2010-04-08 東洋紡績株式会社 Resin composition for adhesive agent, adhesive agent and adhesive sheet each comprising same, and laminate for print circuit board adhered by using same
JP5304152B2 (en) * 2008-09-30 2013-10-02 東洋紡株式会社 RESIN COMPOSITION FOR ADHESIVE, ADHESIVE CONTAINING THE SAME, ADHESIVE SHEET AND PRINTED WIRING BOARD CONTAINING THE SAME AS ADHESIVE LAYER

Also Published As

Publication number Publication date
KR101660083B1 (en) 2016-09-26
CN102782074A (en) 2012-11-14
CN102782074B (en) 2014-06-18
TWI487762B (en) 2015-06-11
KR20130057965A (en) 2013-06-03
JP4978753B2 (en) 2012-07-18
WO2011129278A1 (en) 2011-10-20
JPWO2011129278A1 (en) 2013-07-18

Similar Documents

Publication Publication Date Title
TWI487762B (en) Resin composition for adhesive agent, adhesive agent containing thereof, adhesive sheet and printed wire board containing the same as adhesive layer
TWI504712B (en) Resin composition for adhesive agent, adhesive agent containing thereof, adhesive sheet and printed wire board containing the same as adhesive layer
JP6032318B2 (en) RESIN COMPOSITION FOR ADHESIVE, ADHESIVE CONTAINING THE SAME, ADHESIVE SHEET AND A PRINTED WIRING BOARD CONTAINING THE SAME AS ADHESIVE LAYER
TWI614306B (en) Polyurethane resin composition and adhesive composition, laminate and printed circuit board using the same
CN110268030B (en) Polyester-based adhesive composition containing carboxylic acid group
JP5304152B2 (en) RESIN COMPOSITION FOR ADHESIVE, ADHESIVE CONTAINING THE SAME, ADHESIVE SHEET AND PRINTED WIRING BOARD CONTAINING THE SAME AS ADHESIVE LAYER
JP6380710B1 (en) Carboxylic acid group-containing polymer compound and adhesive composition containing the same
JP7318838B2 (en) Adhesive composition, adhesive sheet, laminate and printed wiring board
WO2024090291A1 (en) Adhesive composition, and adhesive sheet, layered body and printed circuit board containing same
US20220411630A1 (en) Resin composition, layered body including resin composition layer, layered body, flexible copper-clad laminate, flexible flat cable, and electromagnetic wave shielding film
CN118076698A (en) Crosslinked polyester resin, adhesive composition, and adhesive sheet