1374923 九、發明說明： 【發明所屬之技術領域】 本發明關於一種用於膨脹板之黏著性樹脂，其具有長期穩定性 且於室溫下不產生交聯反應，該樹脂係使用相互反應性共聚物而 製備，另關於一種膨脹板（熱剝離性黏著板），其於高溫下可輕 易地自基材剝離且利用該黏著性樹脂而具有優異的黏著強度。 【先前技術】 φ 使用於膨脹板之傳統的黏著性樹脂，係包含丙烯基單體（acryl monomer)及其他含有羥基的單體作為交聯官能基之共聚物樹脂， 且該黏著性樹脂一般係藉由利用異氰酸酯交聯劑所製備。近來電 / 氣δ又備中所應用的膨脹板需於至少150°C之高溫下膨服。然而，因 用於膨脹板之微球（其係於高溫下膨脹）自l50〇c開始膨脹，因此 該微球於高溫下的使用受到限制。這限制可藉由利用具有高内聚 力或承載力的黏著性樹脂以抑制微球之膨脹而解決，或可藉由乙 烯基形成的黏著性樹脂之化學結構而調整，雖然此非易事。 因此，較佳的疋修改考慮到黏著力、内聚力、财熱性、柔軟度、 及彈生的父聯方法。至於用於膨脹板之傳統的黏著性樹脂，需花 費長時間以製造經完全混合及分散的微球。於此製程期間，所添 加的父聯劑係緩慢地反應而增加黏度或導致凝膠化造成塗層中 的缺特疋5之，為抑制微球膨脹而提高的交聯程度，係引起 更多嚴重的問題。 用於熱剝離性膨脹板之傳統黏著性樹脂，係含有—交聯官能基 之以丙烯基為主的樹脂。因此，於添加交聯劑之後，於微球之混 6 1374923 合、分散及塗覆期間交聯反應緩慢地進行而改變黏度，導致不規 則的塗覆。此現象隨著增加用於提高交聯程度的交聯官能基之比 率而變得更顯著。 【發明内容】 <技術問題> 使用本發明黏著性樹脂而設計以解決上述問題的膨脹板，可應 用於下列領域：於高溫下執行或重複執行的製程中，柔性印刷電 • 路板（flexible printed circuit board，FPCB )黏附/剝離、半導體晶 圓研磨、半導體晶片、晶片電容器、晶片壓敏電阻器及晶片電感 器等之製造程序中零件之電極印刷、定影、切割及熱黏附/剝離等。 為克服上述問題，本發明人研究且確認，以相互反應性共聚物 共同處理一含有微球之黏著性樹脂可延長足夠的工作壽命且甚至 ' 於在混合2至3天後仍不引起黏度的改變。發明人根據此發現而 完成本發明。 精確地說，本發明人發現可藉由二種官能基之反應，即羧基及 • 噁唑啉基，引起醯胺-酯之化學交聯且同時引起如氫鍵之物理交 聯。本發明人更確認，提高交聯程度會造成交聯密度及内聚力之 增加，其可使微球於較高溫度下膨脹從而促進高溫膨脹而使黏著 層起泡或膨服。 因此，此熱剝離性黏著板具有的優點是：藉由在較高於微球之 一般膨脹溫度的溫度下膨脹黏著層中所含的微球，以減少黏著力 而可自該基材容易地分離該黏著板。特定言之，於至少15(TC之高 溫下或於重複高溫下之膨脹，會連續地降低膨脹板之膨脹溫度， 7 1374923 該重複高溫意指當於高溫加熱且冷卻，接著再於高溫下加熱之重 複程序。因此，需要可於高溫下膨脹之膨脹板。本發明之一目的 為提供此用途之黏著劑。 本發明黏著性樹脂於室溫下係高度穩定，該黏著性樹脂藉由混 合具有羧基及噁唑啉基作為官能基之相互反應性共聚物而製得。 該共聚物係於100°c或更高之溫度下反應形成酯-醯胺鍵，產生交 聯。因此，當微球膨脹時，黏著劑之内聚力及彈性增加而提高微 球之膨脹溫度。因此，本發明提供一熱剝離性黏著板，其具有優 異的早期黏著強度且成功地維持承載力，且僅當於高溫下加熱處 理時，才可能有黏著強度降低或喪失之情形。 帶來上述效應之本發明黏著劑，係藉由混合二種相互反應性之 共聚物溶液所製造，第一為一含羧基之共聚物且第二為一含噁唑 啉基之共聚物。於此時，室溫下不會引起交聯，意指於室溫下長 期儲存該共聚物溶液係相當安全的，且當於約100°c下引起該交聯 時，該共聚物溶液則促進具有高密度黏著層之膨脹板的生產。 本發明亦藉由利用一黏著劑以提供一在至少150°c之高溫下膨 脹的膨脹板，該黏著劑係藉由混合分別含有羧基及噁唑啉基（相 互反應性基團）的二種丙烯基共聚物所製造，及提供藉由分散微 球所製造而用於膨脹板之塗覆樹脂。 <技術手段〉 本發明關於一種用於膨脹板之黏著性樹脂及一種利用該黏著性 樹脂之膨脹板，該黏著性樹脂係利用相互反應性共聚物而製備。 於此，該黏著性樹脂之特徵在於藉由混合含熱膨脹性微球之相互 8 1374923 反應性共聚物而製備。塗覆該由此製備的黏著性樹脂，以於一基 材之一側或二侧形成一黏著層以製備該膨脹板（熱制離性黏著 板），其中該黏著層藉由熱而起泡或膨脹。 此後，詳細描述本發明之黏著性樹脂及利用該黏著性樹脂之膨 服板。 本發明黏著性樹脂之特徵在於包含熱膨脹性微球及相互反應性 共聚物。 I 該熱膨脹性微球係一物質，其可促進氣化作用的物質且具熱膨 脹性，如異丁烧、丙烧、及戊烧。該微球之外殼係由熱可溶性物 質或熱膨脹性物質所構成，如偏二氣乙烤、丙稀腈、及甲基丙婦 酸甲s旨等共聚物。市場上銷售各種微球，視外殼成份及厚度而具 100至170°c之不同膨脹溫度。然而，上述溫度係最高膨脹溫度且 膨脹膨脹之溫度係低於該最高膨脹溫度20至50eC。 為分散於黏著性樹脂中，微球之平均直徑較佳為10至25微米， 且其黏著層可輕易地以熱來減少黏著強度而改質。較佳的是，經 # 乾燥膨脹黏著層之厚度係大於該熱膨脹性微球之最大直徑，以使 該黏著層之表面平滑且穩定地確保於熱處理之前之黏著強度。 為利用藉熱處理所得之黏著板黏著強度的減少，在以1 〇倍的體 積膨脹速率膨脹之後，該熱膨脹性微球最好不產生破碎。該熱膨 服性微球之含量，係由考量黏著層之膨脹速率或所減少黏著強度 之幅度而決定。一般而言，較佳之微球含量係5至20重量份，以 1 〇〇重里伤之形成黏著層的黏著性樹脂計。 另一方面’該扮演分散該微球角色之相互反應性共聚物，係包 9 1374923 含第一共聚物及第二共聚物之樹脂，該第一共聚物藉由乙烯基單 體、共聚單體及含有羧基之單體的共聚合反應所製備，該第二共 聚物則藉由乙烯基單體、共聚單體及含有噁唑啉基之單體的共聚 合反應所製備。 構成第一共聚物及第二共聚物的乙歸基單體及乙稀基共聚單體 並無限制，但為增加該膨脹板之黏著力、内聚力、耐熱性、及柔 軟度，較佳係選自以下群組：含有炫基的乙稀基單體如丙稀酸甲 •酯、甲基丙烯酸甲酯、丙烯酸乙酯、甲基丙烯酸乙酯、丙烯酸丙 酿、甲基丙烯酸丙酯、丙烯酸丁酯、甲基丙浠酸丁酯、丙烯酸己 酉盲、甲基丙烯酸己酯、丙烯酸辛酯及2-乙基己基丙烯酸酯；含有 羥基的乙烯基單體如羥乙基丙烯酸酯、羥乙基曱基丙烯酸酯、羥 丙基丙稀酸酯、經丙基甲基丙稀酸酯、經丁基丙締酸酯、經丁基 ’ 曱基丙烯酸酯、羥己基丙烯酸酯及羥己基甲基丙烯酸酯；N-取代 醯胺乙烯基單體如N，N-二甲基丙烯醯胺或Ν,Ν-二甲基甲基丙烯醯 胺；烷氧基烷基丙烯酸酯乙烯基單體如甲氧基乙基丙烯酸酯、甲 φ 氧基乙基甲基丙烯酸酯、乙氧基乙基丙烯酸酯及乙氧基乙基甲基 丙烯酸酯；乙烯基單體如乙酸乙烯酯、丙酸乙烯酯、Ν-乙烯基吡 咯烷酮、甲基乙烯基吡咯烷酮、乙烯基吡啶、乙烯基哌啶酮、乙 烤基喷°定、乙稀基派。秦（vinylpiperazine )、乙烯基0比。桊 (vinylpyrazine) '乙烯基°比11各、乙烯基咪。坐、乙烯基。惡唑、乙稀 基嗎啉、N-乙烯基甲醯胺、苯乙烯、α-甲基苯乙烯及N-乙烯基己 内醯胺；氰基丙烯酸酯乙烯基單體如丙烯腈或甲基丙烯腈；含有 環氧基的丙烯酸單體如丙烯酸縮水甘油酯及甲基丙烯酸縮水甘油 1374923 醋；乙一醇丙稀酸醋早體如聚乙二醇丙烤酸醋、聚乙二醇甲基丙 烯酸酯、聚丙二醇丙烯酸酯、聚丙二醇曱基丙烯酸酯、甲氧基乙 二醇丙烯酸酯、甲氧基聚乙二醇曱基丙烯酸酯、甲氧基聚丙二醇 丙稀酸酯及甲氧基聚丙二醇甲基丙埽酸酯；丙婦酸酯單體如四氫 糠基丙烯酸酯、四氫糠基甲基丙烯酸酯及2_甲氧基乙基丙烯酸 酯；如異戊二烯、丁二烯、異丁烯、乙烯基醚的單體；以及前述 至少二者之混合物。 ^ 構成含有羧基的第一共聚物及含有噁唑啉基的第二共聚物之乙 烯基單體及共聚單體，其較佳含量係該黏著性樹脂之總重量的8〇 至95重量％。如果該乙烯基單體及共聚單體之含量低於重量 %，交聯官能基之含量將增加而帶來高交聯，造成黏著力之降低或 喪失並產生脆性。以此等具高極性官能基之單體所進行之共聚合 . 反應，由於極性及反應速率之不同，將使聚合反應速率或該共聚 物之組成比難以控制。該乙烯基共聚單體可為前述單體之至少二 者之混合物或為任何習知的乙烯基共聚單體，其可藉由調整其含 • 量而增加該黏著性樹脂之特性。 為增加交聯程度，含有羧基的第一共聚物係以溶液聚合反應來 衣備尤其至少二或三種單體之共聚合反應，該單體選自以下群 組.含有羧基的單體如丙烯酸、曱基丙烯酸、羧乙基丙烯酸酯、 羧戊基丙烯酸酯、衣康酸、順丁烯二酸、反丁烯二酸及巴豆酸； 以及k針單體如順丁烯二酸酐及衣康酸酐。 為形成該共聚物之交聯官能基，較佳係以該共聚物之總單體 3有5至20重量％之含有羧基的乙烯基單體，且更佳係$至 1374923 ^重量％。如果該含有羧基的乙烯基單體之含量低於5重量％，交 聯程度將不足，致使薄膜之柔軟度增加但内聚力減少，意謂無法 控制微球之膨脹》[Technical Field] The present invention relates to an adhesive resin for an expansion plate which has long-term stability and does not cause a crosslinking reaction at room temperature, and the resin uses mutual reactive copolymerization. It is prepared by an object, and is also related to an expanded plate (heat-peelable adhesive sheet) which can be easily peeled off from a substrate at a high temperature and which has excellent adhesive strength by using the adhesive resin. [Prior Art] φ The conventional adhesive resin used for the expansion plate is a copolymer resin containing an acryl monomer and other hydroxyl group-containing monomers as a crosslinking functional group, and the adhesive resin is generally It is prepared by using an isocyanate crosslinking agent. The near-incoming/gas δ-prepared expansion plate needs to be extruded at a high temperature of at least 150 °C. However, since the microspheres used for the expansion plate, which expand at a high temperature, start to expand from l50〇c, the use of the microspheres at high temperatures is limited. This limitation can be solved by suppressing the expansion of the microspheres by using an adhesive resin having a high cohesive force or a bearing capacity, or can be adjusted by the chemical structure of the adhesive resin formed of vinyl, although this is not an easy task. Therefore, the preferred 疋 modification takes into account adhesion, cohesion, finer, softness, and the father-in-law method of bombing. As for the conventional adhesive resin for the expansion plate, it takes a long time to manufacture the fully mixed and dispersed microspheres. During this process, the added parent-linking agent reacts slowly to increase the viscosity or causes gelation to cause a defect in the coating, and the degree of crosslinking which is increased to inhibit the expansion of the microspheres causes more serious problem. The conventional adhesive resin used for the heat-peelable expansion sheet is a propylene-based resin containing a cross-linking functional group. Therefore, after the addition of the crosslinking agent, the crosslinking reaction proceeds slowly during the mixing, dispersion and coating of the microspheres to change the viscosity, resulting in irregular coating. This phenomenon becomes more remarkable as the ratio of the crosslinking functional groups for increasing the degree of crosslinking is increased. [Technical Problem] <Technical Problem> An expansion plate which is designed to solve the above problems by using the adhesive resin of the present invention can be applied to the following fields: a flexible printed electric circuit board in a process which is performed at a high temperature or repeatedly performed ( Flexible printed circuit board, FPCB) electrode printing, fixing, cutting, and thermal adhesion/peeling of parts in manufacturing processes such as adhesion/peeling, semiconductor wafer polishing, semiconductor wafers, wafer capacitors, wafer varistors, and chip inductors . In order to overcome the above problems, the inventors have studied and confirmed that co-processing a microsphere-containing adhesive resin with a mutually reactive copolymer can extend a sufficient working life and even not cause viscosity after mixing for 2 to 3 days. change. The inventors have completed the present invention based on this finding. Specifically, the inventors have found that the chemical cross-linking of the indoleamine-ester can be caused by the reaction of two functional groups, i.e., the carboxyl group and the oxazoline group, and at the same time cause physical crosslinking such as hydrogen bonding. The present inventors have further confirmed that increasing the degree of crosslinking causes an increase in crosslink density and cohesive force, which allows the microspheres to swell at a higher temperature to promote high temperature expansion to cause foaming or swelling of the adhesive layer. Therefore, the heat-peelable adhesive sheet has the advantage that the microspheres contained in the adhesive layer are expanded at a temperature higher than the general expansion temperature of the microspheres to reduce the adhesion and can be easily obtained from the substrate. The adhesive sheet is separated. In particular, at least 15 (expansion of TC at high temperatures or repeated high temperatures will continuously reduce the expansion temperature of the expansion plate, 7 1374923. This repeated high temperature means heating at a high temperature and cooling, followed by heating at a high temperature. The procedure is repeated. Therefore, an expansion plate which can be expanded at a high temperature is required. One of the objects of the present invention is to provide an adhesive for this purpose. The adhesive resin of the present invention is highly stable at room temperature, and the adhesive resin has a mixture by mixing A carboxyl group and an oxazoline group are prepared as a mutually reactive copolymer of a functional group. The copolymer is reacted at a temperature of 100 ° C or higher to form an ester-melamine bond to cause crosslinking. Therefore, when the microsphere is used When expanding, the cohesive force and elasticity of the adhesive increase to increase the expansion temperature of the microspheres. Therefore, the present invention provides a heat-peelable adhesive sheet which has excellent early adhesion strength and successfully maintains the bearing capacity, and only at high temperatures. In the case of heat treatment, there is a possibility that the adhesive strength is lowered or lost. The adhesive of the present invention which brings about the above effects is obtained by mixing two kinds of mutually reactive copolymer solutions. Manufactured, the first is a carboxyl group-containing copolymer and the second is an oxazoline group-containing copolymer. At this time, no crosslinking is caused at room temperature, which means long-term storage of the copolymer solution at room temperature. It is quite safe, and when the crosslinking is caused at about 100 ° C, the copolymer solution promotes the production of an expanded sheet having a high-density adhesive layer. The present invention also provides an at least by using an adhesive. An expanded plate expanded at a high temperature of 150 ° C, which is produced by mixing two kinds of propylene-based copolymers each containing a carboxyl group and an oxazoline group (reactive group), and by dispersing the microspheres The present invention relates to an adhesive resin for an expansion plate and an expansion plate using the adhesive resin, which utilizes mutual reactive copolymerization. The adhesive resin is prepared by mixing the heat-expandable microspheres with the mutual 8 1374923 reactive copolymer. The adhesive resin thus prepared is coated on a substrate. One side or An adhesive layer is formed on both sides to prepare the expanded plate (heat-separable adhesive sheet), wherein the adhesive layer is foamed or expanded by heat. Hereinafter, the adhesive resin of the present invention and the adhesive resin are used in detail. The adhesive resin of the present invention is characterized by comprising heat-expandable microspheres and a mutually reactive copolymer. I. The heat-expandable microsphere is a substance which promotes gasification and has thermal expansion properties such as isobutylene. The shell of the microsphere is composed of a heat-soluble substance or a heat-expandable substance, such as a second-air bake, a acrylonitrile, and a methyl acetoacetate. Various microspheres are sold on the market, and have different expansion temperatures of 100 to 170 ° C depending on the composition and thickness of the outer casing. However, the temperature is the highest expansion temperature and the temperature of expansion and expansion is lower than the maximum expansion temperature by 20 to 50 eC. In the adhesive resin, the average diameter of the microspheres is preferably from 10 to 25 μm, and the adhesive layer can be easily modified by heat to reduce the adhesive strength. Preferably, the thickness of the dry-expanded adhesive layer is greater than the maximum diameter of the heat-expandable microspheres, so that the surface of the adhesive layer smoothly and stably ensures the adhesive strength before heat treatment. In order to utilize the reduction in the adhesive strength of the adhesive sheet obtained by the heat treatment, it is preferable that the heat-expandable microspheres are not broken after being expanded at a volume expansion rate of 1 〇. The content of the heat-expandable microspheres is determined by considering the expansion rate of the adhesive layer or the magnitude of the reduced adhesive strength. In general, the preferred microsphere content is from 5 to 20 parts by weight based on 1 gram of the adhesive resin forming the adhesive layer. On the other hand, 'this acts as a mutually reactive copolymer that disperses the role of the microspheres, and is a resin containing a first copolymer and a second copolymer, which comprises a vinyl monomer, a comonomer It is prepared by copolymerization of a monomer having a carboxyl group, and the second copolymer is prepared by copolymerization of a vinyl monomer, a comonomer, and a monomer containing an oxazoline group. The ethylenic monomer and the ethylene-based comonomer constituting the first copolymer and the second copolymer are not limited, but in order to increase the adhesion, cohesion, heat resistance and softness of the expanded plate, it is preferred to select From the following groups: Ethyl-based monomers containing thiol such as methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, acrylic acid, propyl methacrylate, acrylic acid Ester, butyl methacrylate, hexamethylene acrylate, hexyl methacrylate, octyl acrylate and 2-ethylhexyl acrylate; hydroxyl-containing vinyl monomers such as hydroxyethyl acrylate, hydroxyethyl Mercapto acrylate, hydroxypropyl acrylate, propyl methacrylate, butyl propionate, butyl ' mercapto acrylate, hydroxyhexyl acrylate and hydroxyhexyl methacrylate Ester; N-substituted guanamine vinyl monomer such as N,N-dimethyl acrylamide or hydrazine, hydrazine-dimethyl methacrylamide; alkoxyalkyl acrylate vinyl monomer such as methoxy Ethyl acrylate, methyl oxyethyl methacrylate, ethoxyethyl acrylate Ester and ethoxyethyl methacrylate; vinyl monomers such as vinyl acetate, vinyl propionate, Ν-vinyl pyrrolidone, methyl vinyl pyrrolidone, vinyl pyridine, vinyl piperidone, B-baked Base spray °, ethylene base. Qin (vinylpiperazine), vinyl 0 ratio.桊 (vinylpyrazine) 'Vinyl ° ratio of 11 each, vinyl microphone. Sitting, vinyl. Oxazole, ethyl morpholine, N-vinylformamide, styrene, α-methylstyrene and N-vinyl caprolactam; cyanoacrylate vinyl monomers such as acrylonitrile or methyl Acrylonitrile; epoxy group-containing acrylic monomers such as glycidyl acrylate and glycidyl methacrylate 1374923 vinegar; acetyl acrylate vinegar precursors such as polyethylene glycol propylene vinegar, polyethylene glycol methacrylate Ester, polypropylene glycol acrylate, polypropylene glycol methacrylate, methoxy ethylene glycol acrylate, methoxy polyethylene glycol methacrylate, methoxy polypropylene glycol acrylate and methoxy polypropylene glycol Methyl propyl phthalate; propyl acrylate monomers such as tetrahydrofurfuryl acrylate, tetrahydrofurfuryl methacrylate and 2-methoxyethyl acrylate; such as isoprene, butadiene, a monomer of isobutylene, vinyl ether; and a mixture of at least two of the foregoing. The vinyl monomer and the comonomer constituting the first copolymer containing a carboxyl group and the second copolymer containing an oxazoline group are preferably contained in an amount of from 8 Å to 95% by weight based on the total mass of the viscous resin. If the content of the vinyl monomer and comonomer is less than % by weight, the content of the crosslinking functional group will increase to cause high crosslinking, resulting in a decrease or loss of adhesion and brittleness. Copolymerization by a monomer having such a highly polar functional group. The reaction, depending on the polarity and the reaction rate, makes it difficult to control the polymerization rate or the composition ratio of the copolymer. The vinyl comonomer can be a mixture of at least two of the foregoing monomers or any conventional vinyl comonomer which can increase the properties of the adhesive resin by adjusting its content. In order to increase the degree of crosslinking, the first copolymer containing a carboxyl group is subjected to a solution polymerization reaction to prepare a copolymerization reaction of at least two or three monomers selected from the group consisting of a carboxyl group-containing monomer such as acrylic acid. Mercaptoacrylic acid, carboxyethyl acrylate, carboxypentyl acrylate, itaconic acid, maleic acid, fumaric acid and crotonic acid; and k-needle monomers such as maleic anhydride and itaconic anhydride . To form the crosslinking functional group of the copolymer, it is preferred that the total monomer 3 of the copolymer has 5 to 20% by weight of a vinyl monomer having a carboxyl group, and more preferably from $1 to 1374923% by weight. If the content of the carboxyl group-containing vinyl monomer is less than 5% by weight, the degree of crosslinking will be insufficient, resulting in an increase in the softness of the film but a decrease in cohesive force, meaning that the expansion of the microspheres cannot be controlled.
為增加交聯程度，含有噁唑啉基的第二共聚物係以溶液聚合反 應來製備，尤其二或多種化合物之共聚合反應，該化合物選自以 下群組：2-乙烯基-2-噁唑啉、2-乙烯基-4-乙烯基噁唑啉、2-乙 稀基5乙稀基-2-°·惡唾琳、2-異丙稀基-2-0惡唾琳、2·異丙婦基_5· 乙基·2-噁唑啉、2·異丙烯基-5·甲基·2·噁唑啉、2 (乙烯节氧基小 曱基乙基)·2-射咕、2-(2-經基小曱基乙基）丙稀酸醋、及2 (2•經 基-1-曱基乙基）甲基丙烯酸酯。 以該共聚物之總單體計，較佳係添加5至2G重量％構成該共聚 物之含有㈣魏的乙稀基單體，且更佳係5 S1G重量％。如果 該含有料㈣的乙職單體之含量低於5重量％，触聯之程度 心足，致使薄膜之錄度增加㈣聚力減少，意謂無法控制微 球之膨服β 利用相互反應性共聚物所製備之本發·於膨脹板之點著性樹 二了下三個步驟製備。步驟1中，合成含娜的第一丘 I物。4 2中，合成含有噁唑啉基的第二共 :微球分散於包含第一及第二共聚物的黏著性樹脂二二 步驟所生產的黏著性樹脂係一非常穩^ 覆溶液，且可使膨脹溫度增力以至崎或更^時間過程改變的塗 一面上以形成—黏著層’該㈣層係、以-離型膜 12 1374923 (releasing film)塗覆。於此時，為增加該基材及該黏著層之間的 黏著力，可包含表面處理製程。第丨圖係一剖面圖，說明本發明 之膨脹板之實例，該膨脹板由基材（1)、表面處理層（2)、藉由相互 反應性共聚物之混合物所製備的膨脹黏著層、及離型膜(句所組 • 成。 <有利功效> 該利用相互反應性共聚物混合物的黏著性溶液，可促進具優異 • 穩定性且用於膨脹板之黏著性樹脂之生產，該混合物由依據本發 明之具有羧基的第一共聚物及含有噁唑啉基的第二共聚物所組 成。 於具高反應性之交聯劑的其他樹脂溶液的情況中，以二種液體 之方式製備該溶液’該等液體於使用為黏著性樹脂之前方才恩 • 合。於此情況下，除具有不方便之缺點外，亦具有難以均勻塗覆 或將其本身塗覆於一基材上之缺點，因為該黏著性樹脂之官能基 與該交聯劑之反應或凝膠化。如果經塗覆而厚度發生改變，則表 示该膨脹板特性上的嚴重偏差。然而，該各自含有叛基及D惡哇琳 基的相互反應性共聚物混合物於室溫下不引起任何反應，素謂含 有該共聚物的黏著性樹脂於室溫下係穩定的、於該黏著性樹脂特 性中具微小偏差。 此外，共聚物交聯劑之使用會引起物理鍵結的形成，如氫鍵， 且增加樹脂中的交聯密度’造成内聚力及承載力之增加而抑制微 球之膨脹，此表示膨脹溫度可提高20至3〇。(：。 【實施方式】 13 丄J/4923 本發明之上収其他目的、㈣及域將藉町較佳的實施方 式及同時隨附的圖式而變得顯而易見。 <最佳方式> : 於以下所顯示的實例中說明本發明之實際的及目前較佳的實施 方式。 然而，將領會本技術領域中熟習此技術者細察本案揭示内容， 可於本發明之精神及範圍内作出修改及改良。 φ [製造實例1] 步轉1:第一共聚物之製備 添加作為單體之丙稀酸乙醋（45克）、作為共聚單體之丙稀酸 正丁酯（45克）及丙烯酸（10克）至一 2升玻璃反應器中並混合， 該玻璃反應器裝有攪拌器、冷凝器、滴液漏斗、溫度計及夾套。 添加溶解於乙酸乙酯（100克）及曱苯（20克）中的α，α，偶氮二 異丁腈（引發劑，0.01克）至該反應器中，接著於7(rc下進行自 由基聚合反應。約30分鐘之後’混合丙稀酸乙酯（135克）、丙 # 烯酸正丁酯（共聚單體，135克）及丙烯酸（30克），並利用滴 液漏斗’於其中滴加溶解於乙酸乙酯（10〇克）及甲笨（4〇克） 中的α，α’-偶氮二異丁腈（引發劑，〇.〇5克）歷時90分鐘。於滴 加期間，維持溫度。該反應完成後，滴加溶解於乙酸乙酯（50克） 及乙醇（50克）中的自由基引發劑（1克），歷時60分鐘以消除 未經反應的單體。額外多引發該反應3小時以產生第一共聚物。 步驟2 :第二共聚物之製備 添加作為單體之丙烯酸乙酯（45克）、作為共聚單體之丙烯酸 1374923 正丁酯（45克）及2-異丙烯基·2·噁唑啉（10克）至一 2升玻璃反 應器中並混合’該玻璃反應器裝有攪拌器、冷凝器、滴液漏斗、 溫度計及夾套。添加溶解於乙酸乙酯（1〇〇克）及甲笨（2〇克） • 中的α，α’_偶氮二異丁腈（引發劑，0.01克）至該反應器中，接著 • 藉由如上述含有羧基的共聚物之聚合反應_所描述的相同方式於 C下進行自由基聚合反應。約3〇分鐘之後，混合丙烯酸乙酯（〗35 克）、丙烯酸正丁酯（共聚單體，135克）及丙烯酸（3〇克）， Φ 並利用滴液漏斗，於其中滴加溶解於乙酸乙酯（100克）及甲苯（40 克）中的α，α’-鸽氮二異丁腈（引發劑，〇〇5克）歷時9〇分鐘。 於滴加期間’維持溫度。該反應完成後，滴加—溶解於乙酸己醋 (5〇克）及乙醇（50克）中的自由基引發劑（1克），歷時60 分鐘以消除未觀應的單體。額❹歸城應3小相產生第 二共聚物。 步驟3 : —黏著性樹脂之製備 以1 . 1之重量比混合該兩個共聚物樹脂，即步驟^及步驟2中 所製備的第一及第二共聚物。禾 ^ Τ勿添加微球F-·(松本油脂製藥株 式會杜，發始膨脹溫度：100至丨 ,,士、 〇5C) (10克）至該樹脂混合物 (100克），接著藉由分散以提供_黏著性樹脂。 [製造實例2] =物"中所描述的相同方式製備該黏著性樹脂但 丙烯酸之重量比為4.5/4.5/1.5。 [製造實例3] 15 1374923 藉由如製造實例1中所描述的相同方式製備該黏著性樹脂，但 於製造實例1之步驟1中調整所使用單體丙稀酸乙_酸正丁 酯/丙烯酸之重量比為4.5/4.5/0.6。 [製造實例4] 藉由如製造實例1中所描述的相同方式製備該黏著性樹脂但 於使用微球F-80GSD (松本油脂製藥株式會社，開始膨服溫度： uo至115。(；）以取代製造實例i之步驟3中所使用的微球f_5〇d。 ^ [製造實例5] 藉由如製造實例1中所描述的相同方式製備該黏著性樹脂除 了使用微球F.8GVSD (松本油脂製藥株式會社，開始膨服溫度： 150至16(TC )代替製造實例i之步驟3中所使用的微球F 5〇D。 [實例1至5] 各自將製造實例1至5中所製備的黏著性樹脂塗覆於聚對笨二 甲酸乙一 S旨薄膜（PET薄膜）（50微米）上，以形成一 37微米厚 的膨脹黏著層。層壓一 36微米的離型膜至該黏著層以產生一膨脹 • 板。老化該膨脹板歷時7天，接著做最後測試。 [比較製造實例1] 添加丙烯酸乙酯（48.5克）、丙烯酸正丁酯（48.5克）、丙豨 酸（2克）及羥丙基丙烯酸酯（1.0克）至一 2升玻璃反應器中並 混合’該玻璃反應器裝有攪拌器、冷凝器、滴液漏斗、溫度計及 夾套。藉由利用滴液漏斗添加溶解於乙酸乙酯（160克）及曱苯（270 克）中的ct，a’-偶氮二異丁腈（引發劑’ 0.01克）至該反應器中， 接著進行氮取代反應。於回流期間，持續於80°C下滴加，接著進 1374923 行自由基聚合反應歷時8小時。於該反應之後期階段中，添加過 量之自由基引發劑以消除未經反應的單體。接著，添加微球f_5〇d (松本油脂製藥株式會社，開始膨脹溫度：1〇〇至l〇5〇c)且經分 散而產生一黏著性樹脂。 [比較製造實例2] 精由如比較製造實例1中所描述的相同方式製備該黏著性樹 脂’但增加具有交聯官能基的羥丙基丙烯酸酯之量（2 〇克），相 I 較於比較製造實例1中的量。 [比較製造實例3] 藉由如比較製造實例1中所描述的相同方式製備該黏著性樹 脂，但使用微球F-80GSD (松本油脂製藥株式會社，開始膨脹溫 度：110 至 115°C )。 ' [比較製造實例4] 藉由如比較製造實例1中所描述的相同方式製備該黏著性樹 脂，但使用微球F-80VSD (松本油脂製藥株式會社，開始膨脹溫 φ 度：150 至 16(TC )。 [比較實例1至4] 以該黏著性樹脂之羥基（官能基）之雙倍量，添加AK—75 (愛 敬化學有限公司），異氰酸酯交聯劑，至各個比較製造實例1至4 中所製備的黏著性樹脂中，接著藉由攪拌而產生一點著性樹脂。 塗覆該黏著性樹脂於PET薄膜（50微米）上以形成—37微求厚 的膨脹黏著層《層壓一 36微米的離型膜至該黏著層以產生一膨脹 板。老化該膨脹板歷時7天，接著做最後測試。 17 1374923 製造實例1至5及比較製造實例1至4係總結於表1中。該製 造實例、實例、及比較製造實例中所製備的黏著性樹脂及膨脹板 之物理性質係經如下測試且結果示於表2及表3中。 1. 黏著性樹脂之黏度改變 於一固定溫度下放置該經製備的黏著性樹脂至一具防止溶劑之 蒸發的容器中，且藉由使用布氏黏度計（DV-II+ )隨時間測量黏 度。 2. 膨脹溫度 藉由於10°C/分鐘之速度下使用珀金·埃爾默之DSC 7測量膨脹 溫度。特定言之，塗覆該含有微球的黏著性樹脂於pET薄膜上， 接著產生老化。交聯完成後，自該薄臈取得樣本。以經調整的溫 度放置10毫米厚的不鏽鋼板於熱板片上。使溫度相同之後，將膨 脹板放置於中間，接著測量膨脹溫度。比較所獲得的溫度與溫度 計測量的溫度。 3·黏著強度 以異丙醇徹底清洗測試板（SUS 3〇4)(厚度2毫米，寬度5〇 毫米、長度200毫米），藉由以3〇公分/分鐘之速度使用2公斤自 動壓力橡膠滚筒以該黏著層朝下的方式與寬度2()毫米及長度15〇 毫米之熱剥純黏著板（實例及比較實例中所得的）黏附，且來To increase the degree of crosslinking, the second copolymer containing an oxazoline group is prepared by solution polymerization, especially a copolymerization of two or more compounds selected from the group consisting of 2-vinyl-2-oxo Oxazoline, 2-vinyl-4-vinyloxazoline, 2-ethylene 5-vinyl-2-(Ethylpyrazine), 2-isopropyls-2-0 oxalate, 2· Isopropyl group _5·ethyl·2-oxazoline, 2·isopropenyl-5·methyl·2·oxazoline, 2 (ethylene ethoxylated fluorenylethyl)·2-fluorene , 2-(2-pyridyl decylethyl) acrylate vinegar, and 2 (2•yl-1-ylethyl) methacrylate. It is preferred to add 5 to 2 g% by weight based on the total monomer of the copolymer to constitute a vinyl group-containing monomer containing (iv) Wei, and more preferably 5 S1 G weight%. If the content of the monomer contained in the material (4) is less than 5% by weight, the degree of contact is sufficient, resulting in an increase in the degree of filming (4) reduction in cohesion, meaning that the expansion of the microspheres cannot be controlled. The hair prepared by the copolymer was prepared in the next three steps on the point of the expansion board. In step 1, the first hilly substance containing Na is synthesized. 4 2, synthesizing a second total of oxazoline groups: the microspheres are dispersed in an adhesive resin comprising the first and second copolymers, and the adhesive resin is a very stable solution, and The expansion temperature is increased to apply to the coated side of the coating or the time course to form an adhesive layer. The (four) layer is coated with a release film 12 1374923 (releasing film). At this time, in order to increase the adhesion between the substrate and the adhesive layer, a surface treatment process may be included. BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a cross-sectional view showing an example of an expansion plate of the present invention comprising a substrate (1), a surface treatment layer (2), an expanded adhesive layer prepared by a mixture of mutually reactive copolymers, And a release film (sentence group; < advantageous effect> The adhesive solution using a mixture of mutually reactive copolymers can promote the production of an adhesive resin having excellent stability and used for an expansion plate, The mixture is composed of a first copolymer having a carboxyl group and a second copolymer containing an oxazoline group according to the present invention. In the case of other resin solutions having a highly reactive crosslinking agent, in the form of two liquids The solution is prepared. The liquids are used before being used as an adhesive resin. In this case, in addition to the inconvenience, it is difficult to uniformly coat or apply itself to a substrate. Disadvantage, because the functional group of the adhesive resin reacts or gels with the cross-linking agent. If the thickness is changed by coating, it indicates a serious deviation in the characteristics of the expanded plate. However, the respective rebellion And the cross-reactive copolymer mixture of D-wowyl group does not cause any reaction at room temperature, and the adhesive resin containing the copolymer is stable at room temperature and has slight deviation in the properties of the adhesive resin. In addition, the use of the copolymer cross-linking agent causes the formation of physical bonds, such as hydrogen bonding, and increases the cross-linking density in the resin, resulting in an increase in cohesive force and bearing capacity and inhibiting the expansion of the microspheres, which means that the expansion temperature can be Increasing 20 to 3 〇. (Embodiment) 13 丄J/4923 The present invention is based on other objects, (4) and the domain will be better understood by the preferred embodiment of the borrowing town and the accompanying drawings. Best Modes: The actual and presently preferred embodiments of the present invention are described in the examples shown below. However, it will be appreciated that those skilled in the art will appreciate the disclosure of the present invention. Modifications and improvements within the spirit and scope of the invention. φ [Manufacturing Example 1] Step 1: Preparation of the first copolymer Adding ethyl acetoacetate (45 g) as a monomer, and acrylic acid as a comonomer Butyl ester 45 g) and acrylic acid (10 g) to a 2 liter glass reactor equipped with a stirrer, condenser, dropping funnel, thermometer and jacket. Add dissolved in ethyl acetate (100 g) And α,α, azobisisobutyronitrile (initiator, 0.01 g) in toluene (20 g) to the reactor, followed by free radical polymerization at 7 (rc. After about 30 minutes) Ethyl acrylate (135 g), n-butyl acrylate (comon monomer, 135 g) and acrylic acid (30 g) were mixed and dissolved in ethyl acetate (10) using a dropping funnel. α,α'-azobisisobutyronitrile (initiator, 〇.〇5g) in 〇克) and 甲(4〇克) lasted for 90 minutes. During the addition, the temperature was maintained. After the reaction was completed A free radical initiator (1 g) dissolved in ethyl acetate (50 g) and ethanol (50 g) was added dropwise over 60 minutes to eliminate unreacted monomers. The reaction was additionally initiated for an additional 3 hours to produce a first copolymer. Step 2: Preparation of the second copolymer, ethyl acrylate (45 g) as a monomer, 1,374,923 n-butyl acrylate (45 g) as a comonomer, and 2-isopropenyl-2 oxazoline (10) were added.克) into a 2 liter glass reactor and mixed 'the glass reactor equipped with a stirrer, condenser, dropping funnel, thermometer and jacket. Add α,α'_azobisisobutyronitrile (initiator, 0.01 g) dissolved in ethyl acetate (1 g) and methyl bromide (2 g) to the reactor, then • borrow The radical polymerization is carried out under C in the same manner as described for the polymerization reaction of the above carboxyl group-containing copolymer. After about 3 minutes, mix ethyl acrylate (35 grams), n-butyl acrylate (comon monomer, 135 grams) and acrylic acid (3 grams), Φ and use a dropping funnel to add and dissolve in acetic acid. The α,α'- pigeon nitrogen diisobutyronitrile (initiator, 5 g) in ethyl ester (100 g) and toluene (40 g) lasted 9 min. The temperature was maintained during the dropwise addition. After completion of the reaction, a free radical initiator (1 g) dissolved in hexylacetic acid (5 gram) and ethanol (50 gram) was added dropwise for 60 minutes to eliminate unacceptable monomers. The forehead should return to the city to produce a second copolymer in 3 small phases. Step 3: - Preparation of Adhesive Resin The two copolymer resins, i.e., the first and second copolymers prepared in Step 2 and Step 2, were mixed at a weight ratio of 1.1.禾 Τ Do not add microspheres F-·(Matsumoto Oil Pharmaceutical Co., Ltd., initial expansion temperature: 100 to 丨,, 士, 〇 5C) (10 grams) to the resin mixture (100 grams), followed by dispersion To provide _ adhesive resin. The adhesive resin was prepared in the same manner as described in [Production Example 2] = "Acts" but the weight ratio of acrylic acid was 4.5 / 4.5 / 1.5. [Manufacturing Example 3] 15 1374923 The adhesive resin was prepared in the same manner as described in Production Example 1, except that the monomer used in the production example 1 was adjusted to n-butyl acrylate/acrylic acid. The weight ratio is 4.5/4.5/0.6. [Manufacturing Example 4] The adhesive resin was prepared in the same manner as described in Production Example 1 except that the microsphere F-80GSD (Matsumoto Oil & Fat Pharmaceutical Co., Ltd., starting temperature: uo to 115. (;) was used. The microspheres f_5〇d used in the step 3 of Production Example i were replaced. ^ [Manufacturing Example 5] The adhesive resin was prepared in the same manner as described in Production Example 1 except that the microsphere F.8GVSD (salt oil) was used. Pharmaceutical Co., Ltd., starting the expansion temperature: 150 to 16 (TC) instead of the microsphere F 5〇D used in the step 3 of Production Example i. [Examples 1 to 5] Each of the preparations prepared in Examples 1 to 5 The adhesive resin was coated on a polyethylene terephthalate film (PET film) (50 μm) to form a 37 μm thick expanded adhesive layer. A 36 μm release film was laminated to the adhesive layer. An expansion plate was produced. The expansion plate was aged for 7 days, and then the final test was performed. [Comparative Manufacturing Example 1] Ethyl acrylate (48.5 g), n-butyl acrylate (48.5 g), and propionic acid (2 g) were added. And hydroxypropyl acrylate (1.0 g) to a 2 liter glass reaction The glass reactor was equipped with a stirrer, a condenser, a dropping funnel, a thermometer and a jacket. It was dissolved in ethyl acetate (160 g) and toluene (270 g) by using a dropping funnel. Ct, a'-azobisisobutyronitrile (initiator '0.01 g) to the reactor, followed by nitrogen substitution reaction. During reflux, continuous addition at 80 ° C, followed by 1374923 free radicals The polymerization reaction was carried out for 8 hours. In the subsequent stage of the reaction, an excess of the radical initiator was added to remove the unreacted monomer. Then, the microspheres f_5〇d were added (Matsumoto Oil & Fat Pharmaceutical Co., Ltd., the expansion temperature was started: 1 〇〇至〇5〇c) and dispersed to produce an adhesive resin. [Comparative Production Example 2] The adhesive resin was prepared in the same manner as described in Comparative Production Example 1 but increased in cross-linking function The amount of the hydroxypropyl acrylate (2 gram), the phase I was compared with the amount in Comparative Production Example 1. [Comparative Production Example 3] The adhesion was prepared in the same manner as described in Comparative Production Example 1. Resin, but using microsphere F-8 0GSD (Matsumoto Oil & Fat Pharmaceutical Co., Ltd., starting expansion temperature: 110 to 115 ° C.) ' [Comparative Production Example 4] The adhesive resin was prepared in the same manner as described in Comparative Production Example 1, but using a microsphere F -80VSD (Matsumoto Oil & Fat Pharmaceutical Co., Ltd., starting expansion temperature φ: 150 to 16 (TC). [Comparative Examples 1 to 4] Add AK-75 (double the amount of hydroxyl (functional group) of the adhesive resin) Ai Jing Chemical Co., Ltd.), an isocyanate crosslinking agent, to each of the adhesive resins prepared in Comparative Production Examples 1 to 4, followed by stirring to produce a point-sensitive resin. The adhesive resin was applied to a PET film (50 micrometers) to form a -37 micro-thickness expanded adhesive layer "a 36 micron release film was laminated to the adhesive layer to produce an expanded sheet. The expansion plate was aged for 7 days, followed by a final test. 17 1374923 Manufacturing Examples 1 to 5 and Comparative Manufacturing Examples 1 to 4 are summarized in Table 1. The physical properties of the adhesive resin and the expanded plate prepared in the production examples, examples, and comparative manufacturing examples were tested as follows and the results are shown in Tables 2 and 3. 1. Viscosity Change of Adhesive Resin The prepared adhesive resin was placed in a container for preventing evaporation of the solvent at a fixed temperature, and the viscosity was measured over time by using a Brookfield viscometer (DV-II+). 2. Expansion temperature The expansion temperature was measured by using Perkin Elmer's DSC 7 at a rate of 10 ° C/min. Specifically, the microsphere-containing adhesive resin is applied to the pET film, followed by aging. After the completion of the cross-linking, samples were taken from the sputum. A 10 mm thick stainless steel plate was placed on the hot plate at an adjusted temperature. After the temperatures were made the same, the expansion plate was placed in the middle, and then the expansion temperature was measured. Compare the temperature obtained with the temperature measured by the thermometer. 3. Adhesive strength Thoroughly clean the test board (SUS 3〇4) (thickness 2 mm, width 5 mm, length 200 mm) with isopropyl alcohol, using 2 kg automatic pressure rubber roller at 3 〇 cm/min. Adhesively adhered to the heat-peeling adhesive sheet (obtained in the example and comparative example) having a width of 2 () mm and a length of 15 mm with the adhesive layer facing downward, and
回地滚動一次’接著將該黏著板留在室溫下30分鐘。根據「KSA "〇7:扇4」，藉由測量丨8〇度外殼黏著強度（剝離速率 毫米/分鐘’ 23。〇所使用的相同方法測量黏著強度。自三個測試 樣本獲得黏著強度之平均值。 1374923 [表i]Roll back to ground once' then leave the adhesive plate at room temperature for 30 minutes. According to "KSA "〇7: Fan 4", the adhesion strength was measured by measuring the adhesion strength of the 〇8 外壳 degree of the outer shell (peeling rate mm/min '23. 黏. The adhesion strength was obtained from three test samples. Average value 1374923 [Table i]
項目 第一共聚物之 單體含量 第二共聚物之 單體含量 微球 製造實例1 ΕΑ 45% ΕΑ 45% F-50D ΒΑ 45% ΒΑ 45% ΑΑ 1 />Λ / 1 W70 TT>/"V irw 1 AO/ IU70 製造實例2 ΕΑ 43% ΕΑ 43% F-50D ΒΑ 43% BA 43% ΑΑ 14% IPO 14% 製造實例3 ΕΑ 47% EA 47% F-50D ΒΑ 47% BA 47% ΑΑ 6% IPO 6% 製造實例4 ΕΑ 45% EA 45% F-80GSD ΒΑ 45% BA 45% ΑΑ 10% IPO 10% 製造實例5 ΕΑ 45% EA 45% F-80VSD ΒΑ 45% BA 45% ΑΑ 10% IPO 10% 比較製造實例 1 ΕΑ 48.5% 2當量之 異氰酸酯交聯劑 F-50D ΒΑ 48.5% ΑΑ 2% ΗΡΑ 1% 比較製造實例 2 ΕΑ 48% 2當量之 異氰酸酷交聯劑 F-50D ΒΑ 48% ΑΑ 2% ΗΡΑ 2% 比較製造實例 3 ΕΑ 48.5% 2當量之 異氰酸酯交聯劑 F-80GSD ΒΑ 48.5% ΑΑ 2% ΗΡΑ 1% 比較製造實例 4 ΕΑ 48.5% 2當量之 異氰酸酯交聯劑 F-80VSD ΒΑ 48.5% ΑΑ 2% ΗΡΑ 1% EA :丙烯酸乙酯：BA :丙烯酸丁酯；AA :丙烯酸； IPO :異丙烯基噁唑啉；ΗΡΑ :羥丙基丙烯酸酯 19 1374923Monomer content of the first copolymer of the item Monomer content of the second copolymer Microsphere production example 1 ΕΑ 45% ΕΑ 45% F-50D ΒΑ 45% ΒΑ 45% ΑΑ 1 />Λ / 1 W70 TT>/" ;V irw 1 AO/ IU70 Manufacturing Example 2 ΕΑ 43% ΕΑ 43% F-50D ΒΑ 43% BA 43% ΑΑ 14% IPO 14% Manufacturing Example 3 ΕΑ 47% EA 47% F-50D ΒΑ 47% BA 47% ΑΑ 6% IPO 6% Manufacturing Example 4 ΕΑ 45% EA 45% F-80GSD ΒΑ 45% BA 45% ΑΑ 10% IPO 10% Manufacturing Example 5 ΕΑ 45% EA 45% F-80VSD ΒΑ 45% BA 45% ΑΑ 10% IPO 10% Comparative Manufacturing Example 1 ΕΑ 48.5% 2 equivalents of isocyanate crosslinker F-50D ΒΑ 48.5% ΑΑ 2% ΗΡΑ 1% Comparative Manufacturing Example 2 ΕΑ 48% 2 equivalents of isocyanate crosslinker F-50D ΒΑ 48% ΑΑ 2% ΗΡΑ 2% Comparative Manufacturing Example 3 ΕΑ 48.5% 2 equivalents of isocyanate crosslinker F-80GSD ΒΑ 48.5% ΑΑ 2% ΗΡΑ 1% Comparative Manufacturing Example 4 ΕΑ 48.5% 2 equivalents of isocyanate crosslinker F- 80VSD ΒΑ 48.5% ΑΑ 2% ΗΡΑ 1% EA: ethyl acrylate: BA: butyl acrylate; AA: acrylic acid; IPO: isopropenyloxazoline; hydrazine: hydroxy Propyl acrylate 19 1374923
[表2] 項目 室溫下黏著性樹脂之黏度變化(厘泊） 0小時 6小時 12小時 18小時 24小時 製造實例1 104 104 106 106 106 製造實例2 105 107 107 109 110 製造實例3 102 102 103 103 103 製造實例4 110 112 112 113 113 製造實例5 119 119 121 121 122 比較製造實例1 97 154 198 325 532 比較製造實例2 126 249 368 498 922 比較製造實例3 146 251 359 573 992 比較製造實例4 164 269 482 805 1112 [表3] 黏著強度 開始膨脹溫度 膨脹板之膨脹溫度 項目 (克/25毫米） (°C) (°C) 實例1 290 100〜105 135〜145 實例2 210 100- 105 145〜145 實例3 350 100-105 130〜140 實例4 320 110〜115 140~ 150 實例5 310 150~ 160 180〜190 20 1374923 比較實例1 280 100〜105 110-120 比較實例2 360 100-105 115-125 比較實例3 280 110-115 135-145 比較實例4 290 150〜160 165-175 如上文中所解釋’難以於本發明之黏著性樹脂中觀察黏度變 化。且本發明之黏著性樹脂有助於生產較使用相同微球的傳統膨 脹板之要高20至3(TC之膨脹溫度下膨脹之膨脹板。 產業可利用性 本發明提供一種含有微球的、可增加約比平常高2〇至3〇。〇之膨 脹’皿度的黏著性樹脂’且提供—種詩膨脹板之塗覆樹脂，該樹 脂具有優異的塗覆性質、黏著強度、承載力、内聚力，以及各種 功此目此’本發明對可應用於電子、電氣及材料領域的高溫膨 脹板之生產係非常有用的。 亦可能於一基材與適當材料之永久黏著上使用本發明之膨脹 板。然而，該板較佳的使用係黏著—基材達所需的時間且於達到 目的之後制離。換έ之’本發明提供之膨脹板可應用於組裝、切 害J及拋光由至少二種高溫材料所組成的電子、電氣設備中，如 聚。物材料及金屬、纖維或紙；電路製程所使用的運送帶中，如 FPCB ’暫時的固定劑或表面保護劑以防止金屬板塑膠板及玻璃 板產生污染或損傷；或應用於罩護劑中。 【圖式簡單說明】 第1圖係-剖面圖，說明本發明之膨服板；以及 第2圖係、_ +咅® 不忍圖，顯示相互反應性共聚物之交聯機制的化學 21 1374923 式。 【主要元件符號說明】 1 基材 2 表面處理層 3 膨脹黏著層 4 離型膜[Table 2] Change in viscosity of the adhesive resin at room temperature (centipoise) 0 hours 6 hours 12 hours 18 hours 24 hours Production Example 1 104 104 106 106 106 Manufacturing Example 2 105 107 107 109 110 Manufacturing Example 3 102 102 103 103 103 Manufacturing example 4 110 112 112 113 113 Manufacturing example 5 119 119 121 121 122 Comparative manufacturing example 1 97 154 198 325 532 Comparative manufacturing example 2 126 249 368 498 922 Comparative manufacturing example 3 146 251 359 573 992 Comparative manufacturing example 4 164 269 482 805 1112 [Table 3] Adhesion strength starts to expand temperature Expansion plate expansion temperature item (g / 25 mm) (°C) (°C) Example 1 290 100~105 135~145 Example 2 210 100-105 145~ 145 Example 3 350 100-105 130~140 Example 4 320 110~115 140~150 Example 5 310 150~ 160 180~190 20 1374923 Comparative Example 1 280 100~105 110-120 Comparative Example 2 360 100-105 115-125 Comparative Example 3 280 110-115 135-145 Comparative Example 4 290 150 to 160 165-175 As explained above, it was difficult to observe the change in viscosity in the adhesive resin of the present invention. Moreover, the adhesive resin of the present invention contributes to the production of an expanded plate which is 20 to 3 higher than the conventional expansion plate using the same microsphere (expansion temperature at the expansion temperature of TC. Industrial Applicability The present invention provides a microsphere-containing, It can be increased by about 2 to 3 inches higher than usual. The expansion of the 'adhesive resin of the dish' and the coating resin of the poetry expansion plate have excellent coating properties, adhesion strength, bearing capacity, Cohesive force, and various advantages. The present invention is very useful for the production of high temperature expansion panels applicable to the fields of electronics, electrical and materials. It is also possible to use the expansion of the present invention on the permanent adhesion of a substrate to a suitable material. However, the board preferably uses an adhesive-substrate for the required time and is produced after the purpose is achieved. The invention provides an expansion panel that can be applied to assembly, damage J and polishing by at least Two kinds of high-temperature materials in electronic and electrical equipment, such as poly materials and metals, fibers or paper; in the transport process used in circuit manufacturing, such as FPCB 'temporary fixative or surface protectant Prevent metal plate plastic plate and glass plate from causing pollution or damage; or apply to cover agent. [Simplified illustration] Fig. 1 is a cross-sectional view showing the expansion plate of the present invention; and Fig. 2, _ +咅® does not endure the graph, showing the chemical mechanism of the cross-linking mechanism of the mutual reaction copolymer 21 1374923. [Main component symbol description] 1 Substrate 2 Surface treatment layer 3 Expanded adhesive layer 4 Release film