TW200535209A - Thermosetting adhesive composition and adhesive tape for electronic parts using the same - Google Patents

Thermosetting adhesive composition and adhesive tape for electronic parts using the same Download PDF

Info

Publication number
TW200535209A
TW200535209A TW093124645A TW93124645A TW200535209A TW 200535209 A TW200535209 A TW 200535209A TW 093124645 A TW093124645 A TW 093124645A TW 93124645 A TW93124645 A TW 93124645A TW 200535209 A TW200535209 A TW 200535209A
Authority
TW
Taiwan
Prior art keywords
adhesive composition
resin
adhesive
layer
film
Prior art date
Application number
TW093124645A
Other languages
Chinese (zh)
Other versions
TWI280971B (en
Inventor
Kyeong-Ho Chang
Kwang-Moo Kim
Jeong-Min Kweon
Kyung-Rok Lee
Duk-Ha Park
Original Assignee
Saehan Micronics Inc
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 Saehan Micronics Inc filed Critical Saehan Micronics Inc
Publication of TW200535209A publication Critical patent/TW200535209A/en
Application granted granted Critical
Publication of TWI280971B publication Critical patent/TWI280971B/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
    • C09J109/00—Adhesives based on homopolymers or copolymers of conjugated diene hydrocarbons
    • C09J109/02—Copolymers with acrylonitrile
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
    • C08L61/04—Condensation polymers of aldehydes or ketones with phenols only
    • C08L61/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
    • 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
    • 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
    • C09J183/00—Adhesives based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Adhesives based on derivatives of such polymers
    • C09J183/04—Polysiloxanes
    • 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
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • C09J7/22—Plastics; Metallised plastics
    • C09J7/25—Plastics; Metallised plastics based on macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds
    • 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
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • C09J7/22—Plastics; Metallised plastics
    • C09J7/25—Plastics; Metallised plastics based on macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds
    • C09J7/255—Polyesters
    • 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
    • C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
    • C09J2203/326—Applications of adhesives in processes or use of adhesives in the form of films or foils for bonding electronic components such as wafers, chips or semiconductors
    • 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
    • C09J2467/00—Presence of polyester
    • C09J2467/006—Presence of polyester in the substrate
    • 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
    • C09J2479/00—Presence of polyamine or polyimide
    • C09J2479/08—Presence of polyamine or polyimide polyimide
    • C09J2479/086—Presence of polyamine or polyimide polyimide in the substrate

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Laminated Bodies (AREA)

Abstract

Disclosed is a thermosetting adhesive composition and an adhesive tape for electronic parts using the same. The thermosetting adhesive composition, includes: (1) a butadiene-acrylonitrile copolymer, containing a carboxyl polyamide aminocarbonyl group (A) and a polysiloxane aniinocarbonyl group (B) and expressed by the following Formula 1; and (2) an epoxy resin. The thermosetting adhesive composition is advantageous in that the adhesive strength of the butadiene-acrylonitrile copolymer to a base substrate is improved, the compatibility of the butadiene-acrylonitrile copolymer with the epoxy resin is improved, adhesion between a base film and the adhesive composition is improved to improve the bend resistance and high temperature reliability, thereby the adhesive composition can be usefully applied to the adhesive tape for electronic parts, such as a coverlay film, a bonding sheet, and particularly a flexible PCB. (wherein A, B, k, m, n, R1, R2, R3, O, P and Q are the same as described in the specification of the present invention)

Description

200535209 九、發明說明·· 【發明所屬之技術領域】 本發明係有關於一種熱固性黏著組成物及使用上述組 成物的電子元件黏著帶。更特而言之，本發明係有關於— 種使用於軟性印刷電路板的熱固性黏著組成物，其包含： 1)丁二烯-丙烯腈共聚物，其含有羧基聚醯胺基胺羰基（八 和聚石夕氧烧胺幾基（B)，並以下列式i表示，及2)環氧樹 脂’以及有關於―種使用上述組成物的電子元件黏著帶/ ch-ch^ C；ry^ CM,- °1 ^ 严 ch/^'ch, CH> CH^ ^ Hr^〇 耳比(：中A 100 - B，此乃是在A是範圍從1至99之莫 ΓΠ的前提下，k、m、和n為莫耳比率，當k為二 】_ R2為C〗至c2G脂族烴，R3為至c 個別為從1至20的整數）。 “基，及 【先前技術】 目前與半導體隹 已非常地先進，因此‘ ‘㈣（例如表面組裝技術） 通訊和光學之電子元件的;;=降低大小和重量以及整合 電子元件需要具有可撓曲：二，.，提高。特別地’曰前的 口此軟性印刷電路板（PCB) 200535209 便：裝設和插進相當小的空間之内，而使電子元件外殼之 :°:二間的效用提高。因此’對於軟性PCB使用為複合 件的應用領域j主$ 、—寺、天擴大’，、中該複合構件可提供電纜和 連接益以及電路線裝置上的應用功能。 0叙[生PCB包括由具有高耐熱性和 機械性質之塑膠樹脂所製得之可挽曲的基板薄膜，=電 Π:圖案化編，及連接至基板薄膜-側it 金屬落已被層積在黏著層上。在此方面，軟性 俱自在基板薄膜與金屬箱之間非常強的黏著性， 炎义的可加工性，撓曲性，耐熱性，和電性質。 目前，-種為壓敏性黏著劑類型之覆蓋膜 合步驟之下，而黏附至軟性pCB的μ 像 為“ 層部份，以便保護做 :电路線層的金屬箱且改良pcB的可撓曲性 “ X «將保蠖性缚膜可移除式地黏合至半硬 者劑的兩面，及今τ對| W ’ 薄膜的伴1 /表在使用之前均受到保護性 千、所… 可知該覆蓋膜必需具有優良的耐熱性、 “生質、和可加工性’所以由黏 良的儲存穩定性。 蚁復盍膜具有優 ^ I!! ’二片軟性PCB可使用黏著膠膜相互黏合而生成 夕層李人性p C B。詳而t之，兮伞 .μ ^ 。之该丰硬化黏著劑被均勻地塗覆 ::f:"CB的-個表面上，然後將另一片軟性PCB :者』換句话说’黏著膠膜係插置在兩片軟性PCB 承^生成多層㈣PCB。在此方面，該㈣㈣具有與 的物里性貝，亦即該黏著膠膜亦需具有極佳的 200535209 ::熱性、電性質、和可加工性，並且由黏著劑組成之黏著 勝具有優良的儲存穩定性。 口此，軟性PCB、覆蓋膜、和黏著膠膜均有必要具 極么的^、曲性和高溫可靠性。依此，在軟性PCB的情況 下，必需確定基板薄膜和黏著劑之間具有的極佳的^性 以滿足上述之物理性質。換句話說，在基板薄膜和黏著劑 :間的黏著性降低之例中’軟性PCB在相當長時間下的抗 •.弓曲性和在軟性PCB吸收水之後的高溫焊接能力方面的評 ㈣示，軟性PCB具有差的抗彎曲性但為高溫可靠性，這 ^因為黏著劑是從黏著劑和基板薄膜之間界面上的基 膜分離出。 广，用來做為平面型產品之基板材料的黏著組成物 必需在基板薄膜和黏著劑之間提供極佳的黏著性，其中平 面型產品例如為使用於線路板、覆蓋膜、和黏著膠膜 性 PCB。 、 日本專利早期公開Hei· 5-62156號，Sh〇. 63_297483 號，Hei. 4_2061 12及汕〇 64_2_號則建議了各種不同 的黏著劑組成物。所揭示之黏著劑組成物可以有利地使用 ^基於尼龍和環氧樹脂’丙烯酸樹脂和苯酉分樹脂，聚醋和 環氧樹脂，及丙烯腈橡膠和環氧樹脂的軟性pcB上。然而， 當含有丙烯腈橡膠之黏著劑組成物在高溫下被熱處理一段 相當長的時間之後，其會很容易分解，使得它的分子結構 含有因具有多個乙稀而不飽和的建結，造成它的抗剝離效 率快速降低。然而，使用以丙稀腈橡膠和環氧樹脂為基礎 200535209 之黏著劑組成物極為普遍。 僅使用以丙烯腈橡膠和環氧樹脂為基礎之黏著 黏著性以及高溫^ 湾膜與黏著劑之間具有所欲 θ ϋ罪性方面疋很困難的。有關於此，已嗆 ::、二電：或電漿方式來增加基板薄膜表面的粗糙度，： 、土板溥膜與黏著劑之間的黏著性。然而，此種嚐 於屬於物理性枯供 ㈢八由 著性改？非a古 u、於基板薄膜和黏著劑之間的黏 =^非以限°關於此點，仍專利號·124揭示_ 種化學技術，其包括 乃不 之斑一 二匕括首先使用—種對薄膜表面具有親和性 臂膜者：一以M，其次使用另—種黏著劑塗覆所得到的 =爭Γ因化學技術由生產性和生產成本方面來考量並 ’、、、 此並不可能將該化學技術商業化。 ，外’亦已提出-種方法，其中將為低聚物類型之偶 =黏著劑組成物混合，以藉此改良基板薄膜 ;:的黏著性。然而’該方法對於金屬基板與黏著劑之： ;=效改良’遠勝於由塑勝製得之基板薄膜與黏i ::者性改良’且由於構成黏著劑組成物的一部份》且 ，擇性地與偶合劑鍵結，而無法得到 ： 合效應。 J堝 【發明内容】 的因此’本發明依據於前案中所產生之缺點，在本發明 的中提供—種使用於軟性咖的熱固性黏著組成 物’其可提供基板薄膜與勸著劑之間的改良黏著性，藉^ 200535209 改良軟性PCB的的物理性質 性。 例如抗T曲性和高溫可靠 本發明的另-個目的為提供一種使用本 著組成物而製得之用於雷 …σ丨生黏 用万、电子凡件的黏著帶。 本發明的進一步目的或坦 ,..#tJ 為如（、一種使用該熱固性黏著4a ;物而製仔之用於覆蓋膜、黏著膠膜和軟…的複合 目'可藉由提供一種熱固性黏著組成物而完 :…固性黏者組成物包含：υ丁二烯-丙烯腈共聚物， u有羧基聚醯胺基胺幾基㈧和聚石夕氧院胺幾基⑻，並 且疋以下列式1表示，及2)環氧樹脂。 式1 ij... ·ί!?! i g；’1 ， “.—·，上， i C*)·^ *Λ* .... ： ίί5ί ' * ;：w ΗΗ-. ..·Η:麵 ，巧 CH, CH^ Ch3 CN 难、卜:卜〇H孓卜:十I”叫制 c卜mi·、 HCX> (其中A = loo _ B，此乃是在A是範圍從丨至99之莫 耳比率的前提下，k、m、和n為莫耳比率，當&為"寺， m 為 3-200 及 η 為 0.2-100，200535209 IX. Description of the invention ... [Technical field to which the invention belongs] The present invention relates to a thermosetting adhesive composition and an electronic component adhesive tape using the above composition. More specifically, the present invention relates to a thermosetting adhesive composition for a flexible printed circuit board, which includes: 1) a butadiene-acrylonitrile copolymer containing a carboxypolyamidoaminocarbonyl group (eight And polyisocyanuric acid (B), and is represented by the following formula i, and 2) epoxy resin 'and related to-a kind of electronic component adhesive tape using the above composition / ch-ch ^ C; ry ^ CM,-° 1 ^ Strict ch / ^ 'ch, CH > CH ^ ^ Hr ^ 〇 Ear ratio (: Medium A 100-B, this is under the premise that A is in the range from 1 to 99 ΓΠ, k , M, and n are mole ratios, when k is two] R2 is C to C2G aliphatic hydrocarbon, and R3 to c are each integer from 1 to 20). "Base, and [prior art] are currently very advanced with semiconductors, so '' (such as surface mount technology) for electronic components of communication and optics; == reduction in size and weight and integration of electronic components need to have flexibility : Two,., Improve. Especially the front of the flexible printed circuit board (PCB) 200535209: install and insert into a relatively small space, so that the electronic component housing: °: the effectiveness of two Improved. So 'for the use of flexible PCBs as application areas for composite parts, the main component is the temple, the sky expands', and the composite components can provide cable and connection benefits and application functions on circuit line devices. 0 述 [生 PCB Including a flexible substrate film made of a plastic resin with high heat resistance and mechanical properties, = electricity: patterned knitting, and a metal film connected to the substrate film-side it has been laminated on the adhesive layer. In this respect, softness is very strong between the substrate film and the metal box, and the processability, flexibility, heat resistance, and electrical properties of the flame. At present, it is a type of pressure-sensitive adhesive cover Under the lamination step, the μ image that is adhered to the soft pCB is "layered part for protection: do the metal box of the circuit line layer and improve the flexibility of pcB" X «Removable protective film Adhesively adhered to both sides of the semi-hard agent, and the current τ pair | W 'film companion 1 / watch are protected before use. Therefore, we know that the cover film must have excellent heat resistance, "biomass, And processability 'so good storage stability from stickiness. The ant complex film has excellent ^ I !! ’Two soft PCBs can be adhered to each other using an adhesive film to form a human layer p C B. In detail, Xi umbrella .μ ^. The abundance of hardening adhesive is evenly coated on one surface of :: f: " CB, and then another piece of flexible PCB: '' In other words, an adhesive film is inserted between two pieces of flexible PCB support ^ Generate multi-layer ㈣PCB. In this respect, the tadpole has the same physical properties, that is, the adhesive film also needs to have excellent 200535209 :: thermal properties, electrical properties, and processability, and the adhesive layer composed of an adhesive has excellent Storage stability. In view of this, flexible PCBs, cover films, and adhesive films all need to be extremely flexible, flexible, and reliable at high temperatures. Accordingly, in the case of a flexible PCB, it is necessary to determine the excellent properties between the substrate film and the adhesive to satisfy the above-mentioned physical properties. In other words, in the case where the adhesiveness between the substrate film and the adhesive: is reduced, the resistance of the flexible PCB over a long period of time • Evaluation of bowing and high-temperature soldering ability after the flexible PCB absorbs water The flexible PCB has poor bending resistance but high temperature reliability, because the adhesive is separated from the base film on the interface between the adhesive and the substrate film. Wide, the adhesive composition used as the substrate material of flat products must provide excellent adhesion between the substrate film and the adhesive. Among them, the flat products are used in circuit boards, cover films, and adhesive films, for example. Sex PCB. Early Japanese Patent Publications Hei 5-62156, Sh. 63_297483, Hei. 4_2061 12 and Shan 0 64_2_ suggest various adhesive compositions. The disclosed adhesive composition can be advantageously used on a soft pcB based on nylon and epoxy resin 'acrylic resin and benzene resin, polyacetate and epoxy resin, and acrylonitrile rubber and epoxy resin. However, when the adhesive composition containing acrylonitrile rubber is heat-treated at a high temperature for a long period of time, it will be easily decomposed, so that its molecular structure contains agglomerations that are unsaturated due to the presence of multiple ethylene monomers. Its anti-peeling efficiency decreases rapidly. However, the use of adhesive compositions based on acrylonitrile rubber and epoxy resin 200535209 is extremely common. It is difficult to use only adhesives based on acrylonitrile rubber and epoxy resins, as well as the desired θ ϋ sinality between the high temperature film and the adhesive. In this regard, the surface roughness of the substrate film has been improved with the :::, two-electrode: or plasma method, and the adhesion between the soil-board film and the adhesive. However, this kind of taste belongs to physical withering. What is the reason for sexual change? Non-a, u, the adhesion between the substrate film and the adhesive = ^ not limited. In this regard, the patent No. 124 reveals _ a kind of chemical technology, which includes the inevitably one or two. First use— Those who have an affinity arm film on the surface of the film: one with M, followed by coating with another type of adhesive = = due to the fact that chemical technology is considered from the perspective of productivity and production cost, and this is not possible Commercialize this chemical technology. In addition, a method has also been proposed in which an adhesive composition that is an oligomer type is mixed to improve the adhesion of the substrate film ;. However, 'this method for metal substrates and adhesives:; = effect improvement' is far better than substrate films and adhesives made from plastic wins :: improvement of human nature 'and because it forms part of the adhesive composition "and , Selectively bonding with the coupling agent, but can not get: the combined effect. [Content of the invention] J pot [The present invention is based on the disadvantages generated in the previous case, and is provided in the present invention-a thermosetting adhesive composition for soft coffee ', which can provide a substrate film and an adjuvant Improved adhesiveness of the PCB, by using 200520052 to improve the physical properties of flexible PCBs. For example, resistance to T-curvature and high temperature reliability. Another object of the present invention is to provide an adhesive tape for lightning ... σ, which is produced by using the composition, and is used for electronic and electronic components. A further object of the present invention or .... # tJ is a composite mesh for covering film, adhesive film and soft ... made by using the thermosetting adhesive 4a; can provide a thermosetting adhesive The composition is finished: ... the solid adhesive composition includes: butadiene-acrylonitrile copolymer, u has a carboxy polyaminoamino amine hydrazone and a polyisocyanurine amine quaternary amine, and the following are Formula 1 shows, and 2) epoxy resin. Formula 1 ij ... · ί!?! Ig; '1, ".— · ， 上 ， i C *) · ^ * Λ * ....: ίί5ί' *;: w ΗΗ-. .. · Η : 面 ， 巧 CH, CH ^ Ch3 CN Difficulty, Bu: 〇〇H 孓 卜: Ten I ”called system c mi ·, HCX > (where A = loo _ B, this is where A is in the range from 丨 to On the premise of a Mohr ratio of 99, k, m, and n are Mohr ratios. When & is " Temple, m is 3-200 and η is 0.2-100.

Ri和R2為C】至C2G脂族烴，R3為c!至C2G烷基，及 0 P和Q個別為從1至20的整數）。 車乂佳者為，丁二烯-丙烯腈共聚物具有之重量平均分子 量為10,000-200,000，及在丁二烯-丙烯腈共聚物中之丙烯 腈單元含量為2_4〇重量％。 10 200535209 此外，該點著組成物在以1〇〇重量 聚物為基準時，可能包括1〇_9〇旦 产一、、腈，、 上，璜气抖昨 重里伤裱氧樹脂。在此點 久脂可能另外包括-或多個選自由被至少一個， 取代之裱乳基歯化物所組成的族群。 “ 該熱固性黏著組成物可 ,. 此另包括笨酚樹脂，在此方式 中，壞虱樹脂與苯酚樹脂的冬 万式 酚樹脂係選自由下列所組 ·.，、中本 酚醛、、主决舛日t田 無群.酚醛苯酚樹潴、苯酚 全…“曰、甲_清漆樹脂、間苯 % 苯樹脂、和它們的混合物。 -、g 一甲 亚且，熱固性黏著組成物在以 基準時，可能另外包括2_20 里伤壤氧樹脂為 化劑係選自由下列所組成史化』心乳硬 入〈秩群·脂肪族胺人、^ 族胺化合物、酸酐化合物、 一 〇 方香 混合物。 雙n =氟化删’和它們的 除此之外，熱固性黏著 ^ A Α Ά 、 在以100重量份環氧樹 月曰為基準時，可能另外包 衣軋树 石垂外作〇 ·〇1·3重量份硬化促進劑，兮 硬化促進劑係選自由下㈣1 5亥 如2_院基_4_曱基味唾化合物、2 化5物（例 及2-苯基味。坐化合物），凡土…乙基哺唾化合物、 錫和氟化硼鋅），全屬辛_彳例如氣化硼 鋅），和它們的混合物。 辛馱錫和辛酸 :時’熱固性黏著組成物可能另包括"〇重量呈 有粒度為5 a m或更低之盔機埴 _…妆填充劑（以1⑻重量份環氧抖 月曰為基準），該無機填充 衣虱树 剎係遠自由下列所組成之族群.气 11 200535209 氧化鋁、氫氧化鎂、氧化鋁、氧化鋅和氧化鎂。 +另外，本發明又提供一種覆蓋膜，其包括由聚醒亞胺 樹脂或聚對苯二甲酸乙二醇s旨樹脂所製成的基板層，由塗 覆本發明熱固性黏著組成物至基板層上所製得之黏著層， 及在形成在黏著層上之保護膜。 此外，本發明提供一種黏著膠臈，λ包括第一保護膜， 由塗覆本發明熱固性黏著組成物至第_保護層上所製得的 黏著層，及形成在黏著層上之第二保護膜。 除此之外，本發明提供一種使用於軟性PCB之複合 帶，其包括由聚醯亞胺樹脂或聚對笨二甲酸乙二醇醋樹脂 斤製成的基板層’纟塗覆本發明熱固性黏著組成物至基板 層其中一側所製得的黏著層，及形成在黏著層之一側上之 金屬镇。 同樣地本發明提供_種使用於軟性KB之複合帶， 其包括由聚酿亞胺樹脂或聚對苯二甲酸乙二醇繼所製 成的基板層’ *塗覆本發明熱固性黏著組成物至基板層之 兩側所製付的黏著層，及形成在黏著層之兩側上之金屬 【實施方式】 ^依據本％明，其係提供—種使用於軟性的熱固性 站者組成物’其包含：υ丁二烯_丙烯腈共聚物，其含有羧 基聚醯胺基胺羰基(Α)和聚矽氧烷胺羰基(Β)，並且是以下 弋1表示及2) 一或多種類型之環氧樹脂。 12 200535209 式 C!i- Η «! % ..〜Ηc............Cr；ti j μ 计博..Η，-pi》「办 Γ ί \ ^ ··Ri and R2 are C] to C2G aliphatic hydrocarbons, R3 is c! To C2G alkyl, and O and Q are each an integer from 1 to 20). It is preferred that the butadiene-acrylonitrile copolymer has a weight average molecular weight of 10,000-200,000, and the acrylonitrile unit content in the butadiene-acrylonitrile copolymer is 2 to 40% by weight. 10 200535209 In addition, when the composition is based on a 100-weight polymer, it may include 10-90 denier, 1, nitrile, sulphur, and sultry gas. The epoxy resin was seriously damaged. At this point, Jiuzhi may additionally include-or more than one group selected from the group consisting of a lactating halide substituted with at least one. "The thermosetting adhesive composition may include, in addition, stupid phenol resin. In this method, the Dongwan type phenol resin of the bad lice resin and the phenol resin is selected from the group consisting of ... The next day, Tian Wuqun. Novolac, phenolic tree phenol, all phenol ... "", varnish resin, m-benzene% benzene resin, and mixtures thereof. -, G-A, and the thermosetting adhesive composition may additionally include 2-20 li of oxidant resin as a chemical agent when selected based on the history selected from the group consisting of: "Central sclerotin and aliphatic amines" , ^ Group amine compounds, acid anhydride compounds, 10 square incense mixture. Double n = fluorinated and 'other than that, thermosetting adhesion ^ A Α Ά, when based on 100 parts by weight of epoxy tree month, it may be coated with rolled tree stones. · 3 parts by weight of a hardening accelerator, which is selected from the group consisting of the following compounds: 2_Yuanji_4_Yanwei saliva compounds, 2 compounds (examples and 2-phenyl flavors), Fantu ... ethyl sialophylline compounds, tin and boron zinc fluoride), all of which are octane (such as boron zinc zincate), and mixtures thereof. Caprylic tin and caprylic acid: The thermosetting adhesive composition may additionally include " 〇 Weight is a helmet machine with a particle size of 5 am or less 埴 _... makeup filler (based on 1 part by weight of epoxy shake month) The inorganically-filled lice tree brake system is far from the following groups. Gas 11 200535209 Alumina, magnesium hydroxide, aluminum oxide, zinc oxide, and magnesium oxide. + In addition, the present invention also provides a cover film, which includes a substrate layer made of polyimide resin or polyethylene terephthalate resin, and is coated with the thermosetting adhesive composition of the present invention to the substrate layer. And a protective film formed on the adhesive layer. In addition, the present invention provides an adhesive glue, λ includes a first protective film, an adhesive layer prepared by coating the thermosetting adhesive composition of the present invention onto the first protective layer, and a second protective film formed on the adhesive layer. . In addition, the present invention provides a composite tape for flexible PCB, which includes a substrate layer made of polyimide resin or polyethylene terephthalate resin, and is coated with the thermosetting adhesive of the present invention. An adhesive layer prepared by the composition to one side of the substrate layer, and a metal ball formed on one side of the adhesive layer. Similarly, the present invention provides a kind of composite tape for flexible KB, which comprises a substrate layer made of polyimide resin or polyethylene terephthalate. * The thermosetting adhesive composition of the present invention is coated to Adhesive layers made on both sides of the substrate layer, and metal formed on both sides of the adhesive layer [Embodiment] ^ According to the present invention, it provides a kind of composition for soft thermosetting station, which contains : Υ butadiene_acrylonitrile copolymer, which contains carboxy polyamidoamine carbonyl (A) and polysilylamine carbonyl (B), and is represented by 弋 1 below and 2) one or more types of epoxy Resin. 12 200535209 Formula C! I- Η «!% .. ~ Ηc ............ Cr; ti j μ Jibo..Η, -pi" 「办 Γ ί \ ^ ··

CN V ν'·"'| CKK ά πνΆ .**"乂:·: j »·. 〇% h R】，R,，R: 〇 ’ P和q為如 (其中 A，B，k，ni，r 同於上文中所述者）。 依據本發明，在以式1表示並含有羧基聚醯胺基胺羰 基（^)和聚矽氧烷胺羰基（B)之丁二烯-丙烯腈共聚物中，其 ，烯腈單元的含量較佳為2-4〇重量％，且更佳為5_35重 里/因此，當丙烯腈單元之含量低於2重量％時，該共 聚物的溶解度降低，且當含量高於40重量％時，該共聚 物之絕緣性質變差。 除此之外，丁二烯·丙烯腈共聚物的重量平均分子量較 佳為10,000- 200,000。當重量平均分子量低於1〇，_時， 该共聚物的熱穩定性會變差，以降低共聚物的耐熱性。另 一方面，#重量平均分子量高力2〇〇,〇〇〇日夺，該共聚物的 各解度會降低，以增加黏著組成物的熔融黏度，且當含有 此共聚物之黏著組成物被用來作為黏著劑時，黏著劑的黏 者強度不佳。 一種製備以式1表示並含有羧基聚醯胺基胺羰基（A)和 聚矽氧烷胺羰基（B)之丁二烯-丙烯腈共聚物的方法包括： 將以下列式2表示之具有重量平均分子量為5,000_18〇,〇〇〇 之含羧基的丁二烯-丙烯腈共聚物溶解於亞磷酸酯和有機溶 劑中，將以下列式3表示之羧基聚醯胺基胺，及以下列式 13 200535209 4表示之具有聚矽氧烷結構之二胺添加至溶液中；及在60-2 00°C下縮合所得到的混合物達1分鐘-24小時。 式2 2 - CH hpH2 - Cli —Ch4™(cH- ™ CH：}-— I ^ ' *Τί \ I hCN V ν '· "' | CKK ά πνΆ. ** " 乂: ·: j »·. 〇% h R], R ,, R: 〇 'P and q are as (where A, B, k , Ni, r are the same as described above). According to the present invention, in the butadiene-acrylonitrile copolymer represented by Formula 1 and containing a carboxypolyamidoaminocarbonyl group (^) and a polysiloxane alkylcarbonyl group (B), the content of the enenitrile unit is greater than It is preferably from 2 to 40% by weight, and more preferably from 5 to 35% by weight. Therefore, when the content of the acrylonitrile unit is less than 2% by weight, the solubility of the copolymer decreases, and when the content is more than 40% by weight, the copolymerization is performed. The insulation properties of the materials deteriorate. In addition, the weight average molecular weight of the butadiene-acrylonitrile copolymer is preferably 10,000 to 200,000. When the weight average molecular weight is less than 10, the thermal stability of the copolymer may be deteriorated to reduce the heat resistance of the copolymer. On the other hand, # the weight average molecular weight of the high-strength 20,000, the resolution of the copolymer will decrease to increase the melt viscosity of the adhesive composition, and when the adhesive composition containing the copolymer is When used as an adhesive, the strength of the adhesive is not good. A method for preparing a butadiene-acrylonitrile copolymer represented by formula 1 and containing a carboxypolyamidoamine carbonyl (A) and a polysiloxane carbonyl (B) includes: having a weight represented by the following formula 2 A carboxyl-containing butadiene-acrylonitrile copolymer having an average molecular weight of 5,000-18,000,000 is dissolved in a phosphite and an organic solvent, and a carboxypolyamidoamine represented by the following formula 3 is represented by the following formula: 13 200535209 4 Diamine with a polysiloxane structure is added to the solution; and the resulting mixture is condensed at 60-2 00 ° C for 1 minute to 24 hours. Formula 2 2-CH hpH2-Cli —Ch4 ™ (cH- ™ CH:} -— I ^ '* Τί \ I h

COOH CN (其中k，m，和η為莫耳比率，當k為1時，m為3-200 及 η 為 0.2-100) 式3 〇 r | ||COOH CN (where k, m, and η are mole ratios, when k is 1, m is 3-200 and η is 0.2-100) Formula 3 〇 r | ||

Η ^R】一Ν— C R,仁 CulM (其中Ri和R2為C】至C20脂族烴，及〇為從1至20 的整數） 式4 CH、 CH：) Q：h CH;；^ R] —N—CR, Ren CulM (where Ri and R2 are C] to C20 aliphatic hydrocarbons, and 0 is an integer from 1 to 20 Formula 4 CH, CH :) Q: h CH ;;

! ί j I !.:iS广 〇 4 S i—() H 沿一(:)卜 Si -N'H:， !.....γ ! 纽 CH3 cn3 01¾ CH, (其中R3為q至C20烷基，及P和Q個別為從1至20 的整數） 對於以式2表示之含羧基之丁二烯-丙烯腈共聚物，k， m，和η為莫耳比率，當k為1時，m為3-200及η為0.2-100。 更佳者為當k為1時，m為5-180及η為0.8-95，及最佳 者為當k為1時，m為9-170及η為1.5-75。 在k為1的情況下，當m低於3時，共聚物的溶解度 14 200535209 降低，及當m高於200時，黏著組成物的耐熱性降低，這 疋因為當共聚物與具有環氧基之化合物混合成黏著性成分 時，其反應性降低。此外，在k為1的情況下，當^低於 〇_2時，共聚物的溶解度降低，及當η高於1〇〇時，共聚 物的電絕緣性質變弱。! ί j I!.: iS 广 〇4 S i— () H Along one (:) Bu Si -N'H :,! ..... γ! New CH3 cn3 01¾ CH, (where R3 is q to C20 alkyl, and P and Q are each an integer from 1 to 20) For a carboxyl-containing butadiene-acrylonitrile copolymer represented by Formula 2, k, m, and η are mole ratios when k is 1 At this time, m is 3-200 and η is 0.2-100. More preferably, when k is 1, m is 5-180 and η is 0.8-95, and most preferably, when k is 1, m is 9-170 and η is 1.5-75. In the case of k being 1, when m is less than 3, the solubility of the copolymer is reduced by 14 200535209, and when m is higher than 200, the heat resistance of the adhesive composition is reduced, because when the copolymer has an epoxy group, When the compound is mixed into an adhesive component, its reactivity decreases. In addition, in the case where k is 1, when ^ is lower than 0_2, the solubility of the copolymer is reduced, and when η is higher than 100, the electrical insulating property of the copolymer becomes weak.

在以式3表示之羧基聚醯胺基胺之例中，作為重複單 兀之醯胺基係導入羧基聚醯胺基胺之支鏈中。此時，〇為 乾圍從1-20的整數。# 〇高於2〇時，支鏈的長度被明顯 地增加，以使羧基聚醯胺基胺共聚物的分子量過度地增 同，藉此降低羧基聚醯胺基胺共聚物的溶解度並同時降低 ' 土 XK Sm私基私共聚物與其它共聚物的相容性。 進 v地，在以式4表示之具聚矽氧烧結構的二胺之 =中，作為重複單元之矽氧烷基係導入二胺的支鏈中。此 =，P和Q分別為範圍從卜20的整數。當P和Q高於2〇 、才支鏈的長度被明顯地增加，&降低二胺的霉 並降低二胺與其他共聚物的相容性。 、 夕’較佳之有機溶劑之例子In the example of the carboxypolyamidoamine represented by Formula 3, the amidoamino group as a repeating unit is introduced into the branch of the carboxypolyamidoamine. At this time, 0 is an integer from 1-20. When # 〇 is higher than 20, the length of the branched chain is significantly increased, so that the molecular weight of the carboxypolyamidoamine copolymer is excessively increased, thereby reducing the solubility of the carboxypolyamidoamine copolymer and reducing it at the same time. 'Compatibility of soil XK Sm-based private copolymers with other copolymers. Further, in the diamine having a polysiloxane structure represented by Formula 4, a siloxane group as a repeating unit is introduced into the branch of the diamine. This =, P and Q are integers ranging from Bu 20, respectively. When P and Q are higher than 20, the length of the branched chain is significantly increased, & reduces the mold of the diamine and reduces the compatibility of the diamine with other copolymers. ， 夕 ’Examples of preferred organic solvents

燒酮，正·丁醇， 一 — 予弟二_ 丁醇，異丙醇，乙酸酐，二氯甲文 己燒，環己燒，一 ^ . —甲基甲醯胺，二甲基乙醯胺，〜 四氫呋喃，吡吩7 ^ 一甲亞兩 匕 乙臏，二氯苯，氯苯，曱苯，和茉， 佳者為該右撼、、^ ^本 ’合蜊可為任何一種吡啶衍生物，其為選^ 基吡。定。，基吡。定，2,6·二甲基毗。定’和3,5-: 15 200535209 同日^之間’亞麟酸酯係做為縮合劑，其可選自由下列 任何一種所組成之族群··亞磷酸三苯酯，亞磷酸二苯酯， 亞石Η I二鄰曱笨酯，亞磷酸三間曱苯酯，亞磷酸二間甲苯 酉曰，亞磷酸二對曱苯酯，亞磷酸二對甲苯酯，亞磷酸二鄰 氯苯酉旨’亞石粦酸三對氯苯酯，及亞磷酸二對氯苯酯。此外， 裒己基厌化一亞私，填酸三苯酯，或膦酸二苯酯亦可做 為亞磷酸酯。Burning ketone, n-butanol, 1-Yi Di-butanol, isopropanol, acetic anhydride, dichloromethyl hexane, cyclohexane, ^.-Methylformamide, dimethylacetamidine Amine, ~ Tetrahydrofuran, Pyphene 7 ^ Dimethylbenzene, dichlorobenzene, chlorobenzene, benzobenzene, and jasmine, the best is the right, ^ ^ Ben 'can be derived from any kind of pyridine It is selected as pyridine. set. , Kipy. Definite, 2,6 · dimethyl. Ding 'and 3,5-: 15 200535209 Same day ^' Linolinate is used as a condensing agent, which can be selected from any of the following groups: triphenyl phosphite, diphenyl phosphite, Phosphite I, Di-o-Phenyl Phosphate, Tri-M-Phenyl Phosphite, Di-M-Toluene Phosphite, Di-P-phenylene Phosphite, Di-P-toluyl Phosphite, Di-O-chlorophenyl Phosphite Tri-p-chlorophenyl lactate and di-p-chlorophenyl phosphite. In addition, hexahexyl anhydrophobic acid, triphenyl phosphate, or diphenyl phosphonate can also be used as the phosphite.

依據所而，亦可將無機鹽類，例如氯化鋰和氯化鈣， 力至丁 一烯丙烯腈共聚物中，以增加構成丁二烯_丙烯腈 共聚物各成分與質子性溶劑的親和性，並可抑制副反應。 依據本餐明，在以式）表示並含有魏基聚酿胺基胺幾 基⑷和聚魏院胺„(B)之丁二稀_丙烯腈共聚物之中， 將&胺基導入丁二條石、说n 一細-丙歸腈的支鏈來增加丁二烯-丙稀靡 共聚物與和基板簿胺;夕卩卩4 极/寻膜之間的黏著性，及將羧基另外與導/ 至支鍵中之聚酸胺終端上的 ^ 女、知上的銥乳基反應，藉此改良黏著翻 成物之黏者強度和耐熱性。Depending on the reason, inorganic salts, such as lithium chloride and calcium chloride, can also be added to the butadiene acrylonitrile copolymer to increase the affinity of each component constituting the butadiene_acrylonitrile copolymer and the protic solvent. And can suppress side reactions. According to this meal, in the succinic-acrylonitrile copolymer represented by the formula) and containing the weiji polyaminoamine kiwi and polyweiamine amine ((B), the & amine group is introduced into the dibutylite , Said n-fine-propionitrile nitrile branching to increase the butadiene-propylene rare copolymer and the substrate amine; 卩 卩 卩 卩 4-pole / membrane-seeking adhesion, and the carboxyl group and the / The iridium-lactide-based reaction on the polyamine terminal in the branched bond, which improves the strength and heat resistance of the adhesive.

夕，係將⑦氧炫基導人丁二烯·丙稀腈的支鍵來大 增加丁二焊·丙稀腈共聚物與基板薄膜之間的黏著性。 =較！使用典型时燒偶合劑’該丁二稀-丙稀腈共 物對基板賴具有增強的接合強纟，藉此改良丁 腈共聚物與基板(含有金屬和基板薄膜)之間的黏；性” 此：外，丁二稀·丙稀腈共聚物的主鍵是相互接合以增加: 则網絡效應’而且使丁二稀-丙_' ““夠具有相當大的自由體積，因而改良含有環氧基之 16 200535209 樹脂之間的互彳目j 直4 相貝通之效應，造成丁二烯-丙烯腈共聚物盘 ^ 艮站者性。而且，烷氧基是被加至矽氧烷基， 使得丁二稀·丙稀腈共聚物與基板薄膜的: 良的黏著性。 K間具有改 本發明之熱固性黏著組成物在以100重量份 :膳共聚，基礎時，含一重量份環氧基樹：。： 構=脂=基樹脂可藉由具有含二或多個環氧乙燒環結 S、θ 目水甘油基驗，縮水甘油基S旨，縮水甘油 土月女線性之脂肪族環氧化物，脂環族環氧化物，及它In the evening, it is to increase the adhesion between the butadiene-acrylonitrile copolymer and the substrate film by using the branched bond of butoxyl-based butadiene-acrylonitrile. = Compare! Using a typical time-fired coupling agent 'The succinic-acrylonitrile copolymer has enhanced bonding strength to the substrate, thereby improving the adhesion between the nitrile copolymer and the substrate (containing the metal and the substrate film); " In addition: In addition, the main bonds of the succinic · acrylonitrile copolymer are joined to each other to increase: then the network effect 'and the succinic-propylene' is sufficient to have a considerable free volume, so the epoxy group is improved. No. 16 200535209 Reciprocity between resins and the effect of 4-phase beton, which results in butadiene-acrylonitrile copolymers. Also, alkoxy groups are added to siloxane groups, making Butadiene-acrylonitrile copolymer and substrate film: Good adhesion. The thermosetting adhesive composition between K and 100% by weight of the present invention: when copolymerized, the base contains one part by weight of epoxy group: ： Structure = lipid = based resin can be made with two or more ethylene oxide ring junctions S, θ mesh water glyceryl group test, glycidyl group S, glycidyl earth female linear aliphatic epoxide , Cycloaliphatic epoxide, and it

的組二)來例示。更詳細言之，環氧基樹脂的例子可能包 括雙吕月Ml環氧樹脂，如雙紛Α型環氧樹脂，雙齡F 氧樹脂，雙齡S型環氧樹脂，和蔡型環氧樹脂；多官能性 基胺型環氧樹脂’如三縮水甘油基異氛胨酸醋型 、衣^月曰，二&水甘油基對胺基酉分型環氧樹脂，四縮水甘 2基=胺基二苯基甲烧型環氧樹脂，四縮水甘油基間二甲 ^ ^月ίΓ環氧樹脂，和四縮水甘油基]，3-雙胺基T基環己 ’ m树月曰’夕吕能性縮水甘油基越型環氧樹脂，如四 苯基縮水甘油基轉乙燒型環氧樹脂和三苯基縮水甘油基_ 甲烧型環氧樹脂；多官能性㈣樹脂型環氧樹脂，如苯紛 ^哀乳樹脂和烧基苯齡型環氧樹脂；和多官能性線型㈣ y泰型環氧樹脂，如㈣型環氧樹脂和甲㈣型環氧樹 月曰。特別者為使用具有優良絕緣性f和耐熱 環氧樹脂。 / e & $ 更詳盡而言，使用於本發明的環氧樹脂例子包括雙齡 17 200535209 型樹脂，如Epicoat 806、828、834和1001，雙官能性環 氧樹脂，如YX-4000和YX-4000H(二苯基型），多官能性 線型酚醛清漆型樹脂，如Epicoat 152、154、180S65、 1032H60、和157S70,和四縮水甘油基二苯基甲烷型樹脂， 如由 Yuka Shell Epoxy Κ·Κ·公司製造之 Epicoat 604 ;多官 能性環氧樹脂，如由Dainippon ink & Chemicals公司製造 之HP_72〇〇、和HP-7200H(二環型）·’和多官能性環氧樹脂， 如EOCN102S、103S、104S、和1020(鄰甲苯酚線型酚酸Group two) to illustrate. In more detail, examples of epoxy-based resins may include Shuangluyue Ml epoxy resins, such as Shuangfan A-type epoxy resin, Shuang-type F-type epoxy resin, Shuang-type S-type epoxy resin, and Cai-type epoxy resin. Polyfunctional amine-type epoxy resins, such as triglycidyl isocyanate-based vinegar type, clothing, month, two & hydroglyceryl p-amino group type epoxy resin, tetraglycidyl 2 group = Amino diphenyl methane-type epoxy resin, tetraglycidyl dimethyl epoxide, and tetraglycidyl], 3-bisamino T-cyclohexyl 'm Luneng glycidyl-based epoxy resins, such as tetraphenyl glycidyl to ethylenic epoxy resin and triphenyl glycidyl_ methylenic epoxy resin; multifunctional fluorene resin epoxy resin , Such as benzophenone resin and benzene-based epoxy resin; and multifunctional linear epoxy resin, such as epoxy resin and formazan epoxy resin. In particular, an epoxy resin having excellent insulation properties f and heat resistance is used. / e & $ In more detail, examples of epoxy resins used in the present invention include two-stage 17 200535209 type resins such as Epicoat 806, 828, 834, and 1001, and bifunctional epoxy resins such as YX-4000 and YX -4000H (diphenyl type), polyfunctional novolac resin, such as Epicoat 152, 154, 180S65, 1032H60, and 157S70, and tetraglycidyl diphenyl methane type resin, such as by Yuka Shell Epoxy K · Epicoat 604 manufactured by KK; polyfunctional epoxy resins, such as HP_72〇〇, and HP-7200H (bicyclic type), and polyfunctional epoxy resins, such as EOCN102S, manufactured by Dainippon ink & Chemicals , 103S, 104S, and 1020 (o-cresol novolac

清漆型）、和由Nippon kayaku公司製造之EPPN501H和 502H(三苯基甲烷型）。Varnish type), and EPPN501H and 502H (triphenylmethane type) manufactured by Nippon Kayaku.

依據本發明，環氧樹脂的當量數較佳為5〇_5〇〇〇， 佳為100-4000，及最佳為1〇〇_2〇〇〇。依此，當環氧基樹 =當量數低於50時，環氧基樹脂在完全硬化之前，在 定的熱和壓力條件下於B階段態時之環氧基樹脂流動性 常高’引起黏著組成物的流動性增加。另外，#環氧樹」 =，後’―部份之環氧樹脂尚未硬化，致使環氧樹脂, t f。另—方面，當環氧樹脂的當量數高於5000時，丨 環氧樹脂對溶劑的溶解产 相容性不佳。_低以及技乳樹脂對其他㈣ °使用環氧基鹵化物 為環氧抖t 特別為娘乳基溴化物樹脂 環氧美、京斗私± ^钻者組成物具有阻燃性。雖然僅 阻燃性，伸僅…：龜之點者組成物具有最 僅有％乳基溴化物樹 熱性以及浐h h 曰化战黏者組成物 乂及抗洛劑性降低， U此#乂仫為裱虱基溴化物樹 18 200535209 同環氧基非鹵化物樹脂共同使用。基於此，可舉例使用之 環氧基溴化物樹脂可為由yuka shell Epoxy Κ·Κ·公司製造 之 Epicoat 5 05 0、4049、5 048、和 5045，其分別含有約 49 重量％、26重量％、25重量％、和；19重量％之溴；由Nipp〇n kayaku公司製造之Brene_s，其含有35重量％之溴；及相 似者。除此之外，商用之環氧基非鹵化物樹脂的例子包括 由 Yuka Shell Epoxy Κ·Κ·公司製造之 Epicoat 828、1〇〇1、 152、和 154,及由 Nippon kayaku 公司製造之 EOCN 102S、According to the present invention, the equivalent number of the epoxy resin is preferably 50-500, more preferably 100-4000, and most preferably 100-200. According to this, when the epoxy group = the number of equivalents is less than 50, the epoxy resin is under high temperature and pressure conditions in a B-stage state before the epoxy resin is completely hardened. Increased material mobility. In addition, the #epoxy tree ”=, the last‘ — part of the epoxy resin has not yet hardened, resulting in epoxy resin, t f. On the other hand, when the equivalent number of the epoxy resin is higher than 5000, the compatibility of the epoxy resin with the solvent is not good. _ Low and technical milk resin for other 氧基 ° use epoxy halides for epoxy tremolo t especially for mother milk-based bromide resin epoxy beauty, Beijing Dou ± ± ^ drill composition is flame retardant. Although only flame retardant, extension only ...: Turtle's point composition has the lowest% milk-based bromide tree heat resistance and 浐 hh said that the chemical composition and anti-losing agent properties are reduced. U 此 # 乂 仫For ticking bromide trees 18 200535209 Used with epoxy non-halide resins. Based on this, the epoxy bromide resin that can be used by way of example can be Epicoat 5 05 0, 4049, 5 048, and 5045 manufactured by Yuka Shell Epoxy K · K · Company, which respectively contain about 49% by weight and 26% by weight , 25% by weight, and; 19% by weight of bromine; Brene_s manufactured by Nippon Kayaku, which contains 35% by weight of bromine; and the like. In addition, examples of commercial epoxy-based non-halide resins include Epicoat 828, 1001, 152, and 154 manufactured by Yuka Shell Epoxy KK Corporation, and EOCN 102S manufactured by Nippon Kayaku Corporation. ,

103S、和104S。環氧基非函化物樹脂與環氧基漠化物樹脂 可單獨地使用或合併使用。 同時，本發明之熱固性黏著組成物含有：1) 丁二烯 丙烯腈共聚物，其以式i表示並含有羧基聚醯胺基胺羰基㈠ 和聚矽氧烷胺羰基(B);及2)環氧樹脂，且另包括硬化劑。103S, and 104S. The epoxy-based non-functional compound resin and the epoxy-based compound resin may be used singly or in combination. Meanwhile, the thermosetting adhesive composition of the present invention contains: 1) a butadiene acrylonitrile copolymer, which is represented by the formula i and contains a carboxypolyamidoaminocarbonyl hydrazone and a polysiloxane carbonyl (B); and 2) Epoxy resin, and additionally includes a hardener.

该硬化劑係做用為促使環氧樹脂的硬化。非限制性之 硬化劑說明性例子可包括脂肪族胺化合物，芳香族胺化么 物，酸酐化合物’雙氮胺，三論，和胺化合物的混： 物特別地，4,4，-二胺基二苯基楓（DDS)和4,4，_二 苯基Μ⑽M)可有用地賦予黏著組成物特別^ ^ ^儲存穩定性。硬化劑的含量，在以_重量份之環氧1 月:為基準時，較佳為2-20重量份，及更佳為5]5 。 “更化劑的含量低& 2重量份時，環氧樹脂並非完全：硬 化□此p牛低對黏著組成物焊接熱的耐熱性以及電性所。 另方面，當硬化劑含量高於1〇〇重量份時: 的硬化會# p成/丨 、j衣乳树脂 使對已硬化黏著組成物焊接熱的耐熱性降低。 19 200535209 本ι明之熱固性黏著組成物含 丙烯腈共聚物，其以式丨#_ )丁一烯_ .„ „ . ^ 式表不並含有幾基聚酸胺基胺幾基（A) 和…炫《基⑻;及 = 化促進劑。 伽且j此另包括硬 硬化促進記之作用是 处、登ή丄 疋進^者組成物之硬化，且可 旎選自由下列所組成之族 丑了 a w ^ °坐化合物丨例如2 -烧美 _4_甲基咪唑化合物、2_烷美 2烷基 味哇化合物；金屬氣化删：合物：::坐化合物、及2·苯基 辞；金屬辛酸鹽化合物，例如辛酸=:w氟化， 混合物。特別地，氟化爛化合==酸鋅；及它們的 於仏予翔# έ日+ 物及孟屬辛酸酯化合物係適 万、、、、ρ于黏者組成物較優儲存 成物之流動性。 #存…，及容易地控制黏著組 該硬化促進劑的含量為〇〇1 15重量份（彼等卩100重旦 里刀’及更佳為〇·2· 絲几扣 里伤之環氧樹脂為基準）。當 硬化促進劑的含量極低時， 田 化，因此降低對黏著組成物丈曰接;^者、、且成物無法迅速地硬 于接熱的耐熱性以及電性質。 另一方面，當硬化促進劑含 、 迅速地硬化，因此降低為著’由於黏著組成物極 強度。 -站者組成物的儲存穩定性以及黏著 埴充本發明之熱固性黏著組成物可能另外包含無機 填充劑，以利於避免抗剝離 户的舌m 雕忒應的降低’並可改良黏著強 勺二1“咖_0。關於此點，無機填充劑的例 =括孟屬氣氧化物如氯氧化紹和氣氧化鎮，和金屬氧化 乳呂、氧化鋅、和氧化鎮。上述的無機填充劑例子 20 200535209 :單獨使用或合併使用’及該無機填充劑的平均粒度較佳 ::或更低’且更佳為1"m或更低。另外，該無機填 ^的含量，moo重量份環氧樹脂為基準時是υ重 :份’及更佳為3_4〇重量份。作為無機填充劑之氧化辞和 :化鎂亦可能作用為腈類橡膠的硬化劑。此外，當組成盔 =充劑的粒子表面經偶合劑（例如以有機編基礎： 口劑和以有機鈦酸酉旨為基礎的偶合劑）處理之後，無機 充2丄’工‘水性化以改良粒子的均勻@，因此構成無機填 :並具有基體相，同時改良黏著組成物之抗水性和耐埶 4無機填充劑可能藉由典型的混合器（如球形磨、球 機、輥軋機、和均化器）與黏著組成物混合。 除此之外，本發明黏著組成物可選擇性包括預定數量 2種不同添加劑’例如已習用地施加至黏著組成物之苯 A ο月日和抗聽劑。關於此點，苯紛樹脂的例子包括苯齡 崎盼樹脂、苯_清漆樹脂、甲_清 :脂、間笨二峨旨、及二甲苯樹脂。環氧樹脂對苯齡 3飞的官能基當量比率m1:1.5,較佳為ι:〇·7_ι·•丨·3， 更L A 1 ·〇·8_ i: i ·2。當環氧樹脂對苯㈣脂的當量比率 :·、、低於1:0.5日夺’則已硬化的環氧樹脂易碎裂，且在當量 比率高於Η.5時’黏著組成物的黏著強度則不欲地降低。 除了使用環氧基漠化物樹脂做為黏著組成物的漠來源 “改良該黏著組成物之阻燃性之外，亦可將防燃助劑，例 L除了漠和二氧化錄以外的齒化化合物⑺為三氧化錄對人 體有毒性且造成污染因而並不推薦使用），與黏著組成物混 21 200535209 合來改良黏著組成物的阻燃性。 此外本％明之熱固性黏著組成物包括：做為美 分之υ 丁二稀_丙稀腈共聚物，其以 丨為基本成 聚酿胺基胺縣（Α)和聚錢烧《基(Β);^)；ί含t叛基 並可額外地包括溶解於有機溶劑中的各 、:嫌旨， 機溶劑的非限制性說明例子包括甲苯，二甲/、加劑。有 酮，四氫呋喃，和它們的混合物。較甲基乙基 物含有1 5重I Φ > 為所传到黏著組成 或更多的固體，當固體含量低於15重旦 %% ’則在製造黏著片或黏著帶時不 二 勻地塗覆在片或帶上。 β者、、且成物均 同時，本發明提供一種使用於電子元件的黏 盆 係由本發明之熱固性黏著組成物製造而得。 ，、 更詳細言之，本發明提供—種覆蓋膜，其包括-種由 聚醯亞胺樹脂或聚對苯二甲酸乙二醇醋樹脂製得之基板 :θ :重：：復本务明的熱固性黏著組成物至基板層上而 衣付之站者層，及於形成於黏著層上之保蠖膜 在製造覆蓋膜時，具有適當黏度之液態熱固性黏著組 成物流體，藉由反向滾動塗佈褒置、逗點塗佈機(― 讀〇、和相似者而均勻地塗覆至包括有電絕緣塑膠樹脂 ㈣基板層上’然後使用在管道中之乾燥箱在4〇_峨下 熱處理2-20分鐘，將之乾燥及半硬化，藉此形成黏著層。 此時，、㈣2〇-16(TC的熱滾筒及〇.2·2〇 kg/cm線性壓力的 使用，在基板層之半硬化黏著層上得以形成保護膜。 較佳者為將本發明的熱固性黏著組成物塗覆在基板層 22 200535209 上使4 般性乾燥之黏著層厚度為1 0 - 5 0 /i m。依據需要， 熱固性黏著組成物可在20-1 60°C下進一步熱處理0.5-48小 時，使黏著層更加地硬化。 當黏著層厚度低於1〇//m時，則該黏著帶之黏著強度 降低，及當黏著層厚度高於5〇//m時，則黏著帶的生產$ 本增加且黏著帶的抗彎曲性降低。 、另外本务明提供一種黏著膠膜，其包括第一保護膜； k復本I月的熱固性黏著組成物至第一保護膜上而製得 之黏著層；及形成在黏著層上之第二保護膜。 本發明之熱固性黏菩細占从及认h m t ^This hardener is used to promote hardening of the epoxy resin. Illustrative examples of non-limiting hardeners may include aliphatic amine compounds, aromatic aminated compounds, anhydride compounds' diazamine, trinity, and mixtures of amine compounds: in particular, 4,4, -diamine Diphenyl maple (DDS) and 4,4, -diphenyl M⑽M) can be useful to give the adhesive composition special storage stability. The content of the hardener is preferably 2 to 20 parts by weight, and more preferably 5] 5 based on _ parts by weight of epoxy January :. "When the content of the modifier is low & 2 parts by weight, the epoxy resin is not completely hardened: This p is low in heat resistance and electrical properties to the welding heat of the adhesive composition. On the other hand, when the content of the hardener is higher than 1 〇〇 重量 份 ： The hardening will reduce the heat resistance of the welding heat to the hardened adhesive composition. 19 200535209 The thermosetting adhesive composition of the present invention contains acrylonitrile copolymer, which is based on The formula 丨 #_) butadiene_. „…. ^ This formula does not contain polyaminoamine amines (A) and… The role of hard hardening is to harden the composition, and it can be selected from the group consisting of the following compounds aw ^ ° seat compounds 丨 such as 2-burning US_4_methylimidazole Compounds, 2-alkyl 2-alkyl melamine compounds; metal gasification compounds ::: compounds, and 2-phenyl groups; metal caprylate compounds, such as caprylic acid =: w fluorinated, mixtures. Especially ， Fluorinated rotative compound == zinc acid; and their 仏 仏 予 翔 # 日 日 + and octanoate compounds are suitable ,,, and ρ are better for the fluidity of the storage composition. #Store ..., and the content of the hardening accelerator in the adhesion group is easily controlled to 0.015 parts by weight 'And more preferably 〇 · 2 · the epoxy resin with a few cracks as a reference). When the content of the hardening accelerator is extremely low, Tianhua, so reduce the adhesion to the adhesive composition; ^ 者, and and The finished product cannot be hardened faster than the heat resistance and electrical properties of heat. On the other hand, when the hardening accelerator is contained, it hardens quickly, so it is reduced to 'due to the extreme strength of the adhesive composition.-The storage stability of the standing composition The thermosetting adhesive composition of the present invention may additionally contain an inorganic filler, which is beneficial to avoid the reduction of tongue peeling resistance of anti-peeling households, and to improve the adhesive strength. In this regard, examples of inorganic fillers include monoxide gas oxides such as oxychloride and gas oxidized towns, and metal oxidized milk, zinc oxide, and oxidized towns. Example of the above-mentioned inorganic filler 20 200535209: used alone or in combination 'and the average particle size of the inorganic filler is preferably :: or lower' and more preferably 1 " m or lower. In addition, the content of the inorganic filler is ν by weight based on the weight of the epoxy resin based on parts by weight, and more preferably from 3 to 40 parts by weight. Oxidation of inorganic fillers: Magnesium may also act as a hardener for nitrile rubber. In addition, when the surface of the particles that make up the helmet = filler is treated with a coupling agent (such as an organic knitting base: a mouthwash and a coupling agent based on an organic titanate), the inorganic filler is water-based to improve The particles are homogeneous @, thus constituting an inorganic filler: and having a matrix phase, while improving the water resistance and resistance to rubidium of the adhesive composition. Mixer) with the adhesive composition. In addition, the adhesive composition of the present invention may optionally include a predetermined amount of 2 different additives' such as benzene A and the anti-hearing agent which have been conventionally applied to the adhesive composition. In this regard, examples of the benzene resin include benzene age, sapphire resin, benzene-varnish resin, methyl-clear resin, methanediene, and xylene resin. The functional group equivalent ratio m1 of the epoxy resin to benzene is 3: 1.5, preferably ι: 〇.7_ι ·· 丨 · 3, and more L A 1 〇 · 8_ i: i · 2. When the equivalent ratio of the epoxy resin to the phenyl sulfonate is less than 1: 0.5, the hardened epoxy resin is easily broken, and when the equivalent ratio is higher than Η.5, the adhesion of the adhesive composition The intensity is undesirably reduced. In addition to using epoxy-based oxide resins as the source of the adhesive composition, "to improve the flame retardance of the adhesive composition, flame retardant additives such as L ⑺ is not recommended for use because it is toxic to the human body and causes pollution. It is mixed with the adhesive composition to improve the flame retardance of the adhesive composition. In addition, the thermosetting adhesive composition of this% includes: Fen butyl butadiene-acrylonitrile copolymer, which is basically made of polyamine amines (A) and polysulfonamides (base); ^ contains t rebel groups and can additionally Includes non-limiting examples of organic solvents that are soluble in organic solvents, including toluene, dimethyl /, adjuvants. Ketones, tetrahydrofuran, and mixtures thereof. Compared with methyl ethyl compounds, it contains 15 Weight I Φ > is the solid that is passed to the adhesive composition or more. When the solid content is less than 15% by weight %% ', it is coated on the sheet or tape unevenly when manufacturing the adhesive sheet or tape. Β If both the product and the product are at the same time, the present invention provides a method for use in an electronic device. The adhesive basin is made from the thermosetting adhesive composition of the present invention. More specifically, the present invention provides a cover film including a polyimide resin or polyethylene terephthalate. Resin-made substrates: θ: Heavy :: Reproduced thermosetting adhesive composition on the substrate layer and the clothing standing layer, and the protective film formed on the adhesive layer has the appropriate viscosity when manufacturing the cover film The liquid thermosetting adhesive composition fluid is uniformly applied to a substrate layer including an electrically insulating plastic resin by using a reverse roll coating device, a comma coater (― read 0, and the like ”, and then used. The drying box in the pipeline was heat-treated at 40 ° E for 2-20 minutes, dried and semi-hardened to form an adhesive layer. At this time, ㈣20-16 (TC's heat roller and 0.2 · 2 The use of a linear pressure of 0 kg / cm can form a protective film on the semi-hardened adhesive layer of the substrate layer. It is preferable to apply the thermosetting adhesive composition of the present invention to the substrate layer 22 200535209 to make the adhesive dry in general. Layer thickness is 1 0-50 / im. The thermosetting adhesive composition can be further heat-treated at 20-1 60 ° C for 0.5-48 hours to make the adhesive layer harder. When the thickness of the adhesive layer is less than 10 // m, the adhesive strength of the adhesive tape is reduced. And when the thickness of the adhesive layer is higher than 50 // m, the production cost of the adhesive tape increases and the bending resistance of the adhesive tape decreases. In addition, the present invention provides an adhesive film including a first protective film; k A copy of the adhesive layer prepared by applying the thermosetting adhesive composition to the first protective film; and a second protective film formed on the adhesive layer. The thermosetting adhesive of the present invention can be recognized and recognized as HMT ^

帶， 製得. 層之-金屬箔。 種使用於軟性PCB的複合 聚對苯二甲酸乙二醇酯樹脂 的熱固性黏著組成物至基板 免層壓至黏著層之一側上之 23 200535209 /王屬冶可為任何選自由下 荡、捲式銅落、鈕$故外 n'且成之族群：電解銅 泊鋁泊、鎢箔、及鐵箔。+ a/_ 荡由於其極佳的掉Λ w β上 电解銅落及捲式銅 ，、位彳土的撓曲性及高導電性而 地，依使用於電子元件κ 土者。進一步 一般為9-70々m。 佳之孟屬浴厚度 在製造使用於軟性pCB的複合帶時， 、、右能由r m ·* /、有適田黏度之 液悲熱固性黏著組成物流體， 精田汉向滾動塗佈裝置、 點塗佈機、和相似者而均 /置、 伋至包括有電絕緣塑膠樹 月曰膜的基板層上，缺後佶用磕 …、俊使用線上乾紐箱在4〇-160。(：下熱處 理2-20分鐘將之半硬化，藉此形成黏著層。除此之外，經 由40 200 C的熱滾筒及〇·2-2〇 kg/cm線性壓力的使用，在 基板=之半硬化黏著層表面上得以形成金屬络，例如銘落 或銅落。插置在基板層與金屬猪之間的乾燥黏著層厚度為 5 0 // m此外，所得到的二層結構可進一步在2 (Μ 6 〇 °c 下加熱0.5-48小時，使得熱固性黏著組成物可進一步地有 效硬化。Strip, made. Layer-to-metal foil. A thermosetting adhesive composition of a composite polyethylene terephthalate resin used for flexible PCBs to the substrate without lamination to one side of the adhesive layer. 23 200535209 / Wang Yeye can be selected from any of the following: Types of copper falling, buttons and old n's: the electrolytic copper, aluminum, tungsten, and iron foil. + a / _ due to its excellent drop of electrolytic copper and rolled copper on Λ w β, its flexibility and high conductivity, depending on the use of electronic components κ soil. Further, it is generally 9-70 μm. When manufacturing the composite bath tape for soft pCB, Jiazhi Mensui's bath thickness can be made from rm · * /, liquid with hot viscosity and sturdy heat-curable adhesive composition fluid, suitable for Hanada roll coating equipment, spot coating The machine and the like are placed on the substrate layer including the film of the electrical insulation plastic tree, and if it is not used, you can use the online button box at 40-160. (: Heat treatment for 2-20 minutes to semi-harden it to form an adhesive layer. In addition, through the use of a thermal roller at 40 200 C and a linear pressure of 0.2-20 kg / cm, the substrate = A metal network, such as a drop or copper drop, is formed on the surface of the semi-hardened adhesive layer. The thickness of the dry adhesive layer interposed between the substrate layer and the metal pig is 5 0 // m. In addition, the obtained two-layer structure can be further 2 (M 6 0 ° C for 0.5-48 hours, so that the thermosetting adhesive composition can be further effectively hardened.

此外’本發明提供一種使用於軟性pCB的複合帶，其 包括由聚亞胺樹脂或聚對苯二曱酸乙二醇酯樹脂製得之 基板層；由塗覆本發明的熱固性黏著組成物至基板層兩面 上而製得之黏著層；及層壓至黏著層兩面之金屬箔。 關於此點，插置在基板層和每個金屬箔之間的每層黏著 層厚度並不受限，但較佳為5-10μ m，及更佳為10-25//m。 經由上文的敘述，聚醯亞胺樹脂或聚對苯二曱酸乙二 醇酯樹脂係使用為基板層的電絕緣膜，但該絕緣膜並未僅 24 200535209 限於亞胺或聚對苯二曱酸 了奴乙二醇酯樹脂，且其可選自 由下列所組成之族群：聚對芏— 一曱酸丁二醇g旨樹脂，聚（乙 二醯脲）樹脂，聚醚酮樹脂，平“山#杜 來（伸本基硫醚）樹脂，和芳酸 胺樹脂。但聚醯亞胺樹脂传Α η 皿 曰係為取佳者，因為其具有絕佳 耐熱性，尺寸穩定性，和物 一 初理性質。進一步地，依使用於 電子元件之帶的種類而定，条 、 心蚁乜之電絕緣塑膠樹脂膜厚度 一般為1 2.5 -1 2 5 // m。此外，冷 卜塗佈在塑膠樹脂膜之一或兩 I上的黏著層材料之決定係依據表面處理製程或表 =製程，例如低溫度電聚製程，電暈放電製程，和喷: 使用於製造覆蓋膜或黏荽 者骖臈的可剝離式保護膜不僅 可由塗佈上聚乙烯、聚而檢 烯、或甲基戊烯共聚物樹脂之紙 扳而I付，亦可以由塗佑 〆 r ^ r ^ 上以矽虱烷為主之防黏劑的塑膠 树月日膑（例如聚乙烯、 對笼_彿t丙烯、甲基戊烯共聚物樹脂、聚 對本一甲@夂乙二醇酯、 _ _ ^ K本一甲酸乙二醇酯樹脂）而萝 付。可剝離保護膜的屋序 ^ 又要係依據產物之種類而定，當 保護Μ疋以塑膠樹脂膜 ^ e 足吋孕乂侄為6-75 " m，及當保 護艇疋以紙板為基礎時較佳為12_2〇〇心。 經由本發明的—般性敛述，再藉由參考於本文 供之特定實施例、比座六每 斤& 一牛 ^男轭例和實驗性實施例則可得到進 的^不立A 除非特別提及否則諸實施例僅為說明之目In addition, the present invention provides a composite tape for soft pCB, which comprises a substrate layer made of a polyimide resin or a polyethylene terephthalate resin, and is coated with the thermosetting adhesive composition of the present invention to An adhesive layer prepared on both sides of the substrate layer; and a metal foil laminated to both sides of the adhesive layer. In this regard, the thickness of each adhesive layer interposed between the substrate layer and each metal foil is not limited, but is preferably 5-10 m, and more preferably 10-25 // m. As described above, polyimide resin or polyethylene terephthalate resin is used as the substrate's electrical insulation film, but the insulation film is not limited to only 24 200535209. Glycolic acid ester resins can be selected from the following groups: poly (p-phenylene) —butanediol monoacetate g resin, poly (ethylene diurea) resin, polyether ketone resin, flat "Mountain #Dulai (extendyl sulfide) resin, and aryl amine resin. But polyimide resins are best, because they have excellent heat resistance, dimensional stability, and First, the physical properties of the object. Further, depending on the type of the belt used for the electronic component, the thickness of the electrically insulating plastic resin film of the strip and the heart ants is generally 1 2.5 -1 2 5 // m. The determination of the material of the adhesive layer on one or both of the plastic resin films is based on the surface treatment process or table = process, such as the low-temperature electropolymerization process, the corona discharge process, and spraying: used in the manufacture of cover films or adhesives. The peelable protective film can not only be coated with polyethylene, Olefin, or methylpentene copolymer resin paper, I can also be made from Tuyou ^ r ^ r ^ plastic silanol-based sunscreen (such as polyethylene, Cage _ Buddha t propylene, methylpentene copolymer resin, polyethylene terephthalate @ 夂 glycol ester, _ _ ^ K monoformic acid formate resin), and pay. House order of peelable protective film ^ It also depends on the type of the product. When the protection resin is made of plastic resin film, it is 6-75 " m, and when the protection boat is made of cardboard, it is preferably 12_2. Through the general description of the present invention, and then by referring to the specific embodiment provided herein, a comparison example & a male yoke example and an experimental example can be obtained Unless specifically mentioned, the examples are for illustrative purposes only.

的而不意欲用以限制。 凡月（S &lt;實施例1至m 使用於軟性PCB之埶固性對輩4氺 物的製造 心…、囚性黏者組成 25 200535209 將如表1中所述之一部份含有羧基聚醯胺基胺羰基和 聚矽氧烷胺羰基之丁二烯·丙烯腈共聚物（A)，環氧樹脂. (B)硬化劑（C) ’硬化促進劑（D)，矽烷偶合劑（E)，和填充 _ 劑依表2所示地選取出，並與7〇毫升之甲基乙基酮混合， 因而構成所得混合物之上述成分的總組成為1〇〇重量％， 亚在至溫至50°C下溶解而生成一溶液。此時，溶液經由控 制使得溶液含有30重量％之固體，藉此生成本發明之使 用於軟性PCB之熱固性黏著組成物。 〈比較實施例1至6&gt;使用於軟性pcB之熱固性黏著、组 % 成物的製造 重複貫施例1至1 8之程序以製造使用於軟性PCB之 熱固性黏著組成物’除了使用經緩基改性之丙稀基橡膠 (A’-l)或苯乙烯-丁二烯-苯乙烯嵌段共聚物（a，_〇來取代含 有羧基聚醯胺基胺羰基和聚矽氧烷胺羰基之丁二烯-丙烯腈 共聚物（A)。 成分 (A)含有羧基聚醯胺 基胺羰基和聚矽氧烷 胺羰基之丁二烯-丙 烯腈共聚物 符號 A-1 〜' — ----~~---- 注解 〜---——-______ ’ n=55，m=L5，〇=3，P=2，Q=2，R】和 ^g：CH2-，R3 爲甲基 A-2 k=i，nm=7 5,〇=3，p=3 Q=3 R· ㉞-叫，R3爲甲基 A-3 ，n=7，m=ii〇,0=5，p=2，Q=2，Rj ’ R;爲乙某 ___ A-4 乙基 26 200535209 經羧基改性之丙烯基 橡膠 (Α，·1) 經羧基改性之丙烯基橡膠(商用名稱：NSA-04, Nisshm化學品工業） 苯乙烯-丁二烯-苯乙 烯嵌段共聚物 (Α，·2) 苯乙烯-丁二烯-苯乙烯嵌段共聚物(商用名 稱：TR2000,日本合成橡膠公司） 環氧樹脂(B) B-l 雙酚A型環氧樹脂，當量數1750-2100(商用 名稱：YD-017，KukDo化學品公司） Β-2 雙酚F型環氧樹脂，當量數900-1000(商用名 稱：YDF2004, Kuk Do化學品公司） Β-3 甲酚酚醛淸漆型環氧樹脂，當量數215-235(商 用名稱：KDCN528, Kuk Do化學品公司） Β-4 縮水甘油基胺型環氧樹脂，當量數160-190(商 用名稱：LER421L，LG化學品公司） 硬化劑(C) C-1 二胺基化合物；3,3’-二胺基二苯基楓 C-2 二胺基化合物；4,4’-二胺基二苯基甲烷 C-3 四胺；3,3’，4,4’-四胺基聯苯 硬化促進劑(D) D-1 咪唑 D-2 4-甲基咪唑 矽烷偶合劑(E) Ε-1 以環氧基爲基礎之矽烷偶合劑(商用名稱： KBM303, Shin Etsu) Ε-2 以胺基爲基礎之矽烷偶合劑(商用名稱： KBM602, Shin Etsu) Ε-3 以胺基爲基礎之矽院偶合劑(商用名稱： KJBE903, Shin Etsu) 塡充劑 無水二氧化砂(商用名稱：AerosealR972，曰 本Aeroseal公司）Not intended to be used to limit. Fanyue (S &lt; Examples 1 to m) Manufacturing of solid substrates used in flexible PCBs ... Manufacturing composition 25 200535209 One of the components described in Table 1 contains Butadiene-acrylonitrile copolymers (A), epoxy resins, (B) hardeners (C) 'hardening accelerators (D), silane coupling agents (E) ), And the filler are selected as shown in Table 2 and mixed with 70 ml of methyl ethyl ketone, so that the total composition of the above components constituting the obtained mixture is 100% by weight. Dissolve at 50 ° C to produce a solution. At this time, the solution is controlled so that the solution contains 30% by weight of solids, thereby generating the thermosetting adhesive composition for a flexible PCB of the present invention. <Comparative Examples 1 to 6> Used in Manufacture of thermosetting adhesive and component of soft pcB Repeat the procedures of Examples 1 to 18 to manufacture the thermosetting adhesive composition for flexible PCB 'except that the acrylic rubber (A'- l) or styrene-butadiene-styrene block copolymer (a, _〇 instead of containing carboxyl Butadiene-acrylonitrile copolymer (A) based on polyamidoamine carbonyl and polysiloxane alkyl amide. Component (A) Butadiene containing carboxy polyamidoamine carbonyl and polysiloxane carbonyl -Acrylonitrile copolymer symbol A-1 ~ '— ---- ~~ ---- Notes ~ ---——-______' n = 55, m = L5, 0 = 3, P = 2, Q = 2, R] and ^ g: CH2-, R3 is methyl A-2 k = i, nm = 75, 0 = 3, p = 3 Q = 3 R · ㉞-call, R3 is methyl A-3 , N = 7, m = ii〇, 0 = 5, p = 2, Q = 2, Rj'R; is B ___ A-4 ethyl 26 200535209 carboxyl-modified propylene-based rubber (Α, · 1) Carboxyl-modified propylene-based rubber (commercial name: NSA-04, Nisshm Chemical Industry) Styrene-butadiene-styrene block copolymer (A, · 2) Styrene-butadiene-benzene Ethylene block copolymer (commercial name: TR2000, Nippon Synthetic Rubber Co., Ltd.) Epoxy resin (B) Bl bisphenol A type epoxy resin, equivalent number 1750-2100 (commercial name: YD-017, KukDo Chemical Co., Ltd.) Β -2 Bisphenol F-type epoxy resin, 900-1000 equivalent (commercial name: YDF2004, Kuk Do Chemical Co., Ltd.) B-3 cresol novolac epoxy resin Fat, equivalent number 215-235 (commercial name: KDCN528, Kuk Do Chemical Company) B-4 glycidylamine epoxy resin, equivalent number 160-190 (commercial name: LER421L, LG Chemical Company) Hardener ( C) C-1 diamine compound; 3,3'-diaminodiphenyl maple C-2 diamine compound; 4,4'-diaminodiphenylmethane C-3 tetraamine; 3, 3 ', 4,4'-Tetraaminobiphenyl hardening accelerator (D) D-1 Imidazole D-2 4-methylimidazole silane coupling agent (E) Ε-1 Epoxy-based silane coupling agent (Commercial name: KBM303, Shin Etsu) Ε-2 amine-based silane coupling agent (commercial name: KBM602, Shin Etsu) Ε-3 amine-based silane coupling agent (commercial name: KJBE903, Shin Etsu) Rhenium filling anhydrous sand dioxide (commercial name: Aeroseal R972, said Aeroseal company)

27 200535209 表2 A A5 B C D E 1 2 3 4 1 2 1 2 3 4 1 2 3 1 2 1 2 3 塡充 劑 E.l 40 - - - 一 25 - - 23 10 - 一 0.5 - 1.5 - - - E.2 - 40 — * - — - 25 - 23.5 10 一 - 0.5 1 - - E.3 - 40 - - - - 20 5 - 23 5 5 - 0.5 - 1.5 - - - E.4 - 一 40 - - 一 5 20 - 23.5 5 5 - - 0.5 • 1 - E.5 - 一 40 - 一 - 18 - - 30 - 10 一 - 0.5 - 1.5 - - E.6 . - - 40 - - - - 30 18.5 - 10 • 0.5 - - - 1 一 E.7 細 — 40 - - - 18 - 30 - 10 _ 細 0.5 1.5 - - E.8 - - - 40 - - - - 30 18.5 - 10 - 0.5 - - 1 - E.9 30 - 12 - - - 嫌 25 5 13 9 3 - 1 - - 2 E.10 30 12 - - - 一 一 25 5 13 9 3 • - 1 - - 2 E.ll - - 20 23 - - 10 - 25 8 9 - 3 一 2 • 一 - 讎 E.12 - - 23 20 - • 10 - 25 8 9 • 3 - 2 - 一 - - E.13 11 - 15 10 - - - 25 - 27 7 1.5 2 - 0.5 - - 1 E.14 7.5 - 15 10 一 一 18 10 - 28 7 1.5 1.5 - 0.5 - - 1 E.15 11 - 15 12 - • - 20 10 18.5 7 1.5 1.5 - 0.5 • - - 3 E.16 _ 15 16 5 - 25 - - 27 8 1.5 1 0.5 - • - - 1 E.17 - 15 5 13 - - 28 一 - 28 8 1.5 0.5 0.5 麵 - 一 1 E.18 - 15 5 18 - 20 一 10 18.5 8 1.5 0.5 0.5 籍 - - 3 C.E.l - 一 • - 40 25 - - 23 10 • - 0.5 • 1.5 • - C.E.2 - - • - - 40 - 25 - 23.5 10 - - - 0.5 麵 1 • - C.E.3 一 - - 40 - 18 - 30 - 10 - - 0.5 • 1.5 • 一 C.E.4 - - - - 40 - - - 30 18.5 - 10 - • - 0.5 - 1 - C.E.5 - - - - 15 20 25.5 - - 28 8 1.5 0.5 0.5 一 1 C.E.6 - - - - 20 18 20 - 10 18.5 8 1.5 0.5 0.5 - - - - 3 28 200535209 &lt;評估測試1 &gt;相容性評估 將依據實施例1至18A Y丨 及比較貫施例1至6製備而得之 使用於軟性PCB的埶固槌私#，丄、n、 '、、、固眭黏者組成物分別塗覆至已進行剝 離處理並為38_厚度之對苯二甲酸乙，膜上，然後 利用熱空氣乾燥器纟13(rc下乾燥5分鐘而形成具有… m編黏著層。將具有5〇”厚度的聚乙浠保護膜層遂 至黏者層上’且於60。〇下姑罢ς Ϊ n 士 从 爷 L下放置5小叶，稭此產生包括聚對 笨二甲酸乙二醇，膜層、黏著層、及聚乙婦保 黏著片。 一曰27 200535209 Table 2 A A5 BCDE 1 2 3 4 1 2 1 2 3 4 1 2 3 1 2 1 2 3 Filler El 40----25--23 10--0.5-1.5---E.2 -40 — *-—-25-23.5 10 one-0.5 1--E.3-40----20 5-23 5 5-0.5-1.5---E.4-one 40--one 5 20 -23.5 5 5--0.5 • 1-E.5-One 40-One-18--30-10 One-0.5-1.5--E.6.--40----30 18.5-10 • 0.5- --1-E.7 fine — 40---18-30-10 _ fine 0.5 1.5--E.8---40----30 18.5-10-0.5--1-E.9 30- 12---25 25 13 9 3-1--2 E.10 30 12---11 25 5 13 9 3 •-1--2 E.ll--20 23--10-25 8 9 -3 One 2 • One-雠 E.12--23 20-• 10-25 8 9 • 3-2-One--E.13 11-15 10---25-27 7 1.5 2-0.5-- 1 E.14 7.5-15 10 11-18 10-28 7 1.5 1.5-0.5--1 E.15 11-15 12-•-20 10 18.5 7 1.5 1.5-0.5 •--3 E.16 _ 15 16 5-25--27 8 1.5 1 0.5-•--1 E.17-15 5 13--28 a-28 8 1.5 0.5 0.5 side -One 1 E.18-15 5 18-20 One 10 18.5 8 1.5 0.5 0.5 Home--3 CEl-One •-40 25--23 10 •-0.5 • 1.5 •-CE2--•--40- 25-23.5 10---0.5 side 1 •-CE3 one--40-18-30-10--0.5 • 1.5 • one CE4----40---30 18.5-10-•-0.5- 1-CE5----15 20 25.5--28 8 1.5 0.5 0.5-1 CE6----20 18 20-10 18.5 8 1.5 0.5 0.5----3 28 200535209 &lt; Evaluation test 1 &gt; Compatibility evaluation will be made according to Examples 1 to 18A Y 丨 and Comparative Examples 1 to 6 and used in flexible PCBs. 埶 固 锤 私 #, 丄, n, ',,, and solid adhesive composition It was coated on ethyl terephthalate with a thickness of 38 μm, and the film was peeled off, and then dried with a hot air dryer 纟 13 (rc for 5 minutes to form an adhesive layer with ... m braid. A protective film layer of polyethylene with a thickness of 50 ″ was then deposited on the adhesive layer, and the leaflets were placed at 60 ° C. Ϊ n 5 leaflets were placed under the sacrifice L. This produced polyethlene Glycol, film layer, adhesive layer, and polyethylenim adhesive sheet.

使用顯微鏡觀察熱固性黏著組成物的表φ來評估黏著 組成物的相容性，結果示於I 3。如表3所示，當黏著組 成物的相谷性良好時，該黏著組成物被評比為〇，當黏著 組成物的相容性不佳時，例如生成層分離，該黏著組成物 被評比為X。 由表3可看到，在使用根據實施例1至之用於軟性 PCB的熱固性黏著組成物所製得的黏著片之情況下，其在 黏著組成物之間具有良好的相容性，但在由比較實施例1 φ 至2及5至6的黏著片情況下，則其黏著組成物之間具有 不良的相谷性。因此比較實施例1至2及5至6的黏著組 成物具有商業化的困難度。 &lt;評估測試2&gt;黏著強度評估 评估根據測試1之包括有聚對苯二曱酸乙二醇酯膜 層 Α著層、及聚乙稀保護膜層的三層黏著片，對於聚· 亞胺膜或鋼箔之黏著強度。 29 200535209 A :對聚醯亞胺膜的黏著強度 在使用根據實施例Μ 8及比較實施例丨_6之用於軟性 PCB的熱固性黏著組成物所製得的三層黏著片之例中，其 個別包括有聚對苯二甲酸乙二醇酯膜層、黏著層、及聚乙 烯保濩膜層，當聚乙烯保護膜從黏著片上移除之後，將這 二黏著片熱壓至厚度為50#mi聚醯亞胺膜上（商業名稱： Apical AH，由Kanegafuchi化學工業公司製造）。然後將 聚對苯二甲酸乙二醇醋膜熱屬至厚度4 5GAm之聚醯亞胺 膜（商業名稱：Apical AH，由Kanegafuchi化學工業公司製 上的黏著層’再於16(rc下加熱5小時使黏著層硬化，、 藉此付到用於坪估黏著強度的試樣。此時，依冑卯。剝離 測試方法進行黏著強度之評估。 。除此之外，使用恆定溫度和濕度之烤箱，在溫度為121 相對濕度⑽）為100%、及時間為小時的條件下， 料樣施以恆定溫度和濕度之後，評估該黏著組成物對聚 醯亞胺膜的黏著強度。 參 B :對銅箔的黏著強度 康平估對聚醯亞胺膜黏著強度的相同步驟 ::個別包括有聚對笨二甲酸乙二醇酷膜層、黏著層= =層黏著片’但其中係使用厚度 名稱冉A =Α’曰本能量公司製造）取代聚醯亞胺膜（商業 冉 P1Cal ΑΗ，由Kanegafuchi化學工業公司，、告 ^ 得到之黏著片他&amp; 衣k )。將 度。 片做為試樣，並評估黏著層對銅落的點著強 30 200535209 同時，使用與評估對聚醯亞胺膜黏著強度情況的相同 條件，將試樣置於恆定溫度和濕度下評估黏著層對銅落的 黏著強度。 黏者層對聚酿亞胺膜及銅笛的黏著強度之評估結果述 於表3。如表3中所示者，在實施例i i 中之黏著组成 物之情況下’當完成恆溫和濕度之處理之後，黏著層對聚 酉盘亞胺膜及銅羯的點英％Λ， _ 口々占者強度_ 19 kgf/cm或更高，更詳而 口之2 2丄3·3 kgf/Cm。另-方面，在比較實施例1至6中 之々占著、、且成物之情況下，黏著層對聚驢亞胺膜的黏著強度 為低於U邮⑽，及黏著層對銅落的黏著強度為低於1&lt;5 kgf/cm。因此在比較實施 的匱况下，黏者層易於 亞胺膜和㈣中剝離，及黏著強度大大地降低，致 ^根據比較實施例！至6的黏著組成物有無法商業化的問 題0 平估測試3&gt;耐化學性評估 將根據评估測試丨之包括 — &gt;、 ,象對本一甲酉夂乙二醇酯膜 屑黏者層、及聚乙烯保護 官译h 曼Μ的二層黏者片’經剪切成 羌度為1 mm的試樣片條後， 八 俛在7〇C下浸潰於甲苯中10 刀知，由含有甲苯之浴池中 同牛_# 取出亚利用與評估測試2的相 同步騄進订黏著強度的評估。处 ! . , 〇 ^ ^ ^ 、、σ果不於表3，使用實施例 8之黏者組成物所製得的 至6，1 ι 士 0钻者片相較於比較實施例1 其具有二至三倍更佳的耐化學性。 &lt;評估測試4&gt;耐焊性評估 當聚乙烯保護膜是從根據 1Μ古劂试1之包括有聚對苯 31 200535209 二曱酸乙二醇酯膜層、黏著層、及聚乙烯保護膜層的三層 黏著片剝離時，將黏著片熱壓至玻璃環氧樹脂基板上，^ 中具有由敍刻製程製得、大小為2·5 cmx2 5⑽且厚度為 200//m之銅元件。 、 後來，在聚對苯二曱酸乙二醇酿膜從所得到之黏著片 剝離之後，該所得黏著片在Mpa及i4〇t下熱塵至具 有大小為0.9 cm x 0.7 cm之玻璃晶片上達3分鐘，於卯。〔 % :加熱丨小時，再於17Gt下加熱2小時使黏著層硬化， 藉此得到使用於耐焊性評估的試樣。 將試樣置於以溫度和濕度之烤箱48小時，其中之條 件為的之溫度及85%之相對濕度⑽），及在260t及28〇 C之二種不同溫度下以IR回燁爐處理。最後觀察所得到 :式樣，並確認在所得試樣上是否有剝離和發泡現象產 生。結果述於表3。 在每個實施例和每個比較實施例中所製得之五個試 及未產生㈣及發泡的試樣數目述於表3。由表3可 看到’當使用本發明的黏荽έ υ者組成物時並未發現剝離及發 泡’但當使用比較實施例 泡。 、々者、、且成物時則產生剝離及發 &lt;評估測試5&gt;熱循環測試 酸乙當::乙稀保護膜從評估測試1中之包括有聚對苯二甲 酉夂乙二醇酯膜層、黏著声、 片亲士收逢 θ及來乙烯保護膜層的三層黏著 有由:”將黏著片熱塵至破璃環氧樹脂基板上，… 有由蝕刻製程製得、大小為 /、Τ /、 …· cm χ 2·5 cm且厚度為200 32 200535209 // m之銅元件。 後來在聚對苯二甲酸乙二醇酯膜由所得到之黏著片 亲,J离隹〇麦’ 5亥所得黏著片在0.1 Mpa及140°C下熱壓至具 有大j為0.9 cm χ 〇·7 cm之玻璃晶片上達3分鐘，於9〇。〇 下加熱1小日^ ’再於17〇°C下加熱2小時使黏著層硬化， 藉此得到使用於熱循環測試的試樣。Table φ of the thermosetting adhesive composition was observed with a microscope to evaluate the compatibility of the adhesive composition. The results are shown in I 3. As shown in Table 3, when the cohesiveness of the adhesion composition is good, the adhesion composition is evaluated as 0, and when the compatibility of the adhesion composition is not good, such as layer separation, the adhesion composition is evaluated as X. It can be seen from Table 3 that in the case of using the adhesive sheet prepared according to Example 1 to the thermosetting adhesive composition for flexible PCB, it has good compatibility between the adhesive compositions, but In the case of the pressure-sensitive adhesive sheets of φ to 2 and 5 to 6 of Comparative Example 1, the adhesive composition had poor phase valleyness. Therefore, the adhesive compositions of Comparative Examples 1 to 2 and 5 to 6 have difficulty in commercialization. &lt; Evaluation Test 2 &gt; Evaluation of Adhesive Strength According to Test 1, a three-layer adhesive sheet including a polyethylene terephthalate film layer A coating layer and a polyethylene protective film layer was used. For polyimide Adhesive strength of film or steel foil. 29 200535209 A: Adhesive strength to polyimide film In the example of a three-layer adhesive sheet made using a thermosetting adhesive composition for flexible PCBs according to Example M 8 and Comparative Example 丨 _6, its Individually includes a polyethylene terephthalate film layer, an adhesive layer, and a polyethylene protective film layer. After the polyethylene protective film is removed from the adhesive sheet, the two adhesive sheets are hot pressed to a thickness of 50 # mi polyfluorene imine membrane (commercial name: Apical AH, manufactured by Kanegafuchi Chemical Industry Co.). Then the polyethylene terephthalate film was heated to a thickness of 4 5 GAm of polyimide film (commercial name: Apical AH, an adhesive layer made by Kanegafuchi Chemical Industry Co., Ltd.) and heated at 16 (rc 5 The adhesive layer is hardened after 1 hour, so that it can be used to evaluate the adhesive strength of the sample. At this time, the adhesive strength is evaluated according to the peel test method. In addition, an oven with a constant temperature and humidity is used. Under the condition that the temperature is 121 relative humidity ⑽) is 100% and the time is hours, the sample is subjected to constant temperature and humidity, and the adhesion strength of the adhesive composition to the polyimide film is evaluated. See B: Copper foil adhesive strength Kangping estimates the same steps for the adhesion strength of polyimide film: individually includes a polyethylene terephthalate film layer, an adhesive layer = = layer adhesive sheet ', but the thickness name is used. A = Α '(manufactured by Benben Energy Co.) to replace polyimide film (commercial Ran P1Cal ΑΗ, manufactured by Kanegafuchi Chemical Industry Co., Ltd., and obtained the adhesive sheet he & k). Will degrees. Sheet as a sample, and evaluated the adhesion strength of the adhesive layer to the copper drop 30 200535209 At the same time, using the same conditions as the evaluation of the adhesion strength to the polyimide film, the sample was placed under constant temperature and humidity to evaluate the adhesive layer Adhesion to copper drops. The evaluation results of the adhesion strength of the adhesive layer to the polyimide film and the copper flute are shown in Table 3. As shown in Table 3, in the case of the adhesive composition in Example ii, 'when the temperature and humidity treatments were completed, the adhesive layer was exposed to the polyimide film and copper foil.% Λ, _ 口々 Occupant strength_ 19 kgf / cm or higher, more detailed 2 223 · 3 kgf / Cm. On the other hand, in the case where the plutonium is occupied by the comparative examples 1 to 6, and the product is formed, the adhesive strength of the adhesive layer to the polydonimine film is lower than that of the U.P.P. Adhesive strength is less than 1 &lt; 5 kgf / cm. Therefore, in the case of comparative implementation, the adhesive layer is easy to peel off from the imine film and the osmium, and the adhesive strength is greatly reduced, resulting in ^ according to the comparative example! There is a problem that the adhesive composition of 6 to 6 cannot be commercialized. 0 Level assessment test 3> Chemical resistance assessment will be based on the assessment test, including — &gt;, such as the present methylformyl glycol film scum adhesion layer, And polyethylene protection official translation h Man M ’s two-layer adhesive sheet 'after cutting into a specimen strip with a degree of 1 mm, Hachiman was immersed in toluene at 70 ° C for 10 knives. Tongniu_ # in the toluene bath was removed and used to synchronize with the evaluation test 2 to evaluate the adhesion strength. Here!. ^^^^, σ are not shown in Table 3, and the diamond tablet made to the 6,1 μm and 0 diamond sheet prepared by using the adhesive composition of Example 8 has two advantages compared to Comparative Example 1. Up to three times better chemical resistance. &lt; Evaluation test 4 &gt; Evaluation of soldering resistance when the polyethylene protective film is based on 1M ancient test 1 including polyparaphenylene 31 200535209 ethylene glycol diacetate film layer, adhesive layer, and polyethylene protective film layer When the three-layer adhesive sheet is peeled off, the adhesive sheet is hot-pressed onto a glass epoxy substrate, and there is a copper element having a size of 2.5 cm × 2 5 mm and a thickness of 200 // m, which is produced by a sculpting process. Later, after the polyethylene terephthalate film was peeled from the obtained adhesive sheet, the obtained adhesive sheet was hot-dusted to a glass wafer having a size of 0.9 cm x 0.7 cm under Mpa and i40t. 3 minutes. [%: Heating 丨 hours, and then heating at 17 Gt for 2 hours to harden the adhesive layer, thereby obtaining a sample for solder resistance evaluation. The samples were placed in an oven with temperature and humidity for 48 hours, the conditions of which were 85% relative humidity ⑽), and were processed in IR oven at two different temperatures of 260t and 28 ° C. Finally, observe the obtained pattern and confirm whether peeling or foaming occurs on the obtained sample. The results are described in Table 3. The number of the five samples produced in each example and each comparative example and no scumming and foaming are shown in Table 3. From Table 3, it can be seen that 'peeling and foaming were not observed when the adhesive composition of the present invention was used', but when the comparative example was used. Peels and hair when it is finished, &lt; evaluation test 5 &gt; thermal cycle test acid ethyl acid :: ethylene protective film includes polyethylene terephthalate from evaluation test 1 The three layers of the ester film, the adhesive sound, the film, and the vinyl protective film are adhered to: "The adhesive sheet is hot-dust to the glass-breaking epoxy substrate, and ... A copper element of /, T /,… · cm χ 2.5 cm and a thickness of 200 32 200535209 // m. Later on the polyethylene terephthalate film from the obtained adhesive sheet, J Li 隹〇 麦 'The adhesive sheet obtained by heating at 0.1 MPa and 140 ° C was hot-pressed on a glass wafer having a large j of 0.9 cm x 0.7 cm for 3 minutes, and heated at 90 ° for 1 day ^' The sample was used for thermal cycle test by heating at 17 ° C for 2 hours to harden the adhesive layer.

4樣的熱循環測試是於-65至1 50°C下進行。關於此 點，忒熱循環測試共進行了丨〇〇〇次循環，其前提是當每 個试樣在150°C下處理30分鐘及_65它處理3〇分鐘後即完 成一次循壤。在每個實施例和每個比較實施例中製造出十 個试樣，經熱循環測試之後，觀察所得到之試樣是否有剝 離和發泡現象產生。結果述於表3。Four samples of the thermal cycle test were performed at -65 to 150 ° C. In this regard, the thermal cycling test was performed for a total of 1,000 cycles, provided that each sample was processed at 150 ° C for 30 minutes and -65 minutes after it was processed for 30 minutes. Ten samples were produced in each example and each comparative example, and after the thermal cycle test, the obtained samples were observed for peeling and foaming. The results are described in Table 3.

未產生剝離及發泡的試樣數目述於表3。如表3所示， 當使用根據實施例1至18中之黏著組成物時未發現剝離 及發泡的試樣數目為10，但當使用比較實施例丨至6之黏 著組成物時則未發現剝離及發泡的試樣數目為3_4。依此 可見剝離及發泡並未發生於本發明之黏著組成物。 〈評估測試6〉吸濕性評估 ^水乙~保遵膜以及I對苯二曱酸乙二醇g旨膜依序由 評估測試1中包括有聚對苯二曱酸乙二醇酯膜層、黏著層、 離時，將所得黏著片於 ，藉此得到使用於吸濕 每個試樣的吸濕性測試 箱’在溫度為12 rc、 及聚乙烯保護膜層的三層黏著片剝 1 70°C下加熱1小時使黏著層硬化 性評估的5 cm X 5 cm大小試樣。 係進行於使用恆定溫度和濕度之烤 33 200535209 相對濕度（RH)為UK)%、及時間為24小時的條件下，之後 評估該試樣的吸濕性。吸濕性（％ )係依下列方程式1計算 而得，結果述於表3。 方程式1 吸濕性=[(吸收後之試樣重量—吸收前之試樣重量)/吸 收前之試樣重量]X 1〇〇 由表3可見，當使用本發明實施例中用於軟性pcB的 熱固性黏著組成物時，試樣的吸濕性Α 〇·6%或更低，但 當使用比較實施例的黏著組成物時，試樣的吸濕性相當 向，致使比較實施例的黏荖έ + 4 拓者組成物有無法商業化的問題。 估測試7&gt;延伸性評估 依據實施例1至1 8及屮如每A ν 比車乂貝加例1至6製備而得之用 於軟性p C β的赦固性斑笨 、 …、性黏者組成物分別塗覆至已進行剝離處 理並為38//m厚度之對 f本一甲酉欠乙二醇酯膜上，然後利用 熱空氣乾燥器在1 3 〇亡下_ . ^ 乾無5为鐘而形成具有60 // m厚 度的黏著層。將具有5〇 + # U 厚度的聚乙烯保護膜層壓至黏 者層上，且於60°C下放晋ς , 士 田分 &gt; 置5小呀，藉此產生包括聚對苯二 甲酉欠乙一醇酯膜層、點菩屉 ”者層、及聚乙烯保護膜的三層黏著 h °Table 3 shows the number of samples without peeling and foaming. As shown in Table 3, the number of samples in which peeling and foaming were not found when using the adhesive composition according to Examples 1 to 18 was 10, but was not found when using the adhesive composition according to Comparative Examples 丨 to 6. The number of peeled and foamed samples was 3_4. Accordingly, it can be seen that peeling and foaming did not occur in the adhesive composition of the present invention. <Evaluation test 6> Hygroscopicity evaluation ^ Shui B ~ Bao Zun film and I ethylene terephthalate g film The film was sequentially included in evaluation test 1 including polyethylene terephthalate film layer When the adhesive layer is removed, the obtained adhesive sheet is applied to obtain a hygroscopicity test box for absorbing each sample. The three-layer adhesive sheet peeled at a temperature of 12 rc and a polyethylene protective film layer 1 A sample of 5 cm X 5 cm in size was evaluated by heating at 70 ° C for 1 hour. The test was performed under conditions of roasting with constant temperature and humidity 33 200535209 Relative humidity (RH) UK)% and time of 24 hours, and then the moisture absorption of the sample was evaluated. The hygroscopicity (%) was calculated according to the following Equation 1, and the results are shown in Table 3. Equation 1 Hygroscopicity = [(weight of sample after absorption-weight of sample before absorption) / weight of sample before absorption] X 100 can be seen from Table 3, when used for soft pcB in the embodiment of the present invention In the case of the thermosetting adhesive composition, the hygroscopicity of the sample was Α.6% or lower, but when the adhesive composition of the comparative example was used, the hygroscopicity of the sample was quite oriented, resulting in the stickiness of the comparative example. έ + 4 There is a problem that the extension composition cannot be commercialized. Estimation test 7> Extensibility evaluation was prepared according to Examples 1 to 18, and was prepared according to Examples 1 to 6 for each A ν than carcass beakers Examples 1 to 6, and was used for soft p C β. The composition was respectively coated on a pair of f-monomethyl ethylglycol film which had been subjected to a peeling treatment to a thickness of 38 // m, and then used a hot air dryer at 130 ° C. ^ Dry without 5 forms an adhesive layer with a thickness of 60 // m for the bell. Laminate a polyethylene protective film with a thickness of 5〇 + # U onto the adhesive layer, and place it at 60 ° C, and place it at 5 minutes to produce poly (phenylene terephthalate). Ethylene glycol film layer, three-layer adhesive layer, and three layers of polyethylene protective film adhesion h °

當聚乙烯保護膜以B 二 、 氷對苯二T酸乙二醇酯膜依序從 二層黏者片剝離時，將 — 栋Μ I mu # 斤侍黏者片於170 °C下加熱1小時 I , 於L伸性評估的1 cm X 12 cm 大小试樣。延伸率、 述於表3。 U)係依下列方…計算而得，結果 34 200535209 方程式2 延伸率=[(試樣延伸後之試樣長度一試樣延伸前之$ 樣長度）/試樣延伸後之試樣長度]χ 1〇〇 由表3可見，當使用本發明實施例中用於軟性pcB 、 熱固性黏著組成物時，試樣的延伸率為i 3〇%或更高，勺 明確地為150-2丨〇%，但當使用比較實施例i和2的黏著 組成物犄，試樣的延伸率相當低至1 00%或更低。When the polyethylene protective film is sequentially peeled from the second-layer adhesive sheet with B, ice-terephthalate T-ethylene glycol ester film, heat the — DongM I mu # Jinshi adhesive sheet at 170 ° C 1 Hour I, 1 cm X 12 cm specimen for L extensibility evaluation. The elongation is described in Table 3. U) Calculated according to the following formula ... Result 34 200535209 Equation 2 Elongation = [(sample length after sample extension-$ sample length before sample extension) / sample length after sample extension] x It can be seen from Table 3 that when the soft pcB and thermosetting adhesive composition is used in the examples of the present invention, the elongation of the sample is i 30% or higher, and the scoop is clearly 150-2 丨 0%. However, when the adhesive composition 犄 of Comparative Examples i and 2 was used, the elongation of the sample was considerably as low as 100% or less.

&lt;-平估測試8&gt;發泡和嵌入能力（embedabiHty)評估 依據評估測試丄製得包括有聚對苯二甲酸乙二醇 層、黏著層、及聚乙烯保護膜層的三層黏著片。 θ、 σ守，將光阻劑層熱壓至軟性基板（商業名稱&lt; -Evaluation test 8 &gt; Evaluation of foaming and embedding ability (embedabiHty) Based on the evaluation test, a three-layer adhesive sheet including a polyethylene terephthalate layer, an adhesive layer, and a polyethylene protective film layer was prepared. θ, σ, heat press the photoresist layer to a flexible substrate (commercial name

朵ΓΓ ’由Nlpp°n steel Chemicai公司製造），’然後钱I 土板上剝離而得到在導體之間的區間） 50“ m的梯形電路。 L^曰^ 護膜層r為：母個黏者片熱壓至電路上，同時將聚乙烯 小時：对 上剝離。所得到之黏著片置於⑽下Do ΓΓ 'manufactured by Nlpp ° n steel Chemicai Co., Ltd.', and then peeled off the ground plate of Qian I to get the interval between the conductors) 50 "m ladder circuit. L ^^^ The coating layer r is: The sheet was hot-pressed onto the circuit, and at the same time the polyethylene was removed: the top was peeled off. The resulting adhesive sheet was placed under a crotch.

著片上剝離。 f本一甲酸乙二醇酯膜層則從 所得結構之發泡（觀察 有發泡部份)和…梯形電路和黏著層之間是否 於黏著&gt; + 力（硯察在梯形電路周圍是否存有 4者層與電路間不完全對 微鏡評估，的鬆脫部份）’可使用 力良好日.、、、。果述…。如表3所示，當發泡和嵌入 R4，所得之結構評 時’所得之結構評比為χ。# ’當發泡和欲入能力不 ”、 特別者為，當本發明黏著組 35 200535209 物被施加至載體膜或黏著膠膜時，發泡及欲入能力 影嚮載體膜或黏著膠膜的重要物理性質。 &lt;評估測試9&gt;電力可靠度評估 &gt;提供依據評估測試1製得之包括有聚對苯二甲酸乙二 S子酯朕層、黏著層、及聚乙烯保護膜層的三層黏著片。 同時，將光阻劑層熱壓至軟性基板（商業名稱.Peel on the sheet. f The ethylene glycol formate film layer is obtained from the foam of the obtained structure (observe the foamed part) and ... is there any adhesion between the ladder circuit and the adhesive layer &gt; + force (check whether there is There are incomplete evaluation of the micromirror between the four layers and the circuit, and the loose part) 'Availability is good. Fruitful ... As shown in Table 3, when R4 was foamed and embedded, the obtained structure was evaluated as χ. # 'When the foaming ability is not suitable,' in particular, when the adhesive group 35 200535209 of the present invention is applied to a carrier film or an adhesive film, the foaming ability and the ability to penetrate affect the carrier film or the adhesive film. Important physical properties. &Lt; Evaluation Test 9 &gt; Electricity Reliability Evaluation &gt; Provides three evaluations made based on Evaluation Test 1 including a polyethylene terephthalate resin layer, an adhesive layer, and a polyethylene protective film layer. At the same time, the photoresist layer was hot pressed to a flexible substrate (commercial name.

Espanex，由 Nipp0n .Espanex by Nipp0n.

emical公司製造），然後蝕刻 光阻劑層並從軟性其刼μ J 、 土板上剝離，以製得在導體之間的區間 為5 0 // m的梳形電路。 接著，將每個黏著片熱壓至電路上，同時將聚乙稀伴 護膜層從黏著片上剝除。 力除所传到之黏著片置於17(rc下i 小時，使黏著層硬化，而取m # 而聚對本二甲酸乙二醇酯膜層則由 所得黏著片上剝除，因此製得用於電力可靠度評估之試 樣。 將試樣置於忸定溫度和濕度之烤箱，纟13代及相對 濕度⑽)為85%下處理300小時，同時施力σ 5V的直流電 :了電路上。接著，觀察梳形電路的狀態，且結果示於 、士表3所不，畲梳形電路（相當於銅箔）中產生遷移 現象時’該試樣評比為χ，但當梳形電路中並未產生遷移 現象時，該試樣評比為〇。 由表3可看到，當使用本發明的黏著組成物時並未發 見、私現象，目此本發明之黏著組成物從與短路有關之電 力可靠度之觀點來看是具有充足的競爭性。 36 200535209 。平估測4 1〇&gt;毛邊（bu^)性質評估 “乙稀保護膜從評估測試1中之包括有聚對苯二甲 層、黏著層、及聚乙稀保護膜層的三層黏著 將黏著驗至具有一厚度之聚醯亞胺 造)(商妙業r:,calAH，由Kanegafuchl化學工業公司製 &lt;將聚對苯二甲酸乙二醇酯膜從黏 所得之聚醯亞胺腔热，乃上利除 鑛設有直…Γ 熱5小時，使黏著層硬化。 ,θέ_.±Λ , 之柱形工具的穿孔器，經由所 ;、：形成細小圓洞’觀察於所得結構上所形成之毛邊 二、男切端上之粗燥突出物），結果述於表3。如表3 :::後當二得結構上形成時造成不良毛邊性f 得結構上形成Si成X:但當因為毛邊並未在所 評比為〇。 炎义毛邊性貝的時後，該所得結構之 和取=的形成可能由各種不同的因素造成，但在黏著層 =膜之間的更佳黏附性會引起較少的毛邊，因此(manufactured by Emical Co., Ltd.), and then the photoresist layer is etched and peeled from the soft 刼 μ J and the soil plate, so as to obtain a comb-shaped circuit with an interval between conductors of 5 0 // m. Next, each adhesive sheet was hot-pressed onto the circuit, and at the same time, the polyethylene film was peeled from the adhesive sheet. The adhesive sheet transferred by force removal was placed at 17 ° C for 1 hour to harden the adhesive layer, and m # was taken and the polyethylene terephthalate film layer was peeled off from the obtained adhesive sheet, so it was prepared for use in Sample for reliability evaluation of electricity. The sample was placed in an oven with a fixed temperature and humidity, 纟 13th generation and relative humidity⑽) for 8 hours at 85%, and a direct current of σ 5V was applied to the circuit. Next, observe the state of the comb circuit, and the results are shown in Table 3, when a migration phenomenon occurs in the comb circuit (corresponding to copper foil) 'The sample is evaluated as χ, but when the comb circuit is When no migration occurs, the sample rating is zero. As can be seen from Table 3, when the adhesive composition of the present invention is used, no private phenomenon is observed. Therefore, the adhesive composition of the present invention is sufficiently competitive from the viewpoint of reliability of electric power related to short circuits. . 36 200535209. Flat evaluation 4 1〇> Evaluation of burr (bu ^) properties "Ethylene protection film from evaluation test 1 includes a three-layer adhesion layer including a polyparaxylene layer, an adhesive layer, and a polyethylene protective film layer. Adhesion test to a polyimide with a thickness (Shang Miaoye r :, calAH, manufactured by Kanegafuchl Chemical Industry Co., Ltd.) &lt; Polyimide cavity obtained by sticking a polyethylene terephthalate film from the adhesive Hot, Naoshiri demineralization is provided with a straight Γ heat for 5 hours to harden the adhesive layer., Θέ_. ± Λ, the perforator of the cylindrical tool, through the formation of; to form a small circular hole 'observe on the resulting structure The burr formed on the two sides, and the rough protrusions on the male cut end), the results are shown in Table 3. As shown in Table 3: ::: When Erde is formed on the structure, it causes poor burr properties f to form Si to X on the structure: but Because the burr is not rated as 0. After the burr of Yanyi, the formation of the obtained structure can be caused by various factors, but the adhesion between the adhesive layer and the film is better. Causes less burrs, so

自表3可看到，當利用本發明之用於軟性PCB 的熱固性黏著組成物情 / ，一相較於利用比較實施例1 至的4者組成物的情況具有更佳之毛邊性質。 &lt;評估測試11 &gt;抗彎曲性評估 -甲保護膜從根據評估測試1中之包括有聚對苯 :著片層、黏著層、及聚乙稀保護膜層的三層 ; =Γ，將黏著片熱壓至具有5。…度之聚酿亞 、（商業名稱：Aplcal ΑΗ，由Kanegafuchi化學工業公司 37 200535209 製造）。然後’將聚對苯二f酸乙二 _子S日膜從孝占# μ 杂丨 在黏著片上熱壓厚度為18_ /、者片上冊 由曰：能量公司製造)。所得之黏著層於⑽t下…小 時使，、硬化：钱刻該銅落並取出而生成具有ι〇_寬度之 对熱^樹脂複合膜。依據KSC647卜在500克負載和〇·38 mm ’曲直梭的條件之下，測試此耐熱樹脂複合膜，計數 彎曲的次數一直到耐熱樹脂複合膜斷裂。 表3 :以用於生PeB的熱固性黏著組成物製得之黏著片的物理性It can be seen from Table 3 that when using the thermosetting adhesive composition of the present invention for flexible PCBs, the burr properties are better than those in the case of using the compositions of Comparative Examples 1 to 4. &lt; Evaluation test 11 &gt; Evaluation of bending resistance-A protective film includes three layers including polyparaphenylene: a film layer, an adhesive layer, and a polyethylene protective film layer according to the evaluation test 1; = Γ, will The adhesive sheet was hot pressed to have 5. … Degree of brewing Asia, (commercial name: Aplcal ΑΗ, manufactured by Kanegafuchi Chemical Industry Company 37 200535209). Then, the polyethylene terephthalate film was made from Xiaozhan # μ Miscellaneous on a pressure-sensitive adhesive sheet with a thickness of 18 mm, and the volume on the sheet was made by Energy Corporation). The obtained adhesive layer is hardened under ⑽ ... for a few hours, and is hardened: the copper is cut and taken out to form a heat-resistant resin composite film having a width of ι0_. The heat-resistant resin composite film was tested according to KSC647 at a load of 500 g and a 0.38 mm 'straight shuttle, and the number of bending was counted until the heat-resistant resin composite film was broken. Table 3: Physical properties of an adhesive sheet made from a thermosetting adhesive composition for raw PeB

38 200535209 】c :相容性 2Im!de:對聚醯亞胺膜之黏著強度（Kgf/cm) 'B ··在固定溫度和濕度之處理前 - 4A ··在固定溫度和濕度之處理後 5CopPer ·•對銅箔之黏著強度（Kgf/cm) 6Ch :耐化學性 7Reflow :耐焊性 SH :吸濕性（％) 9E :延伸率(。/〇) % 1()F :發泡 11 Em :嵌入能力 I2E1 :電力可靠度 Ι3Βιχ :毛邊性質 14Be :抗彎曲性（次數）38 200535209】 c: Compatibility 2Im! De: Adhesive strength to polyimide film (Kgf / cm) 'B ·· Before fixed temperature and humidity treatment-4A ·· After fixed temperature and humidity treatment 5CopPer · • Adhesive strength to copper foil (Kgf / cm) 6Ch: Chemical resistance 7 Reflow: Solder resistance SH: Hygroscopicity (%) 9E: Elongation (./〇)% 1 () F: Foam 11 Em: Embedding ability I2E1: Power reliability I3Bιχ: Unedged property 14Be: Bending resistance (number of times)

如同於上文中所述者，本發明係提供一種熱固性黏著 組成物’其包含：1)丁二烯-丙稀腈共聚物，其以式i表示 並B有羧基承胺基胺基羰基(A)和聚矽氧烷胺基羰基 ⑻，及2)壞乳樹脂。冑關於此，該熱固性黏著組成物具 有下列三項優異處。 第一，該丁二稀-丙稀腈共聚物對基板的黏著強度得以 改良’及丁二稀-丙稀腈共聚物對環氧樹脂的相容性得以改 良。 、 苐二’黏著強度 吸濕性、抗化學性 和電力可靠度 39 200535209 付以改良，及在黏著組成物吸收水之後具有極佳之黏著強 度耐丈干丨生、毛邊（在虑切端上形成之粗燥突出物）性質、 及杬”生’因此，該黏著組成物可有用地施用到電子— 弟三，基板膜和黏著組成物之間的 因此改良抗-曲性和高溫度可靠：者’…改良: 有用地施加至難pCB。 «者組成物； 本兔明已經以例示的方式揭示As described above, the present invention provides a thermosetting adhesive composition 'comprising: 1) a butadiene-acrylonitrile copolymer, which is represented by formula i and B has a carboxylaminoaminocarbonyl group (A ) And polysiloxane alkyl fluorene, and 2) bad milk resin.胄 In this regard, the thermosetting adhesive composition has the following three advantages. First, the adhesive strength of the succinic-acrylonitrile copolymer to the substrate is improved 'and the compatibility of the succinic-acrylonitrile copolymer with the epoxy resin is improved. , 苐 二 'adhesive strength hygroscopicity, chemical resistance and electrical reliability 39 200535209 with improvements, and has excellent adhesive strength after the adhesive composition absorbs water, resistant to dryness, burrs (formed on the cut end) Nature of the rough projection), and the "green" Therefore, the adhesive composition can be usefully applied to the electron-the third, between the substrate film and the adhesive composition, therefore improved resistance to bending and high temperature reliability: '... Improvement: usefully applied to difficult pCB. «Composition of the composition; Ben Tuming has been revealed by way of example

之名詞係為說明性f之描述，而·'應理解者為所使用 示觀點來看，右 有限制之意。從上述麥 應理解者為在戶行本發明的許多修傳和變化。因Γ 午考為在所附的申請專利 &quot;支化因此， 施行。 之内，本發明即可得οNouns are descriptive descriptions of f, and '' should be understood to mean that from the point of view, there is a limitation on the right. From the foregoing, it should be understood that many modifications and changes of the present invention are performed by households. Because the Γ lunch exam is implemented in the attached patent &quot; Branch, therefore. Within the present invention, ο

4040

Claims (1)

200535209 十、申請專利範圍： 1 ·種熱固性黏著組成物，其包含： ) 烯丙烯腈共聚物，其含有羧基聚醯胺基胺基羰 基⑷和聚石夕氧燒胺基幾基⑻’並以下列式i表示；及 2)環氧樹脂 式1 〇—c w •以· yr…r ι·卜卜⑶一::％广皆 % , \ * 5 ^ •厂· 7 ί’ίΜ-_ ·ρ 十勺™，射 “ CH, '5^〇K, *%H^C !_.H.....丨允·，......^C^j;〇〇〇H ί ?% . νΗ^ ·:Η} (其中 A= loo — d , ^乃疋在A是範圍從i至99之莫 耳比率之前提下，k 為3 200及：、和η為莫耳比率，當k為&quot;“ 馬 L200 及 n 為 〇 21〇〇， 〇、p和Q個別為從u20的整數）。為Cl至基’及 中4T:專：範圍第1項之熱固性黏著組成物，-中。亥丁一烯-丙烯腈共聚物具 取 '、 2〇〇,000 ,及在哕丁 千句刀子量為10,000- 含$為2-40重量％。 丙烯腈早兀的 3 _根據申睛專利蔚圖 中在以⑽重量份丁 項之熱固性黏著組成物，其 r ' ^ ^ m ^ 、，且成物包含有〗&quot;00重量份環氧樹见 4.根據申請專利範圍第】項之 中該環氧樹脂進一步句紅 11 4者組成物，其 匕括—或多個選自由經至少-個漠取 一細丙稀腈共聚物為基準時，該黏著 ί分環ϋ傲日运. 41 200535209 夂之％氧基齒化物所組成之族群中。 5.根據申請專利範圍第1項之熱固性$ &amp; 推一本a , M …u Γ生黏者組成物，其 乂 〇括苯齡樹脂，在此方式中 的當量比為105 &quot;&quot;Γ 樹與苯輪旨 其中該苯盼樹月旨係選自由下列所 ' 鮮.酚醛苯酚樹脂、苯酚酚醛清〇 ψ„, ν 酸清漆樹脂、間！-“ t 月曰、曱酉分驗 物。 本一既樹月曰、二甲苯樹脂、和它們的混合 進6牛㈣申請專利範圍第1項之熱固性黏著組成物，其 量〇〇重量份之環氧樹脂為基準下，包括2-20重 ^錢化劑，該環氧硬化劑係選自由下列所組成 礼V0肪族胺化合物、芳香族胺化合物、酸軒化合物、雙 氰胺、二氟化硼和它們的混合物。 7 ·根據申請專利範圍筮 造〇 』乾圍弟1項之熱固性黏著組成物，盆 進一步在以100重量份夢 /、 旦 里知％虱树脂為基準下，包括0·01-3重 里知硬化促進劑，今麻7 里 Μ . . ^匕促進劑是選自由下列所組成之族 群·咪唑化合物（包括 、 括2·蚝基_4-甲基咪唑化合物，2-烷美 _4-乙基咪唑化合物， 土 化入物Γ勺#〃 本基咪唑化合物），金屬氟化硼 化口物（包括氟化硼錫和 ,,^ ^ 貺化硼鋅），金屬辛酸鹽化合物 仏錫和辛酸鋅），和它們的混合物。 8 ·根據申請專利範園筮 、隹本+ 乾圍弟1項之熱固性黏著組成物，复 進一步在以100重量份s β 一 Α ς , 知％乳樹脂為基準下，包括具有粒户 為5 // m或更低之υ〇 旦 又 私 里知…、機填充劑，該無機填充南j 係選自由下列所組成之 #〆 具兄^ ,£ ^ f •虱氧化鋁、氫氧化鎂、氧化 銘、氧化鋅和氧化鎂。 乳化 42 200535209 9. 一種覆蓋膜，其包含： 基板層， 酯樹脂所製成 其係由聚醯亞胺樹脂或 聚對苯二甲酸乙二醇 黏著層，其係由塗覆根據申請專利範圍第&quot;員之熱固 性黏著組成物至該基板層上所製得；及 保護膜’其是形成在黏著層上。 10·—種黏著膠膜，其包含： 第一保護膜； 1項之熱固200535209 10. Scope of patent application: 1. A thermosetting adhesive composition, including:) acrylonitrile copolymer, which contains carboxy polyfluorenylaminoaminocarbonyl fluorene and polyisocyanuric acid amine hydrazone 'and less than Column formula i is indicated; and 2) epoxy resin formula 〇—cw • yr… r ι · bbu ⑶ one:% 广 均%, \ * 5 ^ • plant · 7 ί'ίΜ-_ · ρ Ten Spoons ™, shot "CH, '5 ^ 〇K, *% H ^ C! _. H ..... 丨 Yen ·, ...... ^ C ^ j; 〇〇〇H ί?% νΗ ^ ·: Η} (where A = loo — d, ^ 乃 疋 is raised before A is the Mohr ratio ranging from i to 99, k is 3 200 and:, and η is the Mohr ratio, when k "For horses L200 and n are 〇21〇〇, 〇, p and Q are each an integer from u20). It is Cl to radical 'and middle 4T: special: thermosetting adhesive composition of the range item 1, -medium. The hexabutene-acrylonitrile copolymer has a molecular weight of 20,000, and a knife amount of 10,000-including 2 to 40% by weight. Acrylonitrile early 3_ According to the Shenyan patent Weitu in the thermosetting adhesive composition in terms of ⑽ parts by weight of D, its r '^ ^ m ^, and the product contains 〖00 parts by weight of epoxy resin See 4. According to the item in the scope of the patent application], the epoxy resin is further red. The composition is one or more selected from the group consisting of at least one fine acrylonitrile copolymer. The adhesion is divided into a group consisting of ϋ ϋ ϋ ϋ. 41 200535209 ％% oxydentate. 5. According to the thermoset $ & of the scope of the patent application, push a copy of a, M… u Γ raw adhesive composition, which includes benzene age resin, the equivalent ratio in this way is 105 &quot; &quot; Γ tree and benzene wheel purpose where the phenanthrene tree purpose is selected from the group consisting of the following: fresh. Phenolic phenol resin, phenol novolac 〇ψ „, ν acid varnish resin, m! . This is a thermosetting adhesive composition containing a mixture of xylene resin, xylene resin, and 6 burdock in the first patent application scope. The amount is based on 0.00 parts by weight of epoxy resin, including 2-20 weight. The epoxy hardener is selected from the group consisting of V0 aliphatic amine compounds, aromatic amine compounds, acid compounds, dicyandiamide, boron difluoride, and mixtures thereof. 7 · According to the scope of the patent application, the thermosetting adhesive composition of item 1 is dried. The pot is further hardened based on 100 parts by weight of dreams and dendritic resin, including 0 · 01-3 of Chunglizhi. Accelerator, Jinma 7 Li M.. ^ Accelerator is selected from the group consisting of imidazole compounds (including, including 2. oysteryl_4-methylimidazole compounds, 2-amyl_4-ethyl Imidazole compounds, earthenizing compounds Γ〃 # 〃 本 基 imidazole compounds), metal boron fluoride mouthpieces (including boron tin fluoride and boron zinc boron zinc), metal caprylate compounds tin tin and zinc octoate ), And their mixtures. 8 · According to the thermosetting adhesive composition of the patent application Fan Yuanzhang, transcript + Qianweidi, further based on 100 parts by weight of s β-Α ς, knowing the percentage of milk resin, including 5 // m or lower, and known in private, organic fillers, the inorganic filler is selected from the following consisting of # 下列 具 兄 ^, £ ^ f • lice alumina, magnesium hydroxide, Oxide inscription, zinc oxide and magnesium oxide. Emulsification 42 200535209 9. A cover film comprising: a substrate layer, made of an ester resin, which is an adhesive layer made of polyimide resin or polyethylene terephthalate, which is coated by &quot; A thermosetting adhesive composition is made on the substrate layer; and a protective film is formed on the adhesive layer. 10 · —An adhesive film, including: a first protective film; 1 item of thermosetting 黏著層，其是由塗覆根據申請專利範圍第 性黏著組成物至第一保護膜上所製得；及 第一保護膜，其是形成在黏著層上。 11.一種用於軟性PCB之複合帶，其包含 甲酸乙二醇 基板層，其是由聚醯亞胺樹脂或聚對苯二 酯樹脂所製成； 性黏著組成物至基板層上所製得；及The adhesive layer is prepared by coating the first adhesive composition according to the scope of the patent application on the first protective film; and the first protective film is formed on the adhesive layer. 11. A composite tape for a flexible PCB, comprising a substrate of formic acid formate, which is made of polyimide resin or polyterephthalate resin; and a sex adhesive composition is produced on the substrate layer ;and 孟屬殆’其是形成在黏著層的一側上。 12·—種用於軟性PCB之複合帶，其包含： 基板層，其係由聚醯亞胺樹脂或聚對苯二甲酸乙二 酉旨樹脂所製成； _ ，著層，其是由塗覆根據申請專利範圍帛丨項之· 性黏著組成物至基板層上所製得；及 ” 金屬箔，其是形成在黏著層上。 43Mencius' is formed on one side of the adhesive layer. 12 · —A composite tape for flexible PCB, comprising: a substrate layer, which is made of polyimide resin or polyethylene terephthalate resin; _, a layer, which is made of a coating It is made by coating the adhesive composition on the substrate layer according to item (1) of the scope of patent application; and "metal foil, which is formed on the adhesive layer. 43
TW093124645A 2004-04-19 2004-08-17 Thermosetting adhesive composition and adhesive tape for electronic parts using the same TWI280971B (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
KR1020040026527A KR100444925B1 (en) 2004-04-19 2004-04-19 Thermoset adhesive composition and adhesive tape for electronic application using it

Publications (2)

Publication Number Publication Date
TW200535209A true TW200535209A (en) 2005-11-01
TWI280971B TWI280971B (en) 2007-05-11

Family

ID=35345914

Family Applications (1)

Application Number Title Priority Date Filing Date
TW093124645A TWI280971B (en) 2004-04-19 2004-08-17 Thermosetting adhesive composition and adhesive tape for electronic parts using the same

Country Status (4)

Country Link
JP (1) JP2005307152A (en)
KR (1) KR100444925B1 (en)
CN (1) CN1311042C (en)
TW (1) TWI280971B (en)

Families Citing this family (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2007029979A1 (en) 2005-09-07 2007-03-15 Seong-Min Kim Release film for pcb lamination process
DE102006038330A1 (en) * 2006-08-15 2008-02-21 Phoenix Contact Gmbh & Co. Kg Method for joining plastic parts of electrical or electronic components, in particular of connectors, and products obtained in this way
KR101024937B1 (en) * 2008-07-04 2011-03-31 에스디플렉스(주) Double side flexible copper clad laminate and method for fabricating the same
DE102008046873A1 (en) * 2008-09-11 2010-03-18 Tesa Se Heat-activated adhesive tape, in particular for the bonding of electronic components and printed conductors
CN102786805B (en) * 2012-08-31 2014-10-22 广东银禧科技股份有限公司 High water-damage resistance asphalt mixture modifying agent, preparation method thereof and application in road paving method
KR20170084672A (en) * 2016-01-12 2017-07-20 후지모리 고교 가부시키가이샤 Coverlay film
GB2574223B (en) * 2018-05-30 2023-03-01 Acell Ind Ltd Adhesives and methods of forming adhesives
CN110628348A (en) * 2019-10-28 2019-12-31 南昌正业科技有限公司 Pure rubber protective film for transformer and production process thereof
JP2021155495A (en) * 2020-03-25 2021-10-07 大日本印刷株式会社 Manufacturing method of expandable adhesive sheet and article
CN112271325B (en) * 2020-09-15 2023-08-18 赖见 Three-dimensional solid lithium battery and preparation method thereof

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2732020B2 (en) * 1993-10-22 1998-03-25 株式会社巴川製紙所 Adhesive tape and liquid adhesive for electronic parts
JP2684004B2 (en) * 1993-10-22 1997-12-03 株式会社巴川製紙所 Piperazinylethylaminocarbonyl group-containing butadiene-acrylonitrile copolymer and method for producing the same
JP2732021B2 (en) * 1993-10-22 1998-03-25 株式会社巴川製紙所 Adhesive tape and liquid adhesive for electronic parts
JPH09241601A (en) * 1996-03-14 1997-09-16 Tomoegawa Paper Co Ltd Liquid adhesive for electronic part and formation of insulated adhered layer using the same

Also Published As

Publication number Publication date
TWI280971B (en) 2007-05-11
JP2005307152A (en) 2005-11-04
CN1690153A (en) 2005-11-02
CN1311042C (en) 2007-04-18
KR100444925B1 (en) 2004-08-21

Similar Documents

Publication Publication Date Title
TWI288760B (en) Resin compound for fabricating interlayer dielectric of printed wiring board, resin sheet and resin applied-copper foil for forming insulating layer using the resin compound, and copper-clad laminate using them
TWI490266B (en) A resin composition for forming a bonding layer of a multilayer flexible printed circuit board, a resin varnish, a porous flexible printed circuit board, and a multilayer flexible printed circuit board
CN100489048C (en) Binder composition for semiconductor device and binder sheet for semiconductor device
TWI344804B (en) Flexible laminate board and process
TWI252066B (en) Method for connecting electrodes, surface-treated wiring board and adhesive film used in the method, and electrodes-connected structure
CN108690459A (en) Resin combination
TW200915955A (en) Multiple layer wiring circuit board and semiconductor device
CN107556740A (en) Resin combination
CN106912158A (en) Adhesive film
CN108624218A (en) Resin combination
TW201144346A (en) Epoxy resin composition for circuit board, prepreg, laminate, resin sheet, laminated base material for printed wiring board, printed wiring board and semiconductor device
CN106010421A (en) Adhesive composition, film adhesive, adhesive layer, adhesive sheet, copper-clad laminate, wiring board and printing circuit board
CN1311042C (en) Thermosetting adhesive composition and adhesive band used said composition for electronic member
JP2001234020A (en) Resin composition, adhesive film, metallic foil-adhered adhesive film using the resin composition, circuit board and mounted structure
JP4174274B2 (en) Polyamideimide resin, resin composition containing the same, coating material for electronic parts, and adhesive for electronic parts
CN108727942A (en) Resin combination
TW200846412A (en) Thermosetting resin composition and method for manufacturing printed circuit substrate using the same
TW202200658A (en) Resin composition, resin paste, cured product, resin sheet, printed wiring board, semiconductor chip packaging, and semiconductor device wherein the resin composition contains an epoxy resin and a curing agent
CN108864924A (en) A kind of halogen-free resin composition and the flexible printed-circuit board cover film prepared with it
TW201022029A (en) Shield film and shielded circuit board
TW200904268A (en) Metal foil plated laminated board and printed wiring board
JP4828772B2 (en) Polyamideimide resin and adhesive composition using the same
TWI290945B (en) Application of electrical material in high frequency and manufacturing method of the same
JP2006232984A (en) Adhesive composition, and coverlay film and adhesive sheet obtained using the same
JP2006028521A (en) Addhesive for circuit connection

Legal Events

Date Code Title Description
MM4A Annulment or lapse of patent due to non-payment of fees