TWI797517B - Antistatic Adhesive Sheet - Google Patents
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Abstract
本發明為一種抗靜電之黏著片,其表面電阻係數為等於或小於1011Ω,其包括有:一聚醯亞胺膜;及一導電高分子層,其係黏著於該聚醯亞胺膜上,該導電高分子層必須具有共軛環狀結構,一黏著組成物,其係黏著於該導電高分子層上,該黏著組成物之主體聚合物包含貢獻黏著力單體、貢獻內聚力單體與改性單體,其中貢獻內聚力單體必須選定為聚苯乙烯之衍生物之單體,其結構通式為;及在室溫T溫度下,該主體聚合物之Tg溫度必須符合T-Tg>20℃。 The present invention is an antistatic adhesive sheet, the surface resistivity of which is equal to or less than 10 11 Ω, which includes: a polyimide film; and a conductive polymer layer, which is adhered to the polyimide film On the above, the conductive polymer layer must have a conjugated ring structure, an adhesive composition, which is adhered to the conductive polymer layer, and the main polymer of the adhesive composition includes a monomer that contributes to adhesion and a monomer that contributes to cohesion And modifying monomers, the monomers that contribute to cohesion must be selected as monomers derived from polystyrene, and its general structural formula is ; and at room temperature T, the Tg temperature of the host polymer must meet TT g >20°C.
Description
本發明為一種抗靜電之黏著片,特別係指一種用以使電子元件貼合於抗靜電黏著片上,經過加熱製程後,當電子元件自黏著片移除時,電子元件不會有殘膠現象,且移除過程不因靜電損壞電子元件。 The present invention is an antistatic adhesive sheet, especially an antistatic adhesive sheet for attaching electronic components to the antistatic adhesive sheet. After the heating process, when the electronic components are removed from the adhesive sheet, there will be no glue residue on the electronic components. , and the removal process will not damage electronic components due to static electricity.
在現有技術中,黏著材料諸如黏著片已被廣泛用於各種產品(例如半導體相關元件、LED相關電子元件、面板、電路板等)的生產過程中。更具體而言,一般應用於各種高溫製程過程中承載用之黏著片,為了製程過程中電子元件不至於脫離,所以黏著片的黏著力須足以與電子元件相互固定而於各種高溫製程中不與電子元件分離,即不發生剝離。另外,在電子元件經各種高溫製程後,於進行拾取(pick-up)的步驟中,即黏著片與電子元件分離時,不能發生黏著片殘膠於電子元件上造成污染。因此,用於各種高溫製程,所需之黏著片需要同時具備良好的黏著力與內聚力,以及在經過各種高溫處理後的不易殘膠的特性。 In the prior art, adhesive materials such as adhesive sheets have been widely used in the production process of various products (eg, semiconductor-related components, LED-related electronic components, panels, circuit boards, etc.). More specifically, it is generally used as an adhesive sheet for carrying in various high-temperature processes. In order to prevent the electronic components from detaching during the process, the adhesive force of the adhesive sheet must be sufficient to fix the electronic components and not to be in contact with the electronic components during various high-temperature processes. Electronic components are separated, i.e. no peeling occurs. In addition, after the electronic components undergo various high-temperature processes, during the pick-up step, that is, when the adhesive sheet is separated from the electronic components, the residual glue of the adhesive sheet cannot cause pollution on the electronic components. Therefore, to be used in various high-temperature processes, the required adhesive sheet must have both good adhesion and cohesion, as well as the characteristics of not being prone to adhesive residue after various high-temperature treatments.
且因應現行更複雜之應用,如耐靜電性很差之電子元件的短暫固定,例如:高頻wifi用之電子元件,會更要求不只要過完各種高溫製程後要有不易造成電子元件有殘膠之狀況,且元件脫離黏著片時不會因靜電而損壞電子元件等要素。 And in response to the current more complex applications, such as the short-term fixation of electronic components with poor static resistance, such as: electronic components for high-frequency wifi, it is more required not only to be able to prevent the electronic components from being damaged after various high-temperature processes The state of the glue, and the components will not damage the electronic components due to static electricity when the components are separated from the adhesive sheet.
在現有的黏著片產品中,於進行所需的處理,例如經過各種高溫製程之後,黏著片與被黏附的物件之間的黏著力都會上升,因此,如果設計之黏著片層與層之間接著脆弱,會造成被黏附的物件上的剝離轉印污染量增多進而產生殘膠等問題。 In the existing adhesive sheet products, after the required processing, such as various high-temperature processes, the adhesive force between the adhesive sheet and the adhered object will increase. Therefore, if the designed adhesive sheet is bonded between layers Fragile, it will cause the amount of peeling transfer pollution on the adhered object to increase and cause problems such as residual glue.
而對於抑制電子元件脫離黏著片時產生之靜電,一般技術文獻有提及在組成黏著片上之基膜透過增加導電高分子層,達到優異的防靜電特性,但如果無有效設計構成黏著片上之黏著組成物層搭配導電高分子層,會容易在電子元件經過各種高溫製程後,將黏著片與電子元件剝離時發生殘膠之現象,亦即剝離時破壞面發生在導電高分子層與黏著組成物層之間。因此,在現有技術中,用於承載電子元件過各種高溫製程之黏著片仍然有改善的空間。 As for the suppression of static electricity generated when electronic components are detached from the adhesive sheet, general technical literature mentions that the base film on the adhesive sheet can be added with a conductive polymer layer to achieve excellent antistatic properties. The combination of the composition layer and the conductive polymer layer will easily cause adhesive residue when the adhesive sheet is peeled off from the electronic component after the electronic component has undergone various high-temperature processes, that is, the damaged surface during peeling occurs between the conductive polymer layer and the adhesive composition between layers. Therefore, in the prior art, there is still room for improvement in the adhesive sheet used for carrying electronic components through various high-temperature processes.
本發明所要解決的技術問題在於,針對現有技術的不足提供一種抗靜電黏著片,其中此抗靜電黏著片的表面電阻係數為1011Ω或以下,所述該抗靜電黏著片可以在經選擇的溫度下,自被黏附的物件剝離時無在電子元件上發現殘膠,且不產生靜電導致元件損壞。具體來說,將被黏著體上的剝離轉印污染量控制在為最小值,進而達到不產生殘膠的技術效果。且此抗靜電黏著片中包含導電高分子層,可於電子元件與黏著片剝離過程中不因靜電損壞元件。 The technical problem to be solved by the present invention is to provide an antistatic adhesive sheet for the deficiencies of the prior art, wherein the surface resistivity of the antistatic adhesive sheet is 10 11 Ω or below, and the antistatic adhesive sheet can be used in selected At high temperature, no adhesive residue will be found on the electronic components when peeling off the adhered objects, and no static electricity will be generated to cause damage to the components. Specifically, the amount of peeling transfer pollution on the adherend is controlled to a minimum, so as to achieve the technical effect of no adhesive residue. Moreover, the antistatic adhesive sheet contains a conductive polymer layer, which can prevent the electronic components from being damaged by static electricity during the process of peeling off the adhesive sheet.
為了解決上述的技術問題,本發明提供一種抗靜電黏著片,其包括一聚醯亞胺膜、一導電高分子層以及一黏著組成物層。所述導電高分子層設置於所述聚醯亞胺膜上,而所述該黏著組成物層設置於所述導電高 分子層上。該導電高分子必須具有共軛環狀結構,如聚對苯乙烯、聚吡咯、聚噻吩、聚苯胺、聚苯硫醚。該黏著組成物之主體聚合物包含貢獻黏著力單體、貢獻內聚力單體與改性單體,其中貢獻內聚力單體必須選定為聚苯乙烯之衍生物之單體,其結構通式為。另貢獻黏著力單體歸類為WA、WB…WZ;貢獻內聚力單體歸類為Wa、Wb…Wc;改性單體歸類為W1、W2…W3,定義室溫為T,主體聚合物之玻璃轉移溫度為Tg,符合習知The FOX Equation: In order to solve the above technical problems, the present invention provides an antistatic adhesive sheet, which includes a polyimide film, a conductive polymer layer and an adhesive composition layer. The conductive polymer layer is disposed on the polyimide film, and the adhesive composition layer is disposed on the conductive polymer layer. The conductive polymer must have a conjugated ring structure, such as polystyrene, polypyrrole, polythiophene, polyaniline, polyphenylene sulfide. The main polymer of the adhesive composition includes monomers contributing to adhesion, monomers contributing to cohesion and modified monomers, wherein the monomers contributing to cohesion must be selected as monomers derived from polystyrene, and its general structural formula is . In addition, monomers contributing adhesion are classified as W A , W B ... W Z ; monomers contributing cohesion are classified as W a , W b ... W c ; monomers contributing modification are classified as W 1 , W 2 ... W 3 , Define the room temperature as T, and the glass transition temperature of the host polymer as T g , which conforms to the conventional The FOX Equation:
1/Tg=WA/Tg,A+WB/Tg,B+WC/Tg,C+…+Wa/Tg,a+Wb/Tg,b+Wc/Tg,c+…+W1/Tg,1+W2/Tg,2+W3/Tg,3+…,且需在T-Tg>20℃條件下,電子元件才能與黏著片貼合。 1/T g =WA/T g,A +WB/T g,B +WC/T g,C +...+Wa/T g,a +Wb/T g,b +Wc/T g,c +... +W1/T g, 1 +W2/T g, 2 +W3/T g, 3 +..., and the electronic components can only be attached to the adhesive sheet under the condition of TT g >20°C.
本發明的有益效果在於所提供的抗靜電黏著片,找到黏著組成物層與導電高分子層之匹配關係,可以在經過各種高溫製程過程前,被貼物(電子元件)能與抗靜電黏著片緊密貼合,在過完各種高溫製程過程後,達到電子元件與該抗靜電黏著片剝離過程中無殘膠現象,且有效降低黏著片之表面電阻,進而在將該黏著片與電子元件剝離過程中抑制靜電產生。 The beneficial effect of the present invention is that the provided antistatic adhesive sheet can find the matching relationship between the adhesive composition layer and the conductive polymer layer, and the object (electronic component) can be attached to the antistatic adhesive sheet before going through various high-temperature processes. Closely bonded, after various high-temperature processes, there is no adhesive residue during the peeling process of the electronic components and the antistatic adhesive sheet, and the surface resistance of the adhesive sheet is effectively reduced, and then the adhesive sheet is peeled off from the electronic components. Suppresses static electricity generation.
為使能更進一步瞭解本發明的特徵及技術內容,請參閱以下有關本發明的詳細說明與附圖,然而所提供的附圖僅用於提供參考與說明,並非用來對本發明加以限制。 In order to further understand the features and technical contents of the present invention, please refer to the following detailed description and drawings related to the present invention. However, the provided drawings are only for reference and description, and are not intended to limit the present invention.
10:聚醯亞胺膜 10: Polyimide film
12:導電高分子層 12: Conductive polymer layer
14:黏著組成物層 14: Adhesive composition layer
第1圖為本發明之抗靜電之黏著片之實施例。 Figure 1 is an embodiment of the antistatic adhesive sheet of the present invention.
請參閱第1圖式,本發明抗靜電之黏著片包括一聚醯亞胺膜10、一導電高分子層12以及一黏著組成物層14,導電高分子層12係設置於聚醯亞胺膜10上,且具有共軛環狀結構,而黏著組成物層14係設置於導電高分子層12上。其中黏著組成物層14之主體聚合物包含貢獻黏著力單體、貢獻內聚力單體與改性單體。以下將針對貢獻黏著力單體、貢獻內聚力單體與改性單體進行詳細說明。
Please refer to the first drawing, the antistatic adhesive sheet of the present invention includes a
該主體聚合物,包括衍生自至少一種單體的至少一個結構單元,且上述單體是含有可聚合的碳-碳雙鍵基。在下文中,將被稱為「具有可聚合的碳-碳雙鍵基之單體」。 The host polymer includes at least one structural unit derived from at least one monomer containing a polymerizable carbon-carbon double bond. Hereinafter, it will be referred to as "a monomer having a polymerizable carbon-carbon double bond group".
該貢獻內聚力單體,必須為苯乙烯單體或苯乙烯衍生物之單體,符合結構式如下: The cohesion-contributing monomer must be a styrene monomer or a styrene derivative monomer, which conforms to the following structural formula:
上述可共聚合的單體可以單獨使用以形成主體聚合物的結構單元,或是,可以同時使用兩種以上的可共聚合的單體以形成主體聚合物的結構單元。 The above-mentioned copolymerizable monomers may be used alone to form the structural unit of the host polymer, or two or more kinds of copolymerizable monomers may be used simultaneously to form the structural unit of the host polymer.
該改性單體,以在聚合反應中進行高度交聯反應。舉例而言,改性單體可以是甲基丙烯酸、丙烯酸、甲基苯烯酸羥乙酯、甲基苯烯酸羥丙酯、二氨基乙基甲基丙烯酸酯。 The modified monomers are highly cross-linked during polymerization. For example, the modifying monomer may be methacrylic acid, acrylic acid, hydroxyethyl methacrylate, hydroxypropyl methacrylate, diaminoethyl methacrylate.
上述改性單體可以被單獨使用,或是可以同時使用兩種以上的改性單體。或是,如前針對可共聚合的單體所述,在用以形成主體聚合物的結構單元的單體中,可以單獨使用丙烯酸系的單體或是甲基丙烯酸系的單體。通過使用改性單體,可以使得所衍生而得的主體聚合物具有經改良的凝聚力與耐熱性。 The above-mentioned modifying monomers may be used alone, or two or more kinds of modifying monomers may be used in combination. Alternatively, as described above for the copolymerizable monomer, among the monomers used to form the structural unit of the host polymer, an acrylic monomer or a methacrylic monomer may be used alone. By using the modified monomer, the derived host polymer can have improved cohesion and heat resistance.
上述該黏著組成物之主體聚合物包含貢獻黏著力單體、貢獻內聚力單體與改性單體。其中貢獻黏著力單體歸類為WA、WB…WZ;貢獻內聚力單體歸類為Wa、Wb…Wc;改性單體歸類為W1、W2…W3,可由The FOX Equation: The above-mentioned main polymer of the adhesive composition includes a monomer contributing to adhesion, a monomer contributing to cohesion and a modifying monomer. Among them, monomers contributing adhesion are classified as W A , W B ... W Z ; monomers contributing cohesion are classified as W a , W b ... W c ; monomers contributing modification are classified as W 1 , W 2 ... W 3 , Available from The FOX Equation:
1/Tg=WA/Tg,A+WB/Tg,B+WC/Tg,C+…+Wa/Tg,a+Wb/Tg,b+Wc/Tg,c+…+W1/Tg,1+W2/Tg,2+W3/Tg,3+… 1/T g =WA/T g,A +WB/T g,B +WC/T g,C +...+Wa/T g,a +Wb/T g,b +Wc/T g,c +... +W1/T g,1 +W2/T g,2 +W3/T g,3 +…
推導出主體聚合物之玻璃轉移溫度(Tg),且經由文獻及實驗中觀察,如果室溫T為23℃,經由各種單體排列組合的可能性,得到之主體聚合物的Tg需低於3℃才能明顯於室溫下有黏著力之效果,亦即T-Tg>20℃條件下,形成之黏著片在過各種高溫製程前可貼合電子元件而不產生剝離。 Deduce the glass transition temperature (T g ) of the host polymer, and through literature and experimental observations, if the room temperature T is 23°C, the T g of the host polymer obtained through the possibility of arranging and combining various monomers needs to be low The effect of adhesive force at room temperature is obvious only at 3°C, that is, under the condition of TT g >20°C, the formed adhesive sheet can be bonded to electronic components without peeling off before going through various high-temperature processes.
另一般習知技術中,為了增加黏著組成物層的內聚力,也會添加多異氰酸酯系交聯劑,藉由交聯劑和主體聚合物中之改性單體之官能基反應,進而增加內聚力,且多異氰酸酯系交聯劑在本發明中不加以限制,舉例而言,多異氰酸酯系交聯劑可為甲苯二異氰酸酯(TDI)、異佛爾酮二異氰酸酯(IPDI)、二苯基甲烷二異氰酸酯(MDI)、二環己基甲烷二異氰 酸酯(HMDI)、賴氨酸二異氰酸酯(LDI)或其相關衍生物,其具有通式為R-N=C=O。 In other conventional techniques, in order to increase the cohesive force of the adhesive composition layer, a polyisocyanate-based cross-linking agent is also added, and the cross-linking agent reacts with the functional group of the modified monomer in the host polymer, thereby increasing the cohesive force. And the polyisocyanate crosslinking agent is not limited in the present invention, for example, the polyisocyanate crosslinking agent can be toluene diisocyanate (TDI), isophorone diisocyanate (IPDI), diphenylmethane diisocyanate (MDI), dicyclohexylmethane diisocyanate Lysine diisocyanate (HMDI), lysine diisocyanate (LDI) or related derivatives thereof, which have the general formula R-N=C=O.
如上所述,本發明的主體聚合物可以是通過單獨使用上述單體進行聚合反應而得,或是使用兩種以上的單體的混合物進行聚合反應而得。聚合反應的種類可以是溶液聚合、乳液聚合、整體聚合(mass polymerization)或是懸浮聚合反應。 As described above, the host polymer of the present invention may be obtained by performing polymerization using the above-mentioned monomers alone, or using a mixture of two or more monomers for polymerization. The type of polymerization reaction may be solution polymerization, emulsion polymerization, mass polymerization or suspension polymerization.
經過聚合反應而形成主體聚合物後,主體聚合物可以具有大於20萬的重量平均分子量。較佳地,本發明實施例的主體聚合物是具有介於80萬至350萬之間的重量平均分子量。針對主體聚合物的重量平均分子量,其可以是以膠滲層析法測量並經過計算而得(重量平均分子量是藉由凝膠滲透層析儀(GPC),以聚苯乙烯為標準品換算而得)。 After the host polymer is formed through a polymerization reaction, the host polymer may have a weight average molecular weight greater than 200,000. Preferably, the host polymer of the embodiment of the present invention has a weight average molecular weight between 800,000 and 3.5 million. For the weight average molecular weight of the host polymer, it can be measured and calculated by gel permeation chromatography (the weight average molecular weight is converted by gel permeation chromatography (GPC) with polystyrene as a standard product) have to).
具有介於上述範圍之內的重量平均分子量的主體聚合物可以具有較低的寡聚物含量。如此一來,在包含主體聚合物的熱硬化型黏著組成物經過熱硬化程序而自黏附物的表面剝離後,可以大幅減少殘留在黏附物表面的污染物。具體來說,基於上述針對與主體聚合物有關的單體的選擇,可以使得主體聚合物具有較高的分子量。據此,主體聚合物將具有較佳的物理性質,例如不易殘脫膠以及優良的耐熱性等。如此一來,低分子量物質不會隨時間經過於黏著劑中移動,進而確保熱硬化型黏著劑組合物的穩定性。相對的,若主體聚合物的分子量較低,則在黏著劑產品中的低分子量物質會對熱硬化型黏著劑組合物有不利的影響。 A host polymer having a weight average molecular weight within the above range may have a lower oligomer content. In this way, after the thermosetting adhesive composition including the host polymer is peeled off from the surface of the adherend through a thermosetting process, the pollutants remaining on the surface of the adherend can be greatly reduced. Specifically, based on the above selection of monomers related to the host polymer, the host polymer can have a higher molecular weight. Accordingly, the host polymer will have better physical properties, such as not easy to residue and degumming, and excellent heat resistance. In this way, the low molecular weight substance will not move in the adhesive over time, thereby ensuring the stability of the thermosetting adhesive composition. In contrast, if the molecular weight of the host polymer is low, the low molecular weight substances in the adhesive product will have adverse effects on the thermosetting adhesive composition.
本發明實施例所提供的黏著組成物層14還可以包括用以起始主體聚合物聚合反應的熱聚合起始劑。熱聚合起始劑可以是過氧化苯(benzoyl peroxide)、偶氮二異丁腈(AIBN)或是其等的混合物。
The
以100份的主體聚合物為基準,在熱硬化型黏著組成物層14中的熱聚合起始劑的含量是介於0.1至20重量份之間,較佳地熱聚合起始劑的含量是介於0.5至10重量份。
Based on 100 parts of the main polymer, the content of the thermal polymerization initiator in the thermosetting
抗靜電黏著片所包括的導電高分子層12,可藉由各種方式形成於聚醯亞胺膜10上,在此形成之方式不加以限制,可為塗佈方式形成於聚醯亞胺膜10上,或抑是蒸鍍、濺鍍、噴塗……等各種習知技術所能達成之功效。另黏著片的導電高分子層厚度不加以限制,可以是介於0.3至100微米(μm)之間,較佳地,導電高分子的厚度為介於0.5至25微米之間。
The
該導電高分子層12必須具有共軛環狀結構,如聚對苯乙烯、聚吡咯、聚噻吩、聚苯胺、聚苯硫醚等。
The
適用於本發明中的各種高溫製程之溫度,可以是100~300℃區間,因應不同製程所需之溫度,舉例如LED molding溫度可為130~180℃,如電路板回焊(reflow)溫度可為260~288℃……等。 The temperature suitable for various high-temperature processes in the present invention can be in the range of 100-300°C. According to the temperature required by different processes, for example, the LED molding temperature can be 130-180°C. For example, the circuit board reflow temperature can be It is 260~288°C...etc.
本發明所提供的黏著片可以具有不同形狀。具體來說,黏著片可以是片狀的黏著材料,或者是被捲取成卷狀的黏著材料。另外,黏著片的形狀可以依據應用的領域、用以黏附的產品型態,或是其他製造過程的參數而加以調整,本發明在此並不加以限制。 The adhesive sheet provided by the present invention can have different shapes. Specifically, the adhesive sheet may be a sheet-shaped adhesive material, or an adhesive material rolled into a roll. In addition, the shape of the adhesive sheet can be adjusted according to the field of application, the type of product to be adhered, or other parameters of the manufacturing process, and the present invention is not limited here.
黏著片之聚醯亞胺膜10係用以供導電高分子層12與黏著組成物層14支撐。聚醯亞胺膜10之厚度可以是介於10至300微米(μm)之間,較佳地,其厚度為介於12.5至200微米之間。
The
本發明實施例所提供的黏著片中的黏著組成物層14可以通過塗佈步驟或是轉印步驟而形成在導電高分子層12的表面。舉例而言,可以直接將黏著組成物層14塗佈於導電高分子層12的表面。或者是,可以先將黏著組成物層塗佈於一暫時載體的表面,暫時載體的表面預先設置有脫模劑,待塗佈於暫時載體的脫模劑上的黏著組成物乾燥成形後,再將乾燥成形的黏著組成物轉印至導電高分子層12的表面。
The
在本發明中,由主體聚合物之黏著組成物層14的厚度可以是介於1至100微米(μm)之間的範圍內。實務上,為了確保包括黏著組成物層14的黏著力,黏著組成物層14必須具有大於1微米的厚度。
In the present invention, the thickness of the
本發明實施例所提供的黏著片除了包括聚醯亞胺膜10、導電高分子層12與黏著組成物層14之外,還可以進一步包括離型層。離型層可以設置於黏著組成物層14的表面,使得黏著組成物層14設置於導電高分子層12與離型層之間。離型層可以具有介於10至200微米(μm)之間的厚度,且可以由紙、聚乙烯、聚丙烯、聚對苯二甲酸乙二酯所形成。離型層可以對黏著組成物層14提供保護以及隔離的效果,使得黏著片在儲存時不會受到外界環境的因素影響而降低黏著力等特性。
In addition to the
實務上,為了增加離型層的功能性,還可以賦予離型層抗紫外線的功能,藉此可以有效避免黏著片的黏著組成物層14受到儲存環境的紫外光影響而發生反應。另外,在使用時輕易將離型層自黏著組成物層12分
離,離型層的表面可以經過特定表面處理步驟,舉例而言,對離型層的表面進行改質,諸如進行聚矽氧處理、長鏈烷基處理或是氟處理等剝離處理。
In practice, in order to increase the functionality of the release layer, the release layer can also be endowed with an anti-ultraviolet function, thereby effectively preventing the
本發明實施例所提供的抗靜電黏著片可用於各種高溫製程,但被貼物(電子元件)不限制於哪一個產業之應用,如半導體、半導體封裝、LED相關製程、電路板相關製程、面板……等。且黏著片所黏附的物件的材料並不加以限制,舉例而言可以是金屬、陶瓷、玻璃、半導體元件、軟板、硬板、軟硬結合板、LED等電子材料,於相關電子產業生產過程中保護或是乘載用黏著片。 The antistatic adhesive sheet provided by the embodiment of the present invention can be used in various high-temperature processes, but the object (electronic component) is not limited to the application of any industry, such as semiconductors, semiconductor packaging, LED-related processes, circuit board-related processes, panels ……wait. And the material of the object to which the adhesive sheet is attached is not limited, for example, it can be electronic materials such as metal, ceramics, glass, semiconductor components, flexible boards, hard boards, soft-rigid boards, LEDs, etc., in the production process of related electronics industries Adhesive sheets for medium protection or passenger loading.
本發明所採用的技術方案是,提供一種抗靜電黏著片,其包括一聚醯亞胺膜10、一導電高分子層12以及一黏著組成物層14。所述導電高分子層12設置於所述聚醯亞胺膜10上,而黏著組成物層14設置導電高分子層12上。其中導電高分子層12必須具有共軛環狀結構,黏著組成物層14之主體聚合物包含貢獻黏著力單體、貢獻內聚力單體與改性單體,其中貢獻內聚力單體必須選定為聚苯乙烯之衍生物之單體,其結構通式為
The technical solution adopted by the present invention is to provide an antistatic adhesive sheet, which includes a
。另貢獻黏著力單體歸類為WA、WB…WZ;貢獻內聚力單體歸類為Wa、Wb…Wc;改性單體歸類為W1、W2…W3,定義室溫為T,主體聚合物之玻璃轉移溫度為Tg,符合習知The FOX Equation: . In addition, monomers contributing adhesion are classified as W A , W B ... W Z ; monomers contributing cohesion are classified as W a , W b ... W c ; monomers contributing modification are classified as W 1 , W 2 ... W 3 , Define the room temperature as T, and the glass transition temperature of the host polymer as T g , which conforms to the conventional The FOX Equation:
1/Tg=WA/Tg,A+WB/Tg,B+WC/Tg,C+…+Wa/Tg,a+Wb/Tg,b+Wc/Tg,c+…+W1/Tg,1+W2/Tg,2+W3/Tg,3+…且需在T-Tg>20℃條件下,電子元件才能與黏著片貼合。詳述而言,即本發明的有益效果在於所提供的抗靜電黏著片,找到黏著組成物與導電高分子 之匹配關係,可以在經過各種高溫製程過程前,被貼物(電子元件)能與抗靜電黏著片緊密貼合,在過完各種高溫製程過程後,達到電子元件與該抗靜電黏著片剝離過程中無殘膠現象,且有效降低黏著片之表面電阻,進而在將該黏著片與電子元件剝離過程中抑制靜電產生。接下來將以實施例以及比較例展示本發明所提供的抗靜電黏著片的內容與效果。 1/T g =WA/T g,A +WB/T g,B +WC/T g,C +...+Wa/T g,a +Wb/T g,b +Wc/T g,c +... +W1/T g, 1 +W2/T g, 2 +W3/T g, 3 +...and the electronic components can be attached to the adhesive sheet only under the condition of TT g >20°C. In detail, the beneficial effect of the present invention is that the provided antistatic adhesive sheet finds the matching relationship between the adhesive composition and the conductive polymer, and the object to be attached (electronic component) can be bonded to the The antistatic adhesive sheet is tightly bonded. After various high-temperature processes, there is no adhesive residue during the peeling process of the electronic component and the antistatic adhesive sheet, and the surface resistance of the adhesive sheet is effectively reduced. Suppresses static electricity generation during stripping of electronic components. Next, the content and effect of the antistatic adhesive sheet provided by the present invention will be shown by examples and comparative examples.
在一升(1L)的圓底燒瓶上裝設有分液漏斗、溫度計、氮氣導入管、冷凝管、真空密封件、攪拌棒、攪拌葉片的一般聚合用實驗裝置中添加入構成主體聚合物之單體。 In a one-liter (1L) round-bottomed flask equipped with a separatory funnel, thermometer, nitrogen inlet tube, condenser tube, vacuum seal, stirring rod, and stirring blades, add the main polymer monomer.
熱聚合起始劑使用相對於單體總量為0.3重量%的AIBN。 As a thermal polymerization initiator, 0.3% by weight of AIBN was used based on the total amount of monomers.
接下來,在上述聚合用實驗裝置中通入氮氣,在進行攪拌下利用隔水加熱方式將實驗裝置內溶液溫度控制為65℃±2℃,反應12小時,獲得主體聚合物。 Next, blow nitrogen gas into the above-mentioned experimental device for polymerization, control the temperature of the solution in the experimental device to 65°C±2°C by means of water-proof heating under stirring, and react for 12 hours to obtain the main polymer.
於上述獲得的主體聚合物中混合多異氰酸酯系交聯劑以及乙酸乙酯,均勻攪拌以獲得黏著組成物。 Mix the polyisocyanate-based crosslinking agent and ethyl acetate into the host polymer obtained above, and stir evenly to obtain an adhesive composition.
相對於主體聚合物之單體總量,添加2%多異氰酸酯系交聯劑(甲苯二異氰酸酯,CAS number:584-84-9,由Sigma-Aldrich購得)。 With respect to the total amount of monomers in the main polymer, 2% polyisocyanate crosslinking agent (toluene diisocyanate, CAS number: 584-84-9, purchased from Sigma-Aldrich) was added.
利用塗佈機將所獲得之黏著組成物塗佈於經聚矽氧系化合物進行剝離處理的PET膜的剝離處理面上,並於100℃之乾燥機中乾燥30分鐘,獲得厚度為20μm的黏著組成物層。 Use a coater to apply the obtained adhesive composition on the peeled surface of the PET film that has been peeled with a polysiloxane compound, and dry it in a dryer at 100°C for 30 minutes to obtain an adhesive with a thickness of 20 μm. composition layer.
利用塗佈機控制塗佈厚度,將所獲得之導電高分子塗佈於事先經過電暈處理之基膜上,基膜厚度為25μm,並於100℃之乾燥機中乾燥30分鐘,獲得厚度為2μm的導電高分子層。 Use a coating machine to control the coating thickness, and coat the obtained conductive polymer on the base film that has been treated with corona in advance. 2μm conductive polymer layer.
用手壓輥將黏著組成物層貼合於該基膜上之導電高分子層上,於50℃下密接化處理72小時,製作抗靜電黏著片。將抗靜電黏著片固定在鐵框上,鐵框中間裸露出之黏著片可以將電子元件固定其中,接下來放置於烘箱中模擬高溫製程,控制烘箱溫度在200℃情況下放置10min。 Lay the adhesive composition layer on the conductive polymer layer on the base film with a hand roller, and perform an adhesive treatment at 50°C for 72 hours to make an antistatic adhesive sheet. Fix the antistatic adhesive sheet on the iron frame. The exposed adhesive sheet in the middle of the iron frame can fix the electronic components in it, and then place it in an oven to simulate a high-temperature process, and control the temperature of the oven at 200°C for 10 minutes.
數據量測 data measurement
A.表面電阻量測(Ω): A. Surface resistance measurement (Ω):
表面電阻量測儀器型號:PRS-801;操作規範:參照ASTM D257;操作方法:將黏著片裁成長10公分×寬10公分之樣品。將樣品放置於絕緣的平面上,將檢測筆(PRF-922B)垂直按壓於測試面,再按下RESET後,接著按下TEST鈕,即可量測表面電阻數值。 Surface resistance measuring instrument model: PRS-801; operating specification: refer to ASTM D257; operating method: cut the adhesive sheet into a sample with a length of 10 cm x a width of 10 cm. Place the sample on an insulating plane, press the test pen (PRF-922B) vertically on the test surface, press RESET, and then press the TEST button to measure the surface resistance value.
B.剝離過程後之元件被黏著片汙染情況:在元件經由黏著片乘載情況下,經過烘箱設定200℃/10min模擬高溫製程後,將元件於黏著片上剝離,使用顯微鏡觀察元件之被貼面有無殘膠(倍率:400X)。 B. Contamination of the component by the adhesive sheet after the peeling process: When the component is carried by the adhesive sheet, after setting the oven at 200°C/10min to simulate the high-temperature process, the component is peeled off the adhesive sheet, and the surface of the component is observed using a microscope Whether there is residual glue (magnification: 400X).
C.高溫製程前之黏著片與被貼物之服貼狀況:在元件經由黏著片乘載情況下,使用目視觀察黏著片與被貼物之服貼狀況。 C. Adhesive state of the adhesive sheet and the object to be pasted before the high-temperature process: When the component is carried by the adhesive sheet, use visual observation to observe the state of the adhesive sheet and the object to be pasted.
D.高溫製程後之黏著片與被貼物之服貼狀況:在元件經由黏著片乘載情況下,經過200℃/30min模擬高溫製程條件後,使用目視觀察黏著片與被貼物之服貼狀況。 D. Adhesive state of the adhesive sheet and the attached object after the high-temperature process: When the component is carried by the adhesive sheet, after simulating the high-temperature process conditions at 200°C/30min, use visual observation to observe the adhesive sheet and the attached object situation.
下述含量(%)都以黏著組成物的總重計算,室溫控制在25℃條件下。 The following content (%) is calculated based on the total weight of the adhesive composition, and the room temperature is controlled at 25°C.
實施例1 Example 1
500克(g)的乙酸乙酯、貢獻黏著力單體:丙烯酸丁酯(~73%)、貢 獻內聚力單體:苯乙烯(~11%)、改性單體:丙烯酸(~16%);經The Fox Equation計算得知T-Tg>20℃;導電高分子配方:聚對苯乙烯;基膜:PI膜。 500 grams (g) of ethyl acetate, adhesion-contributing monomer: butyl acrylate (~73%), cohesion-contributing monomer: styrene (~11%), modifying monomer: acrylic acid (~16%); Calculated by The Fox Equation, it is known that TT g >20°C; conductive polymer formula: polystyrene; base film: PI film.
實施例2 Example 2
500克(g)的乙酸乙酯、貢獻黏著力單體:丙烯酸丁酯(~68%)、貢獻內聚力單體:對氯苯乙烯(~9%)、改性單體:丙烯酸(~23%);經The Fox Equation計算得知T-Tg>20℃;導電高分子配方:聚對苯乙烯;基膜:PI膜。 500 grams (g) of ethyl acetate, adhesion-contributing monomer: butyl acrylate (~68%), cohesion-contributing monomer: p-chlorostyrene (~9%), modifying monomer: acrylic acid (~23% ); Calculated by The Fox Equation, TT g >20℃; conductive polymer formula: polystyrene; base film: PI film.
實施例3 Example 3
500克(g)的乙酸乙酯、貢獻黏著力單體:丙烯酸丁酯(~68%)、貢獻內聚力單體:4-乙烯苯胺(~8%)、改性單體:丙烯酸(~24%);經The Fox Equation計算得知T-Tg>20℃;導電高分子配方:聚對苯乙烯;基膜:PI膜。 500 grams (g) of ethyl acetate, adhesion-contributing monomer: butyl acrylate (~68%), cohesion-contributing monomer: 4-vinylaniline (~8%), modifying monomer: acrylic acid (~24% ); Calculated by The Fox Equation, TT g >20℃; conductive polymer formula: polystyrene; base film: PI film.
實施例4 Example 4
500克(g)的乙酸乙酯、貢獻黏著力單體:丙烯酸丁酯(72%)、貢獻內聚力單體:4-乙烯基苯甲酸(10%)、改性單體:丙烯酸(18%);經The Fox Equation計算得知T-Tg>20℃;導電高分子配方:聚對苯乙烯;基膜:PI膜。 500 grams (g) of ethyl acetate, adhesion-contributing monomer: butyl acrylate (72%), cohesion-contributing monomer: 4-vinylbenzoic acid (10%), modifying monomer: acrylic acid (18%) ; Calculated by The Fox Equation, TT g >20℃; conductive polymer formula: polystyrene; base film: PI film.
實施例5 Example 5
500克(g)的乙酸乙酯、貢獻黏著力單體:丙烯酸丁酯(73%)、貢獻內聚力單體:苯乙烯(11%)、改性單體:丙烯酸(16%);經The Fox Equation計算得知T-Tg>20℃;導電高分子配方:聚吡咯;基膜:PI膜。 500 grams (g) of ethyl acetate, adhesion contributing monomer: butyl acrylate (73%), cohesion contributing monomer: styrene (11%), modifying monomer: acrylic acid (16%); via The Fox Equation calculation shows that TT g >20℃; conductive polymer formula: polypyrrole; base film: PI film.
實施例6 Example 6
500克(g)的乙酸乙酯、貢獻黏著力單體:丙烯酸丁酯(73%)、貢獻內聚力單體:苯乙烯(11%)、改性單體:丙烯酸(16%);經The Fox Equation計算得知T-Tg>20℃;導電高分子配方:聚噻吩;基膜:PI膜。 500 grams (g) of ethyl acetate, adhesion contributing monomer: butyl acrylate (73%), cohesion contributing monomer: styrene (11%), modifying monomer: acrylic acid (16%); via The Fox Equation calculation shows that TT g >20℃; conductive polymer formula: polythiophene; base film: PI film.
實施例7 Example 7
500克(g)的乙酸乙酯、貢獻黏著力單體:丙烯酸丁酯(73%)、貢獻內聚力單體:苯乙烯(11%)、改性單體:丙烯酸(16%);經The Fox Equation計算得知T-Tg>20℃;導電高分子配方:聚苯胺;基膜:PI膜。 500 grams (g) of ethyl acetate, adhesion contributing monomer: butyl acrylate (73%), cohesion contributing monomer: styrene (11%), modifying monomer: acrylic acid (16%); via The Fox Equation calculation shows that TT g >20℃; conductive polymer formula: polyaniline; base film: PI film.
實施例8 Example 8
500克(g)的乙酸乙酯、貢獻黏著力單體:丙烯酸丁酯(73%)、貢獻內聚力單體:苯乙烯(11%)、改性單體:丙烯酸(16%);經The Fox Equation計算得知T-Tg>20℃;導電高分子配方:聚苯硫醚;基膜:PI膜。 500 grams (g) of ethyl acetate, adhesion contributing monomer: butyl acrylate (73%), cohesion contributing monomer: styrene (11%), modifying monomer: acrylic acid (16%); via The Fox Equation calculation shows that TT g >20℃; conductive polymer formula: polyphenylene sulfide; base film: PI film.
比較例1 Comparative example 1
500克(g)的乙酸乙酯、貢獻黏著力單體:丙烯酸丁酯(~33%)、貢獻內聚力單體:苯乙烯(~5%)、改性單體:丙烯酸(~62%);經The Fox Equation計算得知T-Tg<20℃;導電高分子配方:聚對苯乙烯;基膜:PI膜。 500 grams (g) of ethyl acetate, adhesion-contributing monomer: butyl acrylate (~33%), cohesion-contributing monomer: styrene (~5%), modifying monomer: acrylic acid (~62%); Calculated by The Fox Equation, TT g <20°C; conductive polymer formula: polystyrene; base film: PI film.
比較例2 Comparative example 2
500克(g)的乙酸乙酯、貢獻黏著力單體:丙烯酸丁酯(~32%)、貢獻內聚力單體:對氯苯乙烯(~4.6%)、改性單體:丙烯酸(~63.4%);經The Fox Equation計算得知T-Tg<20℃;導電高分子配方:聚對苯乙烯;基膜:PI膜。 500 grams (g) of ethyl acetate, adhesion-contributing monomer: butyl acrylate (~32%), cohesion-contributing monomer: p-chlorostyrene (~4.6%), modifying monomer: acrylic acid (~63.4% ); calculated by The Fox Equation, TT g <20℃; conductive polymer formula: polystyrene; base film: PI film.
比較例3 Comparative example 3
500克(g)的乙酸乙酯、貢獻黏著力單體:丙烯酸丁酯(~71%)、貢獻內聚力單體:丙烯酸(~11%)、改性單體:丙烯酸(~18%);經The Fox Equation計算得知T-Tg>20℃;導電高分子配方:聚對苯乙烯;基膜:PI膜。 500 grams (g) of ethyl acetate, monomer contributing adhesion: butyl acrylate (~71%), monomer contributing cohesion: acrylic acid (~11%), monomer modifying: acrylic acid (~18%); The Fox Equation calculates that TT g >20°C; conductive polymer formula: polystyrene; base film: PI film.
比較例4 Comparative example 4
500克(g)的乙酸乙酯、貢獻黏著力單體:丙烯酸丁酯(~67%)、貢 獻內聚力單體:甲基丙烯酸(~10%)、改性單體:丙烯酸(~23%);經The Fox Equation計算得知T-Tg>20℃;導電高分子配方:聚對苯乙烯;基膜:PI膜。 500 grams (g) of ethyl acetate, adhesion contributing monomer: butyl acrylate (~67%), cohesion contributing monomer: methacrylic acid (~10%), modifying monomer: acrylic acid (~23%) ; Calculated by The Fox Equation, TT g >20℃; conductive polymer formula: polystyrene; base film: PI film.
比較例5 Comparative Example 5
500克(g)的乙酸乙酯、貢獻黏著力單體:丙烯酸丁酯(~73%)、貢獻內聚力單體:苯乙烯(~11%)、改性單體:丙烯酸(~16%);經The Fox Equation計算得知T-Tg>20℃;導電高分子配方:無;基膜:PI膜。 500 grams (g) of ethyl acetate, adhesion-contributing monomer: butyl acrylate (~73%), cohesion-contributing monomer: styrene (~11%), modifying monomer: acrylic acid (~16%); Calculated by The Fox Equation, TT g >20°C; conductive polymer formula: none; base film: PI film.
比較例6 Comparative Example 6
500克(g)的乙酸乙酯、貢獻黏著力單體:丙烯酸丁酯(~73%)、貢獻內聚力單體:苯乙烯(~11%)、改性單體:丙烯酸(~16%);經The Fox Equation計算得知T-Tg>20℃;導電高分子配方:聚乙炔;基膜:PI膜。 500 grams (g) of ethyl acetate, adhesion-contributing monomer: butyl acrylate (~73%), cohesion-contributing monomer: styrene (~11%), modifying monomer: acrylic acid (~16%); Calculated by The Fox Equation, TT g >20℃; conductive polymer formula: polyacetylene; base film: PI film.
比較例7 Comparative Example 7
500克(g)的乙酸乙酯、貢獻黏著力單體:丙烯酸丁酯(~73%)、貢獻內聚力單體:苯乙烯(~11%)、改性單體:丙烯酸(~16%);經The Fox Equation計算得知T-Tg>20℃;導電高分子配方:聚對苯乙烯;基膜:PET膜。 500 grams (g) of ethyl acetate, adhesion-contributing monomer: butyl acrylate (~73%), cohesion-contributing monomer: styrene (~11%), modifying monomer: acrylic acid (~16%); Calculated by The Fox Equation, TT g >20℃; conductive polymer formula: polystyrene; base film: PET film.
表格說明如下: The form description is as follows:
上述特定實施例之內容係為了詳細說明本發明,然而,該等實施例係僅用於說明,並非意欲限制本發明。熟習本領域之技藝者可理解,在不悖離後附申請專利範圍所界定之範疇下針對本發明所進行之各種變化或修改係落入本發明之一部分。 The content of the specific embodiments above is for explaining the present invention in detail, however, these embodiments are only for illustration and are not intended to limit the present invention. Those skilled in the art can understand that various changes or modifications made to the present invention are part of the present invention without departing from the scope defined by the appended claims.
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