TW201842107A - Heat-melt adhesive tape and method for manufacturing the same capable of enhancing the curing of an adhesion layer during heating - Google Patents
Heat-melt adhesive tape and method for manufacturing the same capable of enhancing the curing of an adhesion layer during heating Download PDFInfo
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- TW201842107A TW201842107A TW107113359A TW107113359A TW201842107A TW 201842107 A TW201842107 A TW 201842107A TW 107113359 A TW107113359 A TW 107113359A TW 107113359 A TW107113359 A TW 107113359A TW 201842107 A TW201842107 A TW 201842107A
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- 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
- C09J7/10—Adhesives in the form of films or foils without carriers
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- 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
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- 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
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/06—Non-macromolecular additives organic
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- 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
- C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Adhesive Tapes (AREA)
Abstract
Description
本發明關於熱接著膠帶等。更詳細而言,關於在使用形態即接合有被附體的形態中,不設置基材,貼附於玻璃布等之熱接著膠帶等。The present invention relates to heat-adhesive tapes and the like. In more detail, in a use form, that is, a form in which an adherend is bonded, a base material is not provided, and a heat-adhesive tape or the like attached to a glass cloth is used.
自以往以來,已知藉由加熱壓接而接著層硬化,接合被附體之熱接著膠帶。此熱接著膠帶係使用於例如在接著層的一面及另一面各自,藉由加熱壓接而接合玻璃布等的被附體,接合被附體等之用途。Conventionally, it has been known that the adhesive layer is hardened by heat and pressure bonding, and a thermal adhesive tape that joins an adherend is known. This heat-adhesive tape is used, for example, for the purpose of joining an adherend, such as a glass cloth, and joining an adherend by heat and pressure bonding to one side and the other side of an adhesive layer.
專利文獻1揭示於半導體裝置用接著膠帶中,在接著劑層中含有丙烯腈-丁二烯共聚物、酚醛清漆型酚樹脂及環氧樹脂,同時為了NBR在加熱時能自交聯,含有二烷基過氧化物類等。 專利文獻2揭示一種硬化性樹脂組成物,其係由乙烯基苄基醚化酚醛清漆樹脂、酚醛清漆型或可溶型酚樹脂、過氧化二異丙苯等的有機過氧化物及六亞甲基四胺所構成。 專利文獻3揭示一種液晶顯示單元用密封劑,其包含部分酯化環氧(甲基)丙烯酸酯樹脂、辛醯基過氧化物等的有機過氧化物、酚樹脂及有機矽化合物。 [先前技術文獻] [專利文獻]Patent Document 1 discloses that an adhesive tape for a semiconductor device contains an acrylonitrile-butadiene copolymer, a novolac-type phenol resin, and an epoxy resin in an adhesive layer, and contains NBR for self-crosslinking during heating of NBR. Alkyl peroxides and the like. Patent Document 2 discloses a curable resin composition comprising an organic peroxide such as vinyl benzyl etherified novolac resin, novolac type or soluble phenol resin, dicumyl peroxide, and hexamethylene. Composed of tetramine. Patent Document 3 discloses a sealant for a liquid crystal display unit, which includes an organic peroxide such as a partially esterified epoxy (meth) acrylate resin, an octyl peroxide, a phenol resin, and an organic silicon compound. [Prior Art Literature] [Patent Literature]
[專利文獻1]日本特開平5-291360號公報 [專利文獻2]日本特開平6-329875號公報 [專利文獻3]日本特開平9-194567號公報[Patent Document 1] Japanese Patent Laid-Open No. 5-291360 [Patent Document 2] Japanese Patent Laid-Open No. 6-329875 [Patent Document 3] Japanese Patent Laid-Open No. 9-194567
[發明所欲解決的課題][Problems to be Solved by the Invention]
為了以短時間達成熱接著膠帶對於被附體的接著,使接著層中含有酸,於熱接著膠帶的加熱壓接中,藉由此酸,例如利用於促進接著層中所包含的酚樹脂與交聯劑(硬化劑)之反應,會促進接著層之硬化。 然而,若於接著層中含有酸,則即使於熱接著膠帶的保管時等之不加熱熱接著膠帶時,也有因酸而徐徐地促進酚樹脂與交聯劑之反應,而接著層的硬化進行之情況。於熱接著膠帶的加熱壓接前,接著層的硬化已經進行時,即使將被附體加熱壓接於熱接著膠帶,也有不充分得到熱接著膠帶對於被附體的接著力之虞。 本發明之目的在於提供無基材之熱接著膠帶等,其係促進加熱時的接著層之硬化,在保管時等的不加熱時接著層不易硬化者。 [解決課題的手段]In order to achieve the adhesion of the heat-adhesive tape to the adherend in a short time, an acid is contained in the adhesive layer, and the heat and pressure of the heat-adhesive tape is used to promote the adhesion of the phenol resin and the phenol resin contained in the adhesive layer. The reaction of the cross-linking agent (hardener) will promote the hardening of the adhesive layer. However, if an acid is contained in the adhesive layer, the reaction between the phenol resin and the cross-linking agent is gradually promoted by the acid even when the thermal adhesive tape is not heated, such as during storage of the thermal adhesive tape, and the curing of the adhesive layer proceeds. Situation. Before the heat-bonding of the heat-adhesive tape and the curing of the adhesive layer has proceeded, even if the adherend is heat-pressed to the heat-adhesive tape, there is a possibility that the adhesion of the heat-adhesive tape to the adherence may not be sufficiently obtained.之 An object of the present invention is to provide a substrate-free thermal adhesive tape or the like, which promotes curing of the adhesive layer during heating, and does not easily cure the adhesive layer during non-heating such as storage. [Means for solving problems]
本發明之熱接著膠帶係不設置基材,藉由加熱壓接而接合被附體之所謂的無基材之熱接著膠帶,其特徵為具備包含丙烯腈-丁二烯橡膠、酚樹脂、因分解產生酸的過氧化物及酚樹脂交聯劑之接著層。The heat-adhesive tape of the present invention is a so-called non-base-material heat-adhesive tape which is not provided with a base material and is bonded to an adherend by heating and pressure bonding. Decomposition of acid peroxide and adhesive layer of phenol resin crosslinker.
此處,熱接著膠帶較佳為進一步具備剝離襯裡,此剝離襯裡係設置在接著層的至少一面側,可從該接著層剝離。Here, it is preferable that the heat-adhesive tape further includes a release liner which is provided on at least one side of the adhesive layer and can be peeled from the adhesive layer.
又,過氧化物係半衰期溫度較佳為130℃以上170℃以下。The peroxide-based half-life temperature is preferably 130 ° C or higher and 170 ° C or lower.
而且,接著層係將丙烯腈-丁二烯橡膠當作100質量份時,可包含0.5質量份以上5質量份以下的過氧化物。When the acrylonitrile-butadiene rubber is used as 100 parts by mass of the subsequent layer system, it may contain 0.5 to 5 parts by mass of a peroxide.
另外,本發明之不設置基材,藉由加熱壓接而接合被附體的無基材之熱接著膠帶之製造方法係特徵為包含:準備剝離襯裡之剝離襯裡準備步驟;與,將包含丙烯腈-丁二烯橡膠、酚樹脂、因分解產生酸的過氧化物及酚樹脂交聯劑之接著層用溶液塗佈於剝離襯裡,形成接著層之接著層形成步驟。 [發明的效果]In addition, the method for producing a substrate-free heat-adhesive tape of the present invention that does not include a substrate and joins an adherend by heating and pressure bonding is characterized by including: a release liner preparation step for preparing a release liner; and, it will include acrylic A solution for the adhesive layer of a nitrile-butadiene rubber, a phenol resin, a peroxide generated by decomposition and a phenol resin cross-linking agent is applied to a release liner to form an adhesive layer forming step. [Effect of the invention]
依照本發明,可提供一種無基材之熱接著膠帶等,其係促進加熱時的接著層之硬化.在保管時等的不加熱時接著層不易硬化者。According to the present invention, a substrate-free thermal adhesive tape or the like can be provided, which promotes the curing of the adhesive layer when heated. Adhesive layer is not easily hardened when not heated during storage, etc.
[實施發明的形態][Mode for Carrying Out the Invention]
以下,詳細說明實施本發明的形態。還有,本發明不受以下的實施形態所限定。又,於其要旨之範圍內,可各種變形而實施。再者,所使用的圖式係用於說明本實施形態,不是表示實際的大小。Hereinafter, embodiments of the present invention will be described in detail. The present invention is not limited to the following embodiments. In addition, various modifications can be implemented within the scope of the gist. It should be noted that the drawings used are for explaining this embodiment, and do not show actual sizes.
<熱接著膠帶之全體構成的說明> 圖1係顯示採用本實施形態的熱接著膠帶1之剖面圖。 圖示的熱接著膠帶1具備接著層3與在接著層3的一面側所設置之剝離襯裡2。將熱接著膠帶1貼附於被附體後,可剝除剝離襯裡2。再者,雖然未圖示,但是於圖1中,可在接著層3之與剝離襯裡2相反的面側,具備另一剝離襯裡等。<Explanation of the overall structure of a heat-adhesive tape> FIG. 1 is a cross-sectional view showing a heat-adhesive tape 1 according to this embodiment. The heat-adhesive tape 1 shown in the figure includes an adhesive layer 3 and a release liner 2 provided on one side of the adhesive layer 3. After the heat-adhesive tape 1 is attached to the adherend, the release liner 2 can be peeled off. Although not shown, in FIG. 1, another release liner or the like may be provided on the surface side of the adhesive layer 3 opposite to the release liner 2.
熱接著膠帶1係藉由加熱壓接而接合被附體。具體而言,例如當被附體為玻璃布時,於製造玻璃布的製造步驟中,使用於將捲取有長條玻璃布的捲筒狀之原材的端部彼此予以接合等之用途。此時,於捲筒狀的原材之端部彼此,夾住已剝離剝離襯裡2的接著層3,然後一邊加熱,一邊按壓此地方。藉此,接著層3係硬化,隔著熱接著膠帶1而接合捲筒狀的原材之端部彼此。即,本實施形態之熱接著膠帶1若不進行加熱壓接,則無法接合被附體,其係與藉由黏著力接合被附體之黏著膠帶不同。The heat-adhesive tape 1 is bonded to an adherend by thermal compression bonding. Specifically, for example, when the adherend is a glass cloth, in the manufacturing step of manufacturing the glass cloth, it is used for joining the ends of a roll-shaped raw material in which a long glass cloth is wound, and the like. At this time, between the ends of the roll-shaped raw material, the adhesive layer 3 of the peeled release liner 2 was sandwiched, and then this place was pressed while heating. Thereby, the adhesive layer 3 is hardened, and the ends of the roll-shaped raw material are joined to each other with the adhesive tape 1 interposed therebetween. That is, the thermal adhesive tape 1 of this embodiment cannot be bonded to an adherend unless it is heated and pressure-bonded, and is different from an adhesive tape that adheres to an adherend by an adhesive force.
<剝離襯裡> 剝離襯裡2係使用於製造熱接著膠帶1時,要求抑制灰塵等附著於接著層3,維持接著層3的接著性者。可作為剝離襯裡使用者係沒有特別的限制限,例如可舉出聚乙烯、聚丙烯、聚對苯二甲酸乙二酯等之合成樹脂或紙類等,於剝離襯裡之表面,為了提高接著層3的剝離性,可施予聚矽氧系剝離處理劑、長鏈烷基系剝離處理劑、氟系剝離處理劑等所致的剝離處理。剝離襯裡之厚度係沒有特別的限定,可適宜使用10μm以上200μm以下者。<Release Liner> Release Liner 2 is used in the production of the heat-adhesive tape 1, and it is required to suppress adhesion of dust and the like to the adhesive layer 3 and maintain the adhesiveness of the adhesive layer 3. There are no particular restrictions on the user who can use it as a release liner. Examples include synthetic resins such as polyethylene, polypropylene, and polyethylene terephthalate, paper, etc. on the surface of the release liner in order to improve the adhesion layer. The peelability of 3 may be a peeling treatment by a silicone-based peeling treatment agent, a long-chain alkyl-based peeling treatment agent, a fluorine-based peeling treatment agent, or the like. The thickness of the release liner is not particularly limited, and a thickness of 10 μm to 200 μm can be suitably used.
<接著層> 接著層3係因加熱而硬化,為在當時被加壓而在熱接著膠帶1與被附體之間發揮接著力之功能層。 本實施形態之熱接著膠帶1係接著層3之厚度較佳為25μm以上200μm以下。若接著層3之厚度未達25μm,則難以保持對於剪切力的強度。此處,所謂的剪切力,就是沿著熱接著膠帶之表面的方向之力。 又,若接著層3之厚度超過200μm,則在捲繞熱接著膠帶1而成為捲筒狀的製品時,捲筒的直徑變過大,或容易導入皺紋。另外,於熱接著膠帶1之製造步驟中,溶劑易殘存,或在接著層3表面容易形成凹凸而外觀易變差。<Adhesive layer> The adhesive layer 3 is a functional layer that is hardened by heating and exerts an adhesive force between the thermal adhesive tape 1 and the adherend at the time when it is pressed. (2) The thickness of the heat-adhesive tape 1 of this embodiment is preferably 25 μm or more and 200 μm or less. If the thickness of the adhesive layer 3 is less than 25 μm, it is difficult to maintain the strength against the shear force. Here, the so-called shearing force is a force in a direction of thermally bonding the surface of the tape. In addition, if the thickness of the adhesive layer 3 exceeds 200 μm, when the thermal adhesive tape 1 is wound into a roll-shaped product, the diameter of the roll becomes too large, or wrinkles are easily introduced. In addition, in the manufacturing step of the heat-adhesive tape 1, the solvent tends to remain, or unevenness is easily formed on the surface of the adhesive layer 3, and the appearance is liable to deteriorate.
另外,於本實施形態中,接著層3包含丙烯腈-丁二烯橡膠、酚樹脂、過氧化物及酚樹脂交聯劑。In the present embodiment, the adhesive layer 3 includes an acrylonitrile-butadiene rubber, a phenol resin, a peroxide, and a phenol resin crosslinking agent.
丙烯腈-丁二烯橡膠之構造係沒有特別的限定。例如,可使用直鏈狀的丙烯腈-丁二烯橡膠及具有分枝構造的丙烯腈-丁二烯橡膠之任一者。惟,於本實施形態中,更佳為使用具有分枝構造的丙烯腈-丁二烯橡膠。 具有分枝構造的丙烯腈-丁二烯橡膠,係可對於接著層3賦予適度的柔軟性,同時可賦予極高的內聚力。本實施形態中所使用之具有分枝構造的丙烯腈-丁二烯橡膠係在丙烯腈-丁二烯橡膠之中,歸類為在聚合溫度25℃~50℃所製造的熱橡膠,例如以下述化1式表示。The structure of the acrylonitrile-butadiene rubber is not particularly limited. For example, either a linear acrylonitrile-butadiene rubber or an acrylonitrile-butadiene rubber having a branched structure can be used. However, in this embodiment, it is more preferable to use an acrylonitrile-butadiene rubber having a branched structure.的 Acrylonitrile-butadiene rubber having a branched structure can impart moderate softness to the adhesive layer 3, and at the same time can provide extremely high cohesion. The acrylonitrile-butadiene rubber having a branched structure used in this embodiment is among acrylonitrile-butadiene rubbers, and is classified as a hot rubber produced at a polymerization temperature of 25 ° C to 50 ° C. For example, the following Said formula 1 expression.
又,下述化2式之通式(1)為直鏈狀的丙烯腈-丁二烯橡膠之構造式。此處,m、n為1以上之整數。以化1式表示之具有分枝構造的丙烯腈-丁二烯橡膠,係通式(1)中的丁二烯之雙鍵裂開,於該處進一步鍵結以通式(1)表示的構造。即,化1式中曲線所示的各自之線係各自具有以通式(1)表示的構造。 於本實施形態中,作為具有分枝構造的丙烯腈-丁二烯橡膠,例如可使用重量平均分子量(Mw)為30萬者。The general formula (1) of the following formula 2 is a structural formula of a linear acrylonitrile-butadiene rubber. Here, m and n are integers of 1 or more. The acrylonitrile-butadiene rubber having a branched structure represented by the formula (1) is a double bond of butadiene in the general formula (1) is cleaved, and further a compound represented by the general formula (1) is bonded there. structure. That is, each line system shown by a curve in Formula 1 has a structure represented by General formula (1). In this embodiment, as the acrylonitrile-butadiene rubber having a branched structure, for example, a weight average molecular weight (Mw) of 300,000 can be used.
酚樹脂係對於接著層3賦予熱硬化性、耐熱性、接著性。本實施形態所用之酚樹脂係沒有特別的限定,可適宜使用在酸觸媒下將酚類與甲醛合成之酚醛清漆樹脂。又,作為酚類,可舉出苯酚、甲酚、二甲苯酚、烷基苯酚、鹵化苯酚、芳基苯酚、胺基苯酚、硝基苯酚、雙酚A、多元苯酚、此等的衍生物等。另外,可單獨或混合2種以上而使用此等。A phenol resin system provides thermosetting, heat resistance, and adhesiveness to the adhesive layer 3. The phenol resin used in this embodiment is not particularly limited, and a novolak resin that synthesizes phenols and formaldehyde under an acid catalyst can be suitably used. Examples of the phenols include phenol, cresol, xylenol, alkylphenol, halogenated phenol, arylphenol, aminophenol, nitrophenol, bisphenol A, polyphenol, and derivatives thereof. . In addition, these can be used individually or in mixture of 2 or more types.
過氧化物係於熱接著膠帶1的加熱時,進行熱分解,藉由所產生的游離自由基而交聯丙烯腈-丁二烯橡膠。 此處,於本實施形態中,可適宜使用因分解產生酸的過氧化物。即,若此過氧化物含於接著層3中,則在加熱熱接著膠帶1時,接著層3的硬化速度升高。具體而言,若加熱本實施形態之熱接著膠帶1,則如上述,首先過氧化物進行熱分解,藉由所產生的游離自由基而交聯丙烯腈-丁二烯橡膠。此時,游離自由基係與從丙烯腈-丁二烯橡膠所拉出的氫反應,生成酸。接著,藉由此酸,促進酚樹脂與酚樹脂交聯劑之反應,發生酚樹脂之交聯,促進酚樹脂之硬化,而接著層3硬化速度升高。The peroxide is thermally decomposed when the adhesive tape 1 is heated, and the acrylonitrile-butadiene rubber is crosslinked by the generated free radicals. Here, in this embodiment, a peroxide that generates an acid due to decomposition can be suitably used. That is, if this peroxide is contained in the adhesive layer 3, when the adhesive tape 1 is heated and heated, the curing speed of the adhesive layer 3 increases. Specifically, when the heat-adhesive tape 1 of this embodiment is heated, as described above, the peroxide is first thermally decomposed, and the acrylonitrile-butadiene rubber is crosslinked by the generated free radicals. At this time, the free radical system reacts with hydrogen drawn from the acrylonitrile-butadiene rubber to generate an acid. Then, by this acid, the reaction between the phenol resin and the phenol resin cross-linking agent is promoted, crosslinking of the phenol resin occurs, the hardening of the phenol resin is promoted, and then the hardening speed of the layer 3 is increased.
另一方面,本實施形態之接著層3中所包含的過氧化物,係在室溫環境下等之不加熱熱接著膠帶1時,不易發生分解,難以產生酸。又,過氧化物本身係不直接影響酚樹脂之反應。因此,不加熱熱接著膠帶1時,酚樹脂不易硬化。On the other hand, the peroxide contained in the adhesive layer 3 of the present embodiment is hard to decompose when the adhesive tape 1 is heated without heating under room temperature environment, and it is difficult to generate acid. The peroxide itself does not directly affect the reaction of the phenol resin. Therefore, when the adhesive tape 1 is bonded without heating, the phenol resin is hardly hardened.
又,過氧化物係半衰期溫度較佳為130℃以上170℃以下。 此處,所謂的半衰期溫度,就是加熱過氧化物1分鐘時,因過氧化物分解而過氧化物之濃度從即將加熱之前的濃度減半之溫度。The peroxide-based half-life temperature is preferably 130 ° C or higher and 170 ° C or lower. Here, the so-called half-life temperature is the temperature at which the peroxide concentration is reduced by half from the concentration immediately before heating due to peroxide decomposition when the peroxide is heated for 1 minute.
過氧化物的半衰期溫度比170℃更高時,在加熱過氧化物時,過氧化物分解速度慢,不易產生酸。此時,難以促進將熱接著膠帶1加熱時的酚樹脂之硬化。 過氧化物的半衰期溫度比130℃更低時,即使在不加熱過氧化物時,也過氧化物分解而容易產生酸。此時,即使於熱接著膠帶1的保管時等之不加熱熱接著膠帶1時,也酚樹脂的硬化容易進行。When the half-life temperature of the peroxide is higher than 170 ° C, when the peroxide is heated, the peroxide decomposes slowly and it is difficult to generate acid. In this case, it is difficult to promote hardening of the phenol resin when the thermal adhesive tape 1 is heated. When the half-life temperature of gadolinium peroxide is lower than 130 ° C, even when the peroxide is not heated, the peroxide is decomposed and an acid is easily generated. In this case, even when the heat-adhesive tape 1 is not heated during storage of the heat-adhesive tape 1 or the like, the curing of the phenol resin is easy.
又,將丙烯腈-丁二烯橡膠當作100質量份時,接著層3較佳為包含0.5質量份以上5質量份以下的過氧化物。 若過氧化物未達0.5質量份,則由此過氧化物所產生的酸之量少,難以促進將熱接著膠帶1加熱時的酚樹脂之硬化。 另外,若過氧化物超過5質量份,則在不加熱過氧化物時,過氧化物徐徐地分解,所產生的酸之量變多。此時,即使於熱接著膠帶1的保管時等之不加熱熱接著膠帶1時,也酚樹脂的硬化容易進行。When the acrylonitrile-butadiene rubber is taken as 100 parts by mass, the adhesive layer 3 preferably contains 0.5 to 5 parts by mass of a peroxide. If the peroxide is less than 0.5 parts by mass, the amount of acid generated by the peroxide is small, and it is difficult to promote hardening of the phenol resin when the heat-adhesive tape 1 is heated. In addition, when the peroxide exceeds 5 parts by mass, when the peroxide is not heated, the peroxide is slowly decomposed, and the amount of acid generated is increased. In this case, even when the heat-adhesive tape 1 is not heated during storage of the heat-adhesive tape 1 or the like, the curing of the phenol resin is easy.
作為因分解產生酸的過氧化物,可適宜使用二醯基過氧化物或過氧酯。又,於本實施形態中,可單獨或混合2種以上而使用此等。作為二醯基過氧化物,例如可舉出日油股份有限公司製的Nyper(註冊商標)BMT或Peroyl(註冊商標)L等。另外,作為過氧酯,例如可舉出日油股份有限公司製的Perbutyl(註冊商標)O或Perbutyl Z等。As the peroxide that generates an acid due to decomposition, a difluorenyl peroxide or a peroxyester can be suitably used. Moreover, in this embodiment, these can be used individually or in mixture of 2 or more types. Examples of the difluorenyl peroxide include Nyper (registered trademark) BMT or Peroyl (registered trademark) L manufactured by Nippon Oil Co., Ltd. Examples of the peroxyester include Perbutyl (registered trademark) O or Perbutyl Z manufactured by Nippon Oil Corporation.
酚樹脂交聯劑係在加熱熱接著膠帶1時,與酚樹脂發生加成縮合反應,使酚樹脂以更短時間硬化。酚樹脂交聯劑亦稱為酚樹脂的交聯促進劑、硬化劑。作為酚樹脂交聯劑,可舉出六亞甲基四胺(hexamine)、羥甲基三聚氰胺及羥甲基脲等。可單獨或混合2種以上而使用此等。還有,於本實施形態中,在其中可適宜使用六亞甲基四胺(hexamine)。The phenol resin cross-linking agent undergoes an addition condensation reaction with the phenol resin when the adhesive tape 1 is heated and heated, so that the phenol resin hardens in a shorter time. The phenol resin cross-linking agent is also called a phenol resin cross-linking accelerator and a hardener. Examples of the phenol resin crosslinking agent include hexamine tetramethylamine (hexamine), methylolmelamine, and methylolurea. These can be used individually or in mixture of 2 or more types. In this embodiment, hexamine can be suitably used among them.
再者,接著層3係在本實施形態的要旨之範圍內,可進一步包含其他的樹脂或橡膠等。又,於塗佈後述之塗佈液的接著層用溶液時,為了提高塗佈性,可進一步包含增黏劑或抑制發泡、抑制外觀的皸裂用之消泡劑。The adhesive layer 3 is within the scope of the gist of this embodiment, and may further include other resins, rubbers, and the like. In addition, when applying the solution for an adhesive layer of a coating liquid described later, in order to improve the coatability, a thickener or an antifoaming agent for suppressing foaming and cracking of appearance may be further included.
<熱接著膠帶之製造方法> 圖2係說明熱接著膠帶1之製造方法的流程圖。 首先,準備剝離襯裡2之(步驟101:剝離襯裡準備步驟)。<The manufacturing method of a heat-adhesive tape> FIG. 2 is a flowchart explaining the manufacturing method of a heat-adhesive tape 1. First, prepare the release liner 2 (step 101: release liner preparation step).
其次,製作用於塗佈接著層3的接著層用溶液(步驟102:接著層用溶液製作步驟)。此接著層用溶液包含上述的丙烯腈-丁二烯橡膠、酚樹脂、過氧化物及酚樹脂交聯劑,將此等投入至指定的溶劑後,進行攪拌。還有,作為此接著層用溶液,亦可使用市售品。Next, a solution for an adhesive layer for applying the adhesive layer 3 is prepared (step 102: a solution for an adhesive layer production step). This solution for the adhesive layer contains the acrylonitrile-butadiene rubber, phenol resin, peroxide, and phenol resin cross-linking agent described above, and after adding these to a predetermined solvent, stirring is performed. A commercially available product may be used as the solution for the adhesive layer.
然後,於剝離襯裡2上塗佈接著層用溶液,而形成塗佈膜(步驟103)。 再者,使此塗佈膜乾燥,而在剝離襯裡2之上形成接著層3(步驟:104)。此步驟103、步驟104之步驟係在剝離襯裡2上塗佈接著層用溶液,可當作形成接著層3之接著層形成步驟。Then, a solution for an adhesive layer is applied on the release liner 2 to form a coating film (step 103). Furthermore, this coating film is dried, and the adhesive layer 3 is formed on the release liner 2 (step: 104). The steps of step 103 and step 104 are to apply a solution for an adhesive layer on the release liner 2 and can be regarded as an adhesive layer forming step of forming the adhesive layer 3.
藉由以上之步驟,使接著層3之厚度成為25μm以上200μm以下,可製造本實施形態之熱接著膠帶1。 依照以上詳述的形態,可提供不設置基材的無基材之熱接著膠帶1。By the above steps, the thickness of the adhesive layer 3 is 25 μm or more and 200 μm or less, and the thermal adhesive tape 1 of this embodiment can be manufactured. According to the aspect detailed above, a baseless heat-adhesive tape 1 without a base material can be provided.
又,將被附體加熱壓接於熱接著膠帶1時,接著層3中所包含的過氧化物係分解而產生酸,此酸係促進酚樹脂與酚樹脂交聯劑之硬化。因此,接著層3硬化的速度升高,熱接著膠帶1係以短時間接著於被附體。 另一方面,不加熱熱接著膠帶1時,由於過氧化物的分解不易發生而難以產生酸,接著層3的硬化不易進行。因此,在不使用熱接著膠帶1的保管期間,熱接著膠帶1不易喪失接著力。 [實施例]In addition, when the adherend is heated and pressure-bonded to the heat-adhesive tape 1, the peroxide system contained in the adhesive layer 3 is decomposed to generate an acid, and this acid system promotes the hardening of the phenol resin and the phenol resin crosslinking agent. Therefore, the curing speed of the adhesive layer 3 is increased, and the thermal adhesive tape 1 is adhered to the adherend in a short time. On the other hand, when the adhesive tape 1 is adhered without heating, the decomposition of the peroxide is unlikely to occur, and it is difficult to generate an acid, and the curing of the adhesive layer 3 is not easily performed. Therefore, during storage without using the heat-adhesive tape 1, the heat-adhesive tape 1 does not easily lose the adhesive force. [Example]
以下,使用實施例,更詳細地說明本發明。本發明只要不超出其要旨,則不受此等的實施例所限定。Hereinafter, the present invention will be described in more detail using examples. The present invention is not limited to these examples as long as the gist is not exceeded.
製作圖1所示的熱接著膠帶1,進行評價。還有,下述表1中顯示實施條件及評價結果。 [熱接著膠帶1之製作] (實施例1) 於本實施例中,作為剝離襯裡2,使用厚度120μm者。然後,於剝離襯裡2的一面側,如以下地形成接著層3。 首先,使用醋酸乙酯作為溶劑,於此溶劑中投入具有分枝構造的丙烯腈-丁二烯橡膠、酚樹脂、過氧化物及酚樹脂交聯劑,攪拌而使其溶解,製作固體成分濃度40質量%之接著層用溶液。此時,作為具有分枝構造的丙烯腈-丁二烯橡膠,使用日本ZEON股份有限公司製的Nipol(註冊商標)1001LG。又,作為酚樹脂,使用荒川化學工業股份有限公司製的Tamanol(註冊商標)531。再者,於Tamanol 531中,作為酚樹脂交聯劑,包含9質量%的六亞甲基四胺(hexamine)。另外,具有分枝構造的丙烯腈-丁二烯橡膠與酚樹脂之質量比率為100/120。還有,作為過氧化物,使用日油股份有限公司製的Nyper BMT。The heat-adhesive tape 1 shown in FIG. 1 was produced and evaluated. The conditions and evaluation results are shown in Table 1 below. [Production of Thermal Adhesive Tape 1] (Example 1) In this example, as the release liner 2, a thickness of 120 μm was used. Then, on one surface side of the release liner 2, an adhesive layer 3 was formed as follows. First, ethyl acetate is used as a solvent, and acrylonitrile-butadiene rubber having a branched structure, a phenol resin, a peroxide, and a phenol resin cross-linking agent are added to the solvent, and they are stirred and dissolved to prepare a solid content concentration. 40% by mass of a solution for an adhesive layer. At this time, as the acrylonitrile-butadiene rubber having a branched structure, Nipol (registered trademark) 1001LG manufactured by Japan Zeon Corporation was used. As the phenol resin, Tamanol (registered trademark) 531 manufactured by Arakawa Chemical Industries, Ltd. was used. In addition, Tamanol 531 contains 9% by mass of hexamine as a phenol resin crosslinking agent. In addition, the mass ratio of the acrylonitrile-butadiene rubber having a branched structure to the phenol resin was 100/120. As the peroxide, Nyper BMT manufactured by Nippon Oil Co., Ltd. was used.
下述化3式之通式(2)為Nyper BMT之構造式。又,下述化4式之通式(3)為加熱Nyper BMT而使其分解時的反應式,為Nyper BMT的一部分構造之過氧化苯甲醯分解時的反應式。若加熱通式(3)中的過氧化苯甲醯,則氧-氧鍵係裂開,相對於過氧化苯甲醯,生成2當量的苯基自由基,各個苯基自由基係變成苯甲酸。即,若將過氧化苯甲醯予以熱分解,則相對於此過氧化苯甲醯,產生2當量的酸。又,若將通式(2)中的Nyper BMT之另一部分構造的苯甲醯基間甲基苯甲醯基過氧化物予以熱分解,則相對於此苯甲醯基間甲基苯甲醯基過氧化物,產生2當量的酸。另外,若將通式(2)中的Nyper BMT之更另一部分的構造之間甲苯醯基過氧化物予以熱分解,則相對於此間甲苯醯基過氧化物,產生2當量的酸。即,若將Nyper BMT予以熱分解,則相對於此Nyper BMT,產生2當量的酸。 另外,Nyper BMT之半衰期溫度為131℃。又,將丙烯腈-丁二烯橡膠當作100質量份時,接著層3包含3質量份的Nyper BMT。The general formula (2) of the following formula 3 is a structural formula of Nyper BMT. In addition, the general formula (3) of the following formula 4 is a reaction formula when Nyper BMT is heated and decomposed, and is a reaction formula when benzamidine peroxide having a part of the structure of Nyper BMT is decomposed. When benzophenazine peroxide in the general formula (3) is heated, the oxygen-oxygen bond system is cleaved, and 2 equivalents of phenyl radicals are generated relative to benzophenazine peroxide, and each phenyl radical system becomes benzoic acid . That is, if benzophenazine peroxide is thermally decomposed, 2 equivalents of acid will be generated with respect to this benzophenazine peroxide. In addition, if the benzamyl m-toluenyl peroxide structure of another part of Nyper BMT in the general formula (2) is thermally decomposed, the benzamyl m-toluenyl peroxide Radical peroxide, yielding 2 equivalents of acid. In addition, if the toluenyl peroxide of another structure of Nyper BMT in the general formula (2) is thermally decomposed, 2 equivalents of acid are generated relative to the toluenyl peroxide. That is, when Nyper BMT is thermally decomposed, 2 equivalents of acid are generated relative to this Nyper BMT. In addition, the half-life temperature of Nyper BMT is 131 ° C. When acrylonitrile-butadiene rubber is taken as 100 parts by mass, the adhesive layer 3 contains 3 parts by mass of Nyper BMT.
然後,於剝離襯裡2之上塗佈接著層用溶液,使其乾燥而形成接著層3。而且,將接著層3之厚度設為50mm。 藉由以上之步驟,製作本實施例之熱接著膠帶1。Then, the adhesive layer solution was applied on the release liner 2 and dried to form an adhesive layer 3. The thickness of the adhesive layer 3 was set to 50 mm. Through the above steps, the heat-adhesive tape 1 of this embodiment is produced.
(實施例2~8) 除了對於實施例1,如表1所示地進行變更以外,與實施例1同樣地製作熱接著膠帶1。 即,於實施例2、3、6中,使用將接著層3中所包含的過氧化物之種類變更者。具體而言,於實施例2中,使用日油股份有限公司製的Perbutyl O。下述化5式之通式(4)係作為Perbutyl O的2-乙基己醯基第三丁基過氧化物之構造式。若加熱通式(4)中的2-乙基己醯基第三丁基過氧化物,則氧-氧鍵係裂開,相對於2-乙基己醯基第三丁基過氧化物,生成1當量的自由基,此自由基係變成羧酸。即,若將Perbutyl O予以熱分解,則相對於此Perbutyl O,產生1當量的酸。再者,Perbutyl O之半衰期溫度為134℃。又,將丙烯腈-丁二烯橡膠當作100質量份時,接著層3包含3質量份的Perbutyl O。(Examples 2 to 8) 热 A heat-adhesive tape 1 was produced in the same manner as in Example 1 except that Example 1 was changed as shown in Table 1. That is, in Examples 2, 3, and 6, the type of the peroxide contained in the bonding layer 3 was changed. Specifically, in Example 2, Perbutyl O manufactured by Nippon Oil Co., Ltd. was used. The general formula (4) of the following formula 5 is a structural formula of 2-ethylhexyltributyltributyl peroxide which is Perbutyl O. When the 2-ethylhexyltributyltributyl peroxide in the general formula (4) is heated, the oxygen-oxygen bond system is cleaved. One equivalent of free radicals is generated, and this free radical system becomes a carboxylic acid. That is, when Perbutyl O is thermally decomposed, 1 equivalent of acid is generated with respect to this Perbutyl O. The half-life temperature of Perbutyl O was 134 ° C. When acrylonitrile-butadiene rubber is taken as 100 parts by mass, the adhesive layer 3 contains 3 parts by mass of Perbutyl O.
又,於實施例3中,使用日油股份有限公司製的Perbutyl Z。下述化6式之通式(5)係作為Perbutyl Z的第三丁基苯甲醯基過氧化物之構造式。若加熱通式(5)中的第三丁基苯甲醯基過氧化物,則氧-氧鍵係裂開,相對於第三丁基苯甲醯基過氧化物,生成1當量的自由基,此自由基係變成羧酸。即,若將Perbutyl Z予以熱分解,則相對於此Perbutyl Z,產生1當量的酸。再者,Perbutyl Z之半衰期溫度為167℃。又,將丙烯腈-丁二烯橡膠當作100質量份時,接著層3包含3質量份的Perbutyl Z。In Example 3, Perbutyl Z manufactured by Nippon Oil Co., Ltd. was used. The general formula (5) of the following formula 6 is a structural formula of a third butylbenzylhydrazine peroxide as Perbutyl Z. When the third butylbenzylfluorenyl peroxide in the general formula (5) is heated, the oxygen-oxygen bond system is cleaved, and 1 equivalent of a radical is generated relative to the third butylbenzylfluorenyl peroxide. This free radical becomes a carboxylic acid. That is, when Perbutyl Z is thermally decomposed, 1 equivalent of acid is generated with respect to this Perbutyl Z. The half-life temperature of Perbutyl Z is 167 ° C. When acrylonitrile-butadiene rubber is taken as 100 parts by mass, the adhesive layer 3 contains 3 parts by mass of Perbutyl Z.
又,於實施例6中,使用日油股份有限公司製的Peroyl L。下述化7式之通式(6)係作為Peroyl L的雙十二醯基過氧化物之構造式。若加熱通式(6)中的雙十二醯基過氧化物,則氧-氧鍵係裂開,相對於雙十二醯基過氧化物,生成2當量的自由基,各個自由基係變成羧酸。即,若將Peroyl L予以熱分解,則相對於此Peroyl L,產生2當量的酸。另外,Peroyl L之半衰期溫度為116℃。又,將丙烯腈-丁二烯橡膠當作100質量份時,接著層3包含3質量份的Peroyl L。In Example 6, Peroyl L manufactured by Nippon Oil Co., Ltd. was used. The general formula (6) of the following formula 7 is a structural formula of a dodecylfluorene peroxide of Peroyl L. When the dodecylfluorenyl peroxide in the general formula (6) is heated, the oxygen-oxygen bond system is cleaved, and 2 equivalents of free radicals are generated relative to the dodecylfluorenyl peroxide, and each radical system becomes carboxylic acid. That is, when Peroyl L is thermally decomposed, 2 equivalents of acid are generated with respect to this Peroyl L. The half-life temperature of Peroyl L was 116 ° C. When the acrylonitrile-butadiene rubber is taken as 100 parts by mass, the adhesive layer 3 contains 3 parts by mass of Peroyl L.
又,於實施例4、5中,變更接著層3中所包含的過氧化物之量。具體而言,於實施例4中,將丙烯腈-丁二烯橡膠當作100質量份時,包含0.4質量份的Nyper BMT。另外,於實施例5中,將丙烯腈-丁二烯橡膠當作100質量份時,包含6質量份的Nyper BMT。Moreover, in Examples 4 and 5, the amount of the peroxide contained in the adhesion layer 3 was changed. Specifically, in Example 4, when acrylonitrile-butadiene rubber was taken as 100 parts by mass, 0.4 parts by mass of Nyper BMT was included. In addition, in Example 5, when acrylonitrile-butadiene rubber was taken as 100 parts by mass, 6 parts by mass of Nyper BMT was included.
又,於實施例7、8中,變更接著層3之厚度。具體而言,於實施例7中,將接著層3之厚度設為25 μm。再者,於實施例8中,將接著層3之厚度設為200 μm。In Examples 7 and 8, the thickness of the adhesive layer 3 was changed. Specifically, in Example 7, the thickness of the adhesive layer 3 was set to 25 μm. In Example 8, the thickness of the adhesive layer 3 was set to 200 μm.
(比較例1~3) 除了對於實施例1,如表1所示地進行變更以外,與實施例1同樣地製作熱接著膠帶1。 即,於比較例1中,在接著層3中不含過氧化物。 又,於比較例2中,作為過氧化物之替代物的苯甲酸係含於接著層3中。具體而言,將丙烯腈-丁二烯橡膠當作100質量份時,包含3質量份的苯甲酸。 另外,於比較例3中,作為過氧化物,使用日油股份有限公司製的Perhexyl(註冊商標)I。下述化8式之通式(7)係作為Perhexyl I的第三己基過氧異丙基單碳酸酯之構造式。若加熱通式(7)中的第三己基過氧異丙基單碳酸酯,則生成自由基及二氧化碳,但不產生酸。另外,Perhexyl I之半衰期溫度為155℃。又,將丙烯腈-丁二烯橡膠當作100質量份時,接著層3包含3質量份的Perhexyl I。(Comparative Examples 1 to 3) 热 A heat-adhesive tape 1 was produced in the same manner as in Example 1 except that Example 1 was changed as shown in Table 1. That is, in Comparative Example 1, no peroxide was contained in the adhesive layer 3. In addition, in Comparative Example 2, benzoic acid as a substitute for peroxide is contained in the adhesive layer 3. Specifically, when 100 parts by mass of acrylonitrile-butadiene rubber is used, 3 parts by mass of benzoic acid is included. In Comparative Example 3, as a peroxide, Perhexyl (registered trademark) I manufactured by Nippon Oil Co., Ltd. was used. The general formula (7) of the following formula 8 is a structural formula of the third hexylperoxyisopropyl monocarbonate as Perhexyl I. When the third hexylperoxyisopropyl monocarbonate in the general formula (7) is heated, radicals and carbon dioxide are generated, but no acid is generated. The half-life temperature of Perhexyl I was 155 ° C. When the acrylonitrile-butadiene rubber is taken as 100 parts by mass, the adhesive layer 3 contains 3 parts by mass of Perhexyl I.
作為實施例1~8及比較例1~3之評價,進行保管前之熱接著膠帶的接著力之評價(保管前接著力評價)及保管前之熱接著膠帶的不溶解分之評價(保管前不溶解分評價)。又,進行保管後之熱接著膠帶的接著力之評價(保管後接著力評價)及保管後之熱接著膠帶的不溶解分之評價(保管後不溶解分評價)。As the evaluations of Examples 1 to 8 and Comparative Examples 1 to 3, the evaluation of the adhesive strength of the thermal adhesive tape before storage (evaluation of the adhesive strength before storage) and the evaluation of the insoluble content of the thermal adhesive tape before storage (before storage) Evaluation of insoluble content). Further, the evaluation of the adhesive strength of the thermal adhesive tape after storage (evaluation of the adhesive strength after storage) and the evaluation of the insoluble content of the thermal adhesive tape after storage (evaluation of the insoluble content after storage) were performed.
[保管前接著力評價之方法] 作為實施例1~8及比較例1~3之熱接著膠帶的接著力之評價,將剪切力施加於熱接著膠帶,評價對於此的接著力。 具體而言,準備2片玻璃布,以此2片玻璃布夾住熱接著膠帶,藉由加熱壓接,以熱接著膠帶接合2片玻璃布。評價中使用的玻璃布之厚度為0.17mm,斷裂強度約300N/10mm。 再者,準備於2種的加熱壓接之條件下,以熱接著膠帶接合玻璃布者。具體而言,準備以160℃、1.47×105 N/m2 之壓力,進行20秒的按壓,而以熱接著膠帶接合玻璃布者,及以170℃、1.47×105 N/m2 之壓力,進行10秒的按壓,而以熱接著膠帶接合玻璃布者。[Method for evaluating adhesive force before storage] As an evaluation of the adhesive force of the thermal adhesive tapes of Examples 1 to 8 and Comparative Examples 1 to 3, a shearing force was applied to the thermal adhesive tape, and the adhesive force was evaluated. Specifically, two glass cloths were prepared, and the two glass cloths were sandwiched with the heat-adhesive tape, and the two glass cloths were bonded with the heat-adhesive tape by heating and pressure bonding. The thickness of the glass cloth used in the evaluation was 0.17 mm, and the breaking strength was about 300 N / 10 mm. In addition, it is prepared to join glass cloths by heat-adhesive tape under two kinds of conditions of thermocompression bonding. Specifically, it is prepared to press for 20 seconds at a temperature of 160 ° C and a pressure of 1.47 × 10 5 N / m 2 , while bonding the glass cloth with a heat-adhesive tape, and a temperature of 170 ° C and 1.47 × 10 5 N / m 2 . The pressure was applied for 10 seconds, and the glass cloth was joined by heat-adhesive tape.
然後,以拉伸速度200mm/分鐘,拉伸所製作的作為被附體之2片玻璃布,於此條件下在玻璃布與熱接著膠帶之間發生剝離之前,以玻璃布是否被破壞,進行對於剪切力而言接著力之評價。即,關於接著力,在玻璃布與熱接著膠帶之間發生剝離之前,當玻璃布被破壞時,意指剪切力大於玻璃布的斷裂強度,因此將此時評價為合格,當發生剝離時,評價為不合格。Then, the produced two glass cloths as an adherend were stretched at a stretching speed of 200 mm / minute. Under this condition, before the glass cloth was peeled from the heat-adhesive tape, whether the glass cloth was broken or not was performed. Evaluation of the shear force for the shear force. That is, regarding the adhesive force, before the glass cloth and the heat-adhesive tape are peeled off, when the glass cloth is broken, it means that the shearing force is greater than the breaking strength of the glass cloth. , Evaluated as unqualified.
[保管前不溶解分評價之方法] 又,作為實施例1~8及比較例1~3之熱接著膠帶的加熱壓接時,接著層硬化速度之評價,評價加熱壓接後的熱接著膠帶之不溶解分。此處,所謂的熱接著膠帶之不溶解分,就是意指相對於熱接著膠帶的全部重量而言,熱接著膠帶中的不溶解於溶劑之部分的重量比例。 酸與酚樹脂反應而生成的生成物,係具有在溶劑中不溶的性質。因此,茲認為加熱壓接後的熱接著膠帶之不溶解分愈多,在加熱壓接時產生愈多的酸,反應係進行。在加熱壓接時產生的酸量愈多,接著層硬化速度愈快。[Method for evaluating insolubilized content before storage] Also, as the heat-bonding of the heat-adhesive tapes of Examples 1 to 8 and Comparative Examples 1 to 3, the evaluation of the curing speed of the adhesive layer was evaluated to evaluate the heat-adhesive tapes after heat-compression. Its insoluble content. Here, the insoluble content of the heat-adhesive tape refers to the weight ratio of the solvent-insoluble portion of the heat-adhesive tape relative to the total weight of the heat-adhesive tape. The product produced by the reaction of osmic acid and a phenol resin is insoluble in a solvent. Therefore, it is considered that the more the insoluble content of the heat-adhesive tape after the heat-compression bonding, the more acid is generated during the heat-compression bonding, and the reaction proceeds. The more acid is generated during thermal compression, the faster the layer hardens.
作為加熱壓接後的熱接著膠帶之不溶解分的具體評價方法,首先準備2片的由聚對苯二甲酸乙二酯所構成之剝離襯裡,以此2片剝離襯裡夾住熱接著膠帶,藉由加熱壓接,以熱接著膠帶接合2片剝離襯裡。 再者,加熱壓接之條件係與保管前接著力評價中的加熱壓接之條件同樣。即,準備以160℃、1.47×105 N/m2 之壓力,進行20秒的按壓,而以熱接著膠帶接合剝離襯裡者,及以170℃、1.47×105 N/m2 之壓力,進行10秒的按壓,而以熱接著膠帶接合剝離襯裡者。As a specific evaluation method of the insoluble content of the heat-adhesive tape after heat compression bonding, first prepare two pieces of release liners composed of polyethylene terephthalate, and sandwich the heat-adhesive tapes with the two pieces of release liners. The two release liners were bonded by heat and pressure bonding with heat-adhesive tape. In addition, the conditions of thermocompression bonding are the same as the conditions of thermocompression bonding in the force evaluation before storage. That is, a person who is ready to press at 160 ° C. and a pressure of 1.47 × 10 5 N / m 2 for 20 seconds, and is bonded to the release liner with a heat-adhesive tape, and a pressure of 170 ° C. and 1.47 × 10 5 N / m 2 , The pressing was performed for 10 seconds, and the release liner was bonded with heat-adhesive tape.
接著,從熱接著膠帶剝落剝離襯裡,測定已剝落剝離襯裡的熱接著膠帶之重量,將測定值當作W1。再者,作為熱接著膠帶之重量,使用約0.1g~0.2g者。 然後,將此熱接著膠帶浸漬於當作溶劑的10g~20g之甲基乙基酮中,以混合轉子(mix rotor)攪拌24小時。接著,使用不鏽鋼網來過濾溶液,提取熱接著膠帶之不溶解分。不鏽鋼網係使用100網目(mesh)者。再者,將此篩網之未使用時的重量當作重量W2。 然後,藉由防爆型乾燥機,使熱接著膠帶的不溶解分殘存的篩網在80℃之環境下乾燥,然後放置冷卻。接著,測定此篩網的重量,將測定值當作W3。然後,評價由((W3-W2)/W1)所算出的不溶解分。另外,關於實施例1~8及比較例1~3之熱接著膠帶,加熱壓接前的不溶解分皆0%。Next, the release liner was peeled from the heat-adhesive tape, and the weight of the heat-adhesive tape with the peeled release liner was measured, and the measured value was taken as W1. The weight of the heat-adhesive tape is about 0.1 g to 0.2 g. Then, this hot-adhesive tape was immersed in 10 g to 20 g of methyl ethyl ketone as a solvent, and stirred with a mix rotor for 24 hours. Next, the solution was filtered using a stainless steel mesh to extract the insoluble content of the heat-adhesive tape. The stainless steel mesh system uses 100 meshes. The weight of this screen when not in use is taken as the weight W2. Then, the remaining mesh of the insoluble component of the heat-adhesive tape was dried in an environment of 80 ° C. with an explosion-proof dryer, and then left to cool. Next, the weight of this screen was measured, and the measured value was made into W3. Then, the insoluble content calculated from ((W3-W2) / W1) was evaluated. In addition, with respect to the heat-adhesive tapes of Examples 1 to 8 and Comparative Examples 1 to 3, the insoluble content before thermal compression bonding was 0%.
[保管後接著力評價之方法] 又,評價實施例1~8及比較例1~3之熱接著膠帶在一定期間的保管後之接著力。 具體而言,關於實施例1~8及比較例1~3之熱接著膠帶,於此等之熱接著膠帶之製作後,在80°C之環境下保管1星期。然後,藉由於與保管前接著力評價之方法同樣之條件下的加熱壓接,以保管後之熱接著膠帶接合2片玻璃布,對於作為被附體的2片玻璃布,施加剪切力,進行對於此的接著力之評價。[Method of Evaluating Adhesion After Storage] Also, the adhesion of the thermal adhesive tapes of Examples 1 to 8 and Comparative Examples 1 to 3 after storage for a certain period of time were evaluated. Specifically, regarding the heat-adhesive tapes of Examples 1 to 8 and Comparative Examples 1 to 3, after the production of these heat-adhesive tapes, they were stored in an environment at 80 ° C. for one week. Then, the two glass cloths were bonded with adhesive tape by the heat and pressure bonding under the same conditions as in the method of evaluating the adhesion force before storage, and then a shear force was applied to the two glass cloths as an adherend. An evaluation of this adhesion was performed.
[保管後不溶解分評價之方法] 再者,為了評價將熱接著膠帶在不加熱壓接下保管時的接著層之硬化程度,評價實施例1~8及比較例1~3之熱接著膠帶在一定期間的保管後之不溶解分。 茲認為熱接著膠帶之保管後的不溶解分愈多,在保管時由接著層中所包含的過氧化物產生愈多的酸,反應係進行。在保管時產生愈多的酸,加熱壓接前的接著層硬化程度愈大。[Method for evaluating insoluble content after storage] Furthermore, in order to evaluate the degree of hardening of the adhesive layer when the thermal adhesive tape was stored without thermal compression bonding, the thermal adhesive tapes of Examples 1 to 8 and Comparative Examples 1 to 3 were evaluated. Insoluble content after storage for a certain period of time. It is believed that the more insoluble content after thermal adhesive tape storage, the more acid is generated from the peroxide contained in the adhesive layer during storage, and the reaction proceeds. The more acid is generated during storage, the greater the degree of hardening of the adhesive layer before thermal compression bonding.
作為熱接著膠帶之保管後的不溶解分之具體評價方法,關於實施例1~8及比較例1~3之熱接著膠帶,在此等之熱接著膠帶之製作後,於80℃之環境下保管1星期,將此保管後之熱接著膠帶的重量當作W4。 然後,藉由與保管前不溶解分評價之方法同樣之方法,使用不鏽鋼網,提取熱接著膠帶的不溶解分。惟,於保管後不溶解分評價中,為了評價保管時所產生的酸之量,與保管前不溶解分評價不同,提取未加熱壓接的熱接著膠帶之不溶解分。 而且,將篩網之未使用時的重量當作重量W5,將熱接著膠帶之不溶解分殘存的篩網之重量當作重量W6,評價由((W6-W5)/W4)所算出的不溶解分。As a specific evaluation method of the insoluble content after storage of the heat-adhesive tape, regarding the heat-adhesive tapes of Examples 1 to 8 and Comparative Examples 1 to 3, after the production of these heat-adhesive tapes, the environment was 80 ° C. Store for one week, and consider the weight of the heat-adhesive tape after storage as W4. Then, by the same method as the method of evaluating the insoluble matter before storage, the insoluble matter of the heat-adhesive tape was extracted using a stainless steel mesh. However, in the evaluation of the insoluble content after storage, in order to evaluate the amount of acid generated during storage, the evaluation of the insoluble content before storage is different from the evaluation of the insoluble content before storage, and the insoluble content of the heat-adhesive tape that has not been heat-pressed is extracted. The weight of the sieve when it was not used was taken as the weight W5, and the weight of the sieve remaining after the insoluble content of the hot-adhesive tape was taken as the weight W6. Dissolved points.
[評價結果] 表1中顯示接著力之評價結果。 如表1所示,實施例1~8之熱接著膠帶1為藉由任一條件的加熱壓接所製作者,對於保管前的接著力、1星期保管後的接著力各自,全部合格。 又,實施例1~8之熱接著膠帶1為藉由任一條件的加熱壓接所製作者,保管前的不溶解分係大幅增加,茲認為加熱壓接時的接著層3之硬化係被促進。再者,1星期保管後之熱接著膠帶1的不溶解分之增加係被抑制,茲認為保管時的接著層3之硬化係變難以進行[Evaluation Results] Table 1 shows the evaluation results of the adhesion. As shown in Table 1, the thermal adhesive tapes 1 of Examples 1 to 8 were produced by thermal compression bonding under any conditions, and all of them were acceptable for the adhesive force before storage and the adhesive force after one week of storage. In addition, the thermal adhesive tapes 1 of Examples 1 to 8 were produced by thermal compression bonding under any conditions, and the insoluble fraction before storage was greatly increased. It is considered that the curing system of the adhesive layer 3 during thermal compression bonding was promote. In addition, the increase in insolubilization of the heat-adhesive tape 1 after storage for one week is suppressed, and it is considered that the curing of the adhesive layer 3 during storage becomes difficult.
相對而言,於比較例1及比較例3中,保管前之熱接著膠帶係在接著層中發生內聚破壞,發生熱接著膠帶之剝離。又,於此比較例1及比較例3中,關於保管前之熱接著膠帶,加熱壓接後之不溶解分係幾乎不增加。 關於此,於比較例1中,根本不使用過氧化物,另外於比較例3中,雖然使用過氧化物,但是此過氧化物係不因分解產生酸。因此,於此比較例1及比較例3中,皆在熱接著膠帶之加熱壓接時不產生酸,酚樹脂之交聯不會充分地進行,接著層之硬化不充分,因此認為不充分得到熱接著膠帶對於被附體之接著力。In contrast, in Comparative Examples 1 and 3, the thermal adhesive tape before storage was subjected to cohesive failure in the adhesive layer, and peeling of the thermal adhesive tape occurred. In addition, in Comparative Examples 1 and 3, regarding the heat-adhesive tape before storage, the insoluble fraction after heat-compression bonding hardly increased. In this regard, in Comparative Example 1, no peroxide was used at all, and in Comparative Example 3, although a peroxide was used, this peroxide did not generate an acid due to decomposition. Therefore, in both Comparative Example 1 and Comparative Example 3, no acid was generated during the thermal compression bonding of the heat-adhesive tape, the crosslinking of the phenol resin did not proceed sufficiently, and the curing of the adhesive layer was insufficient, so it was considered to be insufficient. Adhesion of the heat-adhesive tape to the adherend.
又,於比較例2中,雖然保管前之熱接著膠帶的接著力皆合格,但是1星期保管後之熱接著膠帶係在被附體發生界面破壞,發生熱接著膠帶之剝離。另外,於此比較例2中,保管前之熱接著膠帶雖然加壓壓接後的不溶解分大幅增加,但是另一方面,1星期保管後之熱接著膠帶的不溶解分大幅增加。 茲認為此係在將熱接著膠帶保管1星期的期間,苯甲酸與酚樹脂反應,酚樹脂之交聯進行,接著層之硬化進行。而且,茲認為於此接著層的硬化充分進行後,即使將被附體加熱壓接於熱接著膠帶,也不充分地得到熱接著膠帶對於被附體的接著力。In Comparative Example 2, although the adhesive force of the thermal adhesive tape before storage was acceptable, the thermal adhesive tape after one week of storage was damaged at the interface of the adherend, and the thermal adhesive tape was peeled off. In addition, in Comparative Example 2, although the insoluble content of the heat-adhesive tape before storage was greatly increased after compression and compression, the insoluble content of the heat-adhesive tape after storage for one week increased significantly. It is believed that this is because during the storage of the heat-adhesive tape for one week, benzoic acid reacts with the phenol resin, the crosslinking of the phenol resin proceeds, and the curing of the layer proceeds. In addition, it is considered that after the curing of the adhesive layer has sufficiently progressed, even if the adherend is heated and pressure-bonded to the thermal adhesive tape, the adhesive force of the thermal adhesive tape to the adherend is not sufficiently obtained.
由實施例1~8及比較例1~3之結果可確認,必須在熱接著膠帶1之接著層3中含有因分解產生酸的過氧化物。From the results of Examples 1 to 8 and Comparative Examples 1 to 3, it was confirmed that the adhesive layer 3 of the thermal adhesive tape 1 must contain a peroxide that generates an acid due to decomposition.
1‧‧‧熱接著膠帶1‧‧‧Heat Adhesive Tape
2‧‧‧剝離襯裡2‧‧‧ peel liner
3‧‧‧接著層3‧‧‧ Adjacent layer
圖1係顯示採用本實施形態的熱接著膠帶之剖面圖。 圖2係說明接著膠帶之製造方法的流程圖。FIG. 1 is a cross-sectional view showing a heat-adhesive tape using this embodiment. FIG. 2 is a flowchart illustrating a manufacturing method of the adhesive tape.
Claims (5)
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JPH01249876A (en) * | 1988-03-30 | 1989-10-05 | Nitto Denko Corp | Polyimide insulating tape |
GB2257707B (en) * | 1991-05-27 | 1995-11-01 | Nippon Zeon Co | Adhesive composition |
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JP2006299131A (en) * | 2005-04-22 | 2006-11-02 | Taoka Chem Co Ltd | Thermosetting type film-like adhesive composition and thermosetting type film-like adhesive tape |
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