TWI712504B - Laminated film and method for manufacturing cleaned laminated film - Google Patents
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Abstract
本發明提供一種疊層膜，於將耐熱高分子膜貼合至支持體之際，可抑制在耐熱高分子膜的外周附近與支持體之間產生氣泡。 The present invention provides a laminated film which can suppress the generation of air bubbles between the vicinity of the outer periphery of the heat-resistant polymer film and the support when the heat-resistant polymer film is attached to a support.
本發明之疊層膜，具備：保護膜，具有基材、及設在基材上之黏接劑層；以及耐熱高分子膜，疊層在黏接劑層上；且側面之高度10μm以上的突起、並且係源自黏接劑層或源自來自外部之附著物者的數量，係10個/cm以下。 The laminated film of the present invention includes: a protective film with a substrate and an adhesive layer provided on the substrate; and a heat-resistant polymer film laminated on the adhesive layer; and a side surface with a height of 10 μm or more The number of protrusions derived from the adhesive layer or from external attachments is 10 per cm or less.
Description
本發明關於疊層膜、邊緣清洗裝置及經清洗之疊層膜的製造方法。 The present invention relates to a laminated film, an edge cleaning device and a method for manufacturing a cleaned laminated film.
近年，吾人以將半導體元件、MEMS(微機電系統；Microelectromechanical Systems)元件、顯示器元件、偏光元件等功能元件加以輕量化、小型．薄型化、可撓性化為目的，而蓬勃進行將此等元件形成在高分子膜上之技術開發。亦即，就資訊通信器材(廣播器材、行動無線電、可攜式通信器材等)、雷達、及高速資訊處理裝置等之類的電子零件的基材的材料而言，往昔使用具有耐熱性、且亦可適應於資訊通信器材的信號頻段之高頻率化(達到GHz段)之陶瓷，但因為陶瓷不僅並非撓性、亦難以薄型化，所以有可使用之領域受限定之缺點，因此吾人最近將高分子膜作為基板使用。 In recent years, we have made functional components such as semiconductor components, MEMS (Microelectromechanical Systems) components, display components, and polarizing components lighter and smaller. For the purpose of thinning and flexibility, the technology development of forming these elements on polymer films is vigorously carried out. That is, in terms of materials for the base materials of electronic parts such as information communication equipment (broadcasting equipment, mobile radios, portable communication equipment, etc.), radars, and high-speed information processing devices, the materials used in the past have heat resistance and It can also be adapted to the high frequency (GHz band) of the signal band of information and communication equipment. However, because ceramics are not only not flexible, but also difficult to thin, they have the disadvantage of being limited in the field of use. The polymer film is used as the substrate.
於將半導體元件、MEMS元件、顯示器元件等功能元件形成在高分子膜表面之際，宜以使用高分子膜的特性即可撓性之所謂之卷對卷製程來加工。然而，於半導體產業、MEMS產業、顯示器產業等的業界之中，至今已建構以晶圓基底或玻璃基板基底等剛性的平面基板作為對象之製程技術。於是，為了使用現 存基礎設備而將功能元件形成在高分子膜上，吾人使用下述步驟：使高分子膜貼合在例如由玻璃板、陶瓷板、矽晶圓、金屬板等無機物所構成之剛性的支持體，並在其上形成期望元件後，將其從支持體剝離。 When forming functional elements such as semiconductor elements, MEMS elements, and display elements on the surface of a polymer film, it is preferable to process them by a so-called roll-to-roll process that uses the properties of the polymer film to be flexible. However, in industries such as the semiconductor industry, MEMS industry, and display industry, process technologies that target rigid flat substrates such as wafer substrates or glass substrate substrates have been constructed. Therefore, in order to use To store the basic equipment and form the functional elements on the polymer film, we use the following steps: the polymer film is attached to a rigid support made of inorganic materials such as glass plates, ceramic plates, silicon wafers, metal plates, etc. , And after the desired element is formed thereon, it is peeled from the support.
然而，在使高分子膜與由無機物所構成之支持體進行貼合而成之疊層體形成期望功能元件之製程中，該疊層體經常曝於高溫。例如，形成多晶矽、氧化物半導體等功能元件，須要處於200℃~600℃左右的溫度範圍之步驟。又，製作氫化非晶矽薄膜之中有將200~300℃左右的溫度施加於膜之情形，且為了將非晶矽加熱、脫氫化而定為低溫多晶矽，有須450℃~600℃左右的加熱之情形。因此，構成疊層體之高分子膜需耐熱性，但就現實問題而言，在該高溫範圍域可承受實際使用之高分子膜，種類有限。 However, in the process of forming a desired functional device into a laminate formed by bonding a polymer film and a support composed of an inorganic substance, the laminate is often exposed to high temperatures. For example, the formation of functional devices such as polysilicon and oxide semiconductors requires steps in the temperature range of about 200°C to 600°C. In addition, in the production of hydrogenated amorphous silicon thin films, a temperature of about 200 to 300°C may be applied to the film. In order to heat and dehydrogenate the amorphous silicon as low-temperature polysilicon, a temperature of about 450°C to 600°C is required. The situation of heating. Therefore, the polymer film constituting the laminate needs heat resistance, but in terms of practical problems, the types of polymer films that can withstand actual use in this high temperature range are limited.
於上述用途使用之高分子膜，為了於貼合至支持體之際不使塵粒等進入支持體與高分子膜之間，直至即將使用為止，兩面或單面係由保護膜所覆蓋(例如參照專利文獻1)。就保護膜而言，使用附黏接劑層的PET(聚對苯二甲酸乙二酯；polyethylene terephthalate)膜、烯烴膜等。 For the polymer film used in the above-mentioned applications, in order to prevent dust particles from entering between the support and the polymer film when it is attached to the support, until it is about to be used, both sides or one side are covered by a protective film (such as Refer to Patent Document 1). As for the protective film, a PET (polyethylene terephthalate) film with an adhesive layer, an olefin film, or the like is used.
專利文獻1：國際公開第2016/031746號 Patent Document 1: International Publication No. 2016/031746
然而，儘管高分子膜直至即將使用為止係由保護膜所覆蓋，但於貼合至支持體之際，有在高分子膜的外周附近與支持體之間產生氣泡之情形。如此氣泡，使高分子膜與支持體之間產生局部不黏接之處。因此，會有以下疑慮：高分子膜與支持體之間的貼合力(剝離強度)降低，且產生高分子膜於步驟中剝離之障礙。 However, although the polymer film is covered with a protective film until just before use, air bubbles may be generated between the vicinity of the outer periphery of the polymer film and the support when it is attached to the support. Such bubbles create local non-adhesion between the polymer film and the support. Therefore, there are doubts that the adhesion force (peel strength) between the polymer film and the support is reduced, and an obstacle to the peeling of the polymer film in the step occurs.
本案發明人深入探討氣泡產生之原因。其結果，查明：構成保護膜之黏接劑溢出高分子膜的側面，且於貼合至支持體之際，殘留在高分子膜的側面之黏接劑侵入支持體與高分子膜之間，成為氣泡產生的原因。 The inventor of this case thoroughly discussed the causes of bubbles. As a result, it was found that the adhesive constituting the protective film overflowed from the side of the polymer film, and when it was attached to the support, the adhesive remaining on the side of the polymer film penetrated between the support and the polymer film , Become the cause of bubbles.
本案發明人深入探討疊層有保護膜與耐熱高分子膜之疊層膜。其結果，發現若黏接劑層朝往疊層膜的側面之溢出少，則可抑制貼合至支持體之際產生氣泡，進而完成本發明。 The inventor of the present case has conducted in-depth research on a laminated film in which a protective film and a heat-resistant polymer film are laminated. As a result, it was found that if the adhesive layer has little overflow to the side surface of the laminated film, it is possible to suppress the generation of air bubbles when bonding to the support, and complete the present invention.
亦即，本發明之疊層膜，其特徵為，具備：保護膜，具有基材、及設在前述基材上之黏接劑層；以及耐熱高分子膜，疊層在前述黏接劑層上；且側面之高度10μm以上之突起、並且係源自前述黏接劑層或源自來自外部的附著物者的數量係10個/cm以下。 That is, the laminated film of the present invention is characterized by comprising: a protective film having a substrate and an adhesive layer provided on the substrate; and a heat-resistant polymer film laminated on the adhesive layer On; and the number of protrusions with a height of 10μm or more on the side surface and derived from the aforementioned adhesive layer or from external attachments is less than 10/cm.
依據前述構成，則因為側面之高度10μm以上的突起係10個/cm以下，所以可說抑制構成黏接劑層之黏接劑溢出、且來自外部之附著物亦少。故，若使用前述疊層膜，並剝除保護膜而將耐熱高分子膜貼合至支持體，則可抑制氣泡產生。 According to the aforementioned structure, since the protrusions with a height of 10 μm or more on the side surface are 10 pieces/cm or less, it can be said that the adhesive that constitutes the adhesive layer is prevented from overflowing, and there are few adhesions from the outside. Therefore, if the aforementioned laminated film is used and the protective film is peeled off to bond the heat-resistant polymer film to the support, the generation of bubbles can be suppressed.
前述構成宜如下：前述基材之在25℃的拉伸彈性係數係0.3GPa以上，前述耐熱高分子膜之在25℃的拉伸彈性係數係2GPa以上。 The aforementioned structure is preferably as follows: the tensile modulus of elasticity at 25°C of the base material is 0.3 GPa or more, and the tensile modulus of elasticity at 25°C of the heat-resistant polymer film is 2 GPa or more.
當前述基材之在25℃的拉伸彈性係數0.3GPa以上、且前述耐熱高分子膜之在25℃的拉伸彈性係數係2GPa以上時，則因湯姆遜刀具等刀具所行之切斷而使柔軟的黏接劑層溢出疊層膜的側面之可能性高。然而，即使係具有如此拉伸彈性係數之疊層膜，因為側面之高度10μm以上的突起係10個/cm以下，所以亦可謂抑制構成黏接劑層之黏接劑溢出。 When the tensile elastic modulus of the base material at 25°C is 0.3 GPa or higher, and the heat-resistant polymer film has a tensile elastic modulus of 2 GPa or higher at 25° C., it is cut due to cutting by Thomson knives. There is a high possibility that the soft adhesive layer may overflow the side surface of the laminated film. However, even if it is a laminated film having such a coefficient of tensile elasticity, since the protrusions with a side height of 10 μm or more are 10 pieces/cm or less, it can be said that overflow of the adhesive constituting the adhesive layer is suppressed.
前述構成之中，前述保護膜宜設在前述耐熱高分子膜的兩面。 In the aforementioned configuration, the protective film is preferably provided on both sides of the heat-resistant polymer film.
當前述保護膜設在前述耐熱高分子膜的兩面時，則可保護前述耐熱高分子膜的兩面直至即將使用為止。 When the protective film is provided on both sides of the heat-resistant polymer film, both sides of the heat-resistant polymer film can be protected until it is about to be used.
又，本發明之邊緣清洗裝置，其特徵為具備：膜固定部，將膜加以固定； 搬運部，將擦拭用薄片加以搬運；以及驅動部，於使前述膜固定部所固定之膜的側面接觸於由前述搬運部所搬運之擦拭用薄片之狀態下，使前述膜與前述擦拭用薄片相對地移動。 In addition, the edge cleaning device of the present invention is characterized by having: a film fixing part for fixing the film; The conveying part conveys the wiping sheet; and the driving part connects the film and the wiping sheet in a state where the side surface of the film fixed by the film fixing part is in contact with the wiping sheet conveyed by the conveying part Move relatively.
依據前述構成，則可藉由擦拭用薄片來抹拭膜的側面。例如，於黏接劑從前述疊層膜的側面溢出之情形下，可由擦拭用薄片來抹拭前述側面，藉以將其拭除，成為潔淨狀態。其結果，獲得側面經清洗之疊層膜。 According to the aforementioned structure, the side surface of the film can be wiped by the wiping sheet. For example, in the case where the adhesive overflows from the side surface of the laminated film, the side surface can be wiped with a wiping sheet to wipe it off and become a clean state. As a result, a laminated film with cleaned sides is obtained.
前述構成之中，宜具備：溶劑供給部，將溶劑供給至前述擦拭用薄片。 Among the aforementioned configurations, it is preferable to include a solvent supply unit that supplies the solvent to the wiping sheet.
若因應於預設之污染膜的側面之物質來選擇溶劑，並供給擦拭用薄片，則更可將膜的側面定為潔淨狀態。 If the solvent is selected according to the preset material that contaminates the side of the film, and the wiping sheet is supplied, the side of the film can be kept clean.
又，本發明之經清洗之疊層膜的製造方法，其特徵為，包括：步驟A，準備具有保護膜與耐熱高分子膜之疊層膜，前述保護膜具備基材及設在前述基材上之黏接劑層，前述耐熱高分子膜疊層在前述黏接劑層上；以及步驟B，於使前述疊層膜的側面接觸於擦拭用薄片之狀態下，使前述疊層膜與前述擦拭用薄片相對地移動，來抹拭前述側面。 In addition, the method for producing a cleaned laminated film of the present invention is characterized by comprising: step A, preparing a laminated film having a protective film and a heat-resistant polymer film, the protective film is provided with a substrate and is provided on the substrate The upper adhesive layer, the heat-resistant polymer film is laminated on the adhesive layer; and step B, with the side surface of the laminate film in contact with the wiping sheet, the laminate film and the The wiping sheet moves relatively to wipe the aforementioned side surface.
依據前述構成，則可於因擦拭用薄片抹拭前述疊層膜的側面而使黏接劑從側面溢出之情形下，將其拭除，並定為潔淨狀態。其結果，獲得側面經清洗之疊層膜。 According to the aforementioned structure, when the adhesive overflows from the side surface of the laminated film by wiping the side surface of the laminated film with the wiping sheet, it can be wiped off and kept in a clean state. As a result, a laminated film with cleaned sides is obtained.
在前述構成，前述步驟B之後的疊層膜之中，側面之高度10μm以上的突起、並且係源自前述黏接劑層或源自來自外部的附著物者的數量宜係10個/cm以下。 In the aforementioned configuration, in the laminated film after the aforementioned step B, the number of protrusions with a height of 10 μm or more on the side surface and derived from the aforementioned adhesive layer or from external attachments is preferably 10 pcs/cm or less .
若側面之高度10μm以上的突起係10個/cm以下，則可謂抑制構成黏接劑層之黏接劑溢出、且來自外部的附著物亦少。故，若使用前述疊層膜，並剝除保護膜而使耐熱高分子膜貼合至支持體，則可抑制氣泡產生。
If the height of the side surface is 10 μm or
依據本發明，則可提供一種疊層膜，可於使耐熱高分子膜貼合至支持體之際，在耐熱高分子膜的外周附近與支持體之間抑制氣泡產生。又，可提供用以製造該疊層膜之邊緣清洗裝置。又，可提供該疊層膜的製造方法。 According to the present invention, it is possible to provide a laminated film which can suppress the generation of air bubbles between the vicinity of the outer periphery of the heat-resistant polymer film and the support when the heat-resistant polymer film is attached to the support. Moreover, an edge cleaning device for manufacturing the laminated film can be provided. In addition, a method for manufacturing the laminated film can be provided.
10:疊層膜 10: Laminated film
20、40、60、80、100、120:邊緣清洗裝置 20, 40, 60, 80, 100, 120: edge cleaning device
22:載置台 22: Mounting table
24:擦拭用薄片 24: Wipe sheet
26:導引滾子 26: Guide roller
28:捲出側輥 28: Roll out side roller
29:捲收側輥 29: Rewinding side roller
42:載置台 42: Mounting table
44:導件 44: guide
46:按壓滾子 46: Press the roller
48:搬運部 48: Transport Department
52:旋轉滾子 52: Rotating roller
54:彈性滾子 54: Elastic roller
56:桿棒部 56: Club
58:汽缸 58: cylinder
61:本體 61: body
62:旋轉滾子 62: Rotating roller
64:槽 64: Slot
66:旋轉軸 66: Rotation axis
68:板狀構件 68: Plate member
70:桿棒構件 70: Rod member
72:汽缸 72: cylinder
82:按壓構件 82: pressing member
84:V字狀構件 84: V-shaped member
86:汽缸 86: cylinder
91:清洗頭治具 91: Cleaning head fixture
92:槽 92: Slot
圖1係用以說明本實施形態之邊緣清洗裝置之示意性立體圖。 Fig. 1 is a schematic perspective view for explaining the edge cleaning device of this embodiment.
圖2係圖1所示之邊緣清洗裝置的側視圖。 Figure 2 is a side view of the edge cleaning device shown in Figure 1.
圖3係用以說明其它實施形態之邊緣清洗裝置之示意性俯視圖。 Fig. 3 is a schematic plan view for explaining the edge cleaning device of other embodiments.
圖4係圖3所示之邊緣清洗裝置的橫剖視圖。 Fig. 4 is a cross-sectional view of the edge cleaning device shown in Fig. 3.
圖5係用以說明其它實施形態之邊緣清洗裝置之示意性俯視圖。 Fig. 5 is a schematic plan view for explaining the edge cleaning device of other embodiments.
圖6A係圖5所示之旋轉滾子的俯視圖。 FIG. 6A is a top view of the rotating roller shown in FIG. 5. FIG.
圖6B係圖5所示之旋轉滾子的側視圖。 Fig. 6B is a side view of the rotating roller shown in Fig. 5.
圖7係用以說明其它實施形態之邊緣清洗裝置之示意性俯視圖。 Fig. 7 is a schematic plan view for explaining an edge cleaning device of another embodiment.
圖8係用以說明其它實施形態之邊緣清洗裝置之示意性俯視圖。 Fig. 8 is a schematic plan view for explaining an edge cleaning device of another embodiment.
圖9係用以說明其它實施形態之邊緣清洗裝置之示意性俯視圖。 Fig. 9 is a schematic plan view for explaining an edge cleaning device of another embodiment.
圖10係用以說明圖9所示之清洗頭治具的俯視圖及側視圖。 FIG. 10 is a top view and a side view for explaining the cleaning head fixture shown in FIG. 9.
以下說明本發明的實施形態。 Hereinafter, embodiments of the present invention will be described.
本實施形態之疊層膜，具備：保護膜，具有基材、及設在前述基材上之黏接劑層；以及耐熱高分子膜，疊層在前述黏接劑層上；且側面之高度10μm以上的突起、並且係源自前述黏接劑層或源自來自外部的附著物者的數量係10個/cm以下。 The laminated film of this embodiment includes: a protective film having a substrate and an adhesive layer provided on the substrate; and a heat-resistant polymer film laminated on the adhesive layer; and the height of the side The number of protrusions of 10 μm or more derived from the aforementioned adhesive layer or from external attachments is 10 per cm or less.
<疊層膜> <Laminated film>
前述疊層膜之中，側面之高度10μm以上的突起的數量係10個/cm以下，且宜係7個/cm以下，更宜係2個/cm以下。前述突起係指源自黏接劑層或源自來自外部的附著物之突起，不包含源自基材還有耐熱高分子膜之突起。意即，源自基材還有耐熱高分子膜之突起，不採計為前述突起的數量。前述突起的數量的採計方法依實施例記載的方法。 In the aforementioned laminated film, the number of protrusions with a height of 10 μm or more on the side surface is 10 pieces/cm or less, preferably 7 pieces/cm or less, and more preferably 2 pieces/cm or less. The aforementioned protrusions refer to protrusions derived from the adhesive layer or from external attachments, and do not include protrusions derived from the substrate or heat-resistant polymer film. This means that the protrusions derived from the substrate and the heat-resistant polymer film are not counted as the number of protrusions mentioned above. The method for measuring the number of protrusions described above follows the method described in the embodiment.
前述疊層膜，因為側面之高度10μm以上的突起係10個/cm以下，所以可謂抑制構成黏接劑層之黏接劑溢出、且來自外部的附著物亦少。故，若使用前述疊層膜，並剝除保護膜而使耐熱高分子膜貼合至支持體，則可抑制氣泡產生。 In the above-mentioned laminated film, since the protrusions with a height of 10 μm or more on the side surface are 10 pieces/cm or less, it can be said that the overflow of the adhesive constituting the adhesive layer is suppressed, and the adhesion from the outside is also small. Therefore, if the aforementioned laminated film is used and the protective film is peeled off to bond the heat-resistant polymer film to the support, the generation of bubbles can be suppressed.
本說明書之中，側面上突起的數量係10個/cm以下意指疊層膜的全部的邊(四邊)之中突起的數量係10個/cm以下。 In this specification, the fact that the number of protrusions on the side surface is 10/cm or less means that the number of protrusions in all sides (four sides) of the laminated film is 10/cm or less.
前述突起係10個/cm以下之疊層膜，不特別限定，例如可藉由後述說明之經清洗之疊層膜的製造方法來製造。 The above-mentioned laminated film of 10 protrusions/cm or less is not particularly limited. For example, it can be produced by the method of producing a cleaned laminated film described later.
前述疊層膜係以下構成：耐熱高分子膜的至少一面疊層有保護膜。前述疊層膜，可係保護膜僅設在耐熱高分子膜的一面之構成，亦可係保護膜設在耐熱高分子膜的兩面之構成。 The above-mentioned laminated film has a structure in which a protective film is laminated on at least one side of a heat-resistant polymer film. The aforementioned laminated film may be a configuration in which the protective film is provided on only one side of the heat-resistant polymer film, or a configuration in which the protective film is provided on both sides of the heat-resistant polymer film.
此外，於係保護膜設在耐熱高分子膜的兩面之構成之情形下，前述突起的數量係指將源自一保護膜的黏接劑層與源自另一保護膜的黏接劑層之突起加以包含之合計突起數。 In addition, in the case of a configuration in which the protective film is provided on both sides of the heat-resistant polymer film, the number of protrusions mentioned above refers to the difference between the adhesive layer derived from one protective film and the adhesive layer derived from the other protective film The total number of protrusions including protrusions.
前述疊層膜宜係一個邊為300~350mm左右(更宜係一個邊為2000~1500mm左右)之矩形薄片狀(不捲繞成輥狀之平面薄片狀)。矩形薄片狀之前述疊層膜可藉由以湯姆遜刀具等刀具來切斷疊層有前述保護膜與前述耐熱高分子膜之長條的膜而獲得。當進行湯姆遜刀具等刀具所行之切斷時，則柔軟的黏接劑層溢出疊層膜的側面之可能性高，但可利用後述說明之經清洗之疊層膜的製造 方法等，而將作為最終產品之矩形薄片狀的前述疊層膜定為前述突起係10個/cm以下。 The aforementioned laminated film should preferably be a rectangular sheet (a flat sheet that is not wound into a roll) with one side of about 300-350mm (more preferably about 2000-1500mm on one side). The laminated film in the shape of a rectangular sheet can be obtained by cutting a long film laminated with the protective film and the heat-resistant polymer film with a tool such as a Thomson knife. When cutting by cutting tools such as Thomson knives, there is a high possibility that the soft adhesive layer will overflow the sides of the laminated film. However, it is possible to use the cleaned laminated film described later Method, etc., and the rectangular sheet-like laminate film as the final product is determined to be 10 protrusions/cm or less.
<保護膜> <Protective Film>
前述保護膜具有基材、及設在前述基材上之黏接劑層。前述保護膜亦可具有前述基材及前述黏接劑層以外的其它層。其中，前述黏接劑層宜以接觸於耐熱高分子膜之態樣疊層。故，前述黏接劑層宜位在前述保護膜的最外表面。 The protective film has a substrate and an adhesive layer provided on the substrate. The said protective film may have other layers other than the said base material and the said adhesive layer. Among them, the aforementioned adhesive layer is preferably laminated in a state in which it is in contact with the heat-resistant polymer film. Therefore, the adhesive layer is preferably located on the outermost surface of the protective film.
<基材> <Substrate>
前述基材成為前述保護膜的強度母體。 The aforementioned base material becomes the strength matrix of the aforementioned protective film.
就前述基材而言，不特別限定，但在25℃的拉伸彈性係數宜係0.3GPa以上，更宜係1GPa以上，尤宜係2GPa以上。當前述基材之在25℃的拉伸彈性係數係0.3GPa以上時，則可合宜保護前述耐熱高分子膜的表面。又，前述基材之在25℃的拉伸彈性係數，由使前述保護膜可於自前述耐熱高分子膜剝離之際彎曲之觀點來看，例如可定為10GPa以下、5GPa以下等。 The aforementioned base material is not particularly limited, but the tensile elastic modulus at 25°C is preferably 0.3 GPa or higher, more preferably 1 GPa or higher, and particularly preferably 2 GPa or higher. When the tensile elastic modulus of the substrate at 25° C. is 0.3 GPa or higher, the surface of the heat-resistant polymer film can be suitably protected. In addition, the tensile elastic modulus of the base material at 25°C can be set to be 10 GPa or less, 5 GPa or less from the viewpoint of allowing the protective film to bend when peeling from the heat-resistant polymer film.
本說明書之中，在25℃之前述基材的拉伸彈性係數係指：將前述基材呈100mm×10mm的箋狀切下者作為試驗片，並使用拉伸試驗機(島津製作所製，AutoGraph(R)，機種名AG-5000A)，以拉伸速度50mm/分、夾頭間距離40mm條件下量測出之值。 In this specification, the coefficient of tensile elasticity of the aforementioned substrate at 25°C means that the aforementioned substrate is cut into a 100mm×10mm paper as a test piece, and a tensile testing machine (manufactured by Shimadzu Corporation, AutoGraph (R), model name AG-5000A), the value measured under the conditions of a stretching speed of 50mm/min and a distance between the chucks of 40mm.
就前述基材之材質而言，可列舉：聚乙烯、聚丙烯等聚烯烴樹脂；尼龍6、尼龍66等聚醯胺樹脂；聚對苯二甲酸乙二酯、聚對苯二甲酸丙二酯、聚對苯二甲酸丁二酯、聚2,6-萘二甲酸乙二酯等聚酯樹脂。該等材質可混合使用亦無妨。前述聚酯樹脂也可為將下列成分作為共聚合成分並進行共聚合而得的聚酯樹脂，例如：二乙二醇、新戊二醇、聚伸烷基二醇等二醇成分；或己二酸、癸二酸、鄰苯二甲酸、間苯二甲酸、2,6-萘二羧酸等二羧酸成分等。其中，考慮機械性強度、耐藥品性、耐熱性之觀點，宜為聚酯樹脂。
As for the material of the aforementioned base material, examples include: polyolefin resins such as polyethylene and polypropylene; polyamide resins such as nylon 6,
前述聚酯樹脂之中，由物性與成本之平衡的觀點來看，最宜係聚對苯二甲酸乙二酯。 Among the aforementioned polyester resins, polyethylene terephthalate is most suitable from the viewpoint of the balance between physical properties and cost.
前述基材宜係雙軸延伸。當係雙軸延伸時，則可提昇抗化學藥品性、抗熱性、機械強度等。 The aforementioned base material is preferably biaxially extended. When it is biaxially extended, it can improve chemical resistance, heat resistance, and mechanical strength.
前述基材係單層或係複層皆無妨。 It does not matter whether the aforementioned substrate is a single layer or a multiple layer.
前述基材可因應需要而使各種添加劑含在前述樹脂中。就前述添加劑而言，例如，列舉抗氧化劑、抗光劑、膠化劑、有機溼潤劑、紫外線吸收劑、界面活性劑、抗靜電劑等。就前述抗靜電劑而言，可採用往昔公知者。當前述基材添加有抗靜電劑時，則可防止吸引塵埃等所導致之汚染。 The aforementioned base material may have various additives contained in the aforementioned resin as required. The aforementioned additives include, for example, antioxidants, light stabilizers, gelling agents, organic wetting agents, ultraviolet absorbers, surfactants, and antistatic agents. As for the aforementioned antistatic agent, those known in the past can be used. When the aforementioned base material is added with an antistatic agent, it can prevent the pollution caused by attracting dust and the like.
前述基材可係透明，亦可著色。就將前述基材加以著色之方法而言，未特別限定，可使其含有顏料、染料而進行著色。例如，可利用將氧化鈦等白色顏料加以混合而定為白色膜並且亦提昇識別性，因此合宜。 The aforementioned substrate may be transparent or colored. The method of coloring the aforementioned substrate is not particularly limited, and it can be colored by containing a pigment or dye. For example, it is suitable to mix white pigments such as titanium oxide to form a white film and improve the recognition.
前述基材，為了確保操作性及生產性，宜在基材中將粒徑係10~1000nm左右的滑材(粒子)以0.03~3質量%左右加以添加而使其含有，而將微細的凹凸賦予至基材表面來確保易滑性。 In order to ensure the handling and productivity of the aforementioned base material, it is preferable to add a sliding material (particles) with a particle size of about 10 to 1000 nm at about 0.03 to 3% by mass in the base material to contain fine unevenness. It is applied to the surface of the substrate to ensure slipperiness.
前述基材的厚度不特別限定，例如可因應在12~500μm範圍下使用之規格來任意決定。前述基材的厚度更宜係350μm以下。若前述基材的厚度係350μm以下，則可抑制生產性或操作性降低。又，前述基材的厚度更宜係25μm~50μm範圍。若前述基材的厚度係25μm以上，則可降低前述基材的機械強度不足，並可防止剝離時斷裂。 The thickness of the aforementioned substrate is not particularly limited. For example, it can be arbitrarily determined in accordance with the specifications used in the range of 12 to 500 μm. The thickness of the aforementioned substrate is more preferably 350 μm or less. If the thickness of the aforementioned base material is 350 μm or less, it is possible to suppress a decrease in productivity or workability. In addition, the thickness of the aforementioned substrate is more preferably in the range of 25 μm to 50 μm. If the thickness of the substrate is 25 μm or more, the insufficient mechanical strength of the substrate can be reduced, and breakage during peeling can be prevented.
前述基材可利用往昔公知的製膜方法進行製膜。就前述製膜方法而言，例如可例示壓延製膜法、在有機溶劑中之鑄造法、在密閉系統之吹袋擠出法、T模擠出法、共擠擠出法、乾式層壓法等。 The aforementioned substrate can be formed into a film by a conventionally known film forming method. As for the aforementioned film forming methods, for example, calendering film forming method, casting method in organic solvent, blown bag extrusion method in closed system, T die extrusion method, co-extrusion extrusion method, and dry lamination method can be exemplified. Wait.
<黏接劑層> <Adhesive Layer>
前述黏接劑層，一般而言，相較於前述基材、前述耐熱高分子膜而言係低彈性係數(例如，相較於基材、耐熱高分子膜而言，拉伸彈性係數降低二位數或以上)。 The aforementioned adhesive layer, generally speaking, has a lower coefficient of elasticity compared to the aforementioned substrate and the aforementioned heat-resistant polymer film (for example, compared with the substrate and heat-resistant polymer film, the tensile elastic coefficient is reduced by two Digits or more).
就前述黏著劑層而言，可使用丙烯酸系、聚矽氧系、橡膠系、聚酯系等公知者，並無特別限制。就操作性的觀點，宜為丙烯酸系樹脂、聚矽氧系樹脂。 For the aforementioned adhesive layer, known ones such as acrylic, silicone, rubber, and polyester can be used, and there is no particular limitation. From the viewpoint of operability, acrylic resin and silicone resin are suitable.
前述丙烯酸系樹脂可藉由將(甲基)丙烯酸烷基酯等單體予以聚合而得。就前述單體之具體例而言，可列舉：(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸丙酯、(甲基)丙烯酸正丁酯、(甲基)丙烯酸異丁酯、(甲基)丙烯酸三級丁酯、(甲基)丙烯酸正己酯、(甲基)丙烯酸-2-乙基己酯、(甲基)丙烯酸正辛酯、(甲基)丙烯酸異辛酯、(甲基)丙烯酸月桂酯、(甲基)丙烯酸硬脂酯等烷基(甲基)丙烯酸酯化合物。它們也可因應需要將多種進行共聚合。 The aforementioned acrylic resin can be obtained by polymerizing monomers such as alkyl (meth)acrylate. Specific examples of the aforementioned monomers include: methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, n-butyl (meth)acrylate, (meth) Isobutyl acrylate, tertiary butyl (meth)acrylate, n-hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, n-octyl (meth)acrylate, (meth)acrylic acid Alkyl (meth)acrylate compounds such as isooctyl ester, lauryl (meth)acrylate, and stearyl (meth)acrylate. They can also copolymerize multiple types as needed.
前述黏接劑層亦可具有抗靜電功能。例如，前述黏接劑層亦可含有抗靜電劑。當前述黏接劑層添加有抗靜電劑時，則可防止吸引塵埃等所導致之汚染。 The aforementioned adhesive layer may also have an antistatic function. For example, the aforementioned adhesive layer may also contain an antistatic agent. When the aforementioned adhesive layer is added with an antistatic agent, it can prevent pollution caused by attracting dust and the like.
前述黏接劑層，通常設在前述基材整面。但是，本發明不限定於此例，前述基材的表面中亦可存有未設黏接劑層之處。例如，前述基材的表面的寬度方向的兩端邊近旁亦可定為未設黏接劑層之構成。 The aforementioned adhesive layer is usually provided on the entire surface of the aforementioned substrate. However, the present invention is not limited to this example, and the surface of the aforementioned substrate may have a place where no adhesive layer is provided. For example, the vicinity of both ends in the width direction of the surface of the aforementioned base material may be configured without an adhesive layer.
前述黏接劑層的厚度，不特別限定，通常3~200μm即可，且宜係5~30μm。 The thickness of the aforementioned adhesive layer is not particularly limited, but usually 3 to 200 μm, and preferably 5 to 30 μm.
前述黏接劑層，可藉由下述方式獲得：於將黏接劑組成物溶液塗佈在前述基材上而形成塗佈膜之後，使該塗佈膜於預定條件下乾燥。前述塗佈方法不特 別限定，例如列舉輥塗佈、網版塗佈、凹版塗佈等。又，就乾燥條件而言，例如於乾燥溫度80~150℃、乾燥時間0.5~5分鐘的範圍內進行。又，亦可在分隔體上塗佈黏接劑組成物而形成塗佈膜之後，於前述乾燥條件下使塗佈膜乾燥而形成黏接劑層。此後，將前述黏接劑層與分隔體一併貼合至前述基材上。藉由上述，獲得保護膜。 The adhesive layer can be obtained by applying the adhesive composition solution on the substrate to form a coating film, and then drying the coating film under predetermined conditions. The aforementioned coating method is not special It is not limited, and examples include roll coating, screen coating, gravure coating, and the like. In addition, as for the drying conditions, for example, the drying temperature is 80 to 150° C., and the drying time is 0.5 to 5 minutes. In addition, after coating the adhesive composition on the separator to form a coating film, the coating film may be dried under the aforementioned drying conditions to form an adhesive layer. After that, the adhesive layer and the separator are attached to the substrate together. Through the above, a protective film is obtained.
<其它層> <Other layers>
前述保護膜，亦可具有前述基材、前述黏接劑層以外之層。例如，前述基材之與設有前述黏接劑層之面係相反側的面，亦可具有剝離處理層。當具有前述剝離處理層時，則可例如於貼合至耐熱高分子膜之前，先將前述保護膜捲繞成輥狀。意即，即使將前述保護膜捲繞成輥狀，亦使前述黏接劑層不直接接觸於前述基材的背面，而係接觸於前述剝離處理層，因此可防止前述黏接劑層貼附(轉印)至前述基材的背面。又，例如，前述基材之設有前述黏接劑層之面、或相反側之面，亦可具有抗靜電層。若具有前述抗靜電層，則可防止吸引塵埃等所導致之汚染。就前述抗靜電層而言，不特別限定，例如例舉含有抗靜電劑、並具有與基材同樣組成之層。 The protective film may have layers other than the base material and the adhesive layer. For example, the surface of the substrate on the opposite side to the surface on which the adhesive layer is provided may have a peeling treatment layer. When the peeling treatment layer is provided, for example, the protective film may be wound into a roll shape before bonding to the heat-resistant polymer film. That is, even if the protective film is wound into a roll, the adhesive layer is not directly in contact with the back surface of the substrate, but is in contact with the peeling treatment layer, thus preventing the adhesive layer from sticking. (Transfer) to the back of the aforementioned substrate. In addition, for example, the surface on which the adhesive layer is provided or the surface on the opposite side of the substrate may have an antistatic layer. If it has the aforementioned antistatic layer, it can prevent pollution caused by attracting dust and the like. The aforementioned antistatic layer is not particularly limited. For example, a layer containing an antistatic agent and having the same composition as the substrate is exemplified.
就前述剝離處理層而言，宜含有選自聚矽氧樹脂及氟樹脂中之一種以上來作為主成份。就前述聚矽氧樹脂而言，一般可採用剝離處理劑所使用之聚矽氧樹脂，可使用選自從「聚矽氧材料手冊」(道康寧東麗編，1993.8)等所記載之該領域通常使用之聚矽氧樹脂。一般而言，使用熱固化型或游離幅射線固化型的聚矽氧樹脂(意指包含樹脂及樹脂組成物)。就熱固型聚矽氧樹脂而言，例如可使 用縮合反應型及加成反應型的聚矽氧樹脂，且就游離幅射線固化型聚矽氧樹脂而言，可使用紫外線或電子束固化型的聚矽氧樹脂等。可藉由將此等塗佈在前述基材上，並使其乾燥或固化，來形成前述剝離處理層。 As for the aforementioned peeling treatment layer, it is preferable to contain one or more selected from silicone resin and fluororesin as a main component. Regarding the aforementioned silicone resin, the silicone resin used in the release treatment agent can generally be used, and can be selected from the "polysilicone material manual" (Dow Corning Toray ed., 1993.8), etc., which are commonly used in this field. The silicone resin. Generally speaking, a thermosetting or free-radiation-curing polysiloxane resin (meaning that it contains a resin and a resin composition) is used. For thermosetting silicone resins, for example, Condensation reaction type and addition reaction type silicone resins are used. For free-radiation radiation curing type silicone resins, ultraviolet or electron beam curing type silicone resins can be used. The release treatment layer can be formed by coating these on the substrate and drying or curing.
<耐熱高分子膜> <Heat-resistant polymer film>
本說明書之中，耐熱高分子係下述高分子：熔點係400℃以上，宜係500℃以上，且玻璃轉化溫度係250℃以上，宜係320℃以上，更宜係380℃以上。以下，為免繁瑣而亦僅稱為高分子。本說明書之中，熔點及玻璃轉化溫度係藉由差示掃描量熱法(DSC；Differential scanning calorimetry)來求取。此外，於熔點超過500℃之情形下，可利用目視觀察該溫度加熱之際的熱畸變行為來判斷是否達到熔點。 In this specification, the heat-resistant polymer is the following polymer: the melting point is 400°C or higher, preferably 500°C or higher, and the glass transition temperature is 250°C or higher, preferably 320°C or higher, and more preferably 380°C or higher. Hereinafter, in order to avoid cumbersomeness, it is also only called polymer. In this specification, the melting point and glass transition temperature are obtained by differential scanning calorimetry (DSC; Differential scanning calorimetry). In addition, in the case where the melting point exceeds 500°C, it is possible to determine whether the melting point is reached by visually observing the thermal distortion behavior during heating at that temperature.
就前述耐熱高分子膜(以下也簡稱為高分子膜)而言，可例示下列成分之膜：聚醯亞胺、聚醯胺醯亞胺、聚醚醯亞胺、氟化聚醯亞胺等聚醯亞胺系樹脂(例如芳香族聚醯亞胺樹脂、脂環族聚醯亞胺樹脂)；聚乙烯、聚丙烯、聚對苯二甲酸乙二酯、聚對苯二甲酸丁二酯、聚2,6-萘二甲酸乙二酯等共聚合聚酯(例如全芳香族聚酯、半芳香族聚酯)；以聚甲基丙烯酸甲酯為代表之共聚合(甲基)丙烯酸酯；聚碳酸酯；聚醯胺；聚碸；聚醚碸；聚醚酮；乙酸纖維素；硝酸纖維素；芳香族聚醯胺；聚氯乙烯；聚苯酚；聚芳酯；聚苯硫醚；聚伸苯醚；聚苯乙烯等。 Regarding the aforementioned heat-resistant polymer film (hereinafter also referred to as polymer film), films with the following components can be exemplified: polyimide, polyimide imide, polyether imide, fluorinated polyimide, etc. Polyimide resin (for example, aromatic polyimide resin, alicyclic polyimide resin); polyethylene, polypropylene, polyethylene terephthalate, polybutylene terephthalate, Polyethylene 2,6-naphthalate and other copolymerized polyesters (such as wholly aromatic polyesters, semi-aromatic polyesters); copolymerized (meth)acrylates represented by polymethyl methacrylate; Polycarbonate; Polyamide; Polysulfide; Polyether sulfide; Polyetherketone; Cellulose acetate; Cellulose nitrate; Aromatic polyamide; Polyvinyl chloride; Polyphenol; Polyarylate; Polyphenylene sulfide; Poly Phenylene oxide; polystyrene, etc.
惟，前述高分子膜之前提為可使用於伴隨有450℃以上之熱處理之製程，故於已例示之高分子膜之範圍中，實際上可適用之物受到限制。前述高分子膜之中，宜為使用所謂超級工程塑膠而得之膜，更具體而言，可列舉：芳香族聚醯
亞胺膜、芳香族醯胺膜、芳香族醯胺醯亞胺膜、芳香族苯并
前述高分子膜，由可合宜裝載功能元件之觀點來看，在25℃的拉伸彈性係數宜係2GPa以上，更宜係4GPa以上，尤宜係7GPa以上。又，前述高分子膜之在25℃的拉伸彈性係數，由定為撓性之觀點來看，例如可定為15GPa以下、10GPa以下等。 For the aforementioned polymer film, from the viewpoint of loading functional components conveniently, the tensile elastic modulus at 25°C is preferably 2 GPa or higher, more preferably 4 GPa or higher, and particularly preferably 7 GPa or higher. In addition, the tensile modulus of elasticity at 25°C of the aforementioned polymer film can be, for example, 15 GPa or less, 10 GPa or less from the viewpoint of flexibility.
本說明書之中，在25℃之前述高分子膜的拉伸彈性係數係指：將前述高分子膜呈100mm×10mm的箋狀切下者作為試驗片，並使用拉伸試驗機(島津製作所製，AutoGraph(R)，機種名AG-5000A)，以拉伸速度50mm/分、夾頭間距離40mm條件下量測出之值。 In this specification, the tensile elastic modulus of the polymer film at 25°C means that the polymer film is cut out in a paper shape of 100mm×10mm as a test piece, and a tensile testing machine (manufactured by Shimadzu Corporation) , AutoGraph(R), model name AG-5000A), the value measured under the conditions of a stretching speed of 50mm/min and a distance between the chucks of 40mm.
以下針對前述高分子膜之一例即聚醯亞胺系樹脂膜之詳細內容進行說明。通常聚醯亞胺系樹脂膜可藉由如下方式獲得：將在溶劑中使二胺類與四羧酸類反應而得之聚醯胺酸(聚醯亞胺前驅物)溶液塗佈於聚醯亞胺膜製作用支持體並進行乾燥而製成生膜(green film，以下也稱為「聚醯胺酸膜」)，再對生膜於聚醯亞胺膜製作用支持體上或從該支持體剝離之狀態下進行高溫熱處理來實施脫水閉環反應。 The details of the polyimide resin film, which is an example of the aforementioned polymer film, will be described below. Generally, a polyimide-based resin film can be obtained by applying a polyimide acid (polyimide precursor) solution obtained by reacting diamines and tetracarboxylic acids in a solvent on the polyimide resin film. The support for amine film production is dried to form a green film (also referred to as "polyamide film" hereinafter), and then the green film is placed on or from the support for polyimide film production. High-temperature heat treatment is performed in the state where the body is peeled off to implement the dehydration ring-closing reaction.
聚醯胺酸(聚醯亞胺前驅物)溶液之塗佈可適當地使用例如：旋塗、刮刀、塗佈器、缺角(comma)塗輪、網版印刷法、縫塗、逆輥塗佈、浸塗、簾式塗佈、縫模塗佈等習知之溶液的塗佈方法。 Coating of polyamide acid (polyimide precursor) solution can be suitably used such as spin coating, doctor blade, coater, comma coating wheel, screen printing method, slit coating, reverse roll coating Conventional solution coating methods such as cloth, dip coating, curtain coating, and slot die coating.
構成聚醯胺酸之二胺類並無特別限制，可使用通常用於聚醯亞胺合成之芳香族二胺類、脂肪族二胺類、脂環族二胺類等。考慮耐熱性之觀點，宜為芳香族二胺類，而在芳香族二胺類之中，具有苯并
具有苯并
就上述具有苯并
就前述脂肪族二胺類而言，例如可列舉：1,2-二胺基乙烷、1,4-二胺基丁烷、1,5-二胺基戊烷、1,6-二胺基己烷、1,8-二胺基辛烷等。 The aforementioned aliphatic diamines include, for example, 1,2-diaminoethane, 1,4-diaminobutane, 1,5-diaminopentane, and 1,6-diamine Hexane, 1,8-diaminooctane, etc.
就前述脂環族二胺類而言，例如可列舉：1,4-二胺基環己烷、4,4’-亞甲基雙(2,6-二甲基環己基胺)等。 The aforementioned alicyclic diamines include, for example, 1,4-diaminocyclohexane, 4,4'-methylenebis(2,6-dimethylcyclohexylamine), and the like.
芳香族二胺類以外的二胺(脂肪族二胺類及脂環族二胺類)之合計量宜佔全部二胺類的20質量%以下，為10質量%以下更佳，為5質量%以下再更佳。換言之，芳香族二胺類宜佔全部二胺類的80質量%以上，為90質量%以上更佳，為95質量%以上再更佳。 The total amount of diamines (aliphatic diamines and alicyclic diamines) other than aromatic diamines should preferably account for 20% by mass or less of all diamines, more preferably 10% by mass or less, and 5% by mass The following is even better. In other words, the aromatic diamines preferably account for 80% by mass or more of all diamines, more preferably 90% by mass or more, and even more preferably 95% by mass or more.
就構成聚醯胺酸之四羧酸類而言，可使用通常用於聚醯亞胺合成之芳香族四羧酸類(包含其酸酐)、脂肪族四羧酸類(包含其酸酐)、脂環族四羧酸類(包含其酸酐)。其中，宜為芳香族四羧酸酐類、脂環族四羧酸酐類，考慮耐熱性的觀點，為芳香族四羧酸酐類更佳，考慮光透射性的觀點，為脂環族四羧酸類更佳。該等若為酸酐時，分子內之酐結構可為1個，亦可為2個，宜為具有2個酐結構者(二酐)。四羧酸類可單獨使用，也可將二種以上合併使用。 As for the tetracarboxylic acids that constitute polyamide acids, aromatic tetracarboxylic acids (including their anhydrides), aliphatic tetracarboxylic acids (including their anhydrides), and alicyclic tetracarboxylic acids commonly used in the synthesis of polyimines can be used. Carboxylic acids (including their anhydrides). Among them, aromatic tetracarboxylic acid anhydrides and alicyclic tetracarboxylic acid anhydrides are preferable. From the viewpoint of heat resistance, aromatic tetracarboxylic acid anhydrides are more preferable, and from the viewpoint of light transmittance, alicyclic tetracarboxylic acid is more preferable. good. If these are acid anhydrides, the anhydride structure in the molecule may be one or two, and it is preferably one with two anhydride structures (dianhydrides). Tetracarboxylic acids may be used alone or in combination of two or more.
就脂環族四羧酸類而言，例如可列舉：環丁烷四甲酸、1,2,4,5-環己烷四甲酸、3,3’,4,4’-雙環己基四甲酸等脂環族四羧酸、及它們的酸酐。它們之中，宜為具有2個酐結構之二酐(例如：環丁烷四甲酸二酐、1,2,4,5-環己烷四甲酸二酐、 3,3’,4,4’-雙環己基四甲酸二酐等)。另外，脂環族四羧酸類可單獨使用，也可將二種以上合併使用。 For alicyclic tetracarboxylic acids, for example, cyclobutanetetracarboxylic acid, 1,2,4,5-cyclohexanetetracarboxylic acid, 3,3',4,4'-dicyclohexyltetracarboxylic acid, etc. Cyclic tetracarboxylic acids and their anhydrides. Among them, dianhydrides with two anhydride structures (for example: cyclobutane tetracarboxylic dianhydride, 1,2,4,5-cyclohexane tetracarboxylic dianhydride, 3,3',4,4'-Biscyclohexyltetracarboxylic dianhydride, etc.). In addition, alicyclic tetracarboxylic acids may be used alone or in combination of two or more kinds.
脂環族四羧酸類若著重在透明性時，例如宜佔全部四羧酸類的80質量%以上，為90質量%以上更佳，為95質量%以上再更佳。 When transparency is emphasized, the alicyclic tetracarboxylic acid preferably accounts for 80% by mass or more of the total tetracarboxylic acid, more preferably 90% by mass or more, and even more preferably 95% by mass or more.
就芳香族四羧酸類而言，並無特別限制，宜為具有均苯四甲酸殘基(亦即來自均苯四甲酸之結構)者，為其酸酐更佳。就如此的芳香族四羧酸類而言，例如可列舉：均苯四甲酸二酐、3,3',4,4'-聯苯四甲酸二酐、4,4'-氧二鄰苯二甲酸二酐、3,3',4,4'-二苯甲酮四甲酸二酐、3,3',4,4'-二苯基碸四甲酸二酐，2,2-雙[4-(3,4-二羧基苯氧基)苯基]丙烷酸酐等。 As far as the aromatic tetracarboxylic acids are concerned, there are no particular restrictions, but those having pyromellitic acid residues (that is, the structure derived from pyromellitic acid) are preferred, and their anhydrides are more preferred. Examples of such aromatic tetracarboxylic acids include: pyromellitic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, and 4,4'-oxydiphthalic acid Dianhydride, 3,3',4,4'-benzophenone tetracarboxylic dianhydride, 3,3',4,4'-diphenyl tetracarboxylic dianhydride, 2,2-bis[4-( 3,4-Dicarboxyphenoxy)phenyl]propane anhydride and the like.
芳香族四羧酸類若著重在耐熱性時，例如宜佔全部四羧酸類的80質量%以上，為90質量%以上更佳，為95質量%以上再更佳。 When the heat resistance is emphasized, the aromatic tetracarboxylic acids preferably account for 80% by mass or more of the total tetracarboxylic acids, more preferably 90% by mass or more, and even more preferably 95% by mass or more.
前述高分子膜的厚度宜係3μm以上，更宜係11μm以上，又宜係24μm以上，尤宜係45μm以上。前述高分子膜的厚度的上限不特別限制，但因為作為撓性電子元件使用，所以宜係250μm以下，更宜係150μm以下，尤宜係90μm以下。 The thickness of the aforementioned polymer film is preferably 3 μm or more, more preferably 11 μm or more, more preferably 24 μm or more, and particularly preferably 45 μm or more. The upper limit of the thickness of the aforementioned polymer film is not particularly limited, but since it is used as a flexible electronic component, it is preferably 250 μm or less, more preferably 150 μm or less, and particularly preferably 90 μm or less.
前述高分子膜之從30℃至500℃之間的平均CTE(熱膨脹係數)，宜係-5ppm/℃~+20ppm/℃，更宜係-5ppm/℃~+15ppm/℃，尤宜係1ppm/℃~+10ppm/℃。當CTE係前述範圍時，則可將與普通支持體(無機基板)之線膨張係數的差異保持為小，且即使增添加熱之製程，亦可避免高分子膜與無機基板剝離。在此，CTE係指將針對溫度而可逆的伸縮加以表示之因子。 The average CTE (Coefficient of Thermal Expansion) of the aforementioned polymer film from 30℃ to 500℃ is preferably -5ppm/℃~+20ppm/℃, more preferably -5ppm/℃~+15ppm/℃, especially 1ppm /℃~+10ppm/℃. When the CTE is in the aforementioned range, the difference between the linear expansion coefficient and the ordinary support (inorganic substrate) can be kept small, and even if the heating process is added, the polymer film and the inorganic substrate can be prevented from peeling off. Here, CTE refers to a factor that expresses reversible expansion and contraction with respect to temperature.
前述高分子膜之從30℃至500℃之間的熱收縮率，宜係±0.9%，更宜係±0.6%。熱收縮率係指將針對溫度而不可逆的伸縮加以表示之因子。 The thermal shrinkage rate of the aforementioned polymer film from 30°C to 500°C is preferably ±0.9%, more preferably ±0.6%. Thermal shrinkage is a factor that expresses irreversible expansion and contraction with respect to temperature.
前述高分子膜的拉伸斷裂強度，宜係60MPa以上，更宜係120MPa以上，尤宜係240MPa以上。拉伸斷裂強度的上限不特別限制，事實上係未滿1000MPa左右。此外，前述高分子膜的拉伸斷裂強度係指高分子膜之在輸送方向(MD方向的拉伸斷裂強度與在寬度方向(TD方向)的拉伸斷裂強度之平均值。 The tensile breaking strength of the aforementioned polymer film is preferably 60 MPa or more, more preferably 120 MPa or more, and particularly preferably 240 MPa or more. The upper limit of the tensile rupture strength is not particularly limited, but in fact it is less than about 1000 MPa. In addition, the aforementioned tensile breaking strength of the polymer film refers to the average value of the tensile breaking strength of the polymer film in the conveying direction (MD direction) and the width direction (TD direction).
前述高分子膜的厚度不均，宜係20%以下，更宜係12%以下，又宜係7%以下，尤宜係4%以下。當厚度不均超過20%時，則會有不易應用至狹小部位之傾向。此外，膜的厚度不均，可例如利用接觸式的膜厚計而自被量測膜隨機抽取十處左右的位置來量測膜厚，並基於下述式而求取。 The uneven thickness of the aforementioned polymer film is preferably less than 20%, more preferably less than 12%, more preferably less than 7%, and particularly preferably less than 4%. When the thickness unevenness exceeds 20%, it will tend to be difficult to apply to narrow parts. In addition, the unevenness of the film thickness can be determined based on the following equation by randomly extracting about ten positions from the film to be measured using a contact-type film thickness meter, for example.
膜的厚度不均(%) =100×(最大膜厚-最小膜厚)÷平均膜厚 Uneven film thickness (%) =100×(maximum film thickness-minimum film thickness)÷average film thickness
定為前述疊層膜前之前述高分子膜，宜於其製造時獲得為捲收成寬度係300mm以上、長度10m係以上之長條高分子膜之形態，更宜為捲收在捲收芯之輥狀高分子膜之形態。 The aforementioned polymer film before the aforementioned laminated film should preferably be rolled into a long polymer film with a width of 300mm or more and a length of 10m or more during its manufacture, and it is more suitable to be wound in the winding core. The form of roll-shaped polymer film.
前述高分子膜，為了確保操作性及生產性，宜在高分子膜中以0.03~3質量%左右添加．含有粒徑係10~1000nm左右的滑材(粒子)，來將微細凹凸賦予至高分子膜表面而確保易滑性。 In order to ensure operability and productivity, the aforementioned polymer film should be added at about 0.03 to 3% by mass in the polymer film. Contains slippery materials (particles) with a particle size of about 10 to 1000 nm to impart fine irregularities to the surface of the polymer film to ensure slipperiness.
<高分子膜的表面活性化處理> <Surface activation treatment of polymer film>
前述高分子膜宜進行表面活性化處理。藉由在高分子膜進行表面活性化處理，而將高分子膜的表面改質成存有官能基之狀態(所謂活性化狀態)，提昇對於無機基板之黏接性。 The aforementioned polymer film is preferably subjected to surface activation treatment. By performing surface activation treatment on the polymer film, the surface of the polymer film is modified into a state in which functional groups exist (the so-called activated state), and the adhesion to the inorganic substrate is improved.
本說明書之中，表面活性化處理係指乾式或溼式的表面處理。就乾式的表面處理而言，例如，可列舉將真空電漿處理、常壓電漿處理、紫外線．電子束．X線等活性能量線照射至表面之處理、電暈處理、火燄處理、ITRO(甲矽烷火燄)處理等。就溼式的表面處理而言，例如，可列舉使酸性至鹼性溶液接觸於高分子膜表面之處理。 In this specification, surface activation treatment refers to dry or wet surface treatment. In terms of dry surface treatment, for example, vacuum plasma treatment, atmospheric pressure plasma treatment, and ultraviolet rays can be cited. Electron beam. X-ray and other active energy rays irradiated to the surface treatment, corona treatment, flame treatment, ITRO (methylsilane flame) treatment, etc. The wet surface treatment includes, for example, a treatment in which an acidic to alkaline solution is brought into contact with the surface of the polymer film.
前述表面活性化處理，亦可組合複數個來進行。該表面活性化處理將高分子膜表面潔淨化，並更產生活性官能基。所產生之官能基，可藉由氫鍵結或化學反應等與後述矽烷偶聯劑層加以結合，來將高分子膜與矽烷偶聯劑層加以堅固黏接。 The aforementioned surface activation treatment can also be performed in combination of a plurality of them. The surface activation treatment cleans the surface of the polymer membrane and generates active functional groups. The generated functional group can be combined with the silane coupling agent layer described later by hydrogen bonding or chemical reaction to firmly bond the polymer film and the silane coupling agent layer.
<矽烷偶聯劑層> <Silane Coupling Agent Layer>
前述高分子膜上，亦可設置含有矽烷偶聯劑之矽烷偶聯劑層。此情形下，疊層膜至少具有將基材、黏接劑層、矽烷偶聯劑層、高分子膜依此順序疊層之構成。 A silane coupling agent layer containing a silane coupling agent can also be provided on the aforementioned polymer film. In this case, the laminated film at least has a structure in which a substrate, an adhesive layer, a silane coupling agent layer, and a polymer film are laminated in this order.
此外，於不將矽烷偶聯劑層設在高分子膜上之構成之情形下，宜使用疊層有矽烷偶聯劑層者作為無機基板。 In addition, in the case where the silane coupling agent layer is not provided on the polymer film, it is preferable to use a laminated silane coupling agent layer as the inorganic substrate.
前述矽烷偶聯劑係物理性或化學性地插介於無機基板與高分子膜之間，並具有提高兩者間之黏接力的作用。 The aforementioned silane coupling agent is physically or chemically inserted between the inorganic substrate and the polymer film, and has the effect of improving the adhesion between the two.
前述偶聯劑並無特別限制，宜為具有胺基或環氧基之矽烷偶聯劑。就矽烷偶聯劑之理想具體例而言，可列舉：N-2-(胺基乙基)-3-胺基丙基甲基二甲氧基矽烷、N-2-(胺基乙基)-3-胺基丙基三甲氧基矽烷、N-2-(胺基乙基)-3-胺基丙基三乙氧基矽烷、3-胺基丙基三甲氧基矽烷、3-胺基丙基三乙氧基矽烷、3-三乙氧基矽基-N-(1,3-二甲基-亞丁基)丙基胺、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-環氧丙氧基丙基甲基二乙氧基矽烷、3-環氧丙氧基丙基三乙氧基矽烷、乙烯基三氯矽烷、乙烯基三甲氧基矽烷、乙烯基三乙氧基矽烷、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-環氧丙氧基丙基甲基二乙氧基矽烷、3-環氧丙氧基丙基三乙氧基矽烷、對苯乙烯基三甲氧基矽烷、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、3-丙烯醯氧基丙基三甲氧基矽烷、N-苯基-3-胺基丙基三甲氧基矽烷、N-(乙烯基苄基)-2-胺基乙基-3-胺基丙基三甲氧基矽烷鹽酸鹽、3-脲基丙基三乙氧基矽烷、3-氯丙基三甲氧基矽烷、3-巰基丙基甲基二甲氧基矽 烷、3-巰基丙基三甲氧基矽烷、雙(三乙氧基矽丙基)四硫醚、3-異氰酸酯基丙基三乙氧基矽烷、參-(3-三甲氧基矽丙基)異氰尿酸酯、氯甲基苯乙基三甲氧基矽烷、氯甲基三甲氧基矽烷、胺基苯基三甲氧基矽烷、胺基苯乙基三甲氧基矽烷、胺基苯胺基甲基苯乙基三甲氧基矽烷等。 The aforementioned coupling agent is not particularly limited, and is preferably a silane coupling agent having an amino group or an epoxy group. The ideal specific examples of the silane coupling agent include: N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl) -3-Aminopropyltrimethoxysilane, N-2-(aminoethyl)-3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-amino Propyl triethoxysilane, 3-triethoxysilyl-N-(1,3-dimethyl-butylene) propylamine, 2-(3,4-epoxycyclohexyl) ethyl trimethyl Oxyoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, Vinyl trichlorosilane, vinyl trimethoxy silane, vinyl triethoxy silane, 2-(3,4-epoxycyclohexyl) ethyl trimethoxy silane, 3-glycidoxy propyl trimethyl Oxyoxysilane, 3-glycidoxypropylmethyl diethoxysilane, 3-glycidoxypropyltriethoxysilane, p-styryltrimethoxysilane, 3-methylpropene Glyoxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methyl Acrylic oxypropyl triethoxy silane, 3-propenoxy propyl trimethoxy silane, N-phenyl-3-aminopropyl trimethoxy silane, N-(vinylbenzyl)- 2-aminoethyl-3-aminopropyltrimethoxysilane hydrochloride, 3-ureidopropyltriethoxysilane, 3-chloropropyltrimethoxysilane, 3-mercaptopropylmethyl Dimethoxide Alkyl, 3-mercaptopropyl trimethoxysilane, bis(triethoxysilylpropyl) tetrasulfide, 3-isocyanatopropyltriethoxysilane, ginseng-(3-trimethoxysilylpropyl) Isocyanurate, chloromethylphenethyltrimethoxysilane, chloromethyltrimethoxysilane, aminophenyltrimethoxysilane, aminophenylethyltrimethoxysilane, aminoanilinomethyl Phenethyl trimethoxysilane, etc.
就前述矽烷偶聯劑而言，除了可使用前述之外，還可使用：正丙基三甲氧基矽烷、丁基三氯矽烷、2-氰乙基三乙氧基矽烷、環己基三氯矽烷、癸基三氯矽烷、二乙醯氧基二甲基矽烷、二乙氧基二甲基矽烷、二甲氧基二甲基矽烷、二甲氧基二苯基矽烷、二甲氧基甲基苯基矽烷、十二烷基三氯矽烷、十二烷基三甲氧基矽烷、乙基三氯矽烷、己基三甲氧基矽烷、十八烷基三乙氧基矽烷、十八烷基三甲氧基矽烷、正辛基三氯矽烷、正辛基三乙氧基矽烷、正辛基三甲氧基矽烷、三乙氧基乙基矽烷、三乙氧基甲基矽烷、三甲氧基甲基矽烷、三甲氧基苯基矽烷、戊基三乙氧基矽烷、戊基三氯矽烷、三乙醯氧基甲基矽烷、三氯己基矽烷、三氯甲基矽烷、三氯十八烷基矽烷、三氯丙基矽烷、三氯十四烷基矽烷、三甲氧基丙基矽烷、烯丙基三氯矽烷、烯丙基三乙氧基矽烷、烯丙基三甲氧基矽烷、二乙氧基甲基乙烯基矽烷、二甲氧基甲基乙烯基矽烷、三氯乙烯基矽烷、三乙氧基乙烯基矽烷、乙烯基參(2-甲氧基乙氧基)矽烷、三氯-2-氰乙基矽烷、二乙氧基(3-環氧丙基氧丙基)甲基矽烷、3-環氧丙基氧丙基(二甲氧基)甲基矽烷、3-環氧丙基氧丙基三甲氧基矽烷等。 Regarding the aforementioned silane coupling agent, in addition to the aforementioned, it can also be used: n-propyltrimethoxysilane, butyltrichlorosilane, 2-cyanoethyltriethoxysilane, cyclohexyltrichlorosilane , Decyl trichlorosilane, diethoxy dimethyl silane, diethoxy dimethyl silane, dimethoxy dimethyl silane, dimethoxy diphenyl silane, dimethoxy methyl Phenylsilane, dodecyltrichlorosilane, dodecyltrimethoxysilane, ethyltrichlorosilane, hexyltrimethoxysilane, octadecyltriethoxysilane, octadecyltrimethoxysilane Silane, n-octyl trichlorosilane, n-octyl triethoxy silane, n-octyl trimethoxy silane, triethoxy ethyl silane, triethoxy methyl silane, trimethoxy methyl silane, trimethyl Oxyphenyl silane, pentyl triethoxy silane, pentyl trichlorosilane, triacetoxymethyl silane, trichlorohexyl silane, trichloromethyl silane, trichlorooctadecyl silane, trichloro Propylsilane, trichlorotetradecylsilane, trimethoxypropylsilane, allyltrichlorosilane, allyltriethoxysilane, allyltrimethoxysilane, diethoxymethylethylene Base Silane, Dimethoxymethylvinyl Silane, Trichlorovinyl Silane, Triethoxy Vinyl Silane, Vinyl Ginseng (2-Methoxyethoxy) Silane, Trichloro-2-cyanoethyl Silane, diethoxy (3-epoxypropyloxypropyl) methyl silane, 3-epoxypropyloxypropyl (dimethoxy) methyl silane, 3-epoxypropyloxypropyl trimethyl Oxysilane, etc.
前述矽烷偶聯劑之中，為1個分子中具有1個矽原子之矽烷偶聯劑特佳，例如可列舉：N-2-(胺基乙基)-3-胺基丙基甲基二甲氧基矽烷、N-2-(胺基乙基)-3-胺 基丙基三甲氧基矽烷、N-2-(胺基乙基)-3-胺基丙基三乙氧基矽烷、3-胺基丙基三甲氧基矽烷、3-胺基丙基三乙氧基矽烷、3-三乙氧基矽基-N-(1,3-二甲基-亞丁基)丙基胺、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-環氧丙氧基丙基甲基二乙氧基矽烷、3-環氧丙氧基丙基三乙氧基矽烷、胺基苯基三甲氧基矽烷、胺基苯乙基三甲氧基矽烷、胺基苯胺基甲基苯乙基三甲氧基矽烷等。因為製程而要求特別高的耐熱性時，宜為矽與胺基之間以芳香族基連結而成者。 Among the aforementioned silane coupling agents, those having one silicon atom in one molecule are particularly preferred. Examples include: N-2-(aminoethyl)-3-aminopropylmethyl bis Methoxysilane, N-2-(aminoethyl)-3-amine Trimethoxysilane, N-2-(aminoethyl)-3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethyl Oxyoxysilane, 3-triethoxysilyl-N-(1,3-dimethyl-butylene) propylamine, 2-(3,4-epoxycyclohexyl) ethyl trimethoxysilane, 3-glycidoxy propyl trimethoxy silane, 3-glycidoxy propyl methyl diethoxy silane, 3-glycidoxy propyl triethoxy silane, amino phenyl Trimethoxysilane, amino phenethyl trimethoxy silane, amino anilino methyl phenethyl trimethoxy silane, etc. When particularly high heat resistance is required due to the manufacturing process, it is preferable to connect the silicon and the amino group with an aromatic group.
就前述偶聯劑而言，除了可使用前述之外，還可使用：1-巰基-2-丙醇、3-巰基丙酸甲酯、3-巰基-2-丁醇、3-巰基丙酸丁酯、3-(二甲氧基甲基矽基)-1-丙烷硫醇、4-(6-巰基己醯基)苄醇、11-胺基-1-十一烯硫醇、11-巰基十一烷基膦酸、11-巰基十一烷基三氟乙酸、2,2’-(伸乙二氧基)二乙烷硫醇、11-巰基十一烷基三(乙二醇)、(1-巰基十一-11-基)四(乙二醇)、1-(甲基羧基)十一-11-基)六(乙二醇)、羥基十一烷基二硫醚、羧基十一烷基二硫醚、羥基六(十二烷基)二硫醚、羧基十六烷基二硫醚、肆(2-乙基己基氧基)鈦、二辛氧基雙(辛二醇酸)鈦、三丁氧基單乙醯丙酮鋯、單丁氧基乙醯丙酮雙(乙基乙醯乙酸)鋯、三丁氧基單硬脂酸鋯、乙醯烷氧基鋁二異丙醇鹽、3-環氧丙基氧丙基三甲氧基矽烷、2,3-丁烷二硫醇、1-丁烷硫醇、2-丁烷硫醇、環己烷硫醇、環戊烷硫醇、1-癸烷硫醇、1-十二烷硫醇、3-巰基丙酸-2-乙基己酯、3-巰基丙酸乙酯、1-庚烷硫醇、1-十六烷硫醇、己基硫醇、異戊基硫醇、異丁基硫醇、3-巰基丙酸、3-巰基丙酸-3-甲氧基丁酯、2-甲基-1-丁烷硫醇、1-十八烷硫醇、1-辛烷硫醇、1-十五烷硫醇、1-戊烷硫醇、1-丙烷硫醇、1-十四烷硫醇、1-十一烷硫醇、1-(12-巰基十二烷基)咪唑、1-(11-巰基十 一烷基)咪唑、1-(10-巰基癸基)咪唑、1-(16-巰基十六烷基)咪唑、1-(17-巰基十七烷基)咪唑、1-(15-巰基)十二酸、1-(11-巰基)十一酸、1-(10-巰基)癸酸等。 As far as the aforementioned coupling agent is concerned, in addition to the aforementioned, it can also be used: 1-mercapto-2-propanol, methyl 3-mercaptopropionate, 3-mercapto-2-butanol, 3-mercaptopropionic acid Butyl ester, 3-(dimethoxymethylsilyl)-1-propanethiol, 4-(6-mercaptohexyl)benzyl alcohol, 11-amino-1-undecenethiol, 11- Mercaptoundecylphosphonic acid, 11-mercaptoundecyltrifluoroacetic acid, 2,2'-(ethylenedioxy)diethanethiol, 11-mercaptoundecyltri(ethylene glycol) , (1-mercaptoundecyl-11-yl)tetrakis (ethylene glycol), 1-(methylcarboxy)undec-11-yl)hexa(ethylene glycol), hydroxyundecyl disulfide, carboxyl Undecyl disulfide, hydroxyhexa(dodecyl) disulfide, carboxyhexadecyl disulfide, tetrakis (2-ethylhexyloxy) titanium, dioctyloxy bis(octanediol) (Acid) titanium, tributoxy monoacetate zirconium, monobutoxyacetone bis(ethylacetate) zirconium, tributoxymonostearate zirconium, acetoxy aluminum diisopropyl Alkoxide, 3-epoxypropyloxypropyltrimethoxysilane, 2,3-butane dithiol, 1-butane thiol, 2-butane thiol, cyclohexane thiol, cyclopentane Mercaptan, 1-decane mercaptan, 1-dodecyl mercaptan, 2-ethylhexyl 3-mercaptopropionate, ethyl 3-mercaptopropionate, 1-heptane mercaptan, 1-hexadecane Alkyl mercaptan, hexyl mercaptan, isoamyl mercaptan, isobutyl mercaptan, 3-mercaptopropionic acid, 3-mercaptopropionic acid-3-methoxybutyl ester, 2-methyl-1-butane sulfide Alcohol, 1-octadecyl mercaptan, 1-octane mercaptan, 1-pentadecane mercaptan, 1-pentane mercaptan, 1-propane mercaptan, 1-tetradecyl mercaptan, 1-undecane mercaptan Alkyl mercaptan, 1-(12-mercaptododecyl) imidazole, 1-(11-mercapto deca Monoalkyl) imidazole, 1-(10-mercaptodecyl) imidazole, 1-(16-mercaptohexadecyl) imidazole, 1-(17-mercapto heptadecyl) imidazole, 1-(15-mercapto) Dodecanoic acid, 1-(11-mercapto)undecanoic acid, 1-(10-mercapto)decanoic acid, etc.
<矽烷偶聯劑層之形成方法> <Method of forming silane coupling agent layer>
就矽烷偶聯劑層之形成方法而言，可使用將矽烷偶聯劑溶液塗佈於前述高分子膜之方法、蒸鍍法等。矽烷偶聯劑層之形成可在高分子膜之任一表面進行，也可在兩側之表面進行。 As for the method of forming the silane coupling agent layer, a method of applying a silane coupling agent solution to the aforementioned polymer film, a vapor deposition method, etc. can be used. The formation of the silane coupling agent layer can be carried out on either surface of the polymer film, or on both surfaces.
就塗佈矽烷偶聯劑溶液之方法而言，可使用將矽烷偶聯劑以醇等溶劑稀釋而成的溶液，並適當地使用旋塗法、簾式塗佈法、浸塗法、縫模塗佈法、凹版塗佈法、棒塗法、缺角輪塗佈法、塗佈器法、網版印刷法、噴塗法等習知的溶液之塗佈方法。 As for the method of applying the silane coupling agent solution, a solution prepared by diluting the silane coupling agent with a solvent such as alcohol can be used, and spin coating, curtain coating, dip coating, and slot die coating can be used as appropriate. Coating method, gravure coating method, bar coating method, chipped wheel coating method, coater method, screen printing method, spraying method and other conventional solution coating methods.
又，可藉由蒸鍍法而形成矽烷偶聯劑層，具體而言，將前述高分子膜曝露於矽烷偶聯劑的蒸氣亦即實質上氣體狀態之矽烷偶聯劑來進行形成。矽烷偶聯劑的蒸氣，可藉由將液體狀態之矽烷偶聯劑加熱至40℃~矽烷偶聯劑的沸點左右為止之溫度來獲得。矽烷偶聯劑的沸點，視化學構造而不同，大概在100~250℃之範圍。其中，200℃以上之加熱，因為有引起矽烷偶聯劑的有機基側的副反應之虞，所以不宜。 In addition, the silane coupling agent layer can be formed by a vapor deposition method. Specifically, the polymer film is exposed to vapor of the silane coupling agent, that is, the silane coupling agent in a substantially gaseous state. The vapor of the silane coupling agent can be obtained by heating the silane coupling agent in a liquid state to a temperature between 40°C and the boiling point of the silane coupling agent. The boiling point of the silane coupling agent varies depending on the chemical structure, and is probably in the range of 100~250℃. Among them, heating at 200°C or higher may cause side reactions on the organic group side of the silane coupling agent, so it is not suitable.
加熱矽烷偶聯劑之環境，係加壓下、常壓下、減壓下皆無妨，其中，於促進矽烷偶聯劑之汽化之情形下，則宜係常壓下至減壓下。多數矽烷偶聯劑係可燃性液體，因此宜在密閉容器內，更宜於將容器內以非活性氣體進行替換之後，進行氣化工作。 The environment for heating the silane coupling agent can be under pressure, normal pressure, or reduced pressure. Among them, in the case of promoting the vaporization of the silane coupling agent, it should be under normal pressure to reduced pressure. Most silane coupling agents are flammable liquids, so they should be kept in a closed container, and it is more suitable to replace the container with an inert gas before vaporizing.
將前述高分子膜曝露於矽烷偶聯劑之時間不特別限制，宜係20小時以內，更宜係60分鐘以內、又宜係15分鐘以內、尤宜係1分鐘以內。 The time for exposing the aforementioned polymer film to the silane coupling agent is not particularly limited, and it is preferably within 20 hours, more preferably within 60 minutes, preferably within 15 minutes, and particularly preferably within 1 minute.
將前述高分子膜曝露於矽烷偶聯劑期間之前述高分子膜的溫度，視矽烷偶聯劑的種類、所期望之矽烷偶聯劑層的厚度，而宜控制為自-50℃至200℃之間的適當溫度。 The temperature of the polymer film during the exposure of the polymer film to the silane coupling agent depends on the type of silane coupling agent and the desired thickness of the silane coupling agent layer, and should be controlled from -50°C to 200°C Between the appropriate temperature.
矽烷偶聯劑層的膜厚，相較於無機基板、高分子膜等而言，係極端薄、且由機械設計的觀點來看被無視程度之厚度，原理上只要有最低限度、單分子層數量級的厚度即充份。一般而言，係未滿400nm，宜係200nm以下，進一步而言，於實用上宜係100nm以下，更宜係50nm以下，尤宜係10nm以下。但是，計算上，當成為5nm以下的區域時，則有以下疑慮：矽烷偶聯劑層非均勻塗膜，而係以叢簇狀存在。此外，矽烷偶聯劑層的膜厚，可由橢圓偏振技術法、或由塗佈時之矽烷偶聯劑溶液的濃度與塗佈量來加以計算求取。 The film thickness of the silane coupling agent layer is extremely thin compared to inorganic substrates, polymer films, etc., and is ignored from the viewpoint of mechanical design. In principle, as long as there is a minimum, monomolecular layer The thickness of the order of magnitude is sufficient. Generally speaking, the range is less than 400nm, preferably less than 200nm, furthermore, it is preferably less than 100nm, more preferably less than 50nm, and particularly preferably less than 10nm. However, in terms of calculation, when it becomes a region below 5nm, there is the following doubt: the silane coupling agent layer is not uniformly coated, but exists in clusters. In addition, the film thickness of the silane coupling agent layer can be calculated by the ellipsometry method, or from the concentration of the silane coupling agent solution and the coating amount during coating.
<其它薄膜層> <Other film layers>
前述矽烷偶聯劑層上，亦可形成有用以使與無機基板之黏接力提昇之薄膜層(例如金屬薄膜)。 On the aforementioned silane coupling agent layer, a thin film layer (such as a metal thin film) useful for improving the adhesion with the inorganic substrate can also be formed.
<經清洗之疊層膜的製造方法> <Method of manufacturing cleaned laminated film>
其次，說明側面之高度10μm以上的突起、並且係源自前述黏接劑層或源自來自外部的附著物者的數量係10個/cm以下之疊層膜(經清洗之疊層膜)的製造方法。 Next, explain the protrusions on the side surface of 10μm or more, and are derived from the aforementioned adhesive layer or from external attachments. The number of laminate films (cleaned laminate films) is 10 pcs/cm or less. Manufacturing method.
本實形態之經清洗之疊層膜的製造方法之中，首先準備耐熱高分子膜，其具備：保護膜，具有基材、及設在前述基材上之黏接劑層；以及疊層膜(清洗前之疊層膜)，疊層在前述黏接劑層上(步驟A)。 In the manufacturing method of the cleaned laminated film of this embodiment, first, a heat-resistant polymer film is prepared, which includes: a protective film, a base material, and an adhesive layer provided on the aforementioned base material; and a laminated film (Laminated film before cleaning), laminated on the aforementioned adhesive layer (step A).
就清洗前之疊層膜而言，例舉已將長條之疊層膜藉由湯姆遜刀具等刀具切斷之狀態之矩形薄片狀的膜。長條之疊層膜，可利用將長條的保護膜的黏接劑層與長條的耐熱高分子膜(高分子膜)加以貼合來獲得。 Regarding the laminated film before cleaning, a rectangular sheet-like film in a state where the long laminated film has been cut by a tool such as a Thomson knife. The long laminated film can be obtained by bonding the adhesive layer of the long protective film and the long heat-resistant polymer film (polymer film).
其次，於使所切斷之矩形薄片狀之膜的側面接觸於擦拭用薄片之狀態下，使前述矩形薄片狀的膜與前述擦拭用薄片相對地移動，而抹拭前述側面(步驟B)。步驟B可藉由以下說明之邊緣清洗裝置來進行。 Next, in a state where the side surface of the cut rectangular thin film is in contact with the wiping sheet, the rectangular thin film and the wiping sheet are moved relative to each other to wipe the side surface (step B). Step B can be performed by the edge cleaning device described below.
<邊緣清洗裝置> <Edge cleaning device>
圖1係用以說明本實施形態之邊緣清洗裝置之示意性立體圖，圖2係其側視圖。 Fig. 1 is a schematic perspective view for explaining the edge cleaning device of this embodiment, and Fig. 2 is a side view thereof.
邊緣清洗裝置20具備：載置台22，將膜加以固定；搬運部(未圖示)，將擦拭用薄片24加以搬運；以及驅動部(未圖示)，用以使載置台22移動。載置台22相當於本發明之膜固定部。
The
載置台22可藉由真空夾盤而將膜加以吸附固持。載置台22的載置面，例如，以等間隔配置有複數個真空夾盤用的孔。藉由從真空夾盤用的孔所連接之真空道進行真空排氣，而將膜吸附在載置面。 The mounting table 22 can adsorb and hold the film by a vacuum chuck. The mounting surface of the mounting table 22 has, for example, a plurality of holes for vacuum chucks arranged at equal intervals. The film is adsorbed on the mounting surface by vacuum exhaust from the vacuum channel connected with the hole for the vacuum chuck.
就擦拭用薄片24而言，使用輥狀者。藉由導引滾子26及未圖示之張力賦予機構來將擦拭用薄片24固持為拉緊狀態。
For the wiping
就擦拭用薄片24而言，只要可抹拭疊層膜10的側面，則無特別限制，可使用由PET長纖維、纖維素長纖維、纖維素短纖維、PET長纖維與木漿之混合、嫘縈與PET長纖維之混合、聚丙烯纖維等所構成之織布、編物、不織布、漉紙等。就擦拭用薄片的單位重量而言，使用20.0~150g/m2、厚度0.1~1.0mm左右者。
As for the wiping
就擦拭用薄片24而言，宜使用適應於潔淨環境中之使用之織布、不織布，且宜係於拭除疊層膜10的側面之際，其摩擦導致起塵係少者。若使用織布、不織布作為擦拭用薄片24，則可容易清除疊層膜10的側面之高度10μm以上的突起。又，可抑制：由擦拭用薄片24產生之異物附著於疊層膜10，並於貼合至支持體之際成為氣泡產生原因。
As for the wiping
就擦拭用薄片24而言，針對10mm平方鋼琴線之摩擦係數宜係0.3以下，尤宜係0.2以下。詳細量測方法依實施例記載的方法。
As for the wiping
就擦拭用薄片24而言，宜係於拭除疊層膜10的側面之際，不損傷疊層膜10的側面及表面者。當疊層膜10的側面或表面損傷時，則因側面的變形而使與所貼附之支持體之間產生浮起、或膜屑而成為氣泡產生原因。
The wiping
就擦拭用薄片24而言，宜係可沿著彈性輥間或旋轉滾子的槽、並以一定程度的彈力回按膜者。具體而言，施加30gf/cm2的壓力之際的變形量(壓縮特性)宜係壓縮前厚度的20%以上70%以下，更宜係25%以上60%以下。詳細量測方法依實施例記載的方法。
As for the wiping
步驟B之中，首先，將疊層膜10固定在載置台22。其次，藉由前述驅動部來使載置台22往擦拭用薄片24的方向(圖2之中係左方向)移動，而將疊層膜10以預定壓力按抵擦拭用薄片24。
In step B, first, the
其次，維持將疊層膜10以預定壓力按抵擦拭用薄片24之狀態下，藉由前述驅動部而使載置台22相對於擦拭用薄片24的面平行移動。藉此，藉由擦拭用薄片24來抹拭疊層膜10的側面。此時的按壓力，只要係疊層膜10不彎曲程度即可，就其一例而言，例如可定為1~4N等。此外，即使係此值的範圍下，當膜的固持方法不良時，亦有會彎曲之情形，因此須妥善進行膜固持。藉此，可合宜抹拭疊層膜10的側面。
Next, while maintaining the state in which the
其後，解除載置台22的真空，獲得經清洗之疊層膜10。藉由上述，可製造經清洗之疊層膜10。
Thereafter, the vacuum of the mounting table 22 is released, and a cleaned
其次，藉由前述搬運部來搬運擦拭用薄片24。藉此，自輥部分送出新的擦拭用薄片24，並且將已於清洗時使用之部分捲收在輥部分。藉此，可抹拭下一個疊層膜10。
Next, the wiping
上述實施形態，說明藉由使作為膜固定部之載置台22移動，來抹拭疊層膜10的側面之情形。然而，本發明不限定於此例，亦可不移動膜固定部，而移動
擦拭用薄片，來抹拭疊層膜的側面。但是，如同上述實施形態，因為清洗中不送出擦拭用薄片，可抑制擦拭用薄片的使用量，所以為宜。
In the above-mentioned embodiment, the case where the side surface of the
又，上述實施形態，說明使用邊緣清洗裝置來抹拭膜的側面之情形。然而，本發明之中，抹拭膜的側面之步驟(步驟B)不限定於此例(使用裝置之例)，例如，亦可係工作者使用擦拭用薄片來抹拭前述矩形薄片狀之膜的側面之步驟。 In addition, in the above embodiment, a case where the edge cleaning device is used to wipe the side surface of the film has been described. However, in the present invention, the step of wiping the side surface of the film (step B) is not limited to this example (example of using the device). For example, a worker may use a wiping sheet to wipe the aforementioned rectangular sheet-like film Of the side steps.
藉由上述而獲得之已抹拭側面之疊層膜10(經清洗之疊層膜10)，其側面成為潔淨狀態。故，可將側面之高度10μm以上的突起、並且係源自黏接劑層或源自來自外部的附著物者的數量定為10個/cm以下。 The side surface of the laminated film 10 (the washed laminated film 10) obtained by the above method is in a clean state. Therefore, the number of protrusions with a height of 10 μm or more on the side surface and derived from the adhesive layer or from external attachments can be set to 10 per cm or less.
邊緣清洗裝置20，亦可具備：溶劑供給部，將溶劑供給至擦拭用薄片24。若因應於所預想之將疊層膜10的側面加以污染之物質來選擇溶劑，並供給至擦拭用薄片24，則更可將膜的側面定為潔淨狀態。
The
於清洗疊層膜10的轉角部之際，在轉角部會有疊層膜10與擦拭用薄片24之接觸面積減少，強勁的力施加至轉角部之疑慮。於是，亦可具備在疊層膜10的轉角部即將與擦拭用薄片24接觸的位置使擦拭用薄片24從疊層膜10離開之公知機構。
When cleaning the corners of the
又，由保護疊層膜10的轉角部之觀點來看，亦可係以下構成：不從疊層膜10的轉角部，而從邊的中途開始清洗，並自該處進行來回動作而藉以清洗整體。
In addition, from the viewpoint of protecting the corners of the
又，由保護疊層膜10的轉角部之觀點來看，亦可如下述：疊層膜10與擦拭用薄片24不呈直角抵接於疊層膜10的平面與擦拭用薄片的平面，而係使擦拭用薄片24彎曲、或使擦拭用薄片24的平面相對於疊層膜10的平面以不成為直角之方式帶角度接觸。
In addition, from the viewpoint of protecting the corners of the
又，由生產效率提昇的觀點來看，亦可定為能同時清洗疊層膜10的二邊以上之構成。
In addition, from the viewpoint of improving production efficiency, it may be configured to be capable of cleaning two or more sides of the
又，亦可使用擦拭用薄片24之寬度方向的上側與下側二處來清洗。例如，吾人考慮具備使擦拭用薄片24沿寬度方向(圖4之上下方向)移動之機構之方法。
Moreover, you may use the upper side and the lower side of the width direction of the wiping
圖3係用以說明其它實施形態之邊緣清洗裝置之示意性俯視圖，圖4係圖3所示之邊緣清洗裝置的橫剖視圖。 FIG. 3 is a schematic plan view for explaining another embodiment of the edge cleaning device, and FIG. 4 is a cross-sectional view of the edge cleaning device shown in FIG. 3.
邊緣清洗裝置40具備：載置台42，將膜加以固定；以及旋轉滾子52。
The
載置台42設有：導件44，在載置台42上沿一方向(圖3之中係上下方向)延伸。此外，比導件44更靠一方側(圖3之中係右側)成為疊層膜10的搬運位置。載置台42的前述搬運位置下表面具備：搬運部48，具有複數個旋轉滾子。又，搬運部48的上部設有按壓滾子46。
The mounting table 42 is provided with a
旋轉滾子52安裝有二個環狀的彈性滾子54。自捲出側輥28捲出之擦拭用薄片24，在旋轉滾子52的側面大約捲繞半圈份量，並捲收在捲收側輥29。
Two annular
旋轉滾子52藉由桿棒部56而軸支在地板面。可由汽缸58來將壓力施加至桿棒部56。當由汽缸58將壓力施加至桿棒部56時，則旋轉滾子52往載置台42上的疊層膜10的方向按壓。此時，設定載置台42的高度、旋轉滾子52的高度、二個彈性滾子54的間隔等，俾使疊層膜10的側面位在二個彈性滾子54之間。
The rotating
邊緣清洗裝置所使用之汽缸，可係單純藉由空氣實施加壓之空氣汽缸，亦可係更組合有彈簧等機構者。 The cylinder used in the edge cleaning device may be an air cylinder that is pressurized by air alone, or it may be combined with a mechanism such as a spring.
藉由以上構成，可於使疊層膜10係其一個邊受導件44按壓、且係由搬運部48與按壓滾子46而在高度方向上加以固定之狀態下，使載置台42沿著導件44而移動。又，可藉由擦拭用薄片24來抹拭疊層膜10的側面。
With the above configuration, one side of the
導件44、搬運部48、及按壓滾子44相當於將膜加以固定之膜固定部。又，搬運部48及按壓滾子44相當於本發明的驅動部。
The
其次，說明邊緣清洗裝置40的動作的一例。
Next, an example of the operation of the
首先，將疊層膜10藉由搬運部48與按壓滾子46而固定在載置台42。此時不將壓力施加至汽缸58。其次，搬運疊層膜10，並使疊層膜10的第一角(圖3之中，
右上角)移動至與旋轉滾子52接觸之位置。其次，將壓力施加至汽缸58。藉此，捲繞在旋轉滾子52之擦拭用薄片24按抵疊層膜10。
First, the
此狀態下，進一步搬運疊層膜10，使疊層膜10的第二角(圖3之中，右下角)移動至與旋轉滾子52接觸之位置。藉此，藉由擦拭用薄片24抹拭疊層膜10的側面。
In this state, the
進行此動作之際，亦可同時搬運擦拭用薄片24。擦拭用薄片24的搬運方向，宜係與疊層膜10之搬運方向相反方向。於同時搬運之情形下，可一邊將擦拭用薄片24的新面加以送出並且一邊進行拭除，此點優異。
When performing this operation, the wiping
其次，釋放汽缸58的壓力，饋送疊層膜10。藉由上述，結束一片疊層膜10之拭除。其次，藉由未圖示之搬運部來搬運擦拭用薄片24。藉此，從輥部分送出新的擦拭用薄片24，並且使已於清洗時使用之部分捲收在輥部分。但是，構成為於疊層膜10的側面之拭除時同時搬運擦拭用薄片24之情形下，亦可不於拭除後進行擦拭用薄片24之搬運。
Next, the pressure of the
以上，說明其它實施形態之邊緣清洗裝置40。
Above, the
圖5係用以說明其它實施形態之邊緣清洗裝置之示意性俯視圖。此外，針對與使用圖3、圖4說明之邊緣清洗裝置40共通之部分，使用同一符號，來將其說明加以簡略化或省略。
Fig. 5 is a schematic plan view for explaining the edge cleaning device of other embodiments. In addition, with respect to the parts common to the
邊緣清洗裝置60具備：載置台42，將膜加以固定；以及二個旋轉滾子62。
The
圖6A係圖5所示之旋轉滾子的俯視圖，圖6B係其側視圖。如圖6A、圖6B所示，旋轉滾子62具有圓柱方向中央部形成有槽64之滑車形狀。又，旋轉滾子62於俯視中央設有旋轉軸66。如圖5所示，二個旋轉滾子62藉由旋轉軸66而在板狀構件68軸支成可旋轉。板狀構件68由桿棒構件70的一端軸支成可旋轉。又，桿棒構件70的另一端由邊緣清洗裝置60的本體61軸支成可旋轉。
Fig. 6A is a top view of the rotating roller shown in Fig. 5, and Fig. 6B is a side view thereof. As shown in FIG. 6A and FIG. 6B, the rotating
可從汽缸72將壓力施加至桿棒構件70。當從汽缸72將壓力施加至桿棒構件70時，則二個旋轉滾子62成為往載置台42上的疊層膜10的方向按壓。此時，設定載置台42的高度、旋轉滾子62的高度等，俾使疊層膜10的側面位在旋轉滾子62的槽64。
The pressure may be applied to the
邊緣清洗裝置60設有導件44、按壓滾子46、搬運部48。已說明導件44、按壓滾子46、搬運部48的構成及功能，故省略在此說明。
The
藉由以上構成，可於疊層膜10係一個邊由導件44按壓、且係藉由搬運部48與按壓滾子46而於高度方向上固定之狀態下，使載置台42沿著導件44移動。又，可藉由擦拭用薄片24抹拭疊層膜10的側面。
With the above structure, one side of the
此外，邊緣清洗裝置60的動作可定為與邊緣清洗裝置40同樣。
In addition, the operation of the
以上說明其它實施形態之邊緣清洗裝置60。
The
圖7係用以說明其它實施形態之邊緣清洗裝置之示意性俯視圖。此外，針對與使用圖5說明之邊緣清洗裝置60共通之部分，使用同一符號，將其說明簡略化或省略。
Fig. 7 is a schematic plan view for explaining an edge cleaning device of another embodiment. In addition, with respect to the parts common to the
邊緣清洗裝置80具備：載置台42，將膜加以固定；以及二個旋轉滾子62。因為已說明旋轉滾子62的構成，所以省略在此說明。
The
二個旋轉滾子62之間設有：板狀的按壓構件82，在與疊層膜10接觸之部分具有槽。按壓構件82與二個旋轉滾子62，分別經由由二個桿棒部所構成之V字狀構件84而連接。具體而言，二個旋轉滾子62，分別經由旋轉軸66(參照圖6A)而由V字狀構件84的一端軸支成可旋轉，且V字狀構件84的另一端由按壓構件82軸支成可旋轉。
A plate-shaped pressing
可由分別獨立設置之二個汽缸86來將壓力施加至二個V字狀構件84。當由汽缸86將壓力施加至V字狀構件84時，則按壓構件82與二個旋轉滾子62成為往載置台42上的疊層膜10的方向按壓。此時，設定載置台42的高度、按壓構件82的高度、旋轉滾子62的高度等，俾使疊層膜10的側面位在旋轉滾子62的槽64及按壓構件82的槽。
The pressure can be applied to the two V-shaped
邊緣清洗裝置80設有導件44、按壓滾子46、搬運部48。因為已說明導件44、按壓滾子46、搬運部48的構成及功能，所以省略在此說明。
The
藉由以上構成，可於疊層膜10係一個邊由導件44按壓、且係藉由搬運部48與按壓滾子46而在高度方向上加以固定之狀態下，使載置台42沿著導件44而移動。又，可藉由擦拭用薄片24來抹拭疊層膜10的側面。
With the above configuration, one side of the
此外，可將邊緣清洗裝置80的動作定為與邊緣清洗裝置40同樣。
In addition, the operation of the
以上說明其它實施形態之邊緣清洗裝置80。
The
圖8係用以說明其它實施形態之邊緣清洗裝置之示意性俯視圖。此外，針對與使用圖5說明之邊緣清洗裝置60共通之部分，使用同一符號，將其說明簡略化或省略。
Fig. 8 is a schematic plan view for explaining an edge cleaning device of another embodiment. In addition, with respect to the parts common to the
邊緣清洗裝置100具備：載置台42，將膜加以固定；以及三個旋轉滾子62。已說明旋轉滾子62的構成，故省略在此說明。
The
如圖8所示，三個旋轉滾子62經由旋轉軸66而由板狀構件68軸支成可旋轉。
As shown in FIG. 8, the three
可由汽缸72將壓力施加至旋轉滾子62。當由汽缸72將壓力施加至旋轉滾子62時，則三個旋轉滾子62成為往載置台42上的疊層膜10的方向按壓。此時，設
定載置台42的高度、旋轉滾子62的高度等，俾使疊層膜10的側面位在旋轉滾子62的槽64。
The pressure may be applied to the
邊緣清洗裝置100設有：桿棒63，用以緩和經由擦拭用薄片24而施加至旋轉滾子之張力。
The
邊緣清洗裝置100設有導件44、按壓滾子46、搬運部48。因為已說明導件44、按壓滾子46、搬運部48的構成及功能，所以省略在此說明。
The
藉由以上構成，可於疊層膜10係一個邊由導件44按壓、且係藉由搬運部48與按壓滾子46而在高度方向上固定之狀態下，使載置台42沿著導件44而移動。又，可藉由擦拭用薄片24來抹拭疊層膜10的側面。
With the above configuration, one side of the
此外，可將邊緣清洗裝置100的動作定為與邊緣清洗裝置40同樣。
In addition, the operation of the
以上已說明其它實施形態之邊緣清洗裝置100。
The
圖9係用以說明其它實施形態之邊緣清洗裝置之示意性俯視圖。此外，針對與使用圖5說明之邊緣清洗裝置60共通，使用同一符號，將其說明簡略化或省略。
Fig. 9 is a schematic plan view for explaining an edge cleaning device of another embodiment. In addition, the same reference numerals are used for the
邊緣清洗裝置120具備：載置台42，將膜加以固定；以及清洗頭治具91。
The
圖10係圖9所示之清洗頭治具的俯視圖及側視圖。如圖10(圖10上側的側視圖)所示，清洗頭治具91具有如下形狀：在與疊層膜10接觸之面的厚度方向中央部形成有槽92。又，如圖9及圖10下側的俯視圖所示，清洗頭治具91具有俯視下矩形形狀。如圖9所示，清洗頭治具91的長邊方向的一個邊係與疊層膜10接觸。又，清洗頭治具91之中，與疊層膜10接觸之邊的兩端部成為和緩的曲線。因為清洗頭治具91之與疊層膜10接觸之邊的兩端部成為和緩的曲線，所以可使擦拭用薄片24滑順饋送。
Fig. 10 is a top view and a side view of the cleaning head fixture shown in Fig. 9. As shown in FIG. 10 (a side view on the upper side of FIG. 10 ), the cleaning
可由汽缸72將壓力施加至清洗頭治具91。當由汽缸72將壓力施加至清洗頭治具91時，則清洗頭治具91成為往載置台42上的疊層膜10的方向按壓。此時，設定載置台42的高度、清洗頭治具91的高度等，俾使疊層膜10的側面位在清洗頭治具91的槽92。
The pressure can be applied to the cleaning
邊緣清洗裝置120設有導件44、按壓滾子46、搬運部48。已說明導件44、按壓滾子46、搬運部48的構成及功能，故省略在此說明。
The
藉由以上構成，可於疊層膜10係一個邊由導件44所按壓、且係藉由搬運部48與按壓滾子46而在高度方向上固定之狀態下，使載置台42沿著導件44移動。又，可藉由擦拭用薄片24來抹拭疊層膜10的側面。
With the above configuration, one side of the
此外，可將邊緣清洗裝置120的動作定為與邊緣清洗裝置40同樣。
In addition, the operation of the
以上已說明其它實施形態之邊緣清洗裝置120。
The
利用邊緣清洗裝置而將膜邊緣加以清潔之際，當過度將膜強力按抵至清洗頭時，則產生膜彎折等損傷，另一方面，當按抵過度微弱時，則有無法去除異物之情形。於是，使用如同上述邊緣清洗裝置之際，若將所使用之擦拭用布的種類與清洗頭的按抵壓力定為最佳條件，則即使膜與清洗頭的相對位置變化，亦容易不對膜造成損傷而去除異物。 When the edge of the film is cleaned by the edge cleaning device, when the film is pressed against the cleaning head excessively, damages such as film bending will occur. On the other hand, if the pressing force is too weak, foreign matter cannot be removed. situation. Therefore, when using the edge cleaning device as described above, if the type of wiping cloth used and the pressing pressure of the cleaning head are set as optimal conditions, even if the relative position of the membrane and the cleaning head changes, it is easy to prevent damage to the membrane. Damage and remove foreign objects.
<使無機基板與高分子膜貼合之疊層體的製造方法> <Method for manufacturing laminate in which inorganic substrate and polymer film are bonded together>
其次，說明使用前述疊層膜之使無機基板與高分子膜貼合之疊層體的製造方法。 Next, a method of manufacturing a laminate in which an inorganic substrate and a polymer film are bonded using the aforementioned laminate film will be explained.
首先，準備作為支持體之無機基板與前述疊層膜(經清洗之疊層膜)。 First, an inorganic substrate as a support and the aforementioned laminated film (cleaned laminated film) are prepared.
<無機基板> <Inorganic Substrate>
就前述無機基板而言，只要係可作為由無機物構成之基板來使用之板狀者即可，例如，列舉將玻璃板、陶瓷板、半導體晶圓、金屬等作為主體者、及作為此等玻璃板、陶瓷板、半導體晶圓、金屬的複合體，而將此等疊層者、將此等分散者、將此等的纖維加以含有者等。 As for the aforementioned inorganic substrates, any plate-shaped ones that can be used as substrates made of inorganic substances are sufficient. For example, glass plates, ceramic plates, semiconductor wafers, metals, etc., as the main body, and such glass Plates, ceramic plates, semiconductor wafers, metal composites, such as laminates, such as dispersed ones, and such fibers containing such composites.
前述玻璃板包含石英玻璃、高矽酸玻璃(96%二氧化矽)、鈉石灰玻璃、鉛玻璃、鋁硼矽酸玻璃、硼矽酸玻璃(PYREX(註冊商標))、硼矽酸玻璃(無鹼)、硼矽酸玻璃(MICRO SHEET)、鋁矽酸鹽玻璃等。它們之中，宜為線膨脹係數為5ppm/K 以下者，若為市售品，則宜為液晶用玻璃即CORNING公司製之「CORNING(註冊商標)7059」、或「CORNING(註冊商標)1737」、「EAGLE」；旭玻璃公司製之「AN100」；Nippon Electric Glass公司製之「OA10」；SCHOTT公司製之「AF32」等。 The aforementioned glass plates include quartz glass, high silica glass (96% silica), soda lime glass, lead glass, aluminoborosilicate glass, borosilicate glass (PYREX (registered trademark)), borosilicate glass (no Alkali), MICRO SHEET, aluminosilicate glass, etc. Among them, the linear expansion coefficient should be 5ppm/K The following ones, if they are commercially available, should be glass for liquid crystals, namely "CORNING (registered trademark) 7059" made by CORNING, or "CORNING (registered trademark) 1737", "EAGLE"; "AN100" made by Asahi Glass "; "OA10" made by Nippon Electric Glass; "AF32" made by SCHOTT, etc.
前述半導體晶圓並無特別限制，可列舉：矽晶圓；鍺、矽-鍺、鎵-砷、鋁-鎵-銦、氮-磷-砷-銻、碳化矽(SiC)、磷化銦(InP)、砷化銦鎵(InGaAs)、氮砷化鎵銦(GaInNAs)、鉭酸鋰(LT)、鈮酸鋰(LN)、氧化鋅(Z否)、碲化鎘(CdTe)、硒化鋅(ZnSe)等之晶圓。其中，理想使用的晶圓為矽晶圓，為8英寸以上之尺寸的鏡面研磨矽晶圓特佳。 The aforementioned semiconductor wafer is not particularly limited, and examples include: silicon wafer; germanium, silicon-germanium, gallium-arsenic, aluminum-gallium-indium, nitrogen-phosphorus-arsenic-antimony, silicon carbide (SiC), indium phosphide ( InP), Indium Gallium Arsenide (InGaAs), Nitrogen Gallium Indium Arsenide (GaInNAs), Lithium Tantalate (LT), Lithium Niobate (LN), Zinc Oxide (Z No), Cadmium Telluride (CdTe), Selenide Wafers such as zinc (ZnSe). Among them, the ideal wafer is a silicon wafer, and mirror polished silicon wafers with a size of 8 inches or more are particularly preferred.
就前述金屬而言，包含W、Mo、Pt、Fe、Ni、Au之類的單一元素金屬，還有英高鎳、蒙乃爾、鎳鉻立克、碳銅、Fe-Ni系因瓦合金、超因瓦合金之類的合金等。又，亦包含由對於此等金屬附加其它金屬層、陶瓷層而構成之多層金屬板。此情形下，只要與附加層之整體的線膨張係數(CTE)係低，則主金屬層亦可使用Cu、Al等。作為附加金屬層使用之金屬，只要係具有使與高分子膜之密著性堅固、不擴散、耐藥品性還有耐熱性優良等特性者，則不限定，其中列舉Cr、Ni、TiN、含Mo的Cu等合宜例。 As far as the aforementioned metals are concerned, they include single element metals such as W, Mo, Pt, Fe, Ni, Au, as well as Invar, Monel, Nichrome, Carbon Copper, Fe-Ni Invar, Super Invar and other alloys. In addition, it also includes a multilayer metal plate formed by adding another metal layer or ceramic layer to these metals. In this case, as long as the coefficient of linear expansion (CTE) as a whole with the additional layer is low, Cu, Al, etc. may also be used for the main metal layer. The metal used as the additional metal layer is not limited as long as it has strong adhesion to the polymer film, non-diffusion, chemical resistance, and excellent heat resistance. Examples include Cr, Ni, TiN, and Suitable examples such as Mo and Cu.
前述無機基板的平面部分，宜係充份平坦。具體而言，表面粗度的P-V值宜係50nm以下、更宜係20nm以下、尤宜係5nm以下。當較此更粗時，則有高分子膜層與無機基板之剝離強度不充份之情形。 The flat part of the aforementioned inorganic substrate is preferably sufficiently flat. Specifically, the P-V value of the surface roughness is preferably 50 nm or less, more preferably 20 nm or less, and particularly preferably 5 nm or less. When it is thicker than this, the peeling strength between the polymer film layer and the inorganic substrate may be insufficient.
前述無機基板的厚度不特別限制，但由處理性的觀點來看，宜係10mm以下的厚度，更宜係3mm以下，尤宜係1.3mm以下。厚度的下限不特別限制，但宜係0.07mm以上、更宜係0.15mm以上、尤宜係0.3mm以上。 The thickness of the aforementioned inorganic substrate is not particularly limited, but from the viewpoint of handling properties, the thickness is preferably 10 mm or less, more preferably 3 mm or less, and particularly preferably 1.3 mm or less. The lower limit of the thickness is not particularly limited, but it is preferably 0.07 mm or more, more preferably 0.15 mm or more, and particularly preferably 0.3 mm or more.
此外，於前述高分子膜未設矽烷偶聯劑層之情形下，亦可在無機基板上設置矽烷偶聯劑層。矽烷偶聯劑層的形成方法，可定為與將矽烷偶聯劑層形成在高分子膜上同樣。 In addition, when the aforementioned polymer film is not provided with a silane coupling agent layer, a silane coupling agent layer can also be provided on the inorganic substrate. The method of forming the silane coupling agent layer may be the same as that of forming the silane coupling agent layer on the polymer film.
其次，從所準備之前述疊層膜(經清洗之疊層膜)剝除保護膜，並將露出之高分子膜的表面、前述無機基板進行加壓加熱而使其貼合。藉此，獲得疊層體。此際，前述疊層膜之中，側面之高度10μm以上的突起、並且係源自前述黏接劑層或源自來自外部的附著物者的數量係10個/cm以下。因此，可謂抑制構成黏接劑層之黏接劑溢出、且來自外部的附著物亦少。故，可於使高分子膜貼合至無機基板之際抑制氣泡產生。 Next, the protective film is peeled off from the prepared laminate film (the cleaned laminate film), and the exposed surface of the polymer film and the inorganic substrate are pressed and heated to bond them together. In this way, a laminate is obtained. At this time, in the laminated film, the number of protrusions with a height of 10 μm or more on the side surface and derived from the adhesive layer or from external attachments is 10 per cm or less. Therefore, it can be said that the adhesive that constitutes the adhesive layer is prevented from overflowing, and there are few adherents from the outside. Therefore, the generation of bubbles can be suppressed when the polymer film is bonded to the inorganic substrate.
加壓加熱處理，例如，於大氣壓環境氣體下或真空中，一邊加熱並且一邊進行沖壓、層壓、輥式層壓等。又，亦可活用於置入至撓性袋的狀態下進行加壓加熱之方法。從生產性之提昇、由高生產性帶來之低加工成本化之觀點來看，宜係於大氣環境氣體下之沖壓或輥式層壓，特別宜係使用輥進行之方法(輥式層壓等)。 Pressure heating treatment, for example, pressing, laminating, roll laminating, etc., while heating under atmospheric pressure atmosphere or in vacuum. In addition, it can also be used as a method of pressurizing and heating while being placed in a flexible bag. From the viewpoint of productivity improvement and low processing cost brought by high productivity, stamping or roll lamination under atmospheric atmosphere is suitable, and the method using rolls is particularly suitable (roll lamination Wait).
就加壓加熱處理之際的壓力而言，宜係1MPa~20MPa，更宜係3MPa~10MPa。當係20MPa以下時，則可抑制無機基板破損。又，當係1MPa以上時，則可防止產生未密著的部分、黏接不充份。就加壓加熱處理之際的溫度而言，宜係150℃~400℃、更宜係250℃~350℃。高分子膜係聚醯亞胺膜之情形下，當溫度過高時，則有造成聚醯亞胺膜損傷之疑慮，且當溫度過低時，則有密著力變弱之傾向。 Regarding the pressure during the pressurizing and heating treatment, the pressure is preferably 1 MPa to 20 MPa, and more preferably 3 MPa to 10 MPa. When it is 20 MPa or less, damage to the inorganic substrate can be suppressed. In addition, when it is 1 MPa or more, it can prevent the occurrence of non-adhered parts and insufficient adhesion. Regarding the temperature during the pressurization and heating treatment, it is preferably 150°C to 400°C, more preferably 250°C to 350°C. In the case of the polymer film-based polyimide film, when the temperature is too high, there is a concern that the polyimide film will be damaged, and when the temperature is too low, the adhesion force tends to weaken.
又，加壓加熱處理，可於如同上述大氣壓環境氣體中進行，但為了獲得整面穩定的剝離強度，宜在真空下進行。此時，真空度係由一般油壓旋轉泵所成之真空度就充份，只要有10Torr以下左右就充份。 In addition, the pressurization and heat treatment can be carried out in an atmosphere of atmospheric pressure as described above, but in order to obtain a stable peel strength over the entire surface, it is preferably carried out under vacuum. At this time, the vacuum degree is sufficient by the general hydraulic rotary pump, as long as it is about 10 Torr or less.
就加壓加熱處理能使用之裝置而言，於真空中進行沖壓，可使用例如井元製作所製之「11FD」等，於進行真空中之輥式的膜層壓機、或定為真空後藉由薄的橡膠膜來針對玻璃整面一次性施加壓力之膜層壓機等者之真空層壓，例如可使用名機製作所製的「MVLP」等。 Regarding the device that can be used for pressurization and heating treatment, press in vacuum, for example, "11FD" manufactured by Imoto Manufacturing Co., Ltd. can be used for roll-type film laminator in vacuum, or by vacuum The thin rubber film is vacuum laminated by a film laminator that applies pressure to the entire surface of the glass at once. For example, "MVLP" manufactured by Meiki Seisakusho can be used.
前述加壓加熱處理之中，可將加壓處理與加熱處理分離進行。此情形下，首先，利用較低溫(例如未滿120℃，更宜係95℃以下之溫度)來將高分子膜與無機基板進行加壓(宜係0.2~50MPa左右)而確保兩者密著，其後，於低壓(宜未滿0.2MPa，更宜係0.1MPa以下)或常壓而利用較高溫(例如係120℃以上，更宜係120~250℃，尤宜係150~230℃)進行加熱，可藉以促進密著界面的化學反應而疊層高分子膜與無機基板。 Among the aforementioned pressure and heat treatments, the pressure treatment and the heat treatment may be performed separately. In this case, first, use a relatively low temperature (for example, less than 120°C, more preferably a temperature below 95°C) to press the polymer film and the inorganic substrate (preferably about 0.2 to 50 MPa) to ensure that the two are tightly adhered After that, use higher temperature under low pressure (preferably less than 0.2MPa, more preferably below 0.1MPa) or normal pressure (for example, above 120℃, more preferably 120~250℃, especially 150~230℃) Heating can promote the chemical reaction of the adhesion interface to laminate the polymer film and the inorganic substrate.
藉由上述，可獲得已將無機基板與高分子膜貼合之疊層體。 Through the above, a laminate in which an inorganic substrate and a polymer film have been bonded can be obtained.
<撓性電子元件的製造方法> <Method of Manufacturing Flexible Electronic Components>
當使用前述疊層體時，則可使用現存之電子元件製造用的設備、製程，而在疊層體的高分子膜上形成電子元件，並從疊層體剝離整個高分子膜，藉以製作撓性電子元件。 When the aforementioned laminate is used, existing equipment and processes for manufacturing electronic components can be used to form electronic components on the polymer film of the laminate, and the entire polymer film is peeled from the laminate, thereby making flexible Sexual electronic components.
本說明書之中，電子元件係指具有擔任電性配線之單面、兩面、或多層構造之配線基板、電晶體、二極體等能動元件、還有包括電阻、電容器、電感器等被動元件之電子電路、其它還有將壓力、溫度、光、溼度等加以感測之感測器元件、生物感測器元件、發光元件、液晶顯示、電泳顯示、自發光顯示等影像顯示元件、無線、有線所成之通信元件、運算元件、記憶元件、MEMS元件、太陽電池、薄膜電晶體等。 In this specification, electronic components refer to active components such as wiring substrates, transistors, and diodes with a single-sided, double-sided, or multilayer structure serving as electrical wiring, as well as passive components such as resistors, capacitors, and inductors. Electronic circuits, other sensor elements that sense pressure, temperature, light, humidity, etc., biosensor elements, light-emitting elements, liquid crystal displays, electrophoretic displays, self-luminous displays and other image display elements, wireless, wired The resulting communication components, computing components, memory components, MEMS components, solar cells, thin film transistors, etc.
本說明書中之元件構造體的製造方法，於利用上述方法製作之疊層體的高分子膜上形成元件之後，將該高分子膜從前述無機基板剝離。 In the method of manufacturing a device structure in this specification, after forming the device on the polymer film of the laminate produced by the above method, the polymer film is peeled from the aforementioned inorganic substrate.
就將附有元件之高分子膜從無機基板剝離之方法而言，不特別限制，可採用利用鑷鉗等而從端緣掀起之方法、在高分子膜加入缺口，並於使黏接膠帶黏貼至缺口部分的一個邊之後，從該膠帶部分掀起之方法、將高分子膜的缺口部分的一個邊加以真空吸附後，從該部分掀起之方法等。此外，於剝離之際，當高分子膜的缺口部分產生曲率小之彎曲時，則會有應力施加至該部分的元件並破壞元件之疑慮，因此宜盡量於曲率大的狀態下剝除。例如，宜一邊捲收至曲 率大的輥並且一邊掀起、或使用構成為曲率大的輥係位在剝離部分之機械來掀起。 The method of peeling the polymer film with the element from the inorganic substrate is not particularly limited. The method of lifting from the edge using tweezers or the like can be used to add a gap in the polymer film, and then stick the adhesive tape After reaching one side of the notch part, the method of lifting from the tape part, the method of vacuuming one side of the notch part of the polymer film and then lifting from the part, etc. In addition, when peeling, when the notch portion of the polymer film is bent with a small curvature, stress may be applied to the part of the device and the device may be damaged. Therefore, it is better to peel off with a large curvature as much as possible. For example, you should roll up to the song The roller with a large curvature can be lifted up on one side, or a machine with a large curvature roller attached to the peeling part can be used.
就將缺口加入前述高分子膜之方法而言，有藉由刀具等切削具來切斷高分子膜之方法、使鐳射與疊層體相對掃描藉以切斷高分子膜之方法、使水刀與疊層體相對掃描藉以切斷高分子膜之方法、於藉由半導體晶片的切削裝置切入些許至玻璃層為止之情況下切斷高分子膜之方法等，但方法不特別限定。例如，可於採用上述方法之際，合宜採用使超音波重疊於切削具、還有附加來回動作或上下動作等而提昇切削性能等手法。 As for the method of adding the notch to the polymer film, there are a method of cutting the polymer film with a cutting tool such as a cutter, a method of scanning the laser and the laminate to cut the polymer film, and a method of cutting the polymer film with a water jet. The method of cutting the polymer film by the relative scanning of the laminated body, the method of cutting the polymer film while cutting into the glass layer by the cutting device of the semiconductor wafer, etc., but the method is not particularly limited. For example, when the above method is adopted, it is appropriate to use methods such as superimposing ultrasonic waves on the cutting tool, and adding back and forth motions or up and down motions to improve cutting performance.
又，預先將其它補強基材貼附至剝離部分，而將補強基材整個剝離之方法亦有用。剝離之撓性電子元件係顯示元件的底板之情形下，亦可提前黏貼顯示元件的前板，而在無機基板上一體化後同時剝除兩者，獲得撓性的顯示元件。 In addition, it is also useful to attach other reinforcing substrates to the peeled part in advance and peel off the entire reinforcing substrate. In the case that the peeled flexible electronic element is the bottom plate of the display element, the front plate of the display element can also be pasted in advance, and after integration on the inorganic substrate, both are peeled off at the same time to obtain a flexible display element.
以下，使用實施例詳細說明本發明，但本發明只要不超出其主旨，則不限定於以下實施例。 Hereinafter, the present invention will be explained in detail using examples, but the present invention is not limited to the following examples as long as it does not exceed the gist.
<基材之在25℃的拉伸彈性係數的量測> <Measurement of the modulus of tensile elasticity of the base material at 25℃>
於基材疊層有黏接劑層之狀態下量測下述基材(基底膜A、基底膜B)之在25℃的拉伸彈性係數。本實施例之中，使用基材之在25℃的拉伸彈性係數係比黏接劑層之在25℃的拉伸彈性係數更高二位數以上者(作為標準，基材之在25℃的拉伸彈性係數係4GPa(4000MPa)前後，且黏接劑層之在25℃的拉伸彈性係數係 10MPa以下)，因此將基材疊層有黏接劑層之狀態下的量測值定為基材之在25℃的拉伸彈性係數。 The following substrates (base film A, base film B) were measured for their tensile elastic coefficients at 25°C in the state where the adhesive layer was laminated on the base material. In this embodiment, the tensile elastic modulus of the base material at 25°C is more than two digits higher than that of the adhesive layer at 25°C (as a standard, the base material The coefficient of tensile elasticity is around 4GPa (4000MPa), and the coefficient of tensile elasticity of the adhesive layer at 25°C is 10MPa or less), therefore, the measured value in the state where the adhesive layer is laminated on the substrate is defined as the tensile elastic coefficient of the substrate at 25°C.
在25℃之基材的拉伸彈性係數，係將基材呈100mm×10mm箋狀切下者定為試驗片，使用拉伸試驗機(島津製作所製，AutoGraph(R)，機種名AG-5000A)，並以拉伸速度50mm/分、夾頭間距離40mm條件來量測。 The tensile elastic coefficient of the substrate at 25°C is determined by cutting the substrate in a 100mm×10mm paper shape as a test piece, using a tensile testing machine (manufactured by Shimadzu Corporation, AutoGraph(R), model name AG-5000A ), and measured under the conditions of a stretching speed of 50mm/min and a distance between the chucks of 40mm.
其結果，基底膜A之在25℃的拉伸彈性係數係4.1GPa。又，基底膜B之在25℃的拉伸彈性係數係4.2GPa。 As a result, the tensile elastic modulus of the base film A at 25°C was 4.1 GPa. In addition, the tensile elastic modulus of base film B at 25°C was 4.2 GPa.
<耐熱高分子膜之在25℃的拉伸彈性係數的量測> <Measurement of the tensile elastic coefficient of heat-resistant polymer film at 25℃>
量測下述耐熱高分子膜(PI(聚醯亞胺)膜C~E)之在25℃的拉伸彈性係數。 The following heat-resistant polymer films (PI (polyimide) films C~E) were measured for their tensile elastic coefficients at 25°C.
在25℃之耐熱高分子膜的拉伸彈性係數，係將耐熱高分子膜呈100mm×10mm箋狀切下者作為試驗片，並使用拉伸試驗機(島津製作所製，AutoGraph(R)，機種名AG-5000A)，以拉伸速度50mm/分、夾頭間距離40mm之條件下量測。 The tensile elasticity coefficient of the heat-resistant polymer film at 25°C is obtained by cutting the heat-resistant polymer film in a 100mm×10mm paper shape as a test piece, and using a tensile testing machine (manufactured by Shimadzu Corporation, AutoGraph(R), model Name AG-5000A), measured under the conditions of a stretching speed of 50mm/min and a distance between the chucks of 40mm.
其結果，PI膜C之在25℃的拉伸彈性係數係8.2GPa。又，PI膜D之在25℃的拉伸彈性係數係8.IGPa。又，PI膜E之在25℃的拉伸彈性係數係8.3GPa。 As a result, the tensile elastic modulus of PI film C at 25°C was 8.2 GPa. In addition, the tensile elastic modulus of PI film D at 25°C is 8.IGPa. In addition, the tensile elastic modulus of PI film E at 25°C was 8.3 GPa.
<擦拭用薄片的摩擦係數量測> <Measurement of friction coefficient of wiping sheet>
擦拭用薄片的摩擦係數量測，係使用加多技術公司製，摩擦感試驗機KES-SE。摩擦子係使用10mm平方鋼琴線，且定為荷重25g/cm2、速度1mm/s，而於20℃65%RH之環境下實施。 The friction coefficient of the wiping sheet was measured using the KES-SE friction tester manufactured by Kador Technology Co., Ltd. The friction element uses a 10mm square piano wire, and is set at a load of 25g/cm 2 and a speed of 1mm/s, and is implemented in an environment of 20°C and 65% RH.
<擦拭用薄片的壓縮特性量測> <Measurement of Compression Characteristics of Wiping Sheet>
擦拭用薄片的壓縮特性量測，係使用加多技術公司製，自動化壓縮試驗機KED-FB3-AUTO-A。壓縮速度定為50s/mm、壓縮荷重定為50gf/cm2、加壓板定為2cm2。求取將30gf/cm2的壓力施加至壓縮前的厚度之際的變形量(%)。 The compression characteristics of the wiping sheet were measured using the KED-FB3-AUTO-A automated compression tester manufactured by Jiaduo Technology. The compression speed is set at 50s/mm, the compression load is set at 50gf/cm 2 , and the compression plate is set at 2cm 2 . The amount of deformation (%) when a pressure of 30 gf/cm 2 is applied to the thickness before compression is obtained.
<疊層膜之製造> <Manufacturing of Laminated Film>
說明於實施例使用之膜。 The films used in the examples are described.
保護膜A：PET(聚對苯二甲酸乙二酯)基底膜A(厚38μm)上形成有黏接劑層A(厚25μm)之膜(FUJICOPIAN公司製，產品名：HG1)。此外，黏接劑層的主成分係聚矽氧。 Protective film A: PET (polyethylene terephthalate) base film A (thickness 38 μm) with adhesive layer A (thickness 25 μm) formed on it (manufactured by Fujicopian, product name: HG1). In addition, the main component of the adhesive layer is silicone.
保護膜B：PET(聚對苯二甲酸乙二酯)基底膜B(厚50μm)上形成有黏接劑層B(厚10μm)之膜(凡納克公司製，產品名：PANAPROTECTET)。此外，黏接劑層的主成分係壓克力系。
Protective film B: A PET (polyethylene terephthalate) base film B (thickness 50 μm) formed with an adhesive layer B (
PI(聚醯亞胺)膜C(厚38μm)：東洋紡股份有限公司製，產品名：XENOMAX F38 PI (polyimide) film C (thickness 38μm): manufactured by Toyobo Co., Ltd., product name: XENOMAX F38
PI(聚醯亞胺)膜D(厚25μm)：東洋紡股份有限公司製，產品名：XENOMAX F25 PI (polyimide) film D (thickness 25μm): manufactured by Toyobo Co., Ltd., product name: XENOMAX F25
PI(聚醯亞胺)膜E(厚16μm)：東洋紡股份有限公司製，產品名：XENOMAX F16 PI (polyimide) film E (thickness 16μm): manufactured by Toyobo Co., Ltd., product name: XENOMAX F16
此外，PET基底膜A、PET基底膜B相當於本發明的基材。又，PI膜C~E相當於本發明的耐熱高分子膜。 In addition, PET base film A and PET base film B correspond to the base material of the present invention. In addition, PI films C to E correspond to the heat-resistant polymer film of the present invention.
(實施例1) (Example 1)
準備寬度730mm之保護膜A。又，準備PI膜C，並分段成寬度734mm寬。其次，使保護膜A與PI膜C進行貼合。貼合係將黏接劑層A與PI膜C定為貼合面。又，貼合係以PI膜C的兩端2mm各別以不與保護膜A重疊之方式進行。使保護膜A貼合至PI膜C的兩面。其後，藉由湯姆遜刀具將貼合體裁斷成720×910mm。就湯姆遜刀具而言，使用具有兩側30°角度之雙刃刀具。裁斷係逐片進行。裁斷係在樣品之下鋪設厚250μm之PET膜而進行。藉由上述，獲得清潔前之疊層膜1。 Prepare protective film A with a width of 730mm. In addition, a PI film C was prepared and divided into sections with a width of 734 mm. Next, the protective film A and the PI film C are bonded together. The bonding system sets the adhesive layer A and PI film C as the bonding surface. In addition, the bonding was performed so that the two ends of the PI film C were 2 mm so as not to overlap with the protective film A. The protective film A is attached to both sides of the PI film C. After that, the fit body was cut into 720×910mm with a Thomson knife. For Thomson knives, double-edged knives with 30° angles on both sides are used. Cutting is done piece by piece. Cutting is performed by laying a 250 μm thick PET film under the sample. Through the above, the laminated film 1 before cleaning is obtained.
其次，藉由下述「突起數之量測」所記載的邊緣清洗方法，清洗湯姆遜切割部。藉由上述，獲得本實施例1之疊層膜1(清潔後的疊層膜1)。 Next, clean the Thomson cut part by the edge cleaning method described in "Measurement of the number of protrusions" below. Through the above, the laminated film 1 of Example 1 (the laminated film 1 after cleaning) was obtained.
此外，表1的「疊層構成」項目之中，「A/C/A」之記載係表示依此順序疊層保護膜A、PI膜C、保護膜A。 In addition, in the item of "Laminated Structure" in Table 1, the description of "A/C/A" means that the protective film A, the PI film C, and the protective film A are laminated in this order.
(實施例2~6) (Examples 2~6)
如表1的「疊層構成」項目所示，於變更保護膜及PI膜的種類以外，係以與實施例1同樣之方式，製作清潔前的疊層膜2~6。又，與實施例1同樣進行清洗湯姆遜切割部，獲得實施例2~6之疊層膜2~6(清潔後的疊層膜2~6)。 As shown in the item of "Laminated Structure" in Table 1, except for changing the types of the protective film and PI film, the laminated films 2 to 6 before cleaning were produced in the same manner as in Example 1. In addition, the Thomson cut part was cleaned in the same manner as in Example 1, and laminated films 2 to 6 of Examples 2 to 6 (laminated films 2 to 6 after cleaning) were obtained.
(實施例7) (Example 7)
以與實施例1同樣之方式，製作清潔前的疊層膜1。其次，藉由下述「突起數之量測」記載的邊緣清洗方法，清洗湯姆遜切割部。藉由上述，獲得本實施例7之疊層膜1(清潔後的疊層膜1)。 In the same manner as in Example 1, a laminated film 1 before cleaning was produced. Next, clean the Thomson cut part by the edge cleaning method described in the following "Measurement of the number of protrusions". Through the above, the laminated film 1 of Example 7 (the laminated film 1 after cleaning) was obtained.
(實施例8) (Example 8)
以與實施例1同樣之方式，製作清潔前的疊層膜1。其次，藉由下述「突起數之量測」記載之邊緣清洗方法，來清洗湯姆遜切割部。藉由上述，獲得本實施例8之疊層膜1(清潔後的疊層膜1)。 In the same manner as in Example 1, a laminated film 1 before cleaning was produced. Next, clean the Thomson cut part by the edge cleaning method described in the following "Measurement of the number of protrusions". Through the above, the laminated film 1 of Example 8 (the laminated film 1 after cleaning) was obtained.
(實施例9) (Example 9)
以與實施例1同樣之方式，製作清潔前的疊層膜1。其次，藉由下述「突起數之量測」所記載的邊緣清洗方法，來清洗湯姆遜切割部。藉由上述，獲得本實施例9之疊層膜1(清潔後的疊層膜1)。 In the same manner as in Example 1, a laminated film 1 before cleaning was produced. Next, the Thomson cut part was cleaned by the edge cleaning method described in "Measurement of the number of protrusions" below. Through the above, the laminated film 1 of Example 9 (the laminated film 1 after cleaning) was obtained.
(實施例10) (Example 10)
以與實施例1同樣之方式，製作清潔前的疊層膜1。其次，藉由下述「突起數之量測」所記載的邊緣清洗方法，來清洗湯姆遜切割部。藉由上述，獲得本實施例10之疊層膜1(清潔後的疊層膜1)。 In the same manner as in Example 1, a laminated film 1 before cleaning was produced. Next, the Thomson cut part was cleaned by the edge cleaning method described in "Measurement of the number of protrusions" below. Through the above, the laminated film 1 of Example 10 (the laminated film 1 after cleaning) was obtained.
(實施例11) (Example 11)
以與實施例1同樣之方式，製作清潔前的疊層膜1。又，在不將溶劑噴射至擦拭用薄片以外，以與實施例1同樣之方式，進行清洗湯姆遜切割部，獲得實施例11之疊層膜1(清潔後的疊層膜1)。 In the same manner as in Example 1, a laminated film 1 before cleaning was produced. In addition, except that the solvent was not sprayed on the wiping sheet, the Thomson cut part was cleaned in the same manner as in Example 1 to obtain the laminated film 1 of Example 11 (the laminated film 1 after cleaning).
(實施例12) (Example 12)
以與實施例1同樣之方式，製作清潔前的疊層膜1。其次，藉由下述「突起數之量測」所記載的邊緣清洗方法，來清洗湯姆遜切割部。藉由上述，獲得本實施例12之疊層膜1(清潔後的疊層膜1)。 In the same manner as in Example 1, a laminated film 1 before cleaning was produced. Next, the Thomson cut part was cleaned by the edge cleaning method described in "Measurement of the number of protrusions" below. Through the above, the laminated film 1 of Example 12 (the laminated film 1 after cleaning) was obtained.
(實施例13) (Example 13)
以與實施例1同樣之方式，製作清潔前的疊層膜1。其次，藉由下述「突起數之量測」所記載的邊緣清洗方法，來清洗湯姆遜切割部。藉由上述，獲得本實施例13之疊層膜1(清潔後的疊層膜1)。 In the same manner as in Example 1, a laminated film 1 before cleaning was produced. Next, the Thomson cut part was cleaned by the edge cleaning method described in "Measurement of the number of protrusions" below. Through the above, the laminated film 1 of Example 13 (the laminated film 1 after cleaning) was obtained.
(實施例14) (Example 14)
以與實施例1同樣之方式，製作清潔前的疊層膜1。其次，藉由下述「突起數之量測」所記載的邊緣清洗方法，來清洗湯姆遜切割部。藉由上述，獲得本實施例14之疊層膜1(清潔後的疊層膜1)。 In the same manner as in Example 1, a laminated film 1 before cleaning was produced. Next, the Thomson cut part was cleaned by the edge cleaning method described in "Measurement of the number of protrusions" below. Through the above, the laminated film 1 of Example 14 (the laminated film 1 after cleaning) was obtained.
<突起數之量測> <Measurement of the number of protrusions>
(實施例1~6) (Examples 1~6)
利用切割器將於實施例1~6製作之清潔前的疊層膜呈6cm×4cm的矩形切下。此際，將6cm的一個邊以成為湯姆遜切割部之方式切下。意即，製作留下6cm的一個邊的、以切割器切割三邊而一個邊係湯姆遜切割部且三個邊係由切割器所成之切割部之6cm×4cm之觀察用樣品。 A cutter was used to cut the pre-cleaning laminate film made in Examples 1 to 6 into a rectangle of 6 cm×4 cm. At this time, cut off one side of 6cm to become a Thomson cutting part. That is, to make a 6cm×4cm observation sample with one side of 6cm, three sides cut by a cutter, one side being the Thomson cut part, and three sides being the cut part made by the cutter.
使用具備同軸落射光源之光學顯微鏡，來觀察所製作之觀察用樣品的湯姆遜切割部。此外，藉由此觀察而觀察裁斷邊的4cm部分。 Use an optical microscope with a coaxial epi-illumination light source to observe the Thomson cut part of the prepared observation sample. In addition, the 4 cm portion of the cut edge was observed by this observation.
將已觀察出之異物分類如下述來採計。將結果示於表1的「清潔前」欄。 The foreign objects that have been observed are classified as follows. The results are shown in the column "before cleaning" in Table 1.
附著(大)：被辨視為邊緣之高度100μm以上的異物 Adhesion (large): foreign matter with a height of 100μm or more, which is recognized as the edge
附著(邊緣)：被辨視為邊緣之高度10μm以上且未滿100μm的異物 Adhesion (edge): foreign matter with a height of 10μm or more and less than 100μm, which is recognized as an edge
此外，「附著(大)」及「附著(邊緣)」係本發明中之「側面之高度10μm以上的突起」的採計對象。 In addition, "adhesion (large)" and "adhesion (edge)" are the subjects of the "protrusion with a side surface height of 10 μm or more" in the present invention.
將清潔前的觀察用樣品加以觀察之後，於邊緣清洗操作之前，藉由清洗滾子將保護膜面同時進行清洗上下表面。 After observing the sample for observation before cleaning, before the edge cleaning operation, the upper and lower surfaces of the protective film are simultaneously cleaned by the cleaning roller.
其後，進行邊緣清洗。邊緣清洗，係將使用圖3、圖4說明之邊緣清洗裝置加以使用而進行。就擦拭用薄片與疊層膜之間的按壓壓力而言，即使利用2N左右的力來按壓膜，膜亦不產生彎曲、變形等，適合清洗。在與布料之間施加壓力之區域假設為5mm時，則係4N/10mm。此外，汽缸的壓力定為0.2MPa。又，就擦拭用薄片而言，使用PET長纖維括刷器(未來工纖股份有限公司製，產品名：多功括刷，不織布)。又，將2-丙醇作為溶劑而噴射至擦拭用薄片(噴射量：0.1cc/次)。拭除將清潔對象部分的長度之移動(本實施例係6cm)定為一來回。藉由上述，獲得清潔後的觀察用樣品。對於清潔後的觀察用樣品，採計異物。異物的採計方法，定為與清潔前之觀察用樣品的異物的採計方法同樣。將結果示於表1的「清潔後」欄。 After that, edge cleaning is performed. Edge cleaning is performed by using the edge cleaning device described in Figs. 3 and 4. Regarding the pressing pressure between the wiping sheet and the laminated film, even if the film is pressed with a force of about 2N, the film does not bend or deform, and is suitable for cleaning. If the area where the pressure is applied to the fabric is 5mm, it is 4N/10mm. In addition, the pressure of the cylinder is set at 0.2 MPa. In addition, for the wiping sheet, a PET long-fiber brush (manufactured by Mirai Koto Fiber Co., Ltd., product name: multi-function brush, non-woven fabric) was used. In addition, 2-propanol was sprayed to the wiping sheet (amount of spraying: 0.1 cc/time) as a solvent. For the erasing, the length of the cleaning target portion (6 cm in this embodiment) is set as one back and forth. Through the above, a cleaned observation sample was obtained. For observation samples after cleaning, foreign matter is collected. The method of collecting foreign objects is set to be the same as the method of collecting foreign objects in the observation sample before cleaning. The results are shown in the column "after cleaning" in Table 1.
此外，本實施例之中，按壓壓力係指清洗之膜經由擦拭用薄片而承受之往導引方向按壓之力。本實施例之中，擦拭用薄片與疊層膜之間的按壓壓力之量 測，係使用下述值：使用張力計(KENIS股份有限公司)，並將張力計的鉤部分固定至邊緣清洗裝置的旋轉滾子部分而量測之值。 In addition, in this embodiment, the pressing pressure refers to the force that the cleaned film bears through the wiping sheet to press in the guiding direction. In this embodiment, the amount of pressing pressure between the wiping sheet and the laminated film For the measurement, the following value is used: the value measured by using a tensiometer (KENIS Co., Ltd.) and fixing the hook part of the tensiometer to the rotating roller part of the edge cleaning device.
<突起數之量測> <Measurement of the number of protrusions>
(實施例7) (Example 7)
以與實施例1同樣之方式，製作觀察用樣品，採計湯姆遜切割部的異物。將結果示於表1的「清潔前」欄。 In the same manner as in Example 1, a sample for observation was prepared, and foreign matter in the Thomson cut portion was collected. The results are shown in the column "before cleaning" in Table 1.
將清潔前之觀察用樣品加以觀察後，於邊緣清洗操作之前，以與實施例1同樣之方式，進行清洗保護膜面。 After observing the sample for observation before cleaning, before the edge cleaning operation, the protective film surface was cleaned in the same manner as in Example 1.
其後，進行邊緣清洗。邊緣清洗係將使用圖3、4說明之邊緣清洗裝置加以使用而進行。按壓壓力定為3.7N。此時，汽缸的壓力係0.3MPa。此外，當將按壓壓力定為4N以上時，則膜產生彎曲、變形。由此，得知本實施例使用之邊緣清洗裝置之中，按壓壓力宜未滿4N。如上所述，於使用邊緣清洗裝置之際，須適當的按壓壓力。在變更按壓壓力以外，以與實施例1同樣之方式清潔膜邊緣，實施採計異物。將結果示於表1「清潔後」欄。 After that, edge cleaning is performed. The edge cleaning is performed by using the edge cleaning device illustrated in Figures 3 and 4. The pressing pressure is set at 3.7N. At this time, the pressure of the cylinder is 0.3 MPa. In addition, when the pressing pressure is 4N or more, the film will bend and deform. Therefore, it is known that in the edge cleaning device used in this embodiment, the pressing pressure should be less than 4N. As mentioned above, when using the edge cleaning device, proper pressing pressure is required. Except for changing the pressing pressure, the edge of the film was cleaned in the same manner as in Example 1, and foreign matter was collected. The results are shown in the column "after cleaning" in Table 1.
<突起數之量測> <Measurement of the number of protrusions>
(實施例8) (Example 8)
在將按壓壓力定為2.3N以外，以與實施例7同樣之方式進行實施。此時，汽缸壓力係0.2MPa。將結果示於表1「清潔前」、「清潔後」。 Except that the pressing pressure was set to 2.3 N, it was carried out in the same manner as in Example 7. At this time, the cylinder pressure is 0.2MPa. The results are shown in Table 1 "before cleaning" and "after cleaning".
<突起數之量測> <Measurement of the number of protrusions>
(實施例9) (Example 9)
利用切割器而將於實施例9製作之清潔前的疊層膜呈6cm×3.7cm的矩形切下。此際，將6cm的一個邊以成為湯姆遜切割部之方式切下。意即，製作留下6cm的一個邊的、以切割器切割三邊而一個邊係湯姆遜切割部且三個邊係由切割器所成之切割部之6cm×3.7cm的觀察用樣品。 The pre-cleaning laminate film produced in Example 9 was cut into a rectangle of 6 cm×3.7 cm using a cutter. At this time, cut off one side of 6cm to become a Thomson cutting part. That is, to make a 6cm×3.7cm observation sample with one side of 6cm, three sides cut by a cutter, one side is the Thomson cut part, and three sides are the cut part made by the cutter.
在使用上述6cm×3.7cm之觀察用樣品以外，以與實施例1同樣之方式，將製作之觀察用樣品的湯姆遜切割部加以觀察，並採計觀察出之異物。將結果示於表1的「清潔前」欄。 Except for using the 6 cm×3.7 cm observation sample, the Thomson cut part of the prepared observation sample was observed in the same manner as in Example 1, and the observed foreign matter was collected. The results are shown in the column "before cleaning" in Table 1.
又，將清潔前的觀察用樣品加以觀察後，以與實施例1的突起數之量測同樣之方法，進行邊緣清洗，獲得清潔後的觀察用樣品。對於清潔後的觀察用樣品，以與實施例1的突起數之量測同樣之方法，採計異物。將結果示於表1的「清潔後」。 In addition, after observing the observation sample before cleaning, edge washing was performed in the same manner as in the measurement of the number of protrusions in Example 1 to obtain a clean observation sample. For the cleaned observation sample, the foreign matter was collected by the same method as the measurement of the number of protrusions in Example 1. The results are shown in Table 1 "after cleaning".
<突起數之量測> <Measurement of the number of protrusions>
(實施例10) (Example 10)
利用切割器而將於實施例10製作之清潔前的疊層膜呈6cm×4.3cm的矩形切下。此際，將6cm的一個邊以成為湯姆遜切割部之方式切下。意即，製作留下6cm的一個邊的、以切割器切割三邊而一個邊係湯姆遜切割部且三個邊係由切割器所成之切割部之6cm×4.3cm的觀察用樣品。 The pre-cleaning laminate film produced in Example 10 was cut into a rectangle of 6 cm×4.3 cm using a cutter. At this time, cut off one side of 6cm to become a Thomson cutting part. That is, a 6cm×4.3cm observation sample with one side of 6cm left, three sides cut by a cutter, one side being a Thomson cut part, and three sides being a cut part made by the cutter, are made.
在使用以上6cm×4.3cm之觀察用樣品以外，以與實施例1同樣之方式，將製作之觀察用樣品的湯姆遜切割部加以觀察，採計觀察出之異物。將結果示於表1的「清潔前」欄。 Except for using the above 6cm×4.3cm observation sample, the Thomson cut part of the prepared observation sample was observed in the same manner as in Example 1, and the observed foreign matter was collected. The results are shown in the column "before cleaning" in Table 1.
又，將清潔前之觀察用樣品加以觀察後，以與實施例1的突起數之量測同樣之方式，進行邊緣清洗，獲得清潔後的觀察用樣品。對於清潔後的觀察用樣品，以與實施例1的突起數之量測同樣之方式，採計異物。將結果示於表1的「清潔後」欄。 In addition, after observing the observation sample before cleaning, edge cleaning was performed in the same manner as the measurement of the number of protrusions in Example 1, to obtain a clean observation sample. For the cleaned observation sample, the foreign matter was collected in the same manner as in the measurement of the number of protrusions in Example 1. The results are shown in the column "after cleaning" in Table 1.
<突起數之量測> <Measurement of the number of protrusions>
(實施例11) (Example 11)
在不將溶劑噴射至擦拭用薄片以外，以於實施例1的突起數之量測同樣之方式，採計異物。將結果示於表1的「清潔前」、「清潔後」欄。 Except not spraying the solvent to the wiping sheet, the foreign matter was collected in the same manner as in the measurement of the number of protrusions in Example 1. The results are shown in the "before cleaning" and "after cleaning" columns of Table 1.
<突起數之量測> <Measurement of the number of protrusions>
(實施例12) (Example 12)
在將TS-507(東和化成，不織布)使用作為擦拭用薄片以外，以與實施例1的突起數之量測同樣之方式，採計異物。將結果示於表1的「清潔前」「清潔後」欄。 Except that TS-507 (Towa Chemicals, Nonwoven) was used as a wiping sheet, the foreign matter was collected in the same manner as in the measurement of the number of protrusions in Example 1. The results are shown in the columns of "before cleaning" and "after cleaning" in Table 1.
<突起數之量測> <Measurement of the number of protrusions>
(實施例13) (Example 13)
在將TS-100(東和化成，不織布)使用作為擦拭用薄片以外，以與實施例1的突起數之量測同樣之方式，採計異物。將結果示於表1的「清潔前」「清潔後」欄。 Except that TS-100 (Towa Kasei, nonwoven fabric) was used as a wiping sheet, the foreign matter was collected in the same manner as in the measurement of the number of protrusions in Example 1. The results are shown in the columns of "before cleaning" and "after cleaning" in Table 1.
<突起數之量測> <Measurement of the number of protrusions>
(實施例14) (Example 14)
在將SD-40(東和化成、不織布)使用作為擦拭用薄片以外，以與實施例1的突起數之量測同樣之方式，採計異物。將結果示於表1的「清潔前」「清潔後」欄。 Except that SD-40 (Towa Chemicals, Nonwoven) was used as a wiping sheet, the foreign matter was collected in the same manner as in the measurement of the number of protrusions in Example 1. The results are shown in the columns of "before cleaning" and "after cleaning" in Table 1.
(參考例1) (Reference example 1)
以與實施例1同樣之方式，製作清潔前的疊層膜1。其次，在將PP(聚丙烯)不織布(ANVIET製)使用作為擦拭用薄片以外，以與實施例1的突起數之量測同樣之方式，清洗湯姆遜切割部，但PP不織布位在彈性滾子的槽而使疊層膜1無法進入。當此狀態下將膜加以按抵而實施清潔時，則膜產生彎折。 In the same manner as in Example 1, a laminated film 1 before cleaning was produced. Next, except using PP (polypropylene) non-woven fabric (manufactured by ANVIET) as a wiping sheet, the Thomson cut part was cleaned in the same manner as in the measurement of the number of protrusions in Example 1, but the PP non-woven fabric was located on the elastic roller The grooves prevent the laminate film 1 from entering. When the film is pressed and cleaned in this state, the film is bent.
(參考例2) (Reference example 2)
以與實施例1同樣之方式，製作清潔前的疊層膜1。其次，在使用尼龍不織布(WAKO集團製)作為擦拭用薄片以外，以與實施例1的突起數之量測同樣之方式清洗湯姆遜切割部之後，因不織布與膜側面磨擦而在膜產生傷痕，因此中斷清潔。 In the same manner as in Example 1, a laminated film 1 before cleaning was produced. Next, after using a nylon nonwoven fabric (made by WAKO Group) as the wiping sheet, the Thomson cut part was cleaned in the same manner as the measurement of the number of protrusions in Example 1, and the film was scratched by the nonwoven fabric and the side of the film. Therefore, cleaning is interrupted.
(參考例3) (Reference example 3)
以與實施例1同樣之方式，製作清潔前的疊層膜1。其次，在將纖維素不織布(不適應於潔淨環境，TRUSCO)使用作為擦拭用薄片以外，以與實施例1的突起數之量測同樣之方式清洗湯姆遜切割部之後，發現許多異物從擦拭用布轉移至疊層膜，因此中斷清潔。 In the same manner as in Example 1, a laminated film 1 before cleaning was produced. Secondly, after using the cellulose non-woven fabric (not suitable for a clean environment, TRUSCO) as a wiping sheet, after washing the Thomson cut section in the same manner as the number of protrusions in Example 1, it was found that many foreign objects were removed from the wiping The cloth is transferred to the laminated film, so cleaning is interrupted.
[表1]
<使用疊層膜之疊層體的製造及氣泡產生評價> <Production and bubble generation evaluation of laminated body using laminated film>
準備已切斷成180mm×230mm尺寸之厚度0.7mm的A10G玻璃(NEG製，無鹼玻璃基板)。 Prepare A10G glass (made of NEG, alkali-free glass substrate) that has been cut into a size of 180mm×230mm with a thickness of 0.7mm.
其次，將前述玻璃基板設置在旋轉塗佈器，並使矽烷偶聯劑(信越化學製，KBM903)的1%IPA溶液(異丙醇溶液)滴下至旋轉中央部之後，以500rpm旋轉，其次以2000rpm旋轉。將其在潔淨台放置一分鐘，使IPA乾燥，獲得具備矽烷偶聯劑層之玻璃基板。 Next, set the aforementioned glass substrate on a spin coater, and drop a 1% IPA solution (isopropanol solution) of a silane coupling agent (manufactured by Shin-Etsu Chemical, KBM903) onto the center of the spinner, and then spin it at 500 rpm. 2000rpm rotation. Place it on the clean bench for one minute to dry the IPA to obtain a glass substrate with a silane coupling agent layer.
其次，將於實施例準備之清潔後的疊層膜切下成130mm×200mm。此時，其一個邊係湯姆遜切割端、且其它邊係利用切割器切下。其次，從切下之疊層膜剝除保護膜，使PI膜露出。其後，使露出之PI膜與上述準備之具備矽烷偶聯劑層之玻璃基板進行貼合。 Next, the cleaned laminated film prepared in the example was cut into 130mm×200mm. At this time, one of its sides is the Thomson cutting end, and the other sides are cut off with a cutter. Next, peel off the protective film from the cut laminated film to expose the PI film. After that, the exposed PI film was bonded to the glass substrate provided with the silane coupling agent layer prepared above.
貼合係使用層壓機(MCK公司製MRK-1000)，並以無塵室內、22℃、55%RH、大氣壓下之方式，藉由空氣汽缸而將壓力施加至滾子來實施。將滾子的氣源壓力定為0.55MPa。此時，藉由感壓膜(富士軟片，PrescaleLLW)而確認出施加有1MPa之壓力。貼合後，放入110℃的烤箱加熱50分鐘，獲得使玻璃基板與PI膜貼合之疊層體。 Laminating is performed by using a laminator (MRK-1000 manufactured by MCK Corporation) and applying pressure to the rollers by means of an air cylinder in a clean room at 22°C, 55% RH, and atmospheric pressure. The air pressure of the roller is set to 0.55MPa. At this time, it was confirmed that a pressure of 1 MPa was applied by the pressure sensitive film (Fuji Film, PrescaleLLW). After bonding, it was placed in an oven at 110°C and heated for 50 minutes to obtain a laminate in which the glass substrate and the PI film were bonded.
從玻璃基板側目視觀察所獲得之疊層體，並採計從湯姆遜切割端起算30mm以內範圍之中直徑500μm以上的氣泡(氣泡)的數量。採計係針對湯姆遜切割端60cm部分整體進行。將結果示於表3。此外，將採計對象的氣泡，定為玻璃基板與PI膜之間產生之氣泡。此氣泡產生的原因係異物(源自黏接劑層、或源自來自 外部的附著物之異物)。將氣泡的數量係8個以下的情形評價為A，並評價為9個以上15個以下的情形定為B、且將16個以上評價為C。將結果示於表2。 The obtained laminate was visually observed from the side of the glass substrate, and the number of bubbles (bubbles) with a diameter of 500 μm or more in a range within 30 mm from the Thomson cut end was counted. The sampling system is performed on the whole 60cm part of the Thomson cutting end. The results are shown in Table 3. In addition, the bubbles to be collected are defined as bubbles generated between the glass substrate and the PI film. The cause of this bubble is foreign matter (from the adhesive layer or from Foreign matter attached to the outside). The case where the number of bubbles was 8 or less was evaluated as A, and the case where it was evaluated as 9 or more and 15 or less was regarded as B, and 16 or more was evaluated as C. The results are shown in Table 2.
10:疊層膜 10: Laminated film
20:邊緣清洗裝置 20: Edge cleaning device
24:擦拭用薄片 24: Wipe sheet
26:導引滾子 26: Guide roller
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| CN204620494U (en) * | 2015-02-12 | 2015-09-09 | 昆山龙腾光电有限公司 | Base-plate terminal cleaning device |
| JP6688450B2 (en) * | 2016-01-15 | 2020-04-28 | 東洋紡株式会社 | Laminate, electronic device, and flexible electronic device manufacturing method |
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| JP7112838B2 (en) * | 2016-09-30 | 2022-08-04 | 住友化学株式会社 | OPTICAL FILM, LAMINATED FILM USING THE SAME, AND OPTICAL FILM MANUFACTURING METHOD |
| JP6837460B2 (en) * | 2017-10-05 | 2021-03-03 | 住友化学株式会社 | Manufacturing method and manufacturing equipment for optical members |
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2019
- 2019-05-17 JP JP2019093750A patent/JP2020128077A/en active Pending
- 2019-07-29 TW TW108126689A patent/TWI712504B/en active
- 2019-07-29 TW TW109128576A patent/TWI828937B/en active
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| TW201244949A (en) * | 2011-05-06 | 2012-11-16 | Corning Inc | Laminated structure for semiconductor devices |
| CN106132688A (en) * | 2014-01-27 | 2016-11-16 | 康宁股份有限公司 | Goods and method for thin slice and the controlled bonding of carrier |
| CN107428599A (en) * | 2015-02-02 | 2017-12-01 | 康宁股份有限公司 | The laminated glass articles strengthened the method at laminated glass articles edge and be consequently formed |
| CN107771168A (en) * | 2015-04-22 | 2018-03-06 | 康宁股份有限公司 | The method that edge finishing is carried out to laminated glass construction |
Also Published As
| Publication number | Publication date |
|---|---|
| TW202026149A (en) | 2020-07-16 |
| TW202045268A (en) | 2020-12-16 |
| JP2020128077A (en) | 2020-08-27 |
| TWI828937B (en) | 2024-01-11 |
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