TWI859665B - Film-shaped adhesive for flexible device, adhesive sheet for flexible device, and method for manufacturing flexible device - Google Patents
Film-shaped adhesive for flexible device, adhesive sheet for flexible device, and method for manufacturing flexible device Download PDFInfo
- Publication number
- TWI859665B TWI859665B TW111148003A TW111148003A TWI859665B TW I859665 B TWI859665 B TW I859665B TW 111148003 A TW111148003 A TW 111148003A TW 111148003 A TW111148003 A TW 111148003A TW I859665 B TWI859665 B TW I859665B
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- Prior art keywords
- film
- flexible device
- adhesive
- film adhesive
- mass
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- 239000000853 adhesive Substances 0.000 title claims abstract description 188
- 230000001070 adhesive effect Effects 0.000 title claims abstract description 188
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- 238000000034 method Methods 0.000 title claims abstract description 20
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Abstract
本發明係一種可撓裝置用膜狀接著劑、將該膜狀接著劑與可撓基材積層而成之可撓裝置用接著片、及使用該等之可撓裝置之製造方法，上述膜狀接著劑之厚度T（μm）與上述膜狀接著劑之硬化物之儲存彈性模數E'（GPa）滿足T×E'≦75。The present invention is a film adhesive for a flexible device, an adhesive sheet for a flexible device formed by laminating the film adhesive and a flexible substrate, and a method for manufacturing a flexible device using the film adhesive. The thickness T (μm) of the film adhesive and the storage elastic modulus E' (GPa) of the cured product of the film adhesive satisfy T×E'≦75.
Description
本發明係關於一種可撓裝置用膜狀接著劑、可撓裝置用接著片、及可撓裝置之製造方法。The present invention relates to a film adhesive for a flexible device, an adhesive sheet for a flexible device, and a method for manufacturing the flexible device.
可撓顯示器等可撓裝置係藉由於具有可撓性之支持基材（可撓基材、可撓膜）上形成有機電致發光（有機EL）元件、液晶面板、微發光二極體（微LED）、電晶體等半導體元件（將該等統稱為功能性元件）而製造。最近，於應用於智慧型手機、平板手機、平板等行動終端之顯示器時，要求一種能夠摺疊或捲曲之可摺疊式可撓裝置。Flexible devices such as flexible displays are manufactured by forming organic electroluminescent (EL) elements, liquid crystal panels, micro-light-emitting diodes (micro-LEDs), transistors and other semiconductor elements (collectively referred to as functional elements) on a flexible support substrate (flexible substrate, flexible film). Recently, when used in displays for mobile terminals such as smartphones, tablets, and tablets, a foldable or rollable flexible device is required.
如上所述，此種可撓裝置具有可撓基材（背板）作為支持裝置整體之支持基材，以提高裝置本體之強度，賦予可靠性。即，將上述功能性元件固定於可撓基材上而製造可撓裝置。功能性元件通常於其兩面積層有各種功能層（例如，保護層、阻氣層（密封層）、偏光板、硬塗層等），包含功能性元件之積層體整體一體地配置於可撓基材上，介隔糊狀或膜狀接著劑加以固定。可撓基材係使用聚對苯二甲酸乙二酯膜、聚醯亞胺膜等。As described above, this flexible device has a flexible substrate (backplane) as a supporting substrate for the entire device to increase the strength of the device body and provide reliability. That is, the above-mentioned functional elements are fixed on the flexible substrate to manufacture the flexible device. Functional elements usually have various functional layers (for example, protective layers, gas barrier layers (sealing layers), polarizing plates, hard coating layers, etc.) laminated on both sides thereof, and the laminated body including the functional elements is integrally arranged on the flexible substrate and fixed via a paste or film adhesive. The flexible substrate uses a polyethylene terephthalate film, a polyimide film, etc.
於製造可撓裝置時，提出一種用於積層構造之層間之接著的接著性片。例如，專利文獻1中記載有一種裝置密封用接著片，其具有第1剝離膜及第2剝離膜、以及被該等夾持之接著劑層。該接著劑層含有具有環狀醚基之化合物，23℃時之儲存彈性模數被調整為9.5×10 5Pa以上3.0×10 7Pa以下。根據專利文獻1中所記載之技術，即便對接著片進行裁剪加工，剝離膜自接著劑層之剝離性亦優異，該接著劑層與被接著體之接著性亦優異。 [先前技術文獻] [專利文獻] When manufacturing a flexible device, an adhesive sheet for bonding between layers of a laminated structure is proposed. For example, Patent Document 1 describes an adhesive sheet for sealing a device, which has a first peeling film and a second peeling film, and an adhesive layer sandwiched therebetween. The adhesive layer contains a compound having a cyclic ether group, and the storage elastic modulus at 23°C is adjusted to be greater than 9.5×10 5 Pa and less than 3.0×10 7 Pa. According to the technology described in Patent Document 1, even if the adhesive sheet is cut, the peeling film has excellent peelability from the adhesive layer, and the adhesive layer also has excellent bonding with the adherend. [Prior art literature] [Patent literature]
[專利文獻1]國際公開第2020/251030號[Patent Document 1] International Publication No. 2020/251030
[發明所欲解決之課題][The problem that the invention wants to solve]
於製造可撓裝置時，對用於積層構造之層間之接著的膜狀接著劑要求高度耐撓曲性，即，不僅承受彎曲，亦能承受反覆嚴格彎折。但是，於以構成上述專利文獻1中所記載之接著片之膜狀接著劑為代表的習知膜狀接著劑中，未達成所需之高度耐撓曲性。 本發明之課題在於提供一種表現出能承受反覆嚴格彎折之高度耐撓曲性之可撓裝置用膜狀接著劑。又，本發明之課題在於提供一種使用上述可撓裝置用膜狀接著劑之可撓裝置用接著片、及可撓裝置之製造方法。 [解決課題之技術手段] When manufacturing a flexible device, a film adhesive used for bonding between layers of a laminated structure is required to have high bending resistance, that is, it should not only withstand bending but also withstand repeated severe bending. However, the required high bending resistance is not achieved in the conventional film adhesive represented by the film adhesive constituting the bonding sheet described in the above-mentioned patent document 1. The subject of the present invention is to provide a film adhesive for a flexible device that exhibits high bending resistance that can withstand repeated severe bending. In addition, the subject of the present invention is to provide a bonding sheet for a flexible device using the above-mentioned film adhesive for a flexible device, and a method for manufacturing a flexible device. [Technical means to solve the problem]
本發明之上述課題係藉由下述手段解決。 [1] 一種可撓裝置用膜狀接著劑，其中，上述膜狀接著劑之厚度T（μm）與上述膜狀接著劑之硬化物之儲存彈性模數E'（GPa）滿足T×E'≦75。 [2] 如[1]所記載之可撓裝置用膜狀接著劑，其中，上述儲存彈性模數E'為5 GPa以下。 [3] 如[1]或[2]所記載之可撓裝置用膜狀接著劑，其中，上述厚度T（μm）為1～100 μm。 [4] 如[1]至[3]中任一項所記載之可撓裝置用膜狀接著劑，其中，上述膜狀接著劑之硬化物之玻璃轉移溫度為30℃以上。 [5] 如[1]至[4]中任一項所記載之可撓裝置用膜狀接著劑，其至少包含：具有環狀醚基之化合物、該化合物之硬化劑、及聚合物成分。 [6] 如[5]所記載之可撓裝置用膜狀接著劑，其中，上述具有環狀醚基之化合物包含環氧樹脂。 [7] 如[6]所記載之可撓裝置用膜狀接著劑，其中，上述環氧樹脂包含：具有脂環結構之環氧樹脂。 [8] 如[5]至[7]中任一項所記載之可撓裝置用膜狀接著劑，其中，上述聚合物成分之玻璃轉移溫度為140℃以下。 [9] 如[1]至[8]中任一項所記載之可撓裝置用膜狀接著劑，其包含矽烷偶合劑。 [10] 如[1]至[9]中任一項所記載之可撓裝置用膜狀接著劑，其為能量線硬化型。 [11] 一種可撓裝置用接著片，其具有：將可撓基材與[1]至[10]中任一項所記載之可撓裝置用膜狀接著劑積層而成之構造。 [12] 一種可撓裝置之製造方法，其包含將[1]至[10]中任一項所記載之可撓裝置用膜狀接著劑或[11]所記載之可撓裝置用接著片用於構成可撓裝置之層間之接著。 [13] 一種可撓裝置之製造方法，其包含將[1]至[10]中任一項所記載之可撓裝置用膜狀接著劑用於可撓裝置之構成材料之密封。 [14] 一種可撓裝置之製造方法，其包含藉由[11]所記載之可撓裝置用接著片形成可撓裝置之支持基材。 [15] 如[12]至[14]中任一項所記載之可撓裝置之製造方法，其中，上述可撓裝置係可撓顯示器。 The above-mentioned problem of the present invention is solved by the following means. [1] A film adhesive for a flexible device, wherein the thickness T (μm) of the film adhesive and the storage elastic modulus E' (GPa) of the cured product of the film adhesive satisfy T×E'≦75. [2] A film adhesive for a flexible device as described in [1], wherein the storage elastic modulus E' is 5 GPa or less. [3] A film adhesive for a flexible device as described in [1] or [2], wherein the thickness T (μm) is 1 to 100 μm. [4] A film-like adhesive for a flexible device as described in any one of [1] to [3], wherein the glass transition temperature of the cured product of the film-like adhesive is 30°C or higher. [5] A film-like adhesive for a flexible device as described in any one of [1] to [4], comprising at least: a compound having a cyclic ether group, a curing agent for the compound, and a polymer component. [6] A film-like adhesive for a flexible device as described in [5], wherein the compound having a cyclic ether group comprises an epoxy resin. [7] A film-like adhesive for a flexible device as described in [6], wherein the epoxy resin comprises an epoxy resin having a lipid ring structure. [8] A film-like adhesive for a flexible device as described in any one of [5] to [7], wherein the glass transition temperature of the polymer component is 140°C or less. [9] A film-like adhesive for a flexible device as described in any one of [1] to [8], comprising a silane coupling agent. [10] A film-like adhesive for a flexible device as described in any one of [1] to [9], which is an energy-beam-curable type. [11] An adhesive sheet for a flexible device, comprising: a structure in which a flexible substrate and a film-like adhesive for a flexible device as described in any one of [1] to [10] are laminated. [12] A method for manufacturing a flexible device, comprising using a film-like adhesive for a flexible device as described in any one of [1] to [10] or a bonding sheet for a flexible device as described in [11] to bond between layers constituting the flexible device. [13] A method for manufacturing a flexible device, comprising using a film-like adhesive for a flexible device as described in any one of [1] to [10] to seal the constituent materials of the flexible device. [14] A method for manufacturing a flexible device, comprising forming a supporting substrate of the flexible device by using the bonding sheet for a flexible device as described in [11]. [15] A method for manufacturing a flexible device as described in any one of [12] to [14], wherein the flexible device is a flexible display.
本發明中，使用「～」所表示之數值範圍意指包含「～」前後所記載之數值作為下限值及上限值之範圍。 [發明之效果] In the present invention, the numerical range represented by "～" means a range including the numerical values recorded before and after "～" as the lower limit and upper limit. [Effect of the invention]
本發明之可撓裝置用膜狀接著劑及可撓裝置用接著片表現出能承受反覆嚴格彎折之高度耐撓曲性。又，根據本發明之可撓裝置之製造方法，能夠進一步提高所獲得之可撓裝置之接著可靠性。The film adhesive for the flexible device and the adhesive sheet for the flexible device of the present invention exhibit high bending resistance capable of withstanding repeated and severe bending. In addition, the manufacturing method of the flexible device of the present invention can further improve the bonding reliability of the obtained flexible device.
[可撓裝置用膜狀接著劑] 本發明之可撓裝置用膜狀接著劑（以下，亦簡稱為「膜狀接著劑」）係適於構成可撓裝置之層間之接著用途之接著劑。本發明之膜狀接著劑藉由硬化反應而硬化，表現出與被接著體之接著力。因此，本發明之膜狀接著劑係由硬化性組成物所構成之膜。關於本發明之膜狀接著劑，膜狀接著劑之厚度T（μm）與膜狀接著劑之硬化物之儲存彈性模數E'（GPa）滿足T×E'≦75。藉由滿足該關係，能夠實現所需之高度耐撓曲性。 [Film-like adhesive for flexible device] The film-like adhesive for flexible device of the present invention (hereinafter, also referred to as "film-like adhesive") is an adhesive suitable for bonding between layers constituting a flexible device. The film-like adhesive of the present invention is hardened by a hardening reaction and exhibits bonding strength with a bonded body. Therefore, the film-like adhesive of the present invention is a film composed of a hardening composition. Regarding the film-like adhesive of the present invention, the thickness T (μm) of the film-like adhesive and the storage elastic modulus E' (GPa) of the hardened material of the film-like adhesive satisfy T×E'≦75. By satisfying this relationship, the required high degree of bending resistance can be achieved.
上述厚度T為硬化反應前之厚度（即，處於B階段之狀態之膜狀接著劑之厚度）。本發明中，厚度T係使用測微計（例如，高精度數顯測微計MDH-25MB（商品名），三豐製造），隨機測定10處膜狀接著劑之厚度，設為其等之算術平均值。於任意部位進行測定，膜狀接著劑之厚度均通常處於T±（T×0.3）之範圍內，較佳為處於T±（T×0.1）之範圍內，更佳為處於T±（T×0.05）之範圍內。The thickness T is the thickness before the curing reaction (i.e., the thickness of the film adhesive in the B stage). In the present invention, the thickness T is measured by using a micrometer (e.g., high-precision digital micrometer MDH-25MB (trade name), manufactured by Mitutoyo) to randomly measure the thickness of the film adhesive at 10 locations, and the arithmetic mean thereof is set. When measured at any location, the thickness of the film adhesive is usually within the range of T±(T×0.3), preferably within the range of T±(T×0.1), and more preferably within the range of T±(T×0.05).
上述儲存彈性模數E'係以如下方式確定。 使用貼合機，於70℃積層膜狀接著劑，直至厚度為0.5 mm，於下述（i）或（ii）之條件下進行硬化反應。將所獲得之硬化物樣品切成5 mm寬度，製成測定樣品。對於測定樣品，使用動態黏彈性測定裝置RSAIII（TA Instruments製造），於夾頭間距離20 mm、頻率10 Hz之拉伸條件下，以測定溫度範圍-40℃～250℃、升溫速度5℃/min之條件進行升溫，確定23℃時之儲存彈性模數。 本發明中，於簡稱為「儲存彈性模數」之情形時，係常溫（23℃）時之儲存彈性模數。 The above storage elastic modulus E' is determined as follows. Using a laminating machine, a film adhesive is laminated at 70°C until the thickness is 0.5 mm, and a curing reaction is performed under the following conditions (i) or (ii). The obtained cured sample is cut into 5 mm widths to prepare a test sample. For the test sample, a dynamic viscoelasticity measuring device RSAIII (manufactured by TA Instruments) is used. Under the conditions of tension with a chuck distance of 20 mm and a frequency of 10 Hz, the temperature is increased in the measuring temperature range of -40°C to 250°C and a heating rate of 5°C/min, and the storage elastic modulus at 23°C is determined. In the present invention, the situation referred to as "storage elastic modulus" is the storage elastic modulus at room temperature (23°C).
（i）於能量線硬化型（典型為包含光陽離子聚合起始劑之形態）之情形時： 使用水銀燈，於23℃以1000 mJ/cm 2之照射條件進行紫外線照射之條件。 （ii）於熱硬化型（典型為包含潛伏性硬化劑或熱陽離子聚合起始劑之形態）之情形時： 於150℃進行1小時熱處理之條件。 (i) In the case of energy-ray curing type (typically containing a photo-cationic polymerization initiator): UV irradiation is performed at 23°C with a mercury lamp at 1000 mJ/ cm2 . (ii) In the case of heat-curing type (typically containing a latent curing agent or a thermal cationic polymerization initiator): Heat treatment is performed at 150°C for 1 hour.
藉由上述（i）或（ii）之硬化條件，可充分地進行本發明之膜狀接著劑之硬化反應，可獲得導入有交聯結構之硬化物。再者，上述（i）及（ii）係使本發明之膜狀接著劑之特性明確者，於實際使用本發明之膜狀接著劑之情形時，硬化條件並不限定於上述（i）或（ii）。By using the curing conditions (i) or (ii) above, the curing reaction of the film adhesive of the present invention can be fully carried out, and a cured product with a cross-linked structure can be obtained. Furthermore, the above (i) and (ii) are to clarify the characteristics of the film adhesive of the present invention. When the film adhesive of the present invention is actually used, the curing conditions are not limited to the above (i) or (ii).
上述T與E'之關係為T×E'≦75，較佳為T×E'≦72。又，通常滿足10≦T×E'。上述T與E'之關係較佳為10≦T×E'≦75，更佳為10≦T×E'≦72。 上述T較佳為1～100 μm，更佳為2～100 μm，進而較佳為4～100 μm，進而較佳為6～100 μm，進而較佳為8～100 μm。T亦可為10～90 μm，亦可為15～80 μm，亦可為20～70 μm，亦可為20～50 μm。 上述E'較佳為0.2～10 GPa，更佳為0.4～8 GPa，進而較佳為0.6～6 GPa。上述E'更佳為5 GPa以下，進而較佳為0.6～5 GPa。上述E'亦可為1.6～4 GPa，亦可為1.4～3.5 GPa。 又，使本發明之膜狀接著劑硬化而成之硬化物（硬化層）之較佳之厚度與上述T之較佳之範圍相同。 The relationship between T and E' is T×E'≦75, preferably T×E'≦72. In addition, 10≦T×E' is usually satisfied. The relationship between T and E' is preferably 10≦T×E'≦75, and more preferably 10≦T×E'≦72. The above T is preferably 1 to 100 μm, more preferably 2 to 100 μm, further preferably 4 to 100 μm, further preferably 6 to 100 μm, and further preferably 8 to 100 μm. T may also be 10 to 90 μm, 15 to 80 μm, 20 to 70 μm, or 20 to 50 μm. The above E' is preferably 0.2 to 10 GPa, more preferably 0.4 to 8 GPa, and further preferably 0.6 to 6 GPa. The above E' is more preferably 5 GPa or less, and further preferably 0.6 to 5 GPa. The above E' may also be 1.6 to 4 GPa, or 1.4 to 3.5 GPa. In addition, the preferred thickness of the cured product (cured layer) formed by curing the film-like adhesive of the present invention is the same as the preferred range of T.
上述膜狀接著劑之硬化物之儲存彈性模數可藉由作為接著劑之構成成分之硬化性化合物之化學結構、分子量、官能基之種類、官能基當量、及含量等（例如，具有環狀醚基之化合物之化學結構或含量、環狀醚基之種類、環狀醚當量等）；聚合物成分之化學結構、分子量、玻璃轉移溫度、及含量等；接著劑中之無機填充材料、硬化劑、及其他添加劑之種類或含量等進行控制。The storage elastic modulus of the cured product of the above-mentioned film-like adhesive can be controlled by the chemical structure, molecular weight, type of functional group, functional group equivalent, and content of the curing compound as a component of the adhesive (for example, the chemical structure or content of the compound having a cyclic ether group, the type of cyclic ether group, the cyclic ether equivalent, etc.); the chemical structure, molecular weight, glass transition temperature, and content of the polymer component; the type or content of the inorganic filler, curing agent, and other additives in the adhesive.
考慮到耐熱性及耐濕性，本發明之膜狀接著劑之硬化物之玻璃轉移溫度（Tg）較佳為30℃以上。上述膜狀接著劑之硬化物之Tg係動態黏彈性測定中之tanδ之峰頂溫度。具體而言，能以如下方式確定Tg。 使用貼合機，於70℃積層膜狀接著劑，直至厚度為0.5 mm，於上述（i）或（ii）之條件下進行硬化反應。將所獲得之硬化物樣品切成5 mm寬度，製成測定樣品。如上所述，對於測定樣品，使用動態黏彈性測定裝置RSAIII（TA Instruments製造），於夾頭間距離20 mm、測定溫度範圍-40℃～250℃、升溫速度5℃/min、及頻率10 Hz之條件下進行測定。將所獲得之tanδ峰頂溫度（tanδ表現出極大值時之溫度）作為膜狀接著劑之硬化物之Tg。 此處，本發明之膜狀接著劑之硬化物之Tg為X℃意指於硬化物之Tg為2個以上之情形時，溫度最低側之Tg為X℃。因此，本發明之膜狀接著劑之硬化物之Tg為30℃以上意指於硬化物之Tg為2個以上之情形時，溫度最低側之Tg為30℃以上。 本發明之膜狀接著劑之硬化物之Tg較佳為5～150℃，更佳為30～150℃，進而較佳為40～140℃，進而較佳為60～130℃，進而較佳為70～120℃，進而較佳為90～115℃，進而較佳為100～115℃。Tg亦可為60℃以上，較佳為80℃以上，進而較佳為100℃以上。 Taking heat resistance and moisture resistance into consideration, the glass transition temperature (Tg) of the cured film adhesive of the present invention is preferably above 30°C. The Tg of the cured film adhesive is the peak temperature of tanδ in the dynamic viscoelasticity measurement. Specifically, Tg can be determined as follows. Using a laminating machine, laminate the film adhesive at 70°C to a thickness of 0.5 mm, and perform the curing reaction under the conditions of (i) or (ii) above. Cut the obtained cured sample into 5 mm width to prepare a measurement sample. As described above, for the measurement sample, the dynamic viscoelasticity measuring device RSAIII (manufactured by TA Instruments) was used to measure the conditions of a chuck distance of 20 mm, a measurement temperature range of -40℃ to 250℃, a heating rate of 5℃/min, and a frequency of 10 Hz. The obtained tanδ peak temperature (the temperature at which tanδ shows a maximum value) is taken as the Tg of the cured film adhesive. Here, the Tg of the cured film adhesive of the present invention is X℃, which means that when the Tg of the cured product is 2 or more, the Tg on the lowest temperature side is X℃. Therefore, the Tg of the cured film adhesive of the present invention is 30℃ or more, which means that when the Tg of the cured product is 2 or more, the Tg on the lowest temperature side is 30℃ or more. The Tg of the cured product of the film adhesive of the present invention is preferably 5 to 150°C, more preferably 30 to 150°C, further preferably 40 to 140°C, further preferably 60 to 130°C, further preferably 70 to 120°C, further preferably 90 to 115°C, further preferably 100 to 115°C. The Tg may also be above 60°C, preferably above 80°C, further preferably above 100°C.
本發明之膜狀接著劑之成分組成並無特別限制，只要滿足本發明所規定之要件即可。作為上述膜狀接著劑之較佳之形態，可例舉含有具有環狀醚基之化合物、及該化合物之硬化劑之形態。於該情形時，膜狀接著劑通常除了具有環狀醚基之化合物以外，還含有聚合物成分（膜成分）。又，為了對表面自由能、彈性模數、線膨脹係數等進行調整等，可視需要含有其他成分。關於膜狀接著劑之構成成分，對較佳之實施方式進行說明。The composition of the film adhesive of the present invention is not particularly limited, as long as it meets the requirements specified in the present invention. As a preferred form of the above-mentioned film adhesive, a form containing a compound having a cyclic ether group and a curing agent for the compound can be cited. In this case, the film adhesive usually contains a polymer component (film component) in addition to the compound having a cyclic ether group. In addition, in order to adjust the surface free energy, elastic modulus, linear expansion coefficient, etc., other components can be contained as needed. Regarding the components of the film adhesive, the preferred implementation method is explained.
（具有環狀醚基之化合物） 上述具有環狀醚基之化合物係於分子內具有至少1個（較佳為2～20個，更佳為2～10個）環狀醚基之化合物。再者，本發明中，具有環狀醚基之化合物即便為聚合物，亦不分類為上述聚合物成分，而分類為具有環狀醚基之化合物。因此，一般之環氧樹脂被分類為具有環狀醚基之化合物。但，下述苯氧基樹脂不包含於具有環狀醚基之化合物。即，下述苯氧基樹脂係聚合物成分。 具有環狀醚基之化合物之分子量較佳為100～3000，更佳為200～1500。 具有環狀醚基之化合物之環狀醚當量較佳為100～3000 g/eq，更佳為120～1500 g/eq，進而較佳為130～1000 g/eq，進而較佳為135～800 g/eq。 於具有環狀醚基之化合物不具有脂環結構之情形時，環狀醚當量較佳為較大。例如較佳為500 g/eq以上，更佳為600～1000 g/eq，進而較佳為650～900 g/eq。 反之，於具有環狀醚基之化合物具有脂環結構之情形時，環狀醚當量可較小。例如較佳為未達500 g/eq，更佳為100～400 g/eq，進而較佳為120～350 g/eq，進而較佳為130～300 g/eq。 「環狀醚當量」係指含有1克當量環狀醚基之化合物之克數（g/eq）。 (Compounds having cyclic ether groups) The above-mentioned compounds having cyclic ether groups are compounds having at least 1 (preferably 2 to 20, more preferably 2 to 10) cyclic ether groups in the molecule. Furthermore, in the present invention, even if the compound having a cyclic ether group is a polymer, it is not classified as the above-mentioned polymer component, but is classified as a compound having a cyclic ether group. Therefore, general epoxy resins are classified as compounds having cyclic ether groups. However, the following phenoxy resins are not included in the compounds having cyclic ether groups. That is, the following phenoxy resins are polymer components. The molecular weight of the compound having a cyclic ether group is preferably 100 to 3000, more preferably 200 to 1500. The cyclic ether equivalent of the compound having a cyclic ether group is preferably 100 to 3000 g/eq, more preferably 120 to 1500 g/eq, further preferably 130 to 1000 g/eq, further preferably 135 to 800 g/eq. In the case where the compound having a cyclic ether group does not have an alicyclic structure, the cyclic ether equivalent is preferably larger. For example, it is preferably 500 g/eq or more, more preferably 600 to 1000 g/eq, further preferably 650 to 900 g/eq. On the contrary, in the case where the compound having a cyclic ether group has an alicyclic structure, the cyclic ether equivalent may be smaller. For example, it is preferably less than 500 g/eq, more preferably 100 to 400 g/eq, further preferably 120 to 350 g/eq, further preferably 130 to 300 g/eq. "Cyclic ether equivalent" refers to the number of grams (g/eq) of a compound containing 1 gram equivalent of a cyclic ether group.
上述環狀醚基之成環原子數較佳為3或4。作為上述環狀醚基，可例舉：環氧乙烷基（環氧基）、氧雜環丁基（oxetanyl）、四氫呋喃基、四氫哌喃基等。其中，較佳為環氧乙烷基或氧雜環丁基，更佳為環氧乙烷基。即，具有環狀醚基之化合物特佳為環氧樹脂。 作為環氧樹脂之骨架，可例舉：苯酚酚醛清漆型、鄰甲酚酚醛清漆型、甲酚酚醛清漆型、二環戊二烯型、聯苯型、茀雙酚型、三型、萘酚型、萘二酚型、三苯甲烷型、四苯基型、雙酚A型、雙酚F型、雙酚AD型、雙酚S型、三羥甲基甲烷型等。其中，從可獲得樹脂之結晶性較低且具有良好之外觀之膜狀接著劑的觀點而言，較佳為三苯甲烷型、雙酚A型、甲酚酚醛清漆型、鄰甲酚酚醛清漆型。 其中，上述環氧樹脂較佳為具有脂環結構之環氧樹脂，進而較佳為氫化（hydrogenation）雙酚型環氧樹脂，進而較佳為氫化雙酚A型環氧樹脂。藉由使用具有脂環結構之環氧樹脂，即便硬化物之Tg或儲存彈性模數為相同程度，亦可達成更加優異之耐撓曲性。 The number of ring atoms of the above-mentioned cyclic ether group is preferably 3 or 4. Examples of the above-mentioned cyclic ether group include: oxirane (epoxy), oxetanyl, tetrahydrofuranyl, tetrahydropyranyl, etc. Among them, oxirane or oxetanyl is preferred, and oxirane is more preferred. That is, the compound having a cyclic ether group is particularly preferably an epoxy resin. Examples of the skeleton of the epoxy resin include: phenol novolac type, o-cresol novolac type, cresol novolac type, dicyclopentadiene type, biphenyl type, fluorene bisphenol type, trisphenol type, and the like. The epoxy resin is preferably a triphenylmethane type, a bisphenol A type, a bisphenol F type, a bisphenol AD type, a bisphenol S type, a trihydroxymethylmethane type, etc. Among them, from the viewpoint of obtaining a film adhesive having a low crystallinity of the resin and a good appearance, the triphenylmethane type, the bisphenol A type, the cresol novolac type, and the o-cresol novolac type are preferred. Among them, the epoxy resin is preferably an epoxy resin having an alicyclic structure, and more preferably a hydrogenated bisphenol type epoxy resin, and more preferably a hydrogenated bisphenol A type epoxy resin. By using epoxy resin with a lipid-ring structure, even if the Tg or storage modulus of the cured product is the same, better bending resistance can be achieved.
上述膜狀接著劑之固形物成分（除了溶劑以外之成分）中，具有環狀醚基之化合物之含量較佳為10～70質量%，較佳為15～65質量%，更佳為20～60質量%，進而較佳為20～55質量%。The content of the compound having a cyclic ether group in the solid components (components other than the solvent) of the film-like adhesive is preferably 10 to 70 mass %, more preferably 15 to 65 mass %, more preferably 20 to 60 mass %, and further preferably 20 to 55 mass %.
（硬化劑） 作為上述具有環狀醚基之化合物之硬化劑，可廣泛地使用胺類、酸酐類、多酚類、陽離子聚合起始劑（較佳為光陽離子聚合起始劑）等一般用作具有環狀醚基之化合物（環氧樹脂等）之硬化劑的硬化劑。於假定有機EL裝置為可撓裝置時，貼合於本發明之膜狀接著劑之被接著體不耐熱，因此有時不適合使用熱陽離子聚合起始劑作為硬化劑。又，熱陽離子聚合起始劑存在使所獲得之硬化層之彈性模數過高之傾向，從該觀點而言，亦不適合使用熱陽離子聚合起始劑作為硬化劑。因此，上述硬化劑較佳為光陽離子聚合起始劑、或潛伏性硬化劑。於使用光陽離子聚合起始劑作為上述硬化劑之情形時，膜狀接著劑為能量線硬化型。作為能量線，可例舉：紫外線之類的光線、或電子束之類的游離輻射。 作為潛伏性硬化劑，可例舉：雙氰胺化合物、咪唑化合物、硬化觸媒複合系多酚化合物、醯肼化合物、三氟化硼-胺錯合物、胺醯亞胺化合物、聚胺鹽、及其等之改質物或微膠囊型者。該等可單獨使用1種，亦可組合2種以上使用。從具有更加優異之潛伏性（室溫之穩定性優異，且藉由加熱而發揮硬化性之性質），硬化速度更快之觀點而言，更佳為使用咪唑化合物。 (Hardener) As the hardener for the compound having a cyclic ether group, amines, acid anhydrides, polyphenols, cationic polymerization initiators (preferably photo-cationic polymerization initiators) and the like which are generally used as hardeners for compounds having a cyclic ether group (epoxy resins, etc.) can be widely used. When the organic EL device is assumed to be a flexible device, the adherend to which the film-like adhesive of the present invention is attached is not heat-resistant, so it is sometimes not suitable to use a thermal cationic polymerization initiator as a hardener. In addition, the thermal cationic polymerization initiator has a tendency to make the elastic modulus of the obtained cured layer too high. From this point of view, it is not suitable to use the thermal cationic polymerization initiator as the curing agent. Therefore, the above-mentioned curing agent is preferably a photo-cationic polymerization initiator or a latent curing agent. When a photo-cationic polymerization initiator is used as the above-mentioned curing agent, the film-like adhesive is an energy ray curing type. As energy rays, there can be cited: light such as ultraviolet rays, or ionizing radiation such as electron beams. As latent curing agents, there can be cited: cyanamide compounds, imidazole compounds, curing catalyst composite polyphenol compounds, hydrazide compounds, boron trifluoride-amine complexes, amine imide compounds, polyamine salts, and their modified products or microcapsules. These can be used alone or in combination of two or more. From the perspective of having better latent properties (excellent stability at room temperature, and the property of curing by heating) and faster curing speed, it is better to use imidazole compounds.
上述膜狀接著劑中，上述硬化劑之含量可根據硬化劑之種類、反應形態適當地設定。例如，相對於上述具有環狀醚基之化合物100質量份，可為0.5～30質量份，亦可為1～20質量份，亦可為1～15質量份，亦較佳為2～10質量份，亦較佳為3～8質量份。In the above-mentioned film adhesive, the content of the above-mentioned curing agent can be appropriately set according to the type of curing agent and the reaction form. For example, relative to 100 mass parts of the above-mentioned compound having a cyclic ether group, it can be 0.5 to 30 mass parts, 1 to 20 mass parts, 1 to 15 mass parts, preferably 2 to 10 mass parts, and preferably 3 to 8 mass parts.
（聚合物成分） 作為上述聚合物成分，只要為抑制常溫（23℃）之膜黏性（即便溫度稍微變化，膜狀態亦容易發生變化之性質），賦予充分之接著性及造膜性（成膜性）之成分即可，可廣泛地使用能夠應用於此種接著劑之聚合物。作為聚合物成分，例如可例舉：天然橡膠、丁基橡膠、異戊二烯橡膠、氯丁二烯橡膠、乙烯-乙酸乙烯酯共聚物、乙烯-(甲基)丙烯酸共聚物、乙烯-(甲基)丙烯酸酯共聚物、聚丁二烯樹脂、聚碳酸酯樹脂、熱塑性聚醯亞胺樹脂、6-尼龍或6,6-尼龍等聚醯胺樹脂、苯氧基樹脂、(甲基)丙烯酸樹脂、聚對苯二甲酸乙二酯及聚對苯二甲酸丁二酯等聚酯樹脂、聚醯胺醯亞胺樹脂、聚胺酯樹脂（polyurethane resin）、氟樹脂、雙馬來醯亞胺樹脂（聚雙馬來醯亞胺）等。該等聚合物成分可單獨使用，亦可組合2種以上使用。 (Polymer component) As the above-mentioned polymer component, any component that can suppress the film viscosity at room temperature (23°C) (the property that the film state is easily changed even if the temperature changes slightly) and provide sufficient adhesion and film-forming properties (film-forming properties) can be used. A wide range of polymers that can be used for such adhesives can be used. Examples of the polymer component include natural rubber, butyl rubber, isoprene rubber, chloroprene rubber, ethylene-vinyl acetate copolymer, ethylene-(meth)acrylic acid copolymer, ethylene-(meth)acrylate copolymer, polybutadiene resin, polycarbonate resin, thermoplastic polyimide resin, polyamide resin such as 6-nylon or 6,6-nylon, phenoxy resin, (meth)acrylic resin, polyester resin such as polyethylene terephthalate and polybutylene terephthalate, polyamide imide resin, polyurethane resin, fluorine resin, dimaleimide resin (polybismaleimide), and the like. These polymer components can be used alone or in combination of two or more.
苯氧基樹脂由於結構與具有環狀醚基之化合物類似，故相溶性良好，就該方面而言，適合作為聚合物成分。苯氧基樹脂可藉由通常方法獲得。例如，可藉由雙酚或聯苯酚化合物與表氯醇之類的表鹵醇之反應、液狀環氧樹脂與雙酚或聯苯酚化合物之反應而獲得。Since the structure of phenoxy resin is similar to that of compounds having a cyclic ether group, it has good compatibility and is suitable as a polymer component in this respect. Phenoxy resin can be obtained by a conventional method. For example, it can be obtained by the reaction of bisphenol or biphenol compound with epihalogen alcohol such as epichlorohydrin, or by the reaction of liquid epoxy resin with bisphenol or biphenol compound.
亦較佳為使用(甲基)丙烯酸樹脂作為上述聚合物成分。作為(甲基)丙烯酸樹脂，可例舉包含(甲基)丙烯酸或(甲基)丙烯酸酯成分作為聚合物之構成成分之共聚物。 作為(甲基)丙烯酸樹脂之構成成分，例如可例舉：來自丙烯酸2-羥基乙酯、甲基丙烯酸2-羥基乙酯、丙烯酸2-羥基丙酯、甲基丙烯酸2-羥基丙酯、丙烯酸、甲基丙烯酸、伊康酸、甲基丙烯酸環氧丙酯、丙烯酸環氧丙酯等之成分。又，(甲基)丙烯酸樹脂亦可具有包含環狀骨架之(甲基)丙烯酸酯（例如，(甲基)丙烯酸環烷基酯、(甲基)丙烯酸苄酯、(甲基)丙烯酸異莰酯、(甲基)丙烯酸雙環戊酯、(甲基)丙烯酸二環戊烯酯及(甲基)丙烯酸二環戊烯氧基乙酯）成分作為構成成分。又，亦可具有(甲基)丙烯酸醯亞胺酯成分、烷基之碳數為1～18之(甲基)丙烯酸烷基酯（例如，(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸丙酯及(甲基)丙烯酸丁酯等）成分。又，亦可為與乙酸乙烯酯、(甲基)丙烯腈、苯乙烯等之共聚物。若(甲基)丙烯酸樹脂具有羥基，則從與具有環狀醚基之化合物之相溶性之觀點而言較佳。 It is also preferred to use a (meth)acrylic acid resin as the above-mentioned polymer component. As the (meth)acrylic acid resin, a copolymer containing a (meth)acrylic acid or (meth)acrylic acid ester component as a constituent component of the polymer can be cited. As constituent components of the (meth)acrylic acid resin, for example, components derived from 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, acrylic acid, methacrylic acid, itaconic acid, glycidyl methacrylate, glycidyl acrylate, etc. can be cited. In addition, the (meth)acrylic resin may also have a (meth)acrylic acid ester containing a cyclic skeleton (for example, cycloalkyl (meth)acrylate, benzyl (meth)acrylate, isoborneol (meth)acrylate, dicyclopentyl (meth)acrylate, dicyclopentenyl (meth)acrylate, and dicyclopentenyloxyethyl (meth)acrylate) as a component. In addition, it may also have a (meth)acrylic acid imide ester component, and a (meth)acrylic acid alkyl ester having an alkyl carbon number of 1 to 18 (for example, methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, and butyl (meth)acrylate). In addition, it may also be a copolymer with vinyl acetate, (meth)acrylonitrile, styrene, etc. If the (meth)acrylic resin has a hydroxyl group, it is preferred from the perspective of compatibility with a compound having a cyclic ether group.
又，亦較佳為使用聚胺酯樹脂或雙馬來醯亞胺樹脂作為上述聚合物成分。Furthermore, it is also preferable to use a polyurethane resin or a dimaleimide resin as the above-mentioned polymer component.
上述聚合物成分之重量平均分子量通常為10000以上。上限值並無特別限制，實際上為5000000以下。 上述聚合物成分之重量平均分子量係利用GPC[凝膠滲透層析法（Gel Permeation Chromatography）]以聚苯乙烯換算而求出之值。 The weight average molecular weight of the above polymer component is usually 10,000 or more. The upper limit is not particularly limited, but is actually 5,000,000 or less. The weight average molecular weight of the above polymer component is a value obtained by GPC (Gel Permeation Chromatography) in terms of polystyrene.
上述聚合物成分之玻璃轉移溫度（Tg）較佳為150℃以下，更佳為140℃以下，進而較佳為120℃以下，進而較佳為100℃以下，進而較佳為90℃以下。聚合物成分之Tg較佳為-30℃以上，亦較佳為-10℃以上，亦較佳為0℃以上，亦較佳為10℃以上，亦較佳為20℃以上，亦可為30℃以上，亦可為40℃以上，亦可為50℃以上，亦可為60℃以上。聚合物成分之Tg較佳為-30～140℃，亦較佳為-10～100℃，亦較佳為0～100℃，亦較佳為10～90℃，亦較佳為20～90℃，亦較佳為30～90℃，亦較佳為40～90℃，亦較佳為50～90℃，亦較佳為60～90℃。 上述聚合物成分之Tg係動態黏彈性測定中之tanδ之峰頂溫度。具體而言，能以如下方式確定Tg。 -Tg之確定方法- 將使聚合物成分溶解而成之溶液塗佈於離型膜上，進行加熱乾燥，於離型膜上形成由聚合物成分所構成之膜（聚合物膜）。將離型膜自該聚合物膜剝離並去除，使用動態黏彈性測定裝置（商品名：Rheogel-E4000F，UBM公司製造），於測定溫度範圍20～300℃、升溫速度5℃/min、及頻率1 Hz之條件下對該聚合物膜進行測定。將所獲得之tanδ峰頂溫度（tanδ表現出極大值時之溫度）設為Tg。 The glass transition temperature (Tg) of the polymer component is preferably 150°C or lower, more preferably 140°C or lower, further preferably 120°C or lower, further preferably 100°C or lower, further preferably 90°C or lower. The Tg of the polymer component is preferably -30°C or higher, preferably -10°C or higher, preferably 0°C or higher, preferably 10°C or higher, preferably 20°C or higher, and may be 30°C or higher, 40°C or higher, 50°C or higher, or 60°C or higher. The Tg of the polymer component is preferably -30 to 140°C, preferably -10 to 100°C, preferably 0 to 100°C, preferably 10 to 90°C, preferably 20 to 90°C, preferably 30 to 90°C, preferably 40 to 90°C, preferably 50 to 90°C, and preferably 60 to 90°C. The Tg of the above-mentioned polymer component is the peak temperature of tanδ in the dynamic viscoelasticity measurement. Specifically, Tg can be determined as follows. - Method for determining Tg - A solution in which the polymer component is dissolved is applied to a release film, and heat-dried to form a film (polymer film) composed of the polymer component on the release film. The release film was peeled off and removed from the polymer film, and the polymer film was measured using a dynamic viscoelasticity measuring device (trade name: Rheogel-E4000F, manufactured by UBM) at a measuring temperature range of 20-300°C, a heating rate of 5°C/min, and a frequency of 1 Hz. The obtained tanδ peak temperature (the temperature at which tanδ shows a maximum value) was set as Tg.
上述膜狀接著劑中，上述聚合物成分之含量例如相對於上述具有環狀醚基之化合物100質量份，可為40～500質量份，亦可為60～400質量份，亦可為70～300質量份，亦較佳為80～250質量份。In the film-like adhesive, the content of the polymer component may be, for example, 40 to 500 parts by mass, 60 to 400 parts by mass, 70 to 300 parts by mass, and preferably 80 to 250 parts by mass, relative to 100 parts by mass of the compound having a cyclic ether group.
（其他成分） 本發明之膜狀接著劑亦可包含無機填充材料。作為無機填充材料，例如可例舉：二氧化矽（silica）、黏土、石膏、碳酸鈣、硫酸鋇、氧化鋁（aluminium oxide）、氧化鈹、氧化鎂、碳化矽、氮化矽、氮化鋁、氮化硼等陶瓷類；鋁、銅、銀、金、鎳、鉻、鉛、錫、鋅、鈀、焊料等金屬、或合金類；奈米碳管、石墨烯等碳類等各種無機粉末。 無機填充材料可經表面處理或表面改質，作為此種表面處理或表面改質，可例舉：矽烷偶合劑、磷酸或磷酸化合物、界面活性劑。 無機填充材料之形狀可例舉：薄片狀、針狀、長絲狀、球狀、鱗片狀，從高填充化及流動性之觀點而言，較佳為球狀粒子。 (Other components) The film adhesive of the present invention may also contain inorganic fillers. Examples of inorganic fillers include: ceramics such as silica, clay, gypsum, calcium carbonate, barium sulfate, aluminum oxide, curium oxide, magnesium oxide, silicon carbide, silicon nitride, aluminum nitride, and boron nitride; metals such as aluminum, copper, silver, gold, nickel, chromium, lead, tin, zinc, palladium, and solder, or alloys; various inorganic powders such as carbon nanotubes and graphene. The inorganic filler may be surface treated or surface modified. Examples of such surface treatment or surface modification include: silane coupling agents, phosphoric acid or phosphoric acid compounds, and surfactants. The shapes of inorganic fillers include: flakes, needles, filaments, spheres, and scales. From the perspective of high filling and fluidity, spherical particles are preferred.
於上述膜狀接著劑包含無機填充材料之情形時，上述膜狀接著劑中之無機填充材料之含量較佳為70質量%以下，更佳為60質量%以下，亦較佳為50質量%以下，亦較佳為40質量%以下。於上述膜狀接著劑包含無機填充材料之情形時，上述膜狀接著劑中之無機填充材料之含量可為1質量%以上，亦可為2質量%以上，亦較佳為4質量%以上。於上述膜狀接著劑包含無機填充材料之情形時，上述膜狀接著劑中之無機填充材料之含量可為1～70質量%，亦可為2～60質量%，亦可為4～50質量%，亦較佳為4～40質量%。When the film-like adhesive contains an inorganic filler, the content of the inorganic filler in the film-like adhesive is preferably 70% by mass or less, more preferably 60% by mass or less, also preferably 50% by mass or less, and also preferably 40% by mass or less. When the film-like adhesive contains an inorganic filler, the content of the inorganic filler in the film-like adhesive may be 1% by mass or more, may be 2% by mass or more, and may be 4% by mass or more. When the film-like adhesive contains an inorganic filler, the content of the inorganic filler in the film-like adhesive may be 1-70% by mass, may be 2-60% by mass, may be 4-50% by mass, and may be 4-40% by mass.
上述樹脂組成物除了包含上述無機填充材料以外，亦可包含矽烷偶合劑。矽烷偶合劑係矽原子上鍵結有至少1個烷氧基、芳氧基之類的水解性基者，除此以外，還可鍵結有烷基、烯基、芳基。矽烷偶合劑較佳為烷基經胺基、烷氧基、環氧基、(甲基)丙烯醯氧基取代者，更佳為烷基經胺基（較佳為苯基胺基）、烷氧基（較佳為環氧丙氧基）、(甲基)丙烯醯氧基取代者。 矽烷偶合劑例如可例舉：2-(3,4-環氧環己基）乙基三甲氧基矽烷、3-環氧丙氧基丙基三甲氧基矽烷、3-環氧丙氧基丙基三乙氧基矽烷、3-環氧丙氧基丙基甲基二甲氧基矽烷、3-環氧丙氧基丙基甲基二乙氧基矽烷、二甲基二甲氧基矽烷、二甲基二乙氧基矽烷、甲基三甲氧基矽烷、甲基三乙氧基矽烷、苯基三甲氧基矽烷、苯基三乙氧基矽烷、N-苯基-3-胺基丙基三甲氧基矽烷、3-甲基丙烯醯氧基丙基甲基二甲氧基矽烷、3-甲基丙烯醯氧基丙基三甲氧基矽烷、3-甲基丙烯醯氧基丙基甲基二乙氧基矽烷、3-甲基丙烯醯氧基丙基三乙氧基矽烷等。 In addition to the inorganic filler, the resin composition may also contain a silane coupling agent. The silane coupling agent is a silane atom having at least one hydrolyzable group such as an alkoxy group or an aryloxy group bonded to it. In addition, it may also be bonded to an alkyl group, an alkenyl group, or an aryl group. The silane coupling agent is preferably an alkyl group substituted by an amino group, an alkoxy group, an epoxy group, or a (meth)acryloyloxy group, and more preferably an alkyl group substituted by an amino group (preferably a phenylamino group), an alkoxy group (preferably a glyoxypropoxy group), or a (meth)acryloyloxy group. Examples of the silane coupling agent include 2-(3,4-epoxyhexyl)ethyltrimethoxysilane, 3-glycyrrhizic acid propyltrimethoxysilane, 3-glycyrrhizic acid propyltriethoxysilane, 3-glycyrrhizic acid propylmethyldimethoxysilane, 3-glycyrrhizic acid propylmethyldiethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, methyltrimethoxysilane, Silane, methyl triethoxysilane, phenyl trimethoxysilane, phenyl triethoxysilane, N-phenyl-3-aminopropyl trimethoxysilane, 3-methacryloyloxypropyl methyl dimethoxysilane, 3-methacryloyloxypropyl trimethoxysilane, 3-methacryloyloxypropyl methyl diethoxysilane, 3-methacryloyloxypropyl triethoxysilane, etc.
上述樹脂組成物亦可進而包含有機溶劑、離子捕捉劑（ion trapping agent）、硬化觸媒、黏度調整劑、抗氧化劑、難燃劑、著色劑等。例如，可包含國際公開第2017/158994號之其他添加物。The resin composition may further include an organic solvent, an ion trapping agent, a hardening catalyst, a viscosity modifier, an antioxidant, a flame retardant, a colorant, etc. For example, other additives of International Publication No. 2017/158994 may be included.
具有環狀醚基之化合物、其硬化劑、聚合物成分之各含量之合計在上述膜狀接著劑中所占之比率例如可為30質量%以上，較佳為40質量%以上，進而較佳為50質量%以上。該比率亦可為60質量%以上，亦可為70質量%以上，亦可為80質量%以上，亦可為90質量%以上。The total content of the compound having a cyclic ether group, its curing agent, and the polymer component in the above-mentioned film adhesive may be, for example, 30% by mass or more, preferably 40% by mass or more, and further preferably 50% by mass or more. The ratio may also be 60% by mass or more, 70% by mass or more, 80% by mass or more, or 90% by mass or more.
本發明之膜狀接著劑係可藉由製備將膜狀接著劑之各構成成分混合而成之組成物（清漆），將該組成物塗佈於離型膜或所需之基材上，視需要使其乾燥，而於上述離型膜或基材上獲得。將接著劑層之各構成成分混合而成之組成物（清漆）通常包含有機溶劑。 作為塗佈方法，可適當地採用公知之方法，例如可例舉使用輥式刮刀塗佈機、凹版塗佈機、模嘴塗佈機、反向塗佈機等之方法。 乾燥只要可實質上不發生硬化反應而去除有機溶劑，形成膜狀接著劑即可，例如，可藉由於80～150℃之溫度保持1～20分鐘來進行。 The film adhesive of the present invention can be obtained by preparing a composition (varnish) obtained by mixing the components of the film adhesive, applying the composition to a release film or a desired substrate, and drying it as needed. The composition (varnish) obtained by mixing the components of the adhesive layer usually contains an organic solvent. As a coating method, a known method can be appropriately adopted, for example, a method using a roller blade coater, a gravure coater, a die-mouth coater, a reverse coater, etc. can be cited. Drying can be performed as long as the organic solvent is removed without substantially causing a hardening reaction to form a film-like adhesive. For example, this can be performed by maintaining a temperature of 80 to 150°C for 1 to 20 minutes.
從抑制膜狀接著劑之硬化反應（具有環狀醚基之化合物之硬化反應）之觀點而言，本發明之膜狀接著劑較佳為在使用前（硬化反應前）於10℃以下之溫度條件下保存。又，於本發明之膜狀接著劑為能量線硬化型之情形時，較佳為在使用前遮光保存。遮光保存時之溫度條件並無特別限定，可為常溫，亦可冷藏。From the viewpoint of inhibiting the curing reaction of the film-like adhesive (the curing reaction of the compound having a cyclic ether group), the film-like adhesive of the present invention is preferably stored at a temperature of 10°C or less before use (before the curing reaction). In addition, when the film-like adhesive of the present invention is an energy ray curing type, it is preferably stored in a light-shielded state before use. The temperature condition during light-shielded storage is not particularly limited and may be room temperature or refrigerated.
[可撓裝置用接著片] 本發明之可撓裝置用接著片（以下，亦簡稱為「本發明之接著片」）具有：將可撓基材（可撓膜）與本發明之膜狀接著劑積層而成之構造。 [Adhesive sheet for flexible device] The adhesive sheet for flexible device of the present invention (hereinafter, also referred to as "adhesive sheet of the present invention") has a structure in which a flexible base material (flexible film) and the film-like adhesive of the present invention are laminated.
＜可撓基材＞ 關於構成本發明之接著片之可撓基材，材質、厚度等並無特別限制，只要具有可撓性，可用作可撓裝置之支持基材即可。即，可廣泛地應用可撓裝置中所使用之可撓基材。 可撓基材之儲存彈性模數較佳為10 GPa以下，更佳為7 GPa以下，進而較佳為5 GPa以下。上述儲存彈性模數通常為0.01 GPa以上，亦較佳為0.05 GPa以上，亦較佳為0.1 GPa以上。可撓基材之儲存彈性模數係將可撓基材切成5 mm寬度，使用動態黏彈性測定裝置RSAIII（TA Instruments製造），於夾頭間距離20 mm、頻率10 Hz之拉伸條件下，以升溫速度5℃/min之條件自-20℃升溫至150℃時的23℃時之儲存彈性模數。 <Flexible substrate> There are no particular restrictions on the material and thickness of the flexible substrate constituting the adhesive sheet of the present invention. As long as it is flexible, it can be used as a supporting substrate for a flexible device. That is, the flexible substrate used in a flexible device can be widely used. The storage elastic modulus of the flexible substrate is preferably 10 GPa or less, more preferably 7 GPa or less, and further preferably 5 GPa or less. The above storage elastic modulus is usually 0.01 GPa or more, preferably 0.05 GPa or more, and preferably 0.1 GPa or more. The storage elastic modulus of the flexible substrate is the storage elastic modulus at 23°C when the flexible substrate is cut into 5 mm width and the temperature is increased from -20°C to 150°C at a heating rate of 5°C/min under the conditions of 20 mm between chucks and 10 Hz tension using the dynamic viscoelasticity tester RSAIII (manufactured by TA Instruments).
作為上述可撓基材之較佳之材質，可例舉：聚酯樹脂、聚醯亞胺樹脂、丙烯酸樹脂（聚甲基丙烯酸甲酯（PMMA）樹脂等）、聚碳酸酯樹脂、丙烯腈/丁二烯/苯乙烯共聚物（ABS）樹脂、聚烯烴樹脂（聚丙烯樹脂、聚乙烯樹脂等）、聚醯胺樹脂、聚胺酯樹脂、聚乙烯醇（PVA）樹脂、聚苯乙烯樹脂、聚苯硫醚（PPS）樹脂、聚醚醚酮（PEEK）樹脂等。其中，較佳為聚酯樹脂或聚醯亞胺樹脂。作為聚酯樹脂之較佳之例，可例舉：聚對苯二甲酸乙二酯樹脂、聚萘二甲酸乙二酯樹脂等。Preferred materials for the above-mentioned flexible substrate include polyester resin, polyimide resin, acrylic resin (polymethyl methacrylate (PMMA) resin, etc.), polycarbonate resin, acrylonitrile/butadiene/styrene copolymer (ABS) resin, polyolefin resin (polypropylene resin, polyethylene resin, etc.), polyamide resin, polyurethane resin, polyvinyl alcohol (PVA) resin, polystyrene resin, polyphenylene sulfide (PPS) resin, polyetheretherketone (PEEK) resin, etc. Among them, polyester resin or polyimide resin is preferred. Preferred examples of the polyester resin include polyethylene terephthalate resin and polyethylene naphthalate resin.
上述可撓基材之厚度通常為1～1000 μm，較佳為5～800 μm，亦較佳為5～400 μm，亦較佳為5～200 μm，亦較佳為10～100 μm。厚度可藉由接觸-線性量規方式（桌上型接觸式厚度測量裝置）進行測定。The thickness of the flexible substrate is usually 1 to 1000 μm, preferably 5 to 800 μm, more preferably 5 to 400 μm, more preferably 5 to 200 μm, and more preferably 10 to 100 μm. The thickness can be measured by a contact-linear gauge method (desktop contact thickness measuring device).
如上所述，本發明之接著片可將本發明之膜狀接著劑之各構成成分混合而製備組成物（清漆），將該組成物塗佈於可撓基材上，視需要使其乾燥而形成。As described above, the adhesive sheet of the present invention can be formed by mixing the components of the film-like adhesive of the present invention to prepare a composition (varnish), applying the composition on a flexible substrate, and drying it as needed.
本發明之接著片可為由可撓基材及膜狀接著劑所構成之構成，亦可為於膜狀接著劑之與可撓基材側相反側之面進而貼合有離型膜之形態。又，亦可於可撓基材之與膜狀接著劑側相反一側之面設置保護膜等。又，本發明之接著片可為切成適當大小之形態，亦可為捲成滾筒狀而成之形態。The adhesive sheet of the present invention may be composed of a flexible substrate and a film-like adhesive, or may be in a form where a release film is attached to the surface of the film-like adhesive opposite to the flexible substrate. In addition, a protective film or the like may be provided on the surface of the flexible substrate opposite to the film-like adhesive. In addition, the adhesive sheet of the present invention may be cut into a suitable size, or may be rolled into a roll.
從抑制膜狀接著劑之硬化反應（例如，具有環狀醚基之化合物之硬化反應）之觀點而言，本發明之接著片較佳為在使用前（硬化反應前）於10℃以下之溫度條件下保存。又，於膜狀接著劑為能量線硬化型之情形時，本發明之接著片較佳為在使用前遮光保存。遮光保存時之溫度條件並無特別限定，可為常溫，亦可冷藏。From the viewpoint of inhibiting the curing reaction of the film-like adhesive (for example, the curing reaction of a compound having a cyclic ether group), the adhesive sheet of the present invention is preferably stored at a temperature of 10°C or less before use (before the curing reaction). In addition, when the film-like adhesive is an energy-ray curing type, the adhesive sheet of the present invention is preferably stored in a light-shielded state before use. The temperature condition during light-shielded storage is not particularly limited and may be room temperature or refrigerated.
[可撓裝置之製造方法] 本發明之可撓裝置之製造方法並無特別限定，只要為使用本發明之膜狀接著劑、或本發明之接著片之任一者來製造可撓裝置之方法即可。 [Manufacturing method of flexible device] The manufacturing method of the flexible device of the present invention is not particularly limited, as long as it is a method of manufacturing the flexible device using either the film adhesive of the present invention or the adhesive sheet of the present invention.
本發明之可撓裝置之製造方法之一實施方式包含將本發明之膜狀接著劑、或本發明之接著片用於構成可撓裝置之層間之接著。 作為應用本發明之膜狀接著劑之構成可撓裝置之層間，並無特別限制，例如可例舉：包含功能性元件之積層體（功能性元件與配置於其單面或兩面之各種功能層之積層體）彼此之間、可撓基材與包含功能性元件之積層體之間、第一可撓基材與第二可撓基材之間（可於第一及第二可撓基材之任一者、或兩個可撓基材之與接著劑層相反側進而形成包含功能性元件之積層體）等。因此，本發明之可撓裝置之製造方法之一實施方式包含以下步驟：將本發明之膜狀接著劑配置於構成可撓裝置之一層之表面，隔著該膜狀接著劑配置構成可撓裝置之另一層，使該膜狀接著劑進行硬化反應。 One embodiment of the method for manufacturing a flexible device of the present invention includes using the film-like adhesive of the present invention or the adhesive sheet of the present invention for bonding between layers constituting the flexible device. There is no particular limitation on the layers constituting the flexible device to which the film-like adhesive of the present invention is applied. Examples thereof include: between laminates containing functional elements (laminates containing functional elements and various functional layers arranged on one or both sides thereof), between a flexible substrate and a laminate containing functional elements, between a first flexible substrate and a second flexible substrate (a laminate containing functional elements can be formed on either the first and second flexible substrates, or on the opposite side of the adhesive layer of the two flexible substrates), etc. Therefore, one implementation method of the manufacturing method of the flexible device of the present invention includes the following steps: disposing the film-like adhesive of the present invention on the surface of one layer constituting the flexible device, disposing another layer constituting the flexible device through the film-like adhesive, and allowing the film-like adhesive to undergo a curing reaction.
又，藉由將本發明之接著片用作可撓裝置之支持基材，可將本發明之接著片用於構成可撓裝置之層間之接著。即，可將構成接著片之可撓基材作為支持可撓裝置整體之支持基材（背板）發揮功能，使接著片之膜狀接著劑作為用以將該支持基材與其上之包含功能性元件之積層體接著的層發揮功能。因此，本發明之可撓裝置之製造方法之一實施方式包含以下步驟：由本發明之接著片形成可撓裝置之支持基材，即，將本發明之接著片之膜狀接著劑側與包含功能性元件之積層體貼合，使膜狀接著劑進行硬化反應。Furthermore, by using the adhesive sheet of the present invention as a supporting substrate of a flexible device, the adhesive sheet of the present invention can be used for bonding between layers constituting the flexible device. That is, the flexible substrate constituting the adhesive sheet can function as a supporting substrate (back plate) supporting the entire flexible device, and the film adhesive of the adhesive sheet can function as a layer for bonding the supporting substrate to the laminate containing functional elements thereon. Therefore, one embodiment of the manufacturing method of the flexible device of the present invention includes the following steps: forming a supporting substrate of the flexible device from the adhesive sheet of the present invention, that is, bonding the film adhesive side of the adhesive sheet of the present invention to the laminate containing functional elements, and allowing the film adhesive to undergo a curing reaction.
本發明之可撓裝置之製造方法之另一實施方式包含將本發明之膜狀接著劑用於可撓裝置之構成材料之密封。 作為應用本發明之膜狀接著劑之可撓裝置之構成材料，並無特別限制，例如可例舉：功能性元件（有機電致發光元件、半導體元件、液晶元件、微LED等）等。具體而言，將本發明之膜狀接著劑應用於功能性元件等目標物之表面等，將該目標物密封。因此，本發明之可撓裝置之製造方法之一實施方式包含以下步驟：將本發明之膜狀接著劑配置於可撓裝置之構成材料之表面，使該膜狀接著劑進行硬化反應。 Another embodiment of the manufacturing method of the flexible device of the present invention includes using the film adhesive of the present invention to seal the constituent material of the flexible device. There is no particular limitation on the constituent material of the flexible device to which the film adhesive of the present invention is applied, and examples thereof include: functional elements (organic electroluminescent elements, semiconductor elements, liquid crystal elements, micro-LEDs, etc.). Specifically, the film adhesive of the present invention is applied to the surface of a target object such as a functional element, etc., to seal the target object. Therefore, one embodiment of the manufacturing method of the flexible device of the present invention includes the following steps: disposing the film adhesive of the present invention on the surface of the constituent material of the flexible device, so that the film adhesive undergoes a curing reaction.
本發明之可撓裝置之製造方法中，上述硬化反應之條件可考慮硬化劑之種類、功能性元件之耐熱性等適當地設定。例如，於使用光陽離子聚合起始劑作為硬化劑之情形時，藉由使用水銀燈等，照射100～3000 mJ/cm 2之紫外線，可使接著劑層充分地硬化。又，於使用潛伏性硬化劑或熱陽離子聚合起始劑之情形時，例如，藉由於150℃以上之溫度下加熱1小時以上，可使接著劑層充分地硬化。 [實施例] In the manufacturing method of the flexible device of the present invention, the conditions of the above-mentioned curing reaction can be appropriately set in consideration of the type of curing agent, the heat resistance of the functional element, etc. For example, when a photo-cationic polymerization initiator is used as a curing agent, the adhesive layer can be fully cured by irradiating 100 to 3000 mJ/ cm2 of ultraviolet light using a mercury lamp, etc. In addition, when a latent curing agent or a thermal cationic polymerization initiator is used, for example, the adhesive layer can be fully cured by heating at a temperature of 150°C or more for more than 1 hour. [Example]
基於實施例及比較例，對本發明更加具體地進行說明，但本發明並不限定於下述實施例之形態。又，室溫意指23℃，MEK為甲基乙基酮，PET為聚對苯二甲酸乙二酯，UV為紫外線。只要無特別說明，則「%」、「份」係以質量為基準。The present invention is described in more detail based on the examples and comparative examples, but the present invention is not limited to the forms of the following examples. In addition, room temperature means 23°C, MEK is methyl ethyl ketone, PET is polyethylene terephthalate, and UV is ultraviolet light. Unless otherwise specified, "%" and "parts" are based on mass.
[實施例1] 於1000 ml之可分離式燒瓶中，於溫度110℃將作為具有環狀醚基之化合物之ST-3000（商品名，氫化雙酚A型液狀環氧樹脂，日鐵化學材料股份有限公司製造）50質量份、作為聚合物成分之YP-50（商品名，苯氧基樹脂，日鐵化學材料股份有限公司製造）50質量份及MEK 30質量份加熱攪拌2小時，獲得樹脂清漆。進而，將該樹脂清漆轉移至800 ml行星式混合機中，加入作為硬化劑之WPI-113（商品名，UV陽離子聚合起始劑，富士膠片和光純藥股份有限公司製造）2質量份，於室溫下攪拌混合1小時後，真空消泡而獲得混合清漆。繼而，將所獲得之混合清漆塗佈於厚度38 μm之經表面離型處理之PET膜（離型膜）上，於130℃加熱乾燥10分鐘，獲得縱300 mm、橫200 mm、接著劑層之厚度為20 μm之附離型膜之膜狀接著劑。 [Example 1] In a 1000 ml separable flask, 50 parts by mass of ST-3000 (trade name, hydrogenated bisphenol A type liquid epoxy resin, manufactured by Nippon Steel Chemical Materials Co., Ltd.) as a compound having a cyclic ether group, 50 parts by mass of YP-50 (trade name, phenoxy resin, manufactured by Nippon Steel Chemical Materials Co., Ltd.) as a polymer component, and 30 parts by mass of MEK were heated and stirred at a temperature of 110°C for 2 hours to obtain a resin varnish. Then, the resin varnish was transferred to an 800 ml planetary mixer, and 2 parts by weight of WPI-113 (trade name, UV cationic polymerization initiator, manufactured by Fuji Film & Wako Pure Chemical Industries, Ltd.) as a hardener was added. After stirring and mixing at room temperature for 1 hour, the mixture was defoamed in a vacuum to obtain a mixed varnish. Then, the obtained mixed varnish was coated on a 38 μm thick PET film (release film) with a surface release treatment, and dried at 130°C for 10 minutes to obtain a film-like adhesive with a length of 300 mm, a width of 200 mm, and an adhesive layer thickness of 20 μm.
[實施例2] 使具有環狀醚基之化合物為828（商品名，雙酚A型環氧樹脂，日鐵化學材料股份有限公司製造）35質量份，使聚合物成分之摻合量為65質量份，除此以外，以與實施例1相同之方式獲得附離型膜之膜狀接著劑。 [Example 2] A film adhesive for a releasable film was obtained in the same manner as in Example 1 except that the compound having a cyclic ether group was 35 parts by mass of 828 (trade name, bisphenol A type epoxy resin, manufactured by Nippon Steel Chemical Materials Co., Ltd.) and the blending amount of the polymer component was 65 parts by mass.
[實施例3] 使具有環狀醚基之化合物之摻合量為35質量份，使聚合物成分之摻合量為65質量份，除此以外，以與實施例1相同之方式獲得附離型膜之膜狀接著劑。 [Example 3] A film adhesive for a releasable film was obtained in the same manner as in Example 1 except that the blending amount of the compound having a cyclic ether group was 35 parts by mass and the blending amount of the polymer component was 65 parts by mass.
[實施例4] 使具有環狀醚基之化合物為828（商品名，雙酚A型環氧樹脂，日鐵化學材料股份有限公司製造）50質量份，除此以外，以與實施例1相同之方式獲得附離型膜之膜狀接著劑。 [Example 4] A film adhesive for a releasable film was obtained in the same manner as in Example 1 except that 828 (trade name, bisphenol A type epoxy resin, manufactured by Nippon Steel Chemical Materials Co., Ltd.) was used as the compound having a cyclic ether group in an amount of 50 parts by mass.
[實施例5] 使具有環狀醚基之化合物為1003（商品名，雙酚A型環氧樹脂，三菱化學股份有限公司製造）50質量份，使接著劑層之厚度為40 μm，除此以外，以與實施例1相同之方式獲得附離型膜之膜狀接著劑。 [Example 5] A film-like adhesive of a releasable film was obtained in the same manner as in Example 1 except that the compound having a cyclic ether group was 50 parts by mass of 1003 (trade name, bisphenol A type epoxy resin, manufactured by Mitsubishi Chemical Co., Ltd.) and the thickness of the adhesive layer was 40 μm.
[實施例6] 使硬化劑為2E4MZ（商品名，咪唑系熱硬化劑，四國化成工業公司製造）2質量份，除此以外，以與實施例1相同之方式獲得附離型膜之膜狀接著劑。 [Example 6] The curing agent was 2 parts by mass of 2E4MZ (trade name, imidazole-based thermosetting agent, manufactured by Shikoku Chemical Industries, Ltd.), and a film-like adhesive for a releasable film was obtained in the same manner as in Example 1, except that the curing agent was 2 parts by mass of 2E4MZ (trade name, imidazole-based thermosetting agent, manufactured by Shikoku Chemical Industries, Ltd.).
[實施例7] 於混合清漆中加入KBM-402（商品名，矽烷偶合劑，信越化學工業公司製造）1質量份，使接著劑層之厚度為40 μm，除此以外，以與實施例1相同之方式獲得附離型膜之膜狀接著劑。 [Example 7] One part by mass of KBM-402 (trade name, silane coupling agent, manufactured by Shin-Etsu Chemical Co., Ltd.) was added to the mixed varnish to make the thickness of the adhesive layer 40 μm. A film-like adhesive of a releasable film was obtained in the same manner as in Example 1.
[實施例8] 使聚合物成分為YP-50（苯氧基樹脂，日鐵化學材料股份有限公司製造）10質量份及YX7180（商品名，苯氧基樹脂，三菱化學股份有限公司製造）40質量份，使接著劑層之厚度為90 μm，除此以外，以與實施例1相同之方式獲得附離型膜之膜狀接著劑。 [Example 8] The polymer components were 10 parts by mass of YP-50 (phenoxy resin, manufactured by Nippon Steel Chemical Materials Co., Ltd.) and 40 parts by mass of YX7180 (trade name, phenoxy resin, manufactured by Mitsubishi Chemical Co., Ltd.), and the thickness of the adhesive layer was 90 μm. A film-like adhesive of a releasable film was obtained in the same manner as in Example 1.
[實施例9] 使具有環狀醚基之化合物之摻合量為20質量份，使聚合物成分之摻合量為80質量份，使接著劑層之厚度為10 μm，除此以外，以與實施例1相同之方式獲得附離型膜之膜狀接著劑。 [Example 9] A film-like adhesive for a releasable film was obtained in the same manner as in Example 1 except that the blending amount of the compound having a cyclic ether group was 20 parts by mass, the blending amount of the polymer component was 80 parts by mass, and the thickness of the adhesive layer was 10 μm.
[實施例10] 於混合清漆中加入SIRMEK50WT%-M01（商品名，二氧化矽漿料填料，CIK NanoTek公司製造）60質量份（以二氧化矽計為30質量份），使接著劑層之厚度為7 μm，除此以外，以與實施例1相同之方式獲得附離型膜之膜狀接著劑。 [Example 10] SIRMEK50WT%-M01 (trade name, silica slurry filler, manufactured by CIK NanoTek) was added to the mixed varnish in an amount of 60 parts by mass (30 parts by mass in terms of silica) to obtain a film-like adhesive of a releasable film in the same manner as in Example 1 except that the adhesive layer had a thickness of 7 μm.
[實施例11] 使具有環狀醚基之化合物為ST-3000（商品名，氫化雙酚A型液狀環氧樹脂，日鐵化學材料股份有限公司製造）25質量份及EPPN-501H（商品名，三苯甲烷型環氧樹脂，日本化藥股份有限公司製造）25質量份，使接著劑層之厚度為10 μm，除此以外，以與實施例1相同之方式獲得附離型膜之膜狀接著劑。 [Example 11] The compound having a cyclic ether group is 25 parts by mass of ST-3000 (trade name, hydrogenated bisphenol A type liquid epoxy resin, manufactured by Nippon Steel Chemical Materials Co., Ltd.) and 25 parts by mass of EPPN-501H (trade name, triphenylmethane type epoxy resin, manufactured by Nippon Kayaku Co., Ltd.), and the thickness of the adhesive layer is 10 μm. A film-like adhesive of a releasable film is obtained in the same manner as in Example 1.
[實施例12] 使聚合物成分為SG-708-6（商品名，丙烯酸樹脂，長瀨化成股份有限公司製造）50質量份，除此以外，以與實施例1相同之方式獲得附離型膜之膜狀接著劑。 [Example 12] A film-like adhesive for a releasable film was obtained in the same manner as in Example 1 except that the polymer component was 50 parts by mass of SG-708-6 (trade name, acrylic resin, manufactured by Nagase Chemicals Co., Ltd.).
[實施例13] 使具有環狀醚基之化合物為828（商品名，雙酚A型環氧樹脂，日鐵化學材料股份有限公司製造）30質量份，使聚合物成分為SG-708-6（商品名，丙烯酸樹脂，長瀨化成股份有限公司製造）70質量份，除此以外，以與實施例1相同之方式獲得附離型膜之膜狀接著劑。 [Example 13] A film adhesive for a releasable film was obtained in the same manner as in Example 1 except that the compound having a cyclic ether group was 30 parts by mass of 828 (trade name, bisphenol A type epoxy resin, manufactured by Nippon Steel Chemical Materials Co., Ltd.) and the polymer component was 70 parts by mass of SG-708-6 (trade name, acrylic resin, manufactured by Nagase Chemicals Co., Ltd.).
[實施例14] 使聚合物成分為DYNALEO VA-9320M（商品名，胺酯樹脂，TOYOCHEM股份有限公司製造）167質量份（以胺酯樹脂計為50質量份），除此以外，以與實施例1相同之方式獲得附離型膜之膜狀接著劑。 [Example 14] A film adhesive for a releasable film was obtained in the same manner as in Example 1 except that the polymer component was 167 parts by mass of DYNALEO VA-9320M (trade name, urethane resin, manufactured by TOYOCHEM Co., Ltd.) (50 parts by mass based on urethane resin).
[實施例15] 使具有環狀醚基之化合物為828（商品名，雙酚A型環氧樹脂，日鐵化學材料股份有限公司製造）40質量份，使聚合物成分為DYNALEO VA-9320M（商品名，胺酯樹脂，TOYOCHEM股份有限公司製造）200質量份（以胺酯樹脂計為60質量份），除此以外，以與實施例1相同之方式獲得附離型膜之膜狀接著劑。 [Example 15] A film adhesive of a releasable film was obtained in the same manner as in Example 1 except that the compound having a cyclic ether group was 40 parts by mass of 828 (trade name, bisphenol A type epoxy resin, manufactured by Nippon Steel Chemical Materials Co., Ltd.) and the polymer component was 200 parts by mass of DYNALEO VA-9320M (trade name, amine resin, manufactured by TOYOCHEM Co., Ltd.) (60 parts by mass based on the amine resin).
[實施例16] 使聚合物成分為BMI-5000（商品名，雙馬來醯亞胺樹脂，Designer Molecules, Inc.公司製造）50質量份，除此以外，以與實施例1相同之方式獲得附離型膜之膜狀接著劑。 [Example 16] A film adhesive for a releasable film was obtained in the same manner as in Example 1 except that the polymer component was 50 parts by weight of BMI-5000 (trade name, bismaleimide resin, manufactured by Designer Molecules, Inc.).
[實施例17] 使具有環狀醚基之化合物為828（商品名，雙酚A型環氧樹脂，日鐵化學材料股份有限公司製造）35質量份，使聚合物成分為BMI-5000（商品名，雙馬來醯亞胺樹脂，Designer Molecules, Inc.公司製造）65質量份，除此以外，以與實施例1相同之方式獲得附離型膜之膜狀接著劑。 [Example 17] A film adhesive for a releasable film was obtained in the same manner as in Example 1 except that the compound having a cyclic ether group was 35 parts by mass of 828 (trade name, bisphenol A type epoxy resin, manufactured by Nippon Steel Chemical Materials Co., Ltd.) and the polymer component was 65 parts by mass of BMI-5000 (trade name, bismaleimide resin, manufactured by Designer Molecules, Inc.).
[比較例1] 於混合清漆中加入SIRMEK50WT%-M01（商品名，二氧化矽漿料填料，CIK NanoTek公司製造）600質量份（以二氧化矽計為300質量份），使接著劑層之厚度為7 μm，除此以外，以與實施例1相同之方式獲得附離型膜之膜狀接著劑。 [Comparative Example 1] 600 parts by mass (300 parts by mass as silica) of SIRMEK50WT%-M01 (trade name, silica slurry filler, manufactured by CIK NanoTek) was added to the mixed varnish to make the thickness of the adhesive layer 7 μm. Except for this, a film-like adhesive of a releasable film was obtained in the same manner as in Example 1.
[比較例2] 將具有環狀醚基之化合物變更為EPPN-501H（商品名，三苯甲烷型環氧樹脂，日本化藥股份有限公司製造）50質量份，除此以外，以與實施例1相同之方式獲得附離型膜之膜狀接著劑。 [Comparative Example 2] A film-like adhesive for a releasable film was obtained in the same manner as in Example 1 except that the compound having a cyclic ether group was changed to 50 parts by mass of EPPN-501H (trade name, triphenylmethane epoxy resin, manufactured by Nippon Kayaku Co., Ltd.).
[比較例3] 使實施例1中具有環狀醚基之化合物為EPPN-501H（商品名，三苯甲烷型環氧樹脂，日本化藥股份有限公司製造）50質量份，使聚合物成分為YX7200B35（苯氧基樹脂與溶劑之混合溶液，三菱化學股份有限公司製造）143質量份（以苯氧基樹脂計為50質量份），使硬化劑為SI-B3（商品名，熱陽離子聚合起始劑，三新化學工業股份有限公司製造）2質量份，使接著劑層之厚度為15 μm，除此以外，以與實施例1相同之方式獲得附離型膜之膜狀接著劑。 [Comparative Example 3] The compound having a cyclic ether group in Example 1 was changed to 50 parts by mass of EPPN-501H (trade name, triphenylmethane type epoxy resin, manufactured by Nippon Kayaku Co., Ltd.), the polymer component was changed to 143 parts by mass of YX7200B35 (mixed solution of phenoxy resin and solvent, manufactured by Mitsubishi Chemical Co., Ltd.) (50 parts by mass based on phenoxy resin), the hardener was changed to 2 parts by mass of SI-B3 (trade name, thermal cationic polymerization initiator, manufactured by Sanshin Chemical Industry Co., Ltd.), and the thickness of the adhesive layer was changed to 15 μm. A film-like adhesive of a releasable film was obtained in the same manner as in Example 1.
[比較例4] 使聚合物成分為YX7200B35（苯氧基樹脂與溶劑之混合溶液，三菱化學股份有限公司製造）143質量份（以苯氧基樹脂計為50質量份），使硬化劑為SI-B3（商品名，熱陽離子聚合起始劑，三新化學工業股份有限公司製造）2質量份，使接著劑層之厚度為15 μm，除此以外，以與實施例1相同之方式獲得附離型膜之膜狀接著劑。 [Comparative Example 4] The polymer component was YX7200B35 (a mixed solution of phenoxy resin and solvent, manufactured by Mitsubishi Chemical Co., Ltd.) 143 parts by mass (50 parts by mass based on phenoxy resin), the hardener was SI-B3 (trade name, thermal cationic polymerization initiator, manufactured by Sanshin Chemical Industry Co., Ltd.) 2 parts by mass, and the thickness of the adhesive layer was 15 μm. A film-like adhesive of a releasable film was obtained in the same manner as in Example 1.
[比較例5] 使具有環狀醚基之化合物為1003（商品名，雙酚A型環氧樹脂，三菱化學股份有限公司製造）25質量份及ST-3000（商品名，氫化雙酚A型液狀環氧樹脂，日鐵化學材料股份有限公司製造）25質量份，使聚合物成分為YP-50（商品名，苯氧基樹脂，日鐵化學材料股份有限公司製造）35質量份及YX7180（商品名，苯氧基樹脂，三菱化學股份有限公司製造）15質量份，於混合清漆中加入SIRMEK50WT%-M01（商品名，二氧化矽漿料填料，CIK NanoTek公司製造）200質量份（以二氧化矽計為100質量份），使接著劑層之厚度為15 μm，除此以外，以與實施例1相同之方式獲得附離型膜之膜狀接著劑。 [Comparative Example 5] The compound having a cyclic ether group is 25 parts by mass of 1003 (trade name, bisphenol A type epoxy resin, manufactured by Mitsubishi Chemical Co., Ltd.) and 25 parts by mass of ST-3000 (trade name, hydrogenated bisphenol A type liquid epoxy resin, manufactured by Nippon Steel Chemical Materials Co., Ltd.), and the polymer component is 35 parts by mass of YP-50 (trade name, phenoxy resin, manufactured by Nippon Steel Chemical Materials Co., Ltd.) and 15 parts by mass of YX7180 (trade name, phenoxy resin, manufactured by Mitsubishi Chemical Co., Ltd.), and SIRMEK50WT%-M01 (trade name, silica slurry filler, CIK 200 parts by mass of silicon dioxide (manufactured by NanoTek) (100 parts by mass of silicon dioxide) was added to make the thickness of the adhesive layer 15 μm. In addition, a film adhesive of a releasable film was obtained in the same manner as in Example 1.
表1中示出各實施例及比較例之膜狀接著劑之組成。 表1中所記載之「膜狀接著劑」之厚度係上述各實施例及比較例中所獲得之硬化前之膜狀接著劑之厚度。 Table 1 shows the composition of the film adhesive of each embodiment and comparative example. The thickness of the "film adhesive" recorded in Table 1 is the thickness of the film adhesive before curing obtained in each embodiment and comparative example.
＜硬化物之玻璃轉移溫度及儲存彈性模數測定＞ 使用貼合機，於70℃，以剝離了離型膜之狀態積層各實施例及比較例中所獲得之膜狀接著劑，直至厚度為0.5 mm。使該積層體於上述硬化條件（i）或（ii）下硬化而獲得接著劑硬化物之積層體，將該接著劑硬化物之積層體切成5 mm寬度，製成測定樣品。使用動態黏彈性測定裝置RSAIII（TA Instruments製造），測定於夾頭間距離20 mm、頻率10 Hz之拉伸條件下，以升溫速度5℃/min之條件自-40℃升溫至250℃時接著劑硬化物之黏彈性舉動，求出23℃時之儲存彈性模數及Tg。Tg係tanδ表現出極大值時之溫度，於極大值存在2個以上之情形時，將表現出溫度最低側之極大值時之溫度設為Tg。將測定結果示於表1中。 <Measurement of glass transition temperature and storage elastic modulus of cured product> Using a laminating machine, the film-like adhesive obtained in each embodiment and comparative example was laminated at 70°C with the release film peeled off until the thickness reached 0.5 mm. The laminate was cured under the above-mentioned curing conditions (i) or (ii) to obtain a laminate of the cured adhesive, and the laminate of the cured adhesive was cut into 5 mm width to prepare a test sample. Using the dynamic viscoelasticity measuring device RSAIII (manufactured by TA Instruments), the viscoelastic behavior of the adhesive cured product was measured under the conditions of a chuck distance of 20 mm and a frequency of 10 Hz, and the temperature was increased from -40°C to 250°C at a heating rate of 5°C/min, and the storage elastic modulus and Tg at 23°C were obtained. Tg is the temperature at which tanδ shows a maximum value. When there are more than two maximum values, the temperature at which the maximum value on the lowest temperature side is shown is set as Tg. The measurement results are shown in Table 1.
＜耐撓曲性評價＞ 將實施例或比較例中所獲得之附離型膜之膜狀接著劑貼合於厚度20 μm之PET膜（可撓基材，23℃之儲存彈性模數為5 GPa），將離型膜剝離，獲得具有可撓基材與膜狀接著劑（接著劑層）積層而成之構造之接著片。將該接著片切成寬度25 mm、長度10 cm，於上述（i）或（ii）之硬化條件下使其硬化，製成試片。以試片之長度方向之中間點為基準，對試片反覆進行1000次下述操作，即，將接著劑層設置於與心軸相反之側，彎折180°。將接著劑層之斷裂、接著劑層之折痕、或接著劑層與可撓基材發生剝離之心軸之直徑（mm）適用於下述評價基準，對耐撓曲性進行評價。評價C以上視為合格。將結果示於表1。 （評價基準） A：4 mm以下 B：5 mm以上14 mm以下 C：15 mm以上29 mm以下 D：30 mm以上、或無法彎折 <Evaluation of flex resistance> The film adhesive of the release film obtained in the embodiment or comparative example was bonded to a PET film (flexible substrate, storage elastic modulus at 23°C of 5 GPa) with a thickness of 20 μm, and the release film was peeled off to obtain an adhesive sheet having a structure in which the flexible substrate and the film adhesive (adhesive layer) were layered. The adhesive sheet was cut into pieces with a width of 25 mm and a length of 10 cm, and cured under the curing conditions of (i) or (ii) above to prepare a test piece. With the midpoint of the length direction of the test piece as the reference, the following operation was repeated 1000 times on the test piece, i.e., the adhesive layer was set on the side opposite to the mandrel and bent 180°. The following evaluation criteria were applied to the fracture of the adhesive layer, the fold of the adhesive layer, or the diameter (mm) of the mandrel where the adhesive layer and the flexible substrate were separated, and the bending resistance was evaluated. Evaluations of C or above were considered acceptable. The results are shown in Table 1. (Evaluation criteria) A: 4 mm or less B: 5 mm or more and 14 mm or less C: 15 mm or more and 29 mm or less D: 30 mm or more, or unable to bend
[表1-1]
[表1-2]
上述表中，接著劑之各成分之摻合量為質量份。空欄意指未含該成分。 如上述表所示，於膜狀接著劑之硬化物之T×E'高於本發明所規定者之情形時，於反覆撓曲時容易發生接著劑層之斷裂、接著劑層之折痕、或接著劑層與可撓基材之間之剝離，耐撓曲性較差（比較例1～5）。 相對於此，滿足本發明之規定之實施例1～17之膜狀接著劑之硬化物均表現出優異之耐撓曲性。可知藉由將本發明之膜狀接著劑、或具備該膜狀接著劑之接著片用於可撓裝置之製造，可提高可撓裝置之可靠性。 又，可知若使用包含「具有脂環結構之環氧樹脂」作為具有環狀醚基之化合物之膜狀接著劑，則即便硬化物之儲存彈性模數或Tg相同，亦能夠以更加高之水準實現耐撓曲性（實施例1與2、實施例3與4之比較）。 In the above table, the blending amount of each component of the adhesive is in parts by mass. A blank column means that the component is not contained. As shown in the above table, when the T×E' of the cured film adhesive is higher than that specified in the present invention, the adhesive layer is prone to cracking, creases in the adhesive layer, or separation between the adhesive layer and the flexible substrate during repeated bending, and the bending resistance is poor (Comparison Examples 1 to 5). In contrast, the cured film adhesives of Examples 1 to 17 that meet the requirements of the present invention all show excellent bending resistance. It is known that by using the film adhesive of the present invention or the adhesive sheet having the film adhesive in the manufacture of a flexible device, the reliability of the flexible device can be improved. In addition, it is known that if a film adhesive containing "epoxy resin having a lipid ring structure" is used as a compound having a cyclic ether group, even if the storage elastic modulus or Tg of the cured product is the same, the bending resistance can be achieved at a higher level (comparison between Examples 1 and 2, and Examples 3 and 4).
雖將本發明與其實施方式一起進行了說明，但吾等認為，只要無特別指定，則吾等之發明並不限定於說明之任何細節，應當在不違反隨附之申請專利範圍所示之發明之精神及範圍的情況下廣泛地進行解釋。Although the present invention has been described together with its embodiments, we believe that unless otherwise specified, our invention is not limited to any details of the description and should be broadly interpreted without violating the spirit and scope of the invention as shown in the attached patent claims.
本案主張基於2022年1月13日於日本提出專利申請之特願2022-003640之優先權，於本文中參照該申請並引用其內容作為本說明書之記載之一部分。This case claims priority based on patent application No. 2022-003640 filed in Japan on January 13, 2022, and the contents of the patent application are incorporated herein by reference and made part of the description of this specification.
1:膜狀接著劑 2:可撓基材（支持基材） 1: Film adhesive 2: Flexible substrate (support substrate)
[圖1]係示意性地表示本發明之可撓裝置用接著片之積層構造之剖面圖。FIG. 1 is a cross-sectional view schematically showing the layered structure of the connecting sheet for the flexible device of the present invention.
1:膜狀接著劑 1: Film adhesive
2:可撓基材(支持基材) 2: Flexible substrate (support substrate)
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| Title |
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| 期刊 横山直樹 等6人 "ハロゲンフリー難燃性FPC接着剤用エポキシ／フェノキシ／シクロフェノキシホスファーゼン(CPP)混合硬化物のモルフォロジーと特性" 日本接着学会誌 45 巻 9 号 2009 p. 330-337. |
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