TWI617459B - Gas barrier film and manufacturing method thereof - Google Patents
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- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
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- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
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Abstract
本發明之課題為提供一種顯示非常高氣體障壁性的氣體障壁性薄膜,其係可作為有機EL裝置等之電子裝置用的基板來使用的程度。 An object of the present invention is to provide a gas barrier film having a very high gas barrier property, which is used to the extent that it can be used as a substrate for an electronic device such as an organic EL device.
作為解決手段,使包含過渡金屬以外之金屬的氧化物之氣體障壁層與包含過渡金屬的氧化物之過渡金屬氧化物含有層相互鄰接地配置在基材的一側的面之後,其構成為存在層之構成材料的氧化物相對於化學計量的組成成為高度缺氧之組成的區域,或是將含有過渡金屬以外之金屬以及過渡金屬之氣體障壁層配置在基材之一側的面之後,其構成為過渡金屬以外之金屬以及過渡金屬之複合氧化物的缺氧區域於前述氣體障壁層之厚度方向連續地以特定值以上之厚度存在。 As a solution, a gas barrier layer containing an oxide of a metal other than a transition metal and a transition metal oxide-containing layer containing an oxide of the transition metal are disposed adjacent to each other on the surface of one side of the substrate, and then they are configured to exist The oxide of the constituent material of the layer becomes a highly hypoxic region with respect to the stoichiometric composition, or after a gas barrier layer containing a metal other than a transition metal and a transition metal is disposed on one side of the substrate, the The oxygen-deficient region composed of a metal other than a transition metal and a composite oxide of the transition metal continuously exists in a thickness direction of the gas barrier layer with a thickness equal to or greater than a specific value.
Description
本發明為關於一種氣體障壁性薄膜以及其製造方法。 The present invention relates to a gas barrier film and a method for manufacturing the same.
可撓式電子裝置,尤其是可撓式有機EL裝置中,作為基板薄膜或密封薄膜是使用氣體障壁性薄膜。對於使用於此等之氣體障壁性薄膜要求較高的障壁性。 In a flexible electronic device, especially a flexible organic EL device, a gas barrier film is used as a substrate film or a sealing film. High barrier properties are required for the gas barrier film used in these.
一般來說,氣體障壁性薄膜是藉由在基材薄膜上以蒸鍍法、濺鍍法、CVD法等之氣相成膜法形成無機氣體障壁層所製造。另一方面,近年來,也有探討對在基材上塗佈溶液所形成之前驅物層施加能量,來形成氣體障壁層之製造方法。尤其是有廣泛地進行使用聚矽氮烷化合物作為前驅物之探討,作為塗佈所致之使高生產性與障壁性兼得之技術也漸漸被探討。尤其是使用波長172nm之準分子光的聚矽氮烷層之改質也受到注目。 Generally, a gas barrier film is manufactured by forming an inorganic gas barrier layer on a base film by a vapor-phase film formation method such as a vapor deposition method, a sputtering method, or a CVD method. On the other hand, in recent years, a method of forming a gas barrier layer by applying energy to a precursor layer formed by applying a solution on a substrate to form a gas barrier layer has also been discussed. In particular, the use of a polysilazane compound as a precursor has been widely investigated, and a technique for achieving both high productivity and barrier properties due to coating has been gradually explored. In particular, the modification of the polysilazane layer using excimer light having a wavelength of 172 nm has attracted attention.
且,以生產性提升之觀點來看,作為使用輥對輥(roll to roll)方式製造氣體障壁性薄膜之技術,有探討例如使用濺鍍等之物理蒸鍍(PVD)製膜裝置,並以輥對輥方式來製 造氣體障壁性薄膜(例如參照日本特開2005-035128號公報)。然而,以往技術中,例如有難以得到一種能夠作為有機EL裝置等之電子裝置用的基板來使用的程度(作為WVTR10-5~10-6左右)之氣體障壁性的問題。 Furthermore, from the viewpoint of improving productivity, as a technology for manufacturing a gas barrier film using a roll-to-roll method, for example, a physical vapor deposition (PVD) film forming apparatus using sputtering or the like has been discussed, and A roll-to-roll method is used to produce a gas barrier film (for example, refer to Japanese Patent Application Laid-Open No. 2005-035128). However, in the conventional technology, for example, it has been difficult to obtain a gas barrier property to the extent that it can be used as a substrate for an electronic device such as an organic EL device (as WVTR10 -5 to 10 -6 ).
且,以往,以濺鍍等之PVD法所得之無機膜的製膜,在透鏡塗層這種光學薄膜的領域中也被廣泛地探討(例如參照日本特開2005-298833號公報以及特許第4178190號公報)。然而,此等之技術是特定化於光學性能之提升,所以能轉用在氣體障壁性薄膜之技術較貧乏,尤其是以PVD製膜之層合構成來表現較高氣體障壁性的技術完全沒有被探討。 In addition, in the past, the formation of inorganic films obtained by the PVD method such as sputtering has been widely discussed in the field of optical films such as lens coatings (for example, refer to Japanese Patent Application Laid-Open No. 2005-298833 and Patent No. 4178190). Bulletin). However, these technologies are specific to the improvement of optical properties, so the technology that can be used for gas barrier films is relatively scarce, especially the technology of high gas barrier properties based on the laminated structure of PVD film formation is completely absent. Being explored.
進而,以往,關於以濺鍍等之PVD法所得的無機膜之製膜,有廣泛檢討使用多種金屬之複合化合物之高障壁化。例如在日本特表2010-524732號公報中有揭示一種技術,其係在透明之熱可塑性薄膜上包含透過障壁層之透明障壁薄膜中,將透過障壁層由鋅、錫以及氧之元素的化合物構成,且將鋅之質量比例控制為特定範圍內之值。日本特表2010-524732號公報之實施例中,雖然藉由使用Zn-Sn合金靶材之濺鍍法來形成厚度200nm的ZnSnOx層,但作為氣體障壁性(WVTR)係2×10-2(g/m2/day)程度,無法得到充分的氣體障壁性。 Furthermore, conventionally, regarding the film formation of an inorganic film obtained by a PVD method such as sputtering, there have been extensive reviews of the formation of high barriers using a composite compound of a plurality of metals. For example, Japanese Patent Publication No. 2010-524732 discloses a technology in which a transparent barrier film including a transparent barrier film on a transparent thermoplastic film is made of a compound of elements of zinc, tin, and oxygen. And control the mass ratio of zinc to a value within a specific range. In the example of Japanese Patent Publication No. 2010-524732, although a ZnSnO x layer having a thickness of 200 nm is formed by a sputtering method using a Zn-Sn alloy target, the gas barrier property (WVTR) is 2 × 10 -2 (g / m 2 / day), sufficient gas barrier properties cannot be obtained.
且,日本特開2011-213102號公報中有揭示一種技術,其係在具有特定表面粗度之高分子薄膜基材的單面或兩面上,形成以含有ZnS以及SiO2而成之混合物作為主 成分的混合薄膜層,將ZnS記成M,將氧化物記成L時,將混合薄膜層之組成設為「MXL(1-X)(0.7≦X≦0.9)」。日本特開2011-213102號公報之實施例中,雖然藉由使用ZnS-SiO2混合燒結材標靶之濺鍍法來形成厚度50nm之ZnS-SiO2層,但作為氣體障壁性(WVTR)係4×10-2(g/m2/day)(40℃ 90%RH)程度,還是無法得到充分的氣體障壁性。 Furthermore, Japanese Patent Application Laid-Open No. 2011-213102 discloses a technique for forming a mixture containing ZnS and SiO 2 as a main component on one or both sides of a polymer film substrate having a specific surface roughness. In the mixed thin film layer of components, when ZnS is expressed as M and oxide is expressed as L, the composition of the mixed thin film layer is set to "M X L (1-X) (0.7 ≦ X ≦ 0.9)”. In the example of Japanese Patent Application Laid-Open No. 2011-213102, although a ZnS-SiO 2 layer having a thickness of 50 nm is formed by a sputtering method using a target of a ZnS-SiO 2 mixed sintered material, it is a gas barrier (WVTR) At a level of 4 × 10 -2 (g / m 2 / day) (40 ° C 90% RH), sufficient gas barrier properties cannot be obtained.
如上所述,以往,雖然有提案各種使用氣相製膜法來製作氣體障壁性薄膜的技術,但現狀為尚無法實現一種顯示非常高氣體障壁性的薄膜,其係可作為有機EL裝置等之電子裝置用的基板來使用的程度。 As described above, although conventionally, various technologies have been proposed for producing gas barrier films using a vapor-phase film formation method, the current situation is that a film exhibiting very high gas barrier properties has not yet been realized, and it can be used as an organic EL device or the like. The degree to which a substrate for an electronic device is used.
有鑑於上述情況,本發明之目的為提供一種顯示非常高氣體障壁性的氣體障壁性薄膜,其係可作為有機EL裝置等之電子裝置用的基板來使用的程度。 In view of the foregoing circumstances, an object of the present invention is to provide a gas barrier film exhibiting a very high gas barrier property, and the film can be used as a substrate for an electronic device such as an organic EL device.
本發明者為了解決上述課題,進行縝密地研究。其結果,發現使包含過渡金屬以外之金屬的氧化物之氣體障壁層與包含過渡金屬的氧化物之過渡金屬氧化物含有層相互鄰接地配置在基材的一側的面之後,其構成為存在層之構成材料的氧化物相對於化學計量的組成成為高度缺氧之組成的區域,或是將含有過渡金屬以外之金屬以及 過渡金屬之氣體障壁層配置在基材之一側的面之後,其構成為過渡金屬以外之金屬以及過渡金屬之複合氧化物的缺氧區域於前述氣體障壁層之厚度方向連續地以特定值以上之厚度存在,藉此,能夠解決上述課題,進而完成本發明。 The present inventors conducted intensive studies in order to solve the above problems. As a result, it was found that a gas barrier layer containing an oxide of a metal other than a transition metal and a transition metal oxide-containing layer containing an oxide of a transition metal were disposed adjacent to each other on the side of the substrate, and then they were constituted so as to exist Areas where the oxide of the constituent material of the layer becomes a highly anoxic composition relative to the stoichiometric composition, or will contain metals other than transition metals and After the gas barrier layer of the transition metal is disposed on one surface of the base material, it is constituted as an oxygen-deficient region of a metal other than the transition metal and a compound oxide of the transition metal in the thickness direction of the gas barrier layer continuously by a certain value or more. The present invention has such a thickness that the above-mentioned problems can be solved and the present invention can be completed.
亦即,本發明之一形態為關於一種氣體障壁性薄膜,其係具有下述層構成:使包含過渡金屬以外之金屬的氧化物之氣體障壁層與包含過渡金屬的氧化物之過渡金屬氧化物含有層相互鄰接地配置在基材之一側的面(以下,將具有如此層構成之氣體障壁性薄膜稱作「第1形態」)。依據此第1形態之一實施形態,能夠提供一種氣體障壁性薄膜,其係具有基材、與配置於前述基材之至少一側的面,且含有過渡金屬以外之金屬(M1)的氧化物之第1氣體障壁層、與配置成與前述第1氣體障壁層鄰接,且含有過渡金屬(M2)的氧化物之過渡金屬氧化物含有層。且,該氣體障壁性薄膜,在滿足下述(1)、(2)或(3)之至少任一者之點上具有特徵:(1)前述第1氣體障壁層中,將前述過渡金屬以外之金屬(M1)的最大價數設為a,氧設為O,氮設為N,碳設為C,並將前述金屬(M1)之氧化物的組成設為(M1)OuNvCw時,在前述氣體障壁層之厚度方向的至少一部分,存在滿足下述數式之區域:u>0,且,v≧0,且,w≧0,且,(2u+3v+2w)/a<0.85; (2)前述過渡金屬氧化物含有層中,將前述過渡金屬(M2)之最大價數設為b,將氧設為O,將氮設為N,前述過渡金屬之氧化物的組成設為(M2)OxNy時,在前述過渡金屬氧化物層之厚度方向的至少一部分,存在滿足下述數式之區域:x>0,且,y≧0,且,(2x+3y)/b<0.85;(3)將前述第1氣體障壁層以及前述過渡金屬氧化物含有層中分別含有的前述氧化物分別以前述(1)以及前述(2)所示之組成來表示時,在前述第1氣體障壁層之厚度方向的至少一部分、以及前述過渡金屬氧化物含有層之厚度方向的至少一部分,存在滿足下述數式之區域的組合:(2u+3v+2w)/a+(2x+3y)/b<1.85。 That is, one aspect of the present invention relates to a gas barrier film having a layer structure including a gas barrier layer containing an oxide of a metal other than a transition metal and a transition metal oxide containing an oxide of a transition metal. The containing layers are arranged adjacent to each other on the surface of one side of the substrate (hereinafter, the gas barrier film having such a layer structure is referred to as a "first aspect"). According to an embodiment of this first aspect, it is possible to provide a gas barrier film having a substrate and a surface disposed on at least one side of the substrate, and containing an oxide of a metal (M1) other than a transition metal. The first gas barrier layer is a transition metal oxide-containing layer arranged adjacent to the first gas barrier layer and containing an oxide of a transition metal (M2). The gas barrier film is characterized by satisfying at least one of the following (1), (2), or (3): (1) In the first gas barrier layer, the transition metal is other than the transition metal. The maximum valence of metal (M1) is set to a, oxygen is set to O, nitrogen is set to N, carbon is set to C, and the composition of the oxide of the aforementioned metal (M1) is set to (M1) O u N v C At w , at least a part of the thickness direction of the gas barrier layer has a region satisfying the following formula: u> 0, and v ≧ 0, and w ≧ 0, and (2u + 3v + 2w) / a <0.85; (2) In the transition metal oxide-containing layer, the maximum valence of the transition metal (M2) is set to b, oxygen is set to O, and nitrogen is set to N. When the composition is (M2) O x N y , at least a part of the thickness direction of the transition metal oxide layer has a region satisfying the following formula: x> 0, and y ≧ 0, and (2x + 3y) / b <0.85; (3) When the oxides contained in the first gas barrier layer and the transition metal oxide-containing layer are represented by the compositions shown in the above (1) and (2), respectively , In the aforementioned first gas barrier A combination of at least a part of the thickness direction of the layer and at least a part of the thickness direction of the transition metal oxide containing layer satisfies the following formula: (2u + 3v + 2w) / a + (2x + 3y) / b <1.85.
依據本發明之第1形態之其他實施形態,亦提供一種具有與上述相同之層構成的氣體障壁性薄膜,且其特徵為前述第1氣體障壁層與前述過渡金屬氧化物含有層之層合體滿足下述(4):(4)具有前述金屬(M1)與前述過渡金屬(M2)同時存在之混合區域,將前述(M1)之最大價數設為a,前述(M2)之最大價數設為b,氧設為O,氮設為N,碳設為C,前述混合區域之組成設為(M1)(M2)pOqNrCs時,在前述混合區域之厚度方向的至少一部分,具有滿足下述數式之區域:0.02≦p≦98,且,q>0,且,r≧0,且,s≧0,且,(2q+3r+2s)/(a+bp)<0.85。 According to another embodiment of the first aspect of the present invention, there is also provided a gas barrier film having the same layer structure as described above, wherein the laminated body of the first gas barrier layer and the transition metal oxide-containing layer is satisfied The following (4): (4) The mixed region where the aforementioned metal (M1) and the aforementioned transition metal (M2) coexist, and the maximum valence of the aforementioned (M1) is set to a, and the maximum valence of the aforementioned (M2) is set B, oxygen is O, nitrogen is N, carbon is C, and when the composition of the mixed region is (M1) (M2) p O q N r C s , at least a part of the thickness direction of the mixed region Has a region that satisfies the following formula: 0.02 ≦ p ≦ 98, and q> 0, and r ≧ 0, and s ≧ 0, and (2q + 3r + 2s) / (a + bp) < 0.85.
依據本發明之其他形態,係關於一種氣體障壁性薄 膜,其係具有下述層構成:將含有過渡金屬以外之金屬以及過渡金屬之氣體障壁層配置在基材之一側的面(以下,將具有如此層構成之氣體障壁性薄膜稱作「第2形態」)。依據該形態,能提供一種氣體障壁性薄膜,其係具有基材、與配置於前述基材之至少一側的面,且含有過渡金屬以外之金屬(M1)以及過渡金屬(M2)之第1氣體障壁層。且,該氣體障壁性薄膜,在上述第1氣體障壁層滿足下述(5)之點上具有特徵:(5)將前述金屬(M1)之最大價數設為a,前述過渡金屬(M2)之最大價數設為b,氧設為O,氮設為N,碳設為C,前述第1氣體障壁層之組成設為(M1)(M2)pOqNrCs時,於前述第1氣體障壁層之厚度方向連續5nm以上之區域係滿足下述數式之區域[a]。 According to another aspect of the present invention, a gas barrier film having a layer structure in which a gas barrier layer containing a metal other than a transition metal and a transition metal is disposed on one side of a substrate (hereinafter, referred to as A gas barrier film having such a layer structure is referred to as a "second aspect"). According to this aspect, it is possible to provide a gas barrier film having a base material and a surface disposed on at least one side of the base material and containing a metal (M1) other than a transition metal and a first transition metal (M2). Gas barrier layer. The gas barrier film is characterized in that the first gas barrier layer satisfies the following (5): (5) The maximum valence of the metal (M1) is set to a, and the transition metal (M2) is described above. The maximum valence is set to b, oxygen is set to O, nitrogen is set to N, and carbon is set to C. When the composition of the first gas barrier layer is set to (M1) (M2) p O q N r C s , The region where the thickness direction of the first gas barrier layer is 5 nm or more is a region [a] that satisfies the following formula.
0.02≦p≦98,且,q>0,且,r≧0,且,s≧0,且,(2q+3r+2s)/(a+bp)<1。 0.02 ≦ p ≦ 98, and q> 0, and r ≧ 0, and s ≧ 0, and (2q + 3r + 2s) / (a + bp) <1.
且,依據本發明之另一其他形態,亦提供一種上述之各形態相關之氣體障壁性薄膜的製造方法。於此,第1形態相關之製造方法包含:在前述基材與前述第1氣體障壁層之層合體之前述第1氣體障壁層之與前述基材相反側的面上,藉由氣相成膜法來形成前述過渡金屬氧化物含有層之步驟,在於形成前述過渡金屬氧化物含有層之步驟中,將選自由製膜原料中之前述過渡金屬(M2)與氧的比率、製膜時之惰性氣體與反應性氣體的比率、製膜時之氣體的供給量、製膜時的真空度、以及製膜時之電力所構成群中的 1種或2種以上之條件調節至滿足上述(2)之點上具有特徵。 Furthermore, according to another aspect of the present invention, a method for manufacturing a gas barrier film related to each of the aspects is also provided. Here, the manufacturing method related to the first aspect includes forming a film by a gas phase on a surface of the first gas barrier layer that is a laminate of the substrate and the first gas barrier layer on the side opposite to the substrate. The step of forming the transition metal oxide-containing layer by a method is that in the step of forming the transition metal oxide-containing layer, a ratio of the transition metal (M2) to oxygen selected from a film-forming raw material, and inertness during film formation are selected. The ratio of gas to reactive gas, the amount of gas supplied during film formation, the degree of vacuum during film formation, and the power in the group formed by film formation It is characteristic that one or more conditions are adjusted to satisfy the above (2).
且,第2形態相關之製造方法包含在前述基材之至少一側的面上形成前述第1氣體障壁層之步驟,在形成前述第1氣體障壁層之步驟包含使包含前述金屬(M1)以及前述過渡金屬(M2)之複合氧化物於前述基材之至少一側的面上共蒸鍍,使所形成之第1氣體障壁層滿足上述(5)之點上具有特徵。 In addition, the manufacturing method related to the second aspect includes a step of forming the first gas barrier layer on at least one side of the substrate, and the step of forming the first gas barrier layer includes including the metal (M1) and The composite oxide of the transition metal (M2) is co-evaporated on at least one side of the substrate, so that the formed first gas barrier layer satisfies the above point (5).
10‧‧‧氣體障壁性薄膜 10‧‧‧Gas barrier film
11‧‧‧基材 11‧‧‧ Substrate
12‧‧‧第1氣體障壁層 12‧‧‧ 1st gas barrier
13‧‧‧過渡金屬氧化物含有層 13‧‧‧ transition metal oxide containing layer
101‧‧‧真空電漿CVD裝置 101‧‧‧Vacuum Plasma CVD Device
102‧‧‧真空槽 102‧‧‧Vacuum tank
103‧‧‧陰極電極 103‧‧‧ cathode electrode
105‧‧‧承受器 105‧‧‧ Acceptor
106‧‧‧熱媒循環系統 106‧‧‧Heat medium circulation system
107‧‧‧真空排氣系統 107‧‧‧Vacuum exhaust system
108‧‧‧氣體導入系統 108‧‧‧Gas introduction system
109‧‧‧高頻電源 109‧‧‧High-frequency power supply
110‧‧‧基板 110‧‧‧ substrate
160‧‧‧加熱冷卻裝置 160‧‧‧Heating and cooling device
[圖1]表示本發明之第1形態相關之氣體障壁性薄膜的剖面示意圖。圖1中,10為氣體障壁性薄膜,11為基材,12為第1氣體障壁層,13為過渡金屬氧化物含有層。 Fig. 1 is a schematic cross-sectional view showing a gas barrier film according to a first aspect of the present invention. In FIG. 1, 10 is a gas barrier film, 11 is a base material, 12 is a 1st gas barrier layer, and 13 is a transition metal oxide containing layer.
[圖2]表示本發明之第2形態相關之氣體障壁性薄膜的剖面示意圖。圖2中,10為氣體障壁性薄膜,11為基材,12為第1氣體障壁層。 Fig. 2 is a schematic cross-sectional view showing a gas barrier film according to a second aspect of the present invention. In FIG. 2, 10 is a gas barrier film, 11 is a substrate, and 12 is a first gas barrier layer.
[圖3]表示真空電漿CVD裝置之一例之示意圖。圖3中,101為電漿CVD裝置,102為真空槽,103為陰極電極,105為承受器(susceptor),106為熱媒循環系統,107為真空排氣系統,108為氣體導入系統,109為高頻電源,110為基板,160為加熱冷卻裝置。 Fig. 3 is a schematic diagram showing an example of a vacuum plasma CVD apparatus. In FIG. 3, 101 is a plasma CVD apparatus, 102 is a vacuum tank, 103 is a cathode electrode, 105 is a susceptor, 106 is a heat medium circulation system, 107 is a vacuum exhaust system, 108 is a gas introduction system, 109 It is a high-frequency power supply, 110 is a substrate, and 160 is a heating and cooling device.
以下說明本發明較佳實施形態。且,本發明並不限定於僅以下實施形態。且,圖面之尺寸比率在便於說明之下較誇大,有時會與實際比率相異。 Hereinafter, preferred embodiments of the present invention will be described. The present invention is not limited to the following embodiments. In addition, the size ratio of the drawing is exaggerated for convenience of explanation, and sometimes it is different from the actual ratio.
本說明書中,只要沒有特別記載,操作以及物性等之測定是在室溫(20~25℃)/相對濕度40~50%RH之條件下進行。 In this specification, unless otherwise stated, measurement of operation and physical properties is performed under conditions of room temperature (20-25 ° C) / relative humidity 40-50% RH.
本發明之第1形態相關之氣體障壁性薄膜,作為其基本構成,具有:基材、與配置於前述基材之至少一側的面,且含有過渡金屬以外之金屬(M1)的氧化物之第1氣體障壁層、與配置成與前述第1氣體障壁層鄰接,且含有過渡金屬(M2)的氧化物之過渡金屬氧化物含有層。且,關於本發明相關之氣體障壁性薄膜之特徵性構成的詳細說明於後述。 The gas barrier film according to the first aspect of the present invention has, as its basic structure, a substrate, a surface disposed on at least one side of the substrate, and an oxide containing a metal (M1) other than a transition metal. The first gas barrier layer and a transition metal oxide-containing layer arranged adjacent to the first gas barrier layer and containing an oxide of a transition metal (M2). A detailed description of the characteristic structure of the gas barrier film according to the present invention will be described later.
圖1為表示本發明之第1形態相關之氣體障壁性薄膜的剖面示意圖。圖1所示之氣體障壁性薄膜10是依序配置有基材11、第1氣體障壁層12、以及過渡金屬氧化物含有層13而成。且,本發明之第1形態中,只要是第1氣體障壁層12以及過渡金屬氧化物含有層13鄰接配置,亦可自基材側依序配置有第1氣體障壁層12以及過渡金屬氧化物含有層13(圖1),亦可自基材側依序配置有過渡 金屬氧化物含有層13以及第1氣體障壁層12。且,不僅是在基材之一側的面配置第1氣體障壁層12以及過渡金屬氧化物含有層13這種形態,亦可在基材的兩面配置氣體障壁層12以及過渡金屬氧化物含有層13。進而,亦可在基材與各層之間、或在各層上配置其他層。 FIG. 1 is a schematic cross-sectional view showing a gas barrier film according to a first aspect of the present invention. The gas barrier film 10 shown in FIG. 1 is formed by sequentially arranging a substrate 11, a first gas barrier layer 12, and a transition metal oxide-containing layer 13. Furthermore, in the first aspect of the present invention, as long as the first gas barrier layer 12 and the transition metal oxide containing layer 13 are arranged adjacent to each other, the first gas barrier layer 12 and the transition metal oxide may be sequentially arranged from the substrate side. Contains layer 13 (Figure 1), and transitions can be arranged in sequence from the substrate side The metal oxide contains a layer 13 and a first gas barrier layer 12. In addition to the configuration in which the first gas barrier layer 12 and the transition metal oxide-containing layer 13 are disposed on one side of the substrate, the gas barrier layer 12 and the transition metal oxide-containing layer may be disposed on both sides of the substrate. 13. Further, another layer may be disposed between the substrate and each layer, or on each layer.
惟,以發揮更高的氣體障壁性之觀點來看,如圖1所示,自基材側依序配置有第1氣體障壁層12以及過渡金屬氧化物含有層13之形態較佳。且,此時,氣體障壁性薄膜滿足上述(2)特別佳。 However, from the viewpoint of exhibiting higher gas barrier properties, as shown in FIG. 1, the first gas barrier layer 12 and the transition metal oxide containing layer 13 are preferably arranged in order from the substrate side. In this case, it is particularly preferable that the gas barrier film satisfies the above (2).
作為本發明(第1形態以及第2形態共通)相關之基材11,具體來說,有舉出包含聚酯樹脂、丙烯酸甲酯樹脂、丙烯酸甲酯酸-馬來酸共聚合物、聚苯乙烯樹脂、透明氟樹脂、聚醯亞胺、氟化聚醯亞胺樹脂、聚醯胺樹脂、聚醯胺醯亞胺樹脂、聚醚醯亞胺樹脂、醯化纖維素樹脂、聚胺基甲酸酯樹脂、聚醚醚酮樹脂、聚碳酸酯樹脂、脂環式聚烯烴樹脂、聚芳香酯樹脂、聚醚碸樹脂、聚碸樹脂、環烯烴共聚物、茀環改質聚碳酸酯樹脂、脂環改質聚碳酸酯樹脂、茀環改質聚酯樹脂、丙烯醯化合物等熱可塑性樹脂之基材。該基材能夠單獨或組合2種以上來使用。 Specific examples of the base material 11 related to the present invention (common to the first aspect and the second aspect) include polyester resin, methyl acrylate resin, methyl acrylate acid-maleic acid copolymer, and polybenzene. Ethylene resin, transparent fluororesin, polyimide, fluorinated polyimide resin, polyimide resin, polyimide resin, polyetherimide resin, trimethylcellulose resin, polyimide Acid ester resins, polyetheretherketone resins, polycarbonate resins, alicyclic polyolefin resins, polyaromatic ester resins, polyether resins, polyfluorene resins, cyclic olefin copolymers, cyclic modified polycarbonate resins, Base material of thermoplastic resins such as alicyclic modified polycarbonate resin, fluorene modified polyester resin, and acrylic fluorene compound. This base material can be used individually or in combination of 2 or more types.
基材由具有耐熱性之素材而成較佳。具體來說,使用線膨脹係數為15ppm/K以上100ppm/K以下,且玻璃轉移溫度(Tg)為100℃以上300℃以下之基材。該基材滿足作 為電子零件用途、顯示用層合薄膜之必要條件。亦即,在此等之用途上使用本發明相關之氣體障壁性薄膜時,氣體障壁性薄膜有時會暴露在150℃以上之步驟中。此時,氣體障壁性薄膜中之基材的線膨脹係數若超過100ppm/K,則將氣體障壁性薄膜往如前述溫度之步驟中前進時,基板尺寸會不安定,伴隨著熱膨脹以及收縮,會容易發生遮斷性性能惡化等不良情形、或無法耐受熱步驟之不良情形。未滿15ppm/K時,有時薄膜會如玻璃般地破裂且可撓性會惡化。 The base material is preferably made of a material having heat resistance. Specifically, a substrate having a linear expansion coefficient of 15 ppm / K or more and 100 ppm / K or less and a glass transition temperature (Tg) of 100 ° C or more and 300 ° C or less is used. The substrate meets the requirements It is a necessary condition for the application of electronic parts and display laminated films. That is, when the gas barrier film according to the present invention is used for such applications, the gas barrier film may be exposed to a step of 150 ° C or higher. At this time, if the linear expansion coefficient of the substrate in the gas barrier film exceeds 100 ppm / K, when the gas barrier film is advanced in the step of the temperature described above, the substrate size will be unstable, accompanied by thermal expansion and contraction. It is prone to adverse conditions such as deteriorating performance, or to fail to withstand thermal steps. When it is less than 15 ppm / K, the film may be cracked like glass and the flexibility may be deteriorated.
基材之Tg或線膨脹係數能夠依照添加劑等來調整。作為能夠作為基材使用的熱可塑性樹脂之再較佳的具體例,舉例有如聚乙烯對苯二甲酸酯(PET:70℃)、聚乙烯萘二甲酸酯(PEN:120℃)、聚碳酸酯(PC:140℃)、脂環式聚烯烴(例如日本Zeon股份有限公司製,ZEONOR(註冊商標)1600:160℃),聚芳香酯(PAr:210℃)、聚醚碸(PES:220℃)、聚碸(PSF:190℃)、環烯烴共聚物(COC:日本特開2001-150584號公報記載之化合物:162℃)、聚醯亞胺(例如三菱氣體化學股份有限公司製,NEOPULIM(註冊商標):260℃)、茀環改質聚碳酸酯(BCF-PC:日本特開2000-227603號公報記載之化合物:225℃)、脂環改質聚碳酸酯(IP-PC:日本特開2000-227603號公報記載之化合物:205℃)、丙烯醯化合物(日本特開2002-80616號公報記載之化合物:300℃以上)等(括弧內表示Tg)。 The Tg or linear expansion coefficient of the substrate can be adjusted in accordance with additives and the like. As further specific examples of the thermoplastic resin that can be used as the base material, examples include polyethylene terephthalate (PET: 70 ° C), polyethylene naphthalate (PEN: 120 ° C), polymer Carbonate (PC: 140 ° C), alicyclic polyolefin (for example, made by Japan Zeon Corporation, ZEONOR (registered trademark) 1600: 160 ° C), polyaromatic ester (PAr: 210 ° C), polyether fluorene (PES: 220 ° C), polyfluorene (PSF: 190 ° C), cyclic olefin copolymer (COC: Compound described in Japanese Patent Laid-Open No. 2001-150584: 162 ° C), polyimide (for example, manufactured by Mitsubishi Gas Chemical Co., Ltd., NEOPULIM (registered trademark): 260 ° C), fluorene modified polycarbonate (BCF-PC: Compound described in JP 2000-227603: 225 ° C), alicyclic modified polycarbonate (IP-PC: Compounds described in Japanese Patent Application Laid-Open No. 2000-227603: 205 ° C), acrylhydrazone compounds (compounds described in Japanese Patent Application Laid-Open No. 2002-80616: 300 ° C or higher), and the like (Tg is shown in parentheses).
本發明相關之氣體障壁性薄膜,由於能夠使用於有機EL元件等之電子裝置,基材為透明較佳。亦即,光線透過率通常為80%以上,較佳為85%以上,更較佳為90%以上。光線透過率能夠使用JIS K7105:1981記載之方法,亦即使用積分球式光線透過率測定裝置來測定全光線透過率以及散射光量,並自全光線透過率扣掉擴散透過率來算出。 Since the gas barrier film according to the present invention can be used in an electronic device such as an organic EL element, the substrate is preferably transparent. That is, the light transmittance is usually 80% or more, preferably 85% or more, and more preferably 90% or more. The light transmittance can be calculated using the method described in JIS K7105: 1981, that is, using an integrating sphere light transmittance measuring device to measure the total light transmittance and the amount of scattered light, and subtracting the diffuse transmittance from the total light transmittance.
惟,即使是將本發明相關之氣體障壁性薄膜使用於顯示用途時,若沒有設置在觀察側等,也並不一定要求透明性。因此,此時,能夠使用不透明材料作為塑膠薄膜。作為不透明材料,舉例有如聚醯亞胺、聚丙烯腈、公知之液晶聚合物等。 However, even when the gas barrier film according to the present invention is used in a display application, transparency is not necessarily required if it is not provided on the observation side or the like. Therefore, at this time, an opaque material can be used as the plastic film. Examples of the opaque material include polyimide, polyacrylonitrile, and a known liquid crystal polymer.
且,上述所舉出之基材亦可為未延伸薄膜,亦可為延伸薄膜。該基材能夠藉由以往公知之一般方法來製造。關於此等之基材的製造方法,能夠適當地採用國際公開第2013/002026號之段落「0051」~「0055」所記載之事項。 In addition, the substrates listed above may be unstretched films or stretched films. This base material can be manufactured by the conventionally well-known general method. Regarding the manufacturing method of these base materials, the matters described in paragraphs "0051" to "0055" of International Publication No. 2013/002026 can be appropriately adopted.
基材之表面亦可進行用來提升密著性之公知的各種處理,例如電暈放電處理、火焰處理、氧化處理、或電漿處理等,亦可因應必要組合上述處理來進行。且,亦可對基材進行易接著處理。 The surface of the substrate may be subjected to various known treatments for improving adhesion, such as a corona discharge treatment, a flame treatment, an oxidation treatment, or a plasma treatment, etc., or a combination of the above treatments may be performed as necessary. In addition, the substrate may be subjected to easy adhesion treatment.
該基材亦可為單層,亦可為2層以上之層合構造。該基材為2層以上之層合構造時,各基材亦可為相同種類,亦可為相異種類。 The substrate may be a single layer or a laminated structure of two or more layers. When the substrate has a laminated structure of two or more layers, each substrate may be the same type or a different type.
本發明相關之基材的厚度(為2層以上之層合構造時 係總厚度)為10~200μm較佳,為20~150μm再較佳。 The thickness of the substrate according to the present invention (in the case of a laminated structure of two or more layers) The total thickness) is preferably 10 to 200 μm, and more preferably 20 to 150 μm.
本發明中,第1氣體障壁層12必須含有過渡金屬以外之金屬(M1)(較佳為該金屬(M1)之氧化物)。藉此,第1氣體障壁層會顯示氣體障壁性。第1氣體障壁層之氣體障壁性,以使該第1氣體障壁層形成在基材上之層合體來算出時,水蒸氣透過率(WVTR)為0.1g/(m2‧day)以下較佳。於此,第1形態中,第1氣體障壁層12必須含有過渡金屬以外之金屬(M1)的氧化物。 In the present invention, the first gas barrier layer 12 must contain a metal (M1) other than a transition metal (preferably an oxide of the metal (M1)). As a result, the first gas barrier layer exhibits gas barrier properties. When the gas barrier property of the first gas barrier layer is calculated as a laminate in which the first gas barrier layer is formed on a substrate, the water vapor transmission rate (WVTR) is preferably 0.1 g / (m 2 ‧day) or less . Here, in the first aspect, the first gas barrier layer 12 must contain an oxide of a metal (M1) other than a transition metal.
作為過渡金屬以外之金屬(M1)並無特別限制,能夠使用單獨的過渡金屬以外之任意金屬或組合來使用,過渡金屬以外之金屬(M1)包含選自由長周期型周期表之第12族~第14族的金屬所構成群中的金屬較佳。作為過渡金屬以外之金屬(M1),舉例有如Si、Al、In、Sn、Zn等。且,第1形態中,第1氣體障壁層中,除了金屬(M1)的氧化物以外,亦可包含該金屬(M1)的氮化物、碳化物(亦即,亦可為氮氧化物或碳氧化物之形態)。其中,M1包含Si、Sn或Zn較佳,包含Si再較佳,單獨地為Si特別佳。且,第1形態中,M1包含Si時,第1氣體障壁層包含Si之氧化物以及/或Si之氮化物作為主成分較佳。且,「第1氣體障壁層包含Si之氧化物以及/或Si之氮化物作為主成分」意指第1氣體障壁層中Si之氧化物以及/或Si之氮化物的量(包含雙方時為其合計量)為50質量%以上,此值較 佳為80質量%以上再較佳,為95質量%以上更較佳,為98質量%以上特別佳,為100質量%最佳。且,關於構成第1形態相關之氣體障壁性薄膜的第1氣體障壁層中的過渡金屬之含量並無特限制,但在不損及另外設置後述過渡金屬氧化物含有層所帶來的意義之觀點來看,相對於構成第1形態相關之氣體障壁性薄膜的第1氣體障壁層中所包含的金屬元素全體,為未滿2原子%較佳。 The metal (M1) other than the transition metal is not particularly limited, and any metal or combination of the transition metals can be used. The metal (M1) other than the transition metal includes Group 12 selected from the long-period periodic table ~ Metals in the group consisting of metals of group 14 are preferred. Examples of the metal (M1) other than the transition metal include Si, Al, In, Sn, Zn, and the like. Furthermore, in the first aspect, the first gas barrier layer may include, in addition to the oxide of the metal (M1), nitrides and carbides of the metal (M1) (that is, oxynitride or carbon) Oxide form). Among them, M1 preferably includes Si, Sn, or Zn, and even more preferably Si, and particularly preferably Si alone. In addition, in the first aspect, when M1 contains Si, it is preferable that the first gas barrier layer contains an oxide of Si and / or a nitride of Si as a main component. In addition, "the first gas barrier layer contains an oxide of Si and / or a nitride of Si as a main component" means the amount of the oxide of Si and / or nitride of Si in the first gas barrier layer (when both sides are included) (The total amount) is 50% by mass or more, and this value is more than It is more preferably 80% by mass or more, more preferably 95% by mass or more, particularly preferably 98% by mass or more, and most preferably 100% by mass. In addition, there is no particular limitation on the content of the transition metal in the first gas barrier layer constituting the gas barrier film according to the first aspect, but the meaning of the transition metal oxide-containing layer provided later will not be impaired From a viewpoint, it is preferable that it is less than 2 atomic% with respect to the whole metal element contained in the 1st gas barrier layer which comprises the gas barrier film of 1st aspect.
第1氣體障壁層之膜厚並無特別限制,為5~1000nm較佳。若在此範圍,則有較高的氣體障壁性能、耐折彎性、切斷加工適性也較優異。且,第1氣體障壁層亦可由鄰接之2層以上來構成。 The film thickness of the first gas barrier layer is not particularly limited, but it is preferably 5 to 1000 nm. If it is in this range, it has high gas barrier performance, bending resistance, and excellent cutting processability. The first gas barrier layer may be composed of two or more adjacent layers.
第1形態中,作為用來形成第1氣體障壁層之方法,並無特別限定,例如能夠使用利用既存之薄膜堆積技術之以往公知的氣相製膜法。作為一例,能夠使用以往公知的蒸鍍法、反應性蒸鍍法、濺鍍法、反應性濺鍍法、化學氣相成長法(Chemical Vapor Deposition、CVD法)等之氣相製膜法。此等之氣相製膜法能夠以公知方法來使用。 In the first aspect, the method for forming the first gas barrier layer is not particularly limited, and for example, a conventionally known vapor-phase film-forming method using an existing film deposition technique can be used. As an example, a conventionally known vapor deposition method such as a vapor deposition method, a reactive vapor deposition method, a sputtering method, a reactive sputtering method, a chemical vapor deposition method (Chemical Vapor Deposition, CVD method), or the like can be used. These vapor-phase film-forming methods can be used by a well-known method.
於此,例如,CVD法,其係將包含作為目的之薄膜的成分的原料氣體供給於基材上,藉由於基材表面或氣相之化學反應來堆積膜之方法。且,以活化化學反應之目的,有使電漿等產生之方法等,可舉出熱CVD法、觸媒化學氣相成長法、光CVD法、將電漿作為激發源之電漿CVD法(PECVD法)的真空電漿CVD法、大氣壓電漿CVD法等公知的CVD方式等。尤其是PECVD法為較佳之方 法。以下,針對此手法作詳細地說明。 Here, for example, the CVD method is a method in which a raw material gas including a component of a target thin film is supplied to a substrate, and a film is deposited by a chemical reaction on the surface of the substrate or a gas phase. In addition, for the purpose of activating chemical reactions, there are methods for generating plasma, etc., and examples include thermal CVD method, catalytic chemical vapor growth method, photo CVD method, and plasma CVD method using plasma as an excitation source ( PECVD method) a well-known CVD method such as a vacuum plasma CVD method, an atmospheric piezoelectric plasma CVD method, and the like. Especially PECVD method is the better method law. This method will be described in detail below.
真空電漿CVD法係使材料氣體流入搭載電漿源之真空容器中,藉由自電源將電力供給於電漿源,在真空容器內使放電電漿產生,並以電漿使材料氣體進行分解反應,使所生成之反應種堆積於基材之方法。由真空電漿CVD法所得之氣相成膜障壁層能夠藉由選擇原材料之金屬化合物、分解氣體、分解溫度、投入電力等條件,來製造目的之化合物,故較佳被使用。 The vacuum plasma CVD method allows a material gas to flow into a vacuum container equipped with a plasma source, and supplies electric power to the plasma source from a power source to generate a discharge plasma in the vacuum container and decompose the material gas with the plasma. A method for reacting and accumulating the generated reactive species on a substrate. The vapor-phase film-forming barrier layer obtained by the vacuum plasma CVD method can be used for manufacturing a desired compound by selecting conditions such as a metal compound of a raw material, a decomposition gas, a decomposition temperature, and an input of electric power.
作為原材料之化合物,使用矽化合物、鋁化合物等包含過渡金屬以外之金屬(M1)的化合物較佳。此等原材料之化合物亦可單獨或組合2種以上來使用。 As the compound of the raw material, a compound containing a metal (M1) other than a transition metal such as a silicon compound or an aluminum compound is preferably used. The compounds of these raw materials may be used alone or in combination of two or more.
作為此等之矽化合物、鋁化合物,能夠使用以往公知之化合物。例如,作為公知之化合物能夠舉出日本特開2013-063658號公報之段落「0028」~「0031」、日本特開2013-047002號公報之段落「0078」~「0081」等所記載之化合物。較佳有舉出矽烷、四甲氧矽烷、四乙氧矽烷、六甲基二矽氧烷等。 As these silicon compounds and aluminum compounds, conventionally known compounds can be used. For example, known compounds include compounds described in paragraphs "0028" to "0031" of Japanese Patent Application Laid-Open No. 2013-063658, and paragraphs "0078" to "0081" of Japanese Patent Laid-Open No. 2013-047002. Preferable examples include silane, tetramethoxysilane, tetraethoxysilane, and hexamethyldisiloxane.
且,作為用來將包含此等之金屬的原料氣體分解並得到氧化物等之無機物的分解氣體,有舉出氫氣、甲烷氣體、乙炔氣體、一氧化碳氣體、二氧化碳氣體、氮氣、氨氣體、一氧化二氮氣體、氧化氮氣體、二氧化氮氣體、氧氣、水蒸氣等。且,亦可將上述分解氣體與氬氣體、氦氣 體等之惰性氣體混合。藉由適當地選擇包含原材料之化合物的原料氣體與分解氣體,能夠得到所期望之氣相成膜障壁層。以下,針對較適當形態之真空電漿CVD法,具體地說明。 In addition, examples of the decomposition gas used to decompose a raw material gas containing these metals and obtain an inorganic substance such as an oxide include hydrogen, methane, acetylene, carbon monoxide, carbon dioxide, nitrogen, ammonia, and monoxide. Dinitrogen gas, nitrogen oxide gas, nitrogen dioxide gas, oxygen, water vapor, etc. In addition, the above-mentioned decomposition gas may be combined with argon gas and helium gas. Mixed with inert gas. By appropriately selecting a raw material gas and a decomposition gas containing a compound of a raw material, a desired vapor-phase film-forming barrier layer can be obtained. Hereinafter, a more suitable form of the vacuum plasma CVD method will be specifically described.
圖3為表示真空電漿CVD裝置之一例的示意圖。圖3中,真空電漿CVD裝置101具有真空槽102,在真空槽102之內部的底面側配置有承受器105。且,真空槽102之內部的天頂側,在與承受器105對向之位置上配置有陰極電極103。真空槽102之外部配置有熱媒循環系統106、與真空排氣系統107、與氣體導入系統108、與高頻電源109。熱媒循環系統106內配置有熱媒體。熱媒循環系統106有設置加熱冷卻裝置160,該加熱冷卻裝置160具有使熱媒體移動之泵浦、與加熱熱媒體之加熱裝置、與冷卻之冷卻裝置、與測定熱媒體之溫度的溫度感應器、與記憶熱媒體之設定溫度的記憶裝置。加熱冷卻裝置160之構成為:測定熱媒體之溫度,加熱或冷卻熱媒體至記憶之設定溫度為止,並供給於承受器105。圖3記載之裝置的詳細能夠參照國際公開第2012/090644號之段落「0080」~「0098」等。 FIG. 3 is a schematic diagram showing an example of a vacuum plasma CVD apparatus. In FIG. 3, the vacuum plasma CVD apparatus 101 includes a vacuum tank 102, and a receiver 105 is disposed on the bottom surface side inside the vacuum tank 102. A cathode electrode 103 is disposed on the zenith side inside the vacuum chamber 102 at a position facing the receiver 105. A heat medium circulation system 106, a vacuum exhaust system 107, a gas introduction system 108, and a high-frequency power source 109 are arranged outside the vacuum tank 102. A heat medium is arranged in the heat medium circulation system 106. The heating medium circulation system 106 is provided with a heating and cooling device 160 having a pump for moving the heating medium, a heating device for heating the heating medium, a cooling device for cooling, and a temperature sensor for measuring the temperature of the heating medium. , And a memory device that stores the set temperature of the thermal medium. The heating and cooling device 160 is configured to measure the temperature of the heat medium, and heat or cool the heat medium to a set temperature in memory, and supply the heat medium to the receiver 105. The details of the device shown in FIG. 3 can be referred to paragraphs "0080" to "0098" of International Publication No. 2012/090644.
過渡金屬氧化物含有層13是本發明之第1形態中必須設置的層,必須含有過渡金屬(M2)之氧化物,且,實質上不含有過渡金屬以外之金屬(M1)的層(惟,除了混合區 域)。過渡金屬氧化物含有層在與上述第1氣體障壁層接觸而形成時,在兩者界面上,會形成第1氣體障壁層所含有之金屬(M1)與過渡金屬(M2)之複合氧化物。此時認為,藉由將氧或氮的比率設在本發明之範圍內,會形成金屬(M1)與過渡金屬(M2)直接鍵結之縝密的構造,藉此提升障壁性。且,在第1形態中,也將如上述之複合氧化物所形成之區域稱作「混合區域」。 The transition metal oxide-containing layer 13 is a layer which must be provided in the first aspect of the present invention. The transition metal oxide-containing layer 13 must contain an oxide of a transition metal (M2), and a layer substantially free of a metal (M1) other than a transition metal (but Except mixed zone area). When the transition metal oxide-containing layer is formed in contact with the first gas barrier layer, a composite oxide of the metal (M1) and the transition metal (M2) contained in the first gas barrier layer is formed at the interface between the two. At this time, it is considered that by setting the ratio of oxygen or nitrogen within the scope of the present invention, a dense structure in which the metal (M1) and the transition metal (M2) are directly bonded is formed, thereby improving barrier properties. Further, in the first aspect, a region formed by the composite oxide as described above is also referred to as a "mixed region".
作為過渡金屬(M2)並無特別限制,能夠單獨使用任意過渡金屬或組合來使用。於此,過渡金屬意指長周期型周期表之自第3族元素至第11族元素,作為過渡金屬,有舉出Sc、Ti、V、Cr、Mn、Fe、Co、Ni、Cu、Zn、Y、Zr、Nb、Mo、Tc、Ru、Pd、Ag、La、Ce、Pr、Nd、Pm、Sm、Eu、Gd、Tb、Dy、Ho、Er、Tm、Yb、Lu、Hf、Ta、W、Re、Os、Ir、Pt、以及Au等。 The transition metal (M2) is not particularly limited, and any transition metal can be used alone or in combination. Here, the transition metal means a long-period periodic table from Group 3 elements to Group 11 elements. Examples of transition metals include Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, and Zn. , Y, Zr, Nb, Mo, Tc, Ru, Pd, Ag, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Hf, Ta , W, Re, Os, Ir, Pt, and Au.
其中,作為能得到良好障壁性之過渡金屬(M2),有舉出Nb、Ta、V、Zr、Ti、Hf、Y、La、Ce等。此等之中,以各種探討結果來看,認為尤其是第5族元素之Nb、Ta、V對第1氣體障壁層中所含有的金屬(M1)之鍵結較容易產生,故能夠較佳地使用。若過渡金屬(M2)為第5族元素(尤其是Nb),且上述金屬(M1)為Si,則能得到顯著的氣體障壁性之提升效果。認為這是因為Si與第5族元素(尤其是Nb)之鍵結特別容易產生。進而,以光學特性之觀點來看,過渡金屬(M2)以能得到透明性良好之化合物的Nb、Ta特別佳。 Among them, examples of transition metals (M2) capable of obtaining good barrier properties include Nb, Ta, V, Zr, Ti, Hf, Y, La, and Ce. Among these, from the results of various investigations, it is considered that the bonding of the metal (M1) contained in the first gas barrier layer, especially Nb, Ta, and V of the Group 5 element, is more likely to occur, so it can be better. To use. If the transition metal (M2) is a Group 5 element (especially Nb) and the above-mentioned metal (M1) is Si, a significant effect of improving gas barrier properties can be obtained. This is considered to be because the bond between Si and a Group 5 element (especially Nb) is particularly easy to occur. Furthermore, from the viewpoint of optical characteristics, transition metals (M2) are particularly preferably Nb and Ta that can obtain compounds with good transparency.
且,過渡金屬氧化物含有層除了過渡金屬(M2)之氧化物以外,亦可包含該過渡金屬(M2)之氮化物(亦即,亦可為氮氧化物之形態)。 In addition, the transition metal oxide-containing layer may include a nitride of the transition metal (M2) in addition to the oxide of the transition metal (M2) (that is, it may also be in the form of an oxynitride).
過渡金屬氧化物含有層中過渡金屬氧化物的含量,只要是會達到本發明之效果,並無特別限定,但過渡金屬氧化物之含量相對於過渡金屬氧化物含有層之全質量,為50質量%以上較佳,為80質量%以上再較佳,為95質量%以上更較佳,為98質量%以上特別佳,為100質量%(亦即,過渡金屬氧化物含有層是由過渡金屬氧化物而成)最佳。且,關於過渡金屬氧化物含有層中的過渡金屬以外之金屬的含量並無特別限制,但以不損及另外設置上述第1氣體障壁層所帶來的意義之觀點來看,相對於過渡金屬氧化物含有層中所含有的金屬元素之全體,為未滿2原子%較佳。 The content of the transition metal oxide in the transition metal oxide-containing layer is not particularly limited as long as it can achieve the effects of the present invention, but the content of the transition metal oxide is 50 masses relative to the total mass of the transition metal oxide-containing layer. It is preferably at least 80% by mass, more preferably at least 80% by mass, more preferably at least 95% by mass, particularly preferably at least 98% by mass, and 100% by mass (that is, the transition metal oxide-containing layer is oxidized by the transition metal From the best). In addition, the content of metals other than transition metals in the transition metal oxide-containing layer is not particularly limited, but from the viewpoint of not impairing the significance of providing the above-mentioned first gas barrier layer, compared to transition metals The total amount of metal elements contained in the oxide-containing layer is preferably less than 2 atomic%.
過渡金屬氧化物含有層以容易調整金屬元素與氧的組成比之觀點來看,由氣相成膜法所形成較佳。作為氣相成膜法,並無特別限制,舉例有如濺鍍法、蒸鍍法、離子電鍍法、離子輔助蒸鍍法等之物理氣相成長(PVD)法、電漿CVD(chemical vapordeposition)法、ALD(Atomic Layer Deposition)法等之化學氣相成長(CVD)法。其中,以能夠在不會對下層造成傷害之下來製膜,並具有較高的生產性來看,由物理氣相成長(PVD)法來形成較佳,由濺鍍法來形成再較佳。 The transition metal oxide-containing layer is preferably formed by a vapor-phase film formation method from the viewpoint that the composition ratio of the metal element and oxygen can be easily adjusted. The vapor-phase film formation method is not particularly limited, and examples thereof include a physical vapor phase growth (PVD) method such as a sputtering method, a vapor deposition method, an ion plating method, and an ion-assisted vapor deposition method, and a plasma CVD (chemical vapordeposition) method. And CVD (Atomic Layer Deposition) methods. Among them, in terms of being able to form a film without causing damage to the lower layer and having high productivity, it is better to form it by a physical vapor phase growth (PVD) method, and it is more preferable to form it by a sputtering method.
由濺鍍法之製膜,能夠單獨使用2極濺鍍、磁控濺 鍍、使用中間的頻率域之對偶磁控(DMS)濺鍍、離子束濺鍍、ECR濺鍍等或組合2種以上來使用。且,標靶之施加方式亦可因應標靶種類來作適當的選擇,使用DC(直流)濺鍍、以及RF(高頻)濺鍍之任一者。且,亦可使用一種反應性濺鍍法,其係利用金屬相與氧化物相之中間的過渡相。藉由控制濺鍍現象使其成為過渡區域,能夠以較高的製膜速度來將金屬氧化物製膜,故較佳。進行DC濺鍍或DMS濺鍍時,藉由於標靶中使用過渡金屬,且進而將氧導入處理氣體中,能夠形成過渡金屬氧化物之薄膜。且,以RF(高頻)濺鍍來製膜時,能夠使用過渡金屬的氧化物之標靶。作為處理氣體所使用之惰性氣體,能夠使用He、Ne、Ar、Kr、Xe等,使用Ar較佳。進而,藉由將氧、氮、二氧化碳、一氧化碳導入處理氣體中,能夠製作過渡金屬的氧化物、氮氧化物、碳氧化物等之過渡金屬化合物薄膜。作為濺鍍法中之製膜條件,有舉出施加電力、放電電流、放電電壓、時間等,但此等能夠因應濺鍍裝置、或膜之材料、膜厚等來進行適當地選擇。 Film formation by sputtering method, can use 2 pole sputtering, magnetron sputtering alone Plating, dual magnetron (DMS) sputtering in the middle frequency range, ion beam sputtering, ECR sputtering, or a combination of two or more of them is used. In addition, the target application method can be appropriately selected according to the type of target, and either DC (direct current) sputtering or RF (high frequency) sputtering is used. Also, a reactive sputtering method may be used, which uses a transition phase between a metal phase and an oxide phase. By controlling the sputtering phenomenon to make it a transition region, a metal oxide can be formed at a higher film forming speed, which is preferable. When performing DC sputtering or DMS sputtering, a thin film of a transition metal oxide can be formed by using a transition metal in the target and further introducing oxygen into the processing gas. When forming a film by RF (high frequency) sputtering, a target of an oxide of a transition metal can be used. As the inert gas used for the processing gas, He, Ne, Ar, Kr, Xe, etc. can be used, and Ar is preferably used. Furthermore, by introducing oxygen, nitrogen, carbon dioxide, and carbon monoxide into the processing gas, a thin film of a transition metal compound such as a transition metal oxide, a nitrogen oxide, or a carbon oxide can be produced. Examples of film forming conditions in the sputtering method include application of electric power, discharge current, discharge voltage, time, and the like, but these can be appropriately selected depending on the sputtering apparatus, the material of the film, the film thickness, and the like.
其中,以製膜速率更高,且具有更高的生產性來看,以使用過渡金屬之氧化物作為標靶之濺鍍法較佳。 Among them, a sputtering method using an oxide of a transition metal as a target is preferable in view of a higher film formation rate and higher productivity.
過渡金屬氧化物含有層亦可為單層亦可為2層以上之層合構造。過渡金屬氧化物含有層為2層以上之層合構造時,過渡金屬氧化物含有層中所包含之過渡金屬氧化物亦可為相同者亦可為相異者。 The transition metal oxide-containing layer may be a single layer or a laminated structure of two or more layers. When the transition metal oxide-containing layer has a laminated structure of two or more layers, the transition metal oxides contained in the transition metal oxide-containing layer may be the same or different.
由於認為過渡金屬氧化物含有層是具有抑制第1氣體 障壁層之氧化且維持氣體障壁性之機能之層,故並非一定要有氣體障壁性。因此,過渡金屬氧化物含有層即使是比較薄的層也能夠發揮效果。具體來說,過渡金屬氧化物含有層之厚度(2層以上之層合構造時係其總厚度)以氣體障壁性的面內均一性之觀點來看,為1~200nm較佳,為2~100nm再較佳,為3~50nm更較佳。尤其是若在50nm以下,則過渡金屬氧化物含有層之製膜的生產性會更加提升。 Since the transition metal oxide-containing layer is considered to have a suppression of the first gas The barrier layer is oxidized and maintains the function of gas barrier properties, so it is not necessary to have gas barrier properties. Therefore, the transition metal oxide-containing layer is effective even if it is a relatively thin layer. Specifically, the thickness of the transition metal oxide-containing layer (the total thickness in the case of a laminated structure of two or more layers) is preferably 1 to 200 nm from the viewpoint of in-plane uniformity of gas barrier properties, and is 2 to 200 nm. 100 nm is more preferable, and 3 to 50 nm is more preferable. Especially if it is 50 nm or less, the productivity of film formation of a transition metal oxide containing layer will be further improved.
具有上述基本構成之本發明之第1形態相關之氣體障壁性薄膜之特徵為滿足下述(1)、(2)或(3)之至少任一者:(1)前述第1氣體障壁層中,將前述過渡金屬以外之金屬(M1)的最大價數設為a、氧設為O,氮設為N,碳設為C,前述金屬(M1)之氧化物的組成設為(M1)OuNvCw時,在前述氣體障壁層之厚度方向的至少一部分,存在滿足下述數式之區域,u>0,且,v≧0,且,w≧0,且,(2u+3v+2w)/a<0.85;(2)前述過渡金屬氧化物含有層中,將前述過渡金屬(M2)之最大價數設為b,氧設為O,氮設為N,前述過渡金屬之氧化物的組成設為(M2)OxNy時,前述過渡金屬氧化物層之厚度方向的至少一部分,存在滿足下述數式之區域, x>0,且,y≧0,且,(2x+3y)/b<0.85;(3)將前述第1氣體障壁層以及前述過渡金屬氧化物含有層中分別含有的前述氧化物分別以前述(1)以及前述(2)所示之組成來表示時,在前述第1氣體障壁層之厚度方向的至少一部分、以及前述過渡金屬氧化物含有層之厚度方向的至少一部分,存在滿足下述數式之區域的組合,(2u+3v+2w)/a+(2x+3y)/b<1.85。 The gas barrier film according to the first aspect of the present invention having the above-mentioned basic structure is characterized in that it satisfies at least any one of the following (1), (2), or (3): (1) the first gas barrier layer Let the maximum valence of a metal (M1) other than the transition metal be a, oxygen be O, nitrogen be N, carbon be C, and the composition of the oxide of the metal (M1) be (M1) O When u N v C w , at least a part of the thickness direction of the gas barrier layer has a region satisfying the following formula, u> 0, and v ≧ 0, and w ≧ 0, and (2u + 3v + 2w) / a <0.85; (2) In the transition metal oxide containing layer, set the maximum valence of the transition metal (M2) to b, oxygen to O, nitrogen to N, and oxidation of the transition metal. When the composition of the material is (M2) O x N y , at least a part of the thickness direction of the transition metal oxide layer has a region satisfying the following formula, x> 0, and y ≧ 0, and (2x + 3y) / b <0.85; (3) the oxides contained in the first gas barrier layer and the transition metal oxide-containing layer are represented by the compositions shown in the above (1) and (2), respectively At The combination of the at least a part of the thickness direction of the first gas barrier layer and the at least a part of the thickness direction of the transition metal oxide containing layer satisfies the following formula: (2u + 3v + 2w) / a + (2x + 3y) / b <1.85.
本發明之第1形態相關之氣體障壁性薄膜的特徵之(1)~(3)皆在下述點共有相同技術特徵:在第1氣體障壁層以及/或過渡金屬氧化物含有層中,至少一部分包含特定程度以上的缺氧組成。 (1) to (3) of the characteristics of the gas barrier film according to the first aspect of the present invention share the same technical characteristics in the following points: At least a part of the first gas barrier layer and / or the transition metal oxide-containing layer Contains a certain level of hypoxia composition.
於此,若配置第1氣體障壁層以及過渡金屬氧化物含有層使滿足上述(1)~(3)中至少任一者(亦即,使此等之層的至少一部分存在特定程度以上之缺氧損組成),則金屬(M1)與過渡金屬(M2)會同時存在,且,如後述,會形成推測會存在金屬(M1)與過渡金屬(M2)之直接鍵結的區域(亦即,混合區域)。此混合區域之組成是以(M1)(M2)pOqNrCs所示。於此,將金屬(M1)之最大價數設為a,過渡金屬(M2)之最大價數設為b,O之價數設為2,N之價數設為3,C之價數原本是4,但是在本發明中所形成之上述層當中,認為C是如-CH2-般地以包含氫原子之狀態來鍵結,故C之價數是設為2。且,混合區域成為化學計量的組成時,會成為(2q+3r+2s)/(a+bp)=1.0。此式意指金屬(M1)以及過渡金屬(M2)之鍵結的合計、與O、N、C之鍵結的合 計為相同數,此時,金屬(M1)以及過渡金屬(M2)會一起與O、N、C之任一者鍵結。且,本發明中,作為金屬(M1)併用2種以上時,或作為過渡金屬(M2)併用2種以上時,將各元素之最大價數以各元素之存在比率來加重平均,並採用由此算出的複合價數作為「最大價數」之a以及b之值(參照後述之氣體障壁性薄膜3-16之製作欄)。 Here, if the first gas barrier layer and the transition metal oxide-containing layer are disposed so as to satisfy at least any one of the above (1) to (3) (that is, at least a part of these layers is defective to a certain degree or more). Oxygen loss composition), the metal (M1) and the transition metal (M2) will coexist, and, as will be described later, a region where a direct bond between the metal (M1) and the transition metal (M2) is supposed to exist (i.e., Mixed area). The composition of this mixed region is represented by (M1) (M2) p O q N r C s . Here, the maximum valence of the metal (M1) is set to a, the maximum valence of the transition metal (M2) is set to b, the valence of O is set to 2, the valence of N is set to 3, and the valence of C was originally It is 4, but among the above-mentioned layers formed in the present invention, C is considered to be bonded in a state including a hydrogen atom like -CH 2- , so the valence of C is set to 2. When the mixed region has a stoichiometric composition, it becomes (2q + 3r + 2s) / (a + bp) = 1.0. This formula means that the total of the bonds of the metal (M1) and the transition metal (M2) and the total of the bonds of O, N, and C are the same number. At this time, the metal (M1) and the transition metal (M2) will be together. It is bonded to any one of O, N, and C. Moreover, in the present invention, when two or more kinds are used as the metal (M1) or two or more kinds are used as the transition metal (M2), the maximum valence of each element is weighted and averaged by the existence ratio of each element. The calculated compound valence is taken as the value of a and b of the "maximum valence" (refer to the production columns of the gas barrier film 3-16 described later).
另一方面,成為(2q+3r+2s)/(a+bp)<1.0時,意指相對於金屬(M1)以及過渡金屬(M2)之鍵結的合計,O、N、C之鍵結的合計不足,此狀態為混合區域之「缺氧」。在缺氧狀態中,有金屬(M1)以及過渡金屬(M2)之多餘的鍵結會互相鍵結之可能性,若金屬(M1)或過渡金屬(M2)之金屬彼此直接鍵結,則相較於金屬之間介隔著O或N或C來鍵結的情況,會形成更緻密且高密度之構造,作為其結果,認為氣體障壁性會提升。 On the other hand, when (2q + 3r + 2s) / (a + bp) <1.0, it means that O, N, and C are bonded to the total of the bonds of the metal (M1) and the transition metal (M2). The total is insufficient, this state is "hypoxia" in the mixed area. In the hypoxic state, there is a possibility that the extra bonding of the metal (M1) and the transition metal (M2) will be bonded to each other. If the metals of the metal (M1) or the transition metal (M2) are directly bonded to each other, the phase will be Compared with the case where metals are bonded via O, N, or C, a denser and higher-density structure is formed. As a result, gas barrier properties are considered to be improved.
以上是說明,第1氣體障壁層以及過渡金屬氧化物含有層具有特定之缺氧組成時,混合區域也成為缺氧狀態,這能夠造成氣體障壁性之提升。於此,本發明者進一步探討後得知,本發明之第1形態型態相關之具有層構成之氣體障壁性薄膜中,並不須規定第1氣體障壁層以及過渡金屬氧化物含有層具有特定的缺氧組成(亦即,滿足上述(1)~(3)中至少任一者),即能夠特定氣體障壁性提升之構成。以這樣的觀點來看,經規定後的本發明之第1形態之其他實施形態相關之氣體障壁性薄膜具有上述之基本構成,且,在第1氣體障壁層與過渡金屬氧化物含有層之層 合體為滿足下述(4)具有特徵:(4)具有前述金屬(M1)與前述過渡金屬(M2)同時存在之混合區域,將前述(M1)之最大價數設為a,前述(M2)之最大價數設為b,氧設為O,氮設為N,碳設為C,前述混合區域之組成設為(M1)(M2)pOqNrCs時,在前述混合區域之厚度方向的至少一部分,具有滿足下述數式之區域:0.02≦p≦98,且,q>0,且,r≧0,且,s≧0,且,(2q+3r+2s)/(a+bp)<0.85。 The above description is that when the first gas barrier layer and the transition metal oxide-containing layer have a specific oxygen-depleted composition, the mixed region also becomes an oxygen-deficient state, which can improve the gas barrier properties. Here, the inventors have further studied and found that, in the gas barrier film having a layer structure related to the first aspect of the present invention, it is not necessary to specify that the first gas barrier layer and the transition metal oxide-containing layer have specific characteristics. An anoxic composition (that is, satisfying at least any one of (1) to (3) above) is a composition capable of improving the gas barrier property. From such a point of view, the gas barrier film according to another aspect of the first aspect of the present invention that has been defined has the basic structure described above, and the first gas barrier layer and the transition metal oxide-containing layer are layers. The combination has the following characteristics (4): (4) It has a mixed region in which the aforementioned metal (M1) and the aforementioned transition metal (M2) coexist, and the maximum valence of the aforementioned (M1) is set to a, and the aforementioned (M2) When the maximum valence is set to b, oxygen is set to O, nitrogen is set to N, carbon is set to C, and when the composition of the aforementioned mixed region is set to (M1) (M2) p O q N r C s , At least a part of the thickness direction has a region satisfying the following formula: 0.02 ≦ p ≦ 98, and q> 0, r ≧ 0, and s ≧ 0, and (2q + 3r + 2s) / ( a + bp) <0.85.
並認為混合區域中,若滿足0.02≦p≦98,則金屬(M1)以及過渡金屬(M2)雙方會與金屬彼此的直接鍵結有關係,並且對氣體障壁性之提升帶來貢獻。於此,p較佳為0.05≦p≦95,再較佳為0.10≦p≦90,更較佳為0.20≦p≦80。如此,本發明之第1形態相關之(4)亦在下述之點與上述(1)~(3)共有相同的技術特徵:表示金屬(M1)以及/或過渡金屬(M2)共存之區域中,至少一部分包含特定程度以上之缺氧組成。 It is considered that in the mixed region, if 0.02 ≦ p ≦ 98 is satisfied, both the metal (M1) and the transition metal (M2) will have a direct bond with the metal, and will contribute to the improvement of gas barrier properties. Here, p is preferably 0.05 ≦ p ≦ 95, more preferably 0.10 ≦ p ≦ 90, and still more preferably 0.20 ≦ p ≦ 80. In this way, (4) related to the first aspect of the present invention also shares the same technical characteristics as the above (1) to (3) in the following points: it indicates that the metal (M1) and / or the transition metal (M2) coexist in the region At least part of it contains a certain degree of anoxic composition.
且,如上述,若存在滿足(2q+3r+2s)/(a+bp)<0.85之混合區域,則能夠確認氣體障壁性之提升效果會發揮,但較佳為(2q+3r+2s)/(a+bp)<0.80,再較佳為(2q+3r+2s)/(a+bp)<0.70,更較佳為(2q+3r+2s)/(a+bp)<0.65。另一方面,以透明性等之光學特性之觀點來看,較佳為(2q+3r+2s)/(a+bp)>0.40,再較佳為(2q+3r+2s)/(a+bp)>0.50。 And, as described above, if there is a mixed region satisfying (2q + 3r + 2s) / (a + bp) <0.85, it can be confirmed that the improvement effect of the gas barrier property will be exerted, but (2q + 3r + 2s) is preferred /(a+bp)<0.80, more preferably (2q + 3r + 2s) / (a + bp) <0.70, more preferably (2q + 3r + 2s) / (a + bp) <0.65. On the other hand, from the viewpoint of optical characteristics such as transparency, it is preferably (2q + 3r + 2s) / (a + bp)> 0.40, and more preferably (2q + 3r + 2s) / (a + bp)> 0.50.
且,本發明中,能夠得到良好氣體障壁性之具有滿足上述(4)記載的關係之組成的混合區域之厚度,只要是能 夠由後述XPS分析所檢測出之厚度即可,並無特別限制,但具體來說,作為SiO2換算之濺鍍厚度,較佳為1nm以上,再較佳為2nm以上,更較佳為4nm以上。且,以透明性等之光學特性之觀點來看,第1氣體障壁層與過渡金屬氧化物含有層之層合體滿足上述(4)時,該層合體所具有的p>98之區域的厚度較佳為5nm以下。 In addition, in the present invention, the thickness of the mixed region having a composition that satisfies the relationship described in (4) above, which has good gas barrier properties, is not particularly limited as long as the thickness can be detected by the XPS analysis described later. However, specifically, the sputtering thickness in terms of SiO 2 is preferably 1 nm or more, more preferably 2 nm or more, and even more preferably 4 nm or more. From the viewpoint of optical characteristics such as transparency, when the laminate of the first gas barrier layer and the transition metal oxide-containing layer satisfies the above (4), the thickness of the region of p> 98 of the laminate is smaller than It is preferably 5 nm or less.
具有如上述構成之氣體障壁性薄膜會顯示非常高的氣體障壁性,其係能夠作為有機EL裝置等之電子裝置用的基板之程度。 The gas barrier film having the above-mentioned structure exhibits a very high gas barrier property, and it is such that it can be used as a substrate for an electronic device such as an organic EL device.
於此,本發明者進行各種探討之結果,若單獨使用過渡金屬以外之金屬(M1)的化合物(氧化物)之缺氧組成膜來形成氣體障壁層、或是單獨使用過渡金屬(M2)的化合物(氧化物)之缺氧組成膜來形成氣體障壁層,則隨著缺氧程度變大,雖然會觀察到氣體障壁性提升之傾向,但尚未關係到顯著的氣體障壁性之提升。相對於此判明,如上述本發明之第1形態相關之構成,層合包含將過渡金屬以外之金屬(M1)作為主要成分之化合物(氧化物)的層、與包含將過渡金屬(M2)作為主要成分之化合物(氧化物)的層,形成過渡金屬以外之金屬(M1)與過渡金屬(M2)同時存在之混合區域,進一步將混合區域設為缺氧組成時,隨著缺氧程度變大,氣體障壁性會顯著地提升。這是推測起因於如上述所示,過渡金屬以外之金屬(M1)與過渡金屬(M2)之鍵結會比過渡金屬以外之金屬(M1)彼此之鍵結或過渡金屬(M2)彼此之鍵結更容易產生,而藉由設為本發明相關之構成,在 混合區域形成緻密且高密度之構造之故。 Here, as a result of various investigations made by the present inventors, if an oxygen-deficient composition film of a compound (oxide) of a metal (M1) other than a transition metal is used alone to form a gas barrier layer, or a transition metal (M2) is used alone Compounds (oxides) form an oxygen-deficient film to form a gas barrier layer. As the degree of oxygen deficiency increases, although a tendency to increase the gas barrier properties is observed, it has not been related to a significant improvement in gas barrier properties. On the other hand, it was found that, as in the configuration related to the first aspect of the present invention described above, a layer containing a compound (oxide) containing a metal (M1) other than a transition metal as a main component and a layer containing a transition metal (M2) as a main component were laminated. The layer of the compound (oxide) of the main component forms a mixed region where a metal other than the transition metal (M1) and a transition metal (M2) coexist. When the mixed region is further set to an anoxic composition, the degree of anoxic becomes larger , Gas barrier properties will be significantly improved. This is presumably due to the fact that the bond between a metal other than the transition metal (M1) and the transition metal (M2) is higher than that between the metal other than the transition metal (M1) or the bond between the transition metal (M2) as shown above. Knots are easier to produce, and by making the structure relevant to the present invention, The reason why the mixed region forms a dense and high-density structure.
為了製造本發明之第1形態相關之氣體障壁性薄膜,將第1氣體障壁層以及過渡金屬氧化物含有層以滿足上述(1)~(3)中至少任一者(進而存在如上述(4)所規定之缺氧狀態之混合區域)來形成時,只要適當地調節形成各層時的條件即可。 In order to manufacture the gas barrier film according to the first aspect of the present invention, the first gas barrier layer and the transition metal oxide-containing layer are formed so as to satisfy at least any one of (1) to (3) (and further exist as described in (4) above. ) To form a mixed region in a state of anoxic conditions), it is only necessary to appropriately adjust conditions for forming each layer.
例如,作為將第1氣體障壁層以滿足上述(1)來形成之方法,將第1氣體障壁層以氣相製膜法來製膜時,藉由調節選自由製膜原料中的金屬(M1)與氧之比率、製膜時的惰性氣體與反應性氣體之比率、製膜時的氣體之供給量、製膜時之真空度、以及製膜時之電力所構成群中的1種或2種以上之條件,能夠控制氧化度(將第1氣體障壁層中之金屬(M1)的氧化物組成設為(M1)OuNvCw時之u的值)。 For example, as a method for forming the first gas barrier layer to satisfy the above (1), when the first gas barrier layer is formed by a vapor-phase film formation method, the metal (M1 1 or 2 of the ratio of oxygen to oxygen, the ratio of inert gas to reactive gas during film formation, the amount of gas supplied during film formation, the degree of vacuum during film formation, and the power during film formation The above conditions can control the degree of oxidation (the oxide composition of the metal (M1) in the first gas barrier layer is set to the value of u when (M1) O u N v C w ).
同樣地,作為將過渡金屬氧化物含有層以滿足上述(2)來形成之方法,將過渡金屬氧化物含有層以氣相製膜法來製膜時,藉由調節選自由製膜原料中的過渡金屬(M2)與氧之比率、製膜時的惰性氣體與反應性氣體之比率、製膜時的氣體之供給量、製膜時之真空度、以及製膜時之電力所構成群中的1種或2種以上之條件,能夠控制氧化度(將過渡金屬氧化物含有層中之過渡金屬(M2)的氧化物組成設為(M2)OxNy時之x的值)。亦即,依據本發明之另外的其他形態,亦提供一種上述本發明之第1形態相關之氣體障壁性薄膜的製造方法。該製造方法係包含下述步驟:在上述基材與上述第1氣體障壁層之層合體之第1氣體障 壁層之與基材相反側的面上,藉由氣相製膜法來形成過渡金屬氧化物含有層。且其特徵為,在形成過渡金屬氧化物含有層之步驟中,調節選自由製膜原料中的前述過渡金屬(M2)與氧之比率、製膜時的惰性氣體與反應性氣體之比率、製膜時的氣體之供給量、製膜時之真空度、以及製膜時之電力所構成群中的1種或2種以上之條件,使其滿足上述(2)。且,藉由氣相製膜法將第1氣體障壁層以及過渡金屬氧化物含有層雙方製膜時,藉由調節上述各條件,能夠使其皆不滿足上述(1)以及(2),且使其滿足上述(3)來控制。 Similarly, as a method for forming a transition metal oxide-containing layer to satisfy the above (2), when a transition metal oxide-containing layer is formed by a vapor-phase film-forming method, the material selected from the film-forming raw materials is adjusted by adjustment. The ratio of transition metal (M2) to oxygen, the ratio of inert gas to reactive gas during film formation, the amount of gas supplied during film formation, the degree of vacuum during film formation, and the power at the time of film formation One or two or more conditions can control the degree of oxidation (the oxide composition of the transition metal (M2) in the transition metal oxide-containing layer is the value of x when (M2) O x N y ). That is, according to still another aspect of the present invention, there is also provided a method for producing a gas barrier film according to the first aspect of the present invention. This manufacturing method includes the steps of forming a transition metal by a vapor-phase film-forming method on a surface of the first gas barrier layer that is a laminate of the substrate and the first gas barrier layer on the side opposite to the substrate. The oxide contains a layer. In addition, in the step of forming the transition metal oxide-containing layer, the ratio is selected from the ratio of the aforementioned transition metal (M2) and oxygen in the film-forming raw material, the ratio of the inert gas and the reactive gas during film formation, and One or two or more of the conditions of the amount of gas supplied during the film formation, the degree of vacuum during the film formation, and the electric power during the film formation satisfy the above (2). In addition, when both the first gas barrier layer and the transition metal oxide-containing layer are formed by a vapor-phase film-forming method, by adjusting the above-mentioned conditions, neither of the above (1) and (2) can be satisfied, and It is controlled so that it satisfies the above (3).
在上述本發明之第1形態相關之氣體障壁性薄膜之製造方法中,在基材上依序形成第1形態中必需的層之第1氣體障壁層以及過渡金屬氧化物含有層時,亦可以分批式進行,但連續性地進行較佳。作為連續性地進行此等層之形成的方法,有舉出利用輥對輥方式之方法。藉由使用輥對輥方式連續性地來製膜,從一層形成後到下一層形成為止之間,不需要捲繞成卷,故生產性會提升,並能夠進一步防止捲繞成卷時對層表面之傷害發生等所起因之氣體障壁層等的惡化。亦即,上述本發明之第1形態相關之製造方法的較佳實施形態進一步包含下述步驟:在基材之至少一側之面上以輥對輥方式形成第1氣體障壁層之步驟、以及在第1氣體障壁層之與基材相反側的面上以輥對輥方式形成過渡金屬氧化物含有層之步驟,此時,形成第1氣體障壁層之步驟後,不需捲繞薄膜,即能進行形成 過渡金屬氧化物含有層之步驟。 In the method for producing a gas barrier film according to the first aspect of the present invention, the first gas barrier layer and the transition metal oxide-containing layer may be formed on the substrate in order to form the first gas barrier layer and the transition metal oxide-containing layer necessary for the first aspect. It is performed batchwise, but it is preferably performed continuously. As a method for continuously forming these layers, there is a method using a roll-to-roll method. By using the roll-to-roll method to continuously form a film, it is not necessary to roll into a roll from the formation of one layer to the formation of the next layer, so the productivity is improved, and it is possible to further prevent the layer from being wound when winding into a roll Deterioration of the gas barrier layer and the like caused by surface damage. That is, the above-mentioned preferred embodiment of the manufacturing method related to the first aspect of the present invention further includes the steps of forming a first gas barrier layer on a surface of at least one side of the substrate in a roll-to-roll manner, and The step of forming a transition metal oxide-containing layer on a surface of the first gas barrier layer on the side opposite to the substrate by a roll-to-roll method. At this time, after the step of forming the first gas barrier layer, it is not necessary to roll a film, that is, Can form Step of transition metal oxide containing layer.
且,上述本發明之第1形態相關之製造方法包含形成第2氣體障壁層(詳細如後述)之步驟時,連續性地進行該第2氣體障壁層之下層的過渡金屬氧化物含有層之形成、與該第2氣體障壁層之形成較佳。亦即,上述本發明之第1形態相關之製造方法較佳的實施形態為進一步包含:在第1氣體障壁層之與基材相反側的面上,以輥對輥方式來形成過渡金屬氧化物含有層之步驟、以及在過渡金屬氧化物含有層之與第1氣體障壁層相反側的面上,以輥對輥方式來形成含有金屬氧化物之第2氣體障壁層之步驟,且此時,在形成過渡金屬氧化物含有層之步驟之後,不需捲繞薄膜,即能進行形成第2氣體障壁層之步驟。 In addition, when the manufacturing method related to the first aspect of the present invention includes the step of forming a second gas barrier layer (described in detail later), the formation of a transition metal oxide-containing layer under the second gas barrier layer is continuously performed. And formation of the second gas barrier layer is preferred. That is, the preferred embodiment of the manufacturing method related to the first aspect of the present invention further includes: forming a transition metal oxide on a surface of the first gas barrier layer on the side opposite to the base material by a roll-to-roll method. A step of containing a layer, and a step of forming a second gas barrier layer containing a metal oxide on a surface of the transition metal oxide containing layer on the side opposite to the first gas barrier layer, and in this case, After the step of forming the transition metal oxide-containing layer, the step of forming the second gas barrier layer can be performed without winding the film.
進而,上述本發明之第1形態相關之製造方法包含上述形成第2氣體障壁層之步驟時,將第1氣體障壁層之形成、過渡金屬氧化物含有層之形成、第2氣體障壁層之形成全部以輥對輥方式來連續地進行,藉此能夠將氣體障壁性薄膜之生產性更提升一層。亦即,上述本發明之第1形態相關之製造方法之較佳的實施形態為進一步包含:在基材之至少一側之面上以輥對輥方式形成第1氣體障壁層之步驟、在第1氣體障壁層之與基材相反側的面上,以輥對輥方式形成過渡金屬氧化物含有層之步驟、以及在過渡金屬氧化物含有層之與第1氣體障壁層相反側的面上,以輥對輥方式形成含有金屬氧化物之第2氣體障壁層之步驟,且此時,在形成第1氣體障壁層之步驟之後,不需捲繞薄 膜,即能進行形成過渡金屬氧化物含有層之步驟,且,在形成過渡金屬氧化物含有層之步驟之後,不需捲繞薄膜,即能進行形成第2氣體障壁層之步驟。 Furthermore, when the manufacturing method related to the first aspect of the present invention includes the step of forming the second gas barrier layer, the first gas barrier layer is formed, the transition metal oxide-containing layer is formed, and the second gas barrier layer is formed. All are carried out continuously in a roll-to-roll manner, thereby improving the productivity of the gas barrier film. That is, a preferred embodiment of the manufacturing method related to the first aspect of the present invention described above further includes a step of forming a first gas barrier layer on a surface of at least one side of the substrate in a roll-to-roll manner, 1 a step of forming a transition metal oxide-containing layer on a surface of the gas barrier layer on the side opposite to the substrate, and a surface of the transition metal oxide-containing layer on the side opposite to the first gas barrier layer, The step of forming a second gas barrier layer containing a metal oxide in a roll-to-roll manner, and at this time, after the step of forming the first gas barrier layer, it is not necessary to roll thin The film can perform the step of forming the transition metal oxide-containing layer, and after the step of forming the transition metal oxide-containing layer, the step of forming the second gas barrier layer can be performed without winding the film.
且,在使用上述輥對輥方式之連續製膜中,關於連續製膜裝置之具體構成並無特別限制,能夠適當地參照以往公知之知識。例如,在連續製膜裝置中,鄰接的製膜裝置之環境亦可為大氣壓製膜→真空製膜,相反地亦可為真空製膜→大氣壓製膜。 Moreover, in the continuous film formation using the above-mentioned roll-to-roll method, the specific configuration of the continuous film formation device is not particularly limited, and conventionally known knowledge can be appropriately referred to. For example, in a continuous film forming apparatus, the environment of an adjacent film forming apparatus may be atmospheric pressing film → vacuum film forming, and conversely may be vacuum film forming → air pressing film.
例如,亦可將第1氣體障壁層之形成、過渡金屬氧化物含有層之形成、第2氣體障壁層之形成,進一步將過渡金屬氧化物含有層之形成、含有金屬氧化物之第3氣體障壁層之形成全部以輥對輥方式來連續地進行,進而亦可重複相同之層合構成之形成,並將全部以輥對輥方式來連續地進行。且,亦可將第1氣體障壁層之形成、過渡金屬氧化物含有層之形成、第2氣體障壁層之形成全部以輥對輥方式來連續地進行並捲繞後,將此卷出,在其上方進一步重複將第1氣體障壁層之形成、過渡金屬氧化物含有層之形成、第2氣體障壁層之形成全部以輥對輥方式來連續地進行並捲繞,成為多層層合構成。 For example, the formation of a first gas barrier layer, the formation of a transition metal oxide containing layer, the formation of a second gas barrier layer, and the formation of a transition metal oxide containing layer and a third gas barrier containing a metal oxide may be further formed. The layer formation is all performed continuously in a roll-to-roll manner, and the formation of the same layered structure can also be repeated, and all of the layer formation can be continuously performed in a roll-to-roll manner. In addition, the formation of the first gas barrier layer, the formation of the transition metal oxide-containing layer, and the formation of the second gas barrier layer may all be continuously performed in a roll-to-roll manner and wound, and then rolled out, and Above it, the formation of the first gas barrier layer, the formation of the transition metal oxide-containing layer, and the formation of the second gas barrier layer were all continuously carried out by a roll-to-roll method and wound up to form a multilayer laminate structure.
本發明之第2形態相關之氣體障壁性薄膜,具有基材、與配置於前述基材之至少一側的面之氣體障壁層作為其基本構成。第2形態相關之氣體障壁層在必須含有過渡 金屬以外之金屬(M1)以及過渡金屬(M2)這一點上,與上述第1形態之氣體障壁層相異。惟,為了說明方便,關於第2形態相關之氣體障壁性薄膜中的氣體障壁層,也稱作「第1氣體障壁層」,只要沒有特別記載,在不區別第1形態與第2形態之文章中之「第1氣體障壁層」的概念,也包含第2形態相關之「(第1)氣體障壁層」。 The gas barrier film according to the second aspect of the present invention has a base material and a gas barrier layer disposed on at least one side of the base material as its basic structure. The gas barrier layer related to the second aspect must contain a transition A metal (M1) and a transition metal (M2) other than metal are different from the gas barrier layer of the first embodiment described above. However, for convenience of explanation, the gas barrier layer in the gas barrier film related to the second aspect is also referred to as a "first gas barrier layer", unless otherwise noted, the article of the first aspect and the second aspect is not distinguished. The concept of "the first gas barrier layer" in "2" also includes the "(1) gas barrier layer" related to the second aspect.
圖2為表示本發明之第2形態相關之氣體障壁性薄膜的剖面示意圖。圖2所示之氣體障壁性薄膜10係在基材11上配置第1氣體障壁層12而成。且,不只有在基材之一側的面配置第1氣體障壁層12之形態而已,亦可在基材的兩面配置第1氣體障壁層12。進而,在基材與第1氣體障壁層之間,或在第1氣體障壁層上,亦可配置其他層。 2 is a schematic cross-sectional view showing a gas barrier film according to a second aspect of the present invention. The gas barrier film 10 shown in FIG. 2 is obtained by disposing a first gas barrier layer 12 on a substrate 11. In addition, the first gas barrier layer 12 is not limited to the configuration in which the first gas barrier layer 12 is disposed on one surface of the substrate, and the first gas barrier layer 12 may be disposed on both surfaces of the substrate. Further, another layer may be disposed between the substrate and the first gas barrier layer, or on the first gas barrier layer.
如上述,第1氣體障壁層12為發揮氣體障壁性之層,且設置在基材11之至少一側的面上,是必須含有過渡金屬以外之金屬(M1)(較佳為該金屬(M1)之氧化物)的層。於此,第2形態中,第1氣體障壁層必須含有過渡金屬以外之金屬(M1)以及過渡金屬(M2)。 As described above, the first gas barrier layer 12 is a layer exhibiting gas barrier properties, and is provided on at least one side of the substrate 11 and must contain a metal (M1) other than a transition metal (preferably the metal (M1) ) Of oxide). Here, in the second aspect, the first gas barrier layer must contain a metal (M1) other than a transition metal and a transition metal (M2).
如後述,第2形態相關之氣體障壁層係在下述點具有特徵:構成為過渡金屬以外之金屬(M1)以及過渡金屬(M2)之複合氧化物的缺氧區域會於氣體障壁層之厚度方向連續地以特定值以上(具體來說為5nm以上)的厚度存在(將此 點在本說明書中表現為「氣體障壁層具有區域[a]」)。關於此特徵之詳細如後述,但只要是滿足此特徵,氣體障壁層之區域[a]以外的區域能夠是例如不相當於區域[a]之金屬(M1)以及過渡金屬(M2)之複合氧化物(亦可為缺氧區域,亦可為化學計量的組成之區域)的區域。且,氣體障壁層之區域[a]以外的區域亦可為金屬(M1)之氧化物、氮化物、氮氧化物、碳氧化物(亦可為缺氧區域,亦可為化學計量的組成之區域)等之區域,亦可為過渡金屬(M2)之氧化物、氮化物、氮氧化物、碳氧化物(亦可為缺氧區域,亦可為化學計量的組成之區域)等之區域。 As described later, the gas barrier layer related to the second aspect is characterized in that the oxygen-deficient region composed of a compound oxide other than a transition metal (M1) and a transition metal (M2) is in the thickness direction of the gas barrier layer Continuously exists in a thickness of a certain value or more (specifically 5 nm or more) The point is expressed in this specification as "the gas barrier layer has an area [a]"). The details of this feature will be described later, but as long as this feature is satisfied, the region other than the region [a] of the gas barrier layer can be, for example, the composite oxidation of the metal (M1) and the transition metal (M2) that do not correspond to the region [a]. Area (which may also be an anoxic area, or an area of stoichiometric composition). In addition, the area other than the area [a] of the gas barrier layer may also be an oxide, nitride, oxynitride, or carbon oxide of the metal (M1) (it may also be an anoxic area, or it may be a stoichiometric composition) Regions) and the like may also be regions such as oxides, nitrides, oxynitrides, and carbon oxides of transition metals (M2) (also hypoxic regions or regions with stoichiometric composition).
作為過渡金屬以外之金屬(M1)並無特別限制。該金屬(M1)之具體例,關於較佳之種類等,由於與上述第1形態相同,故於此省略詳細說明。 The metal (M1) other than the transition metal is not particularly limited. Specific examples of the metal (M1), and preferable types and the like are the same as those in the first embodiment described above, and thus detailed descriptions thereof are omitted here.
關於過渡金屬(M2)也無特別限制。該過渡金屬(M2)之具體例,關於較佳之種類等,也與上述第1形態相同,故於此省略詳細說明。 There is also no particular limitation on the transition metal (M2). The specific examples of the transition metal (M2), the preferred types, and the like are also the same as those in the first embodiment described above, and thus detailed descriptions thereof are omitted here.
在第2形態中,也與上述同樣地,第1氣體障壁層之膜厚並無特別限制,為5~1000nm較佳。若在如此之範圍的話,會有較高之氣體障壁性能、耐折彎性、切斷加工適性優異。且,氣體障壁層亦可由鄰接的2層以上所構成。 In the second aspect, as in the above, the film thickness of the first gas barrier layer is not particularly limited, but is preferably 5 to 1000 nm. If it is in such a range, it will have high gas barrier performance, excellent bending resistance, and excellent cutting processability. The gas barrier layer may be composed of two or more adjacent layers.
在第2形態相關之氣體障壁性薄膜中,在第1氣體障壁層為滿足下述(5)之點具有特徵。 The gas barrier film according to the second aspect is characterized in that the first gas barrier layer satisfies the following point (5).
(5)將前述金屬(M1)之最大價數設為a,前述過渡金屬(M2)之最大價數設為b,氧設為O,氮設為N,碳設為C,前述第1氣體障壁層之組成設為(M1)(M2)pOqNrCs時,於前述氣體障壁層之厚度方向連續5nm以上之區域係滿足下述數式之區域[a]。 (5) Set the maximum valence of the metal (M1) to a, the maximum valence of the transition metal (M2) to b, oxygen to O, nitrogen to N, carbon to C, and the first gas When the composition of the barrier layer is (M1) (M2) p O q N r C s , a region continuously in the thickness direction of the gas barrier layer by 5 nm or more is a region [a] that satisfies the following formula.
0.02≦p≦98,且,q>0,且,r≧0,且,s≧0,且,(2q+3r+2s)/(a+bp)<1 0.02 ≦ p ≦ 98, and q> 0, and r ≧ 0, and s ≧ 0, and (2q + 3r + 2s) / (a + bp) <1
上述(5)是表示氣體障壁層在特定的厚度以上包含金屬(M1)與過渡金屬(M2)之複合氧化物的缺氧組成。 The above (5) indicates the oxygen-deficient composition of the gas barrier layer containing a composite oxide of the metal (M1) and the transition metal (M2) at a specific thickness or more.
如上述,本發明相關之金屬(M1)與過渡金屬(M2)之複合氧化物的組成係以(M1)(M2)pOqNrCs所示。由此組成可明顯得知,上述複合氧化物一部分亦可包含氮化物或碳化物之構造。此時,將金屬(M1)之最大價數設為a,過渡金屬(M2)之最大價數設為b,O之價數設為2,N之價數設為3,C之價數本來是4,但本發明所形成的上述層中,認為C是如-CH2-般地以包含氫原子之狀態來鍵結,故C之價數是設為2。且,上述複合氧化物(一部分包含成為氮化物或碳化物者)成為化學計量的組成時,會成為(2q+3r+2s)/(a+bp)=1.0。此式是意指金屬(M1)以及過渡金屬(M2)之鍵結合的合計、與O、N、C之鍵結的合計為相同數,此時,金屬(M1)以及過渡金屬(M2)會一起與O、N、C之任一者鍵結。且,本發明中,作為金屬(M1)併用2種以上時,或作為過渡金屬(M2)併用2種以上時,將各元素之最大價數以各元素之存在比率來加重平均,並採用 由此算出的複合價數作為「最大價數」之a以及b之值(參照後述實施例之欄)。 As described above, the composition of the composite oxide of the metal (M1) and the transition metal (M2) according to the present invention is represented by (M1) (M2) p O q N r C s . It is clear from this composition that a part of the composite oxide may include a structure of a nitride or a carbide. At this time, the maximum valence of the metal (M1) is set to a, the maximum valence of the transition metal (M2) is set to b, the valence of O is set to 2, the valence of N is set to 3, and the valence of C was originally It is 4, but in the above-mentioned layer formed by the present invention, it is considered that C is bonded in a state including a hydrogen atom like -CH 2- , so the valence of C is set to 2. In addition, when the composite oxide (a part of which includes nitrides or carbides) has a stoichiometric composition, it becomes (2q + 3r + 2s) / (a + bp) = 1.0. This formula means that the total of the bond of the metal (M1) and the transition metal (M2) and the total of the bond with O, N, and C are the same number. At this time, the metal (M1) and the transition metal (M2) will It is bonded to any one of O, N, and C together. Moreover, in the present invention, when two or more kinds are used as the metal (M1) or two or more kinds are used as the transition metal (M2), the maximum valence of each element is weighted and averaged by the existence ratio of each element. The calculated compound price is the value of a and b of the "maximum price" (refer to the column of the embodiment described later).
另一方面,如第2形態中之區域[a],成為(2q+3r+2s)/(a+bp)<1.0時,意指相對於金屬(M1)以及過渡金屬(M2)之鍵結的合計,O、N、C之鍵結合之合計不足,此狀態為上述複合氧化物之「缺氧」。在缺氧狀態中,有金屬(M1)以及過渡金屬(M2)之多餘的鍵結會互相鍵結之可能性,若金屬(M1)或過渡金屬(M2)之金屬彼此直接鍵結,則相較於金屬之間介隔著O或N或C來鍵結的情況,會形成更緻密且高密度之構造,作為其結果,認為氣體障壁性會提升。 On the other hand, if the area [a] in the second aspect becomes (2q + 3r + 2s) / (a + bp) <1.0, it means a bond to the metal (M1) and the transition metal (M2). In total, the total of O, N, and C bond bonding is insufficient, and this state is the "oxygen deficiency" of the above-mentioned composite oxide. In the hypoxic state, there is a possibility that the extra bonding of the metal (M1) and the transition metal (M2) will be bonded to each other. If the metals of the metal (M1) or the transition metal (M2) are directly bonded to each other, the phase will be Compared with the case where metals are bonded via O, N, or C, a denser and higher-density structure is formed. As a result, gas barrier properties are considered to be improved.
且,本發明中,區域[a]為滿足0.02≦x≦98之區域。認為此區域中,金屬(M1)以及過渡金屬(M2)雙方會與金屬彼此的直接鍵結有關係,故藉由滿足此條件之區域[a]以特定值以上(5nm)之厚度存在,會對氣體障壁性之提升帶來貢獻。且,認為金屬(M1)以及過渡金屬(M2)的存在比率越相近,越會對氣體障壁性之提升帶來貢獻,故區域[a]以5nm之厚度包含滿足0.1<x<90之區域較佳,以5nm之厚度包含滿足0.2<x<80之區域再較佳,以5nm之厚度包含滿足0.3<x<70之區域更較佳。 In the present invention, the region [a] is a region satisfying 0.02 ≦ x ≦ 98. It is considered that in this region, both the metal (M1) and the transition metal (M2) are related to the direct bonding between the metals. Therefore, the region [a] that satisfies this condition exists in a thickness greater than a specific value (5nm). Contribute to the improvement of gas barrier properties. In addition, it is considered that the closer the existence ratio of the metal (M1) and the transition metal (M2) is, the more it will contribute to the improvement of the gas barrier property. Therefore, the area [a] with a thickness of 5nm includes a region satisfying 0.1 <x <90. It is more preferable to include a region satisfying 0.2 <x <80 with a thickness of 5nm, and it is more preferable to include a region satisfying 0.3 <x <70 with a thickness of 5nm.
於此,如上述,若存在滿足(2q+3r+2s)/(a+bp)<1.0之區域[a],則能夠確認氣體障壁性之提升效果會發揮,但區域[a]滿足(2q+3r+2s)/(a+bp)≦0.9較佳,滿足(2q+3r+2s)/(a+bp)≦0.85再較佳,滿足(2q+3r+2s)/(a+bp)≦0.8更較 佳。於此,區域[a]中的(2q+3r+2s)/(a+bp)之值越小,氣體障壁性之提升效果變高者在可見光之吸收也會越大。因此,為使用在期望透明性之用途中的氣體障壁性薄膜時,為(2q+3r+2s)/(a+bp)≧0.2較佳,為(2q+3r+2s)/(a+bp)≧0.3再較佳,為(2q+3r+2s)/(a+bp)≧0.4更較佳。 Here, as described above, if there exists a region [a] satisfying (2q + 3r + 2s) / (a + bp) <1.0, it can be confirmed that the improvement effect of the gas barrier property will be exerted, but the region [a] satisfies (2q + 3r + 2s) / (a + bp) ≦ 0.9 is better, satisfying (2q + 3r + 2s) / (a + bp) ≦ 0.85 is even better, satisfying (2q + 3r + 2s) / (a + bp) ≦ 0.8 is more good. Here, the smaller the value of (2q + 3r + 2s) / (a + bp) in the region [a], the higher the effect of improving the gas barrier property will be greater in the absorption of visible light. Therefore, when using a gas barrier film in applications where transparency is desired, (2q + 3r + 2s) / (a + bp) ≧ 0.2 is preferred, and (2q + 3r + 2s) / (a + bp ) ≧ 0.3 is more preferable, and (2q + 3r + 2s) / (a + bp) ≧ 0.4 is more preferable.
且,本發明中,可得到良好氣體障壁性之區域[a]的厚度,作為SiO2換算之濺鍍厚度,為5nm以上。此厚度為8nm以上較佳,為10nm以上再較佳,為20nm以上更較佳。 In addition, in the present invention, the thickness of the region [a] where good gas barrier properties can be obtained, as the sputtering thickness in terms of SiO 2 conversion, is 5 nm or more. The thickness is preferably 8 nm or more, more preferably 10 nm or more, and even more preferably 20 nm or more.
具有如上述構成之氣體障壁性薄膜與第1形態相關之氣體障壁性薄膜一樣,表示非常高的氣體障壁性,其係能夠作為有機EL裝置等之電子裝置用的基板來使用之程度。 The gas barrier film having the above-mentioned configuration, like the gas barrier film according to the first aspect, represents a very high gas barrier property, and is used to the extent that it can be used as a substrate for an electronic device such as an organic EL device.
於此,第1形態之欄中,如上述,本發明者進行各種探討之結果,即使單獨使用過渡金屬以外之金屬(M1)的化合物(氧化物)之缺氧組成膜來形成氣體障壁層,或單獨使用過渡金屬(M2)的化合物(氧化物)之缺氧組成膜來形成氣體障壁層,都尚未關係到顯著的氣體障壁性之提升。基於此發現:層合包含將過渡金屬以外之金屬(M1)作為主要成分之化合物(氧化物)的層、與包含將過渡金屬(M2)作為主要成分之化合物(氧化物)的層,形成過渡金屬以外之金屬(M1)與過渡金屬(M2)同時存在之混合區域,進一步將該混合區域設為缺氧組成時,隨著缺氧程度變大,氣體障壁性會進一步提升。這是認為起因於如上述所示,過渡金屬以 外之金屬(M1)與過渡金屬(M2)之鍵結會比過渡金屬以外之金屬(M1)彼此之鍵結或過渡金屬(M2)彼此之鍵結更容易產生,而藉由將混合區域設為缺氧組成,在混合區域形成緻密且高密度之構造之故(這是上述「第1形態」所具有的技術性意義)。 Here, in the column of the first aspect, as described above, as a result of various investigations by the present inventors, even if an oxygen-deficient composition film of a compound (oxide) of a metal (M1) other than a transition metal is used alone to form a gas barrier layer, Or using the oxygen-deficient composition film of the compound (oxide) of the transition metal (M2) alone to form the gas barrier layer has not been related to the significant improvement of the gas barrier property. Based on this finding, a layer containing a compound (oxide) containing a metal (M1) other than a transition metal as a main component and a layer containing a compound (oxide) containing a transition metal (M2) as a main component are laminated to form a transition When a mixed region in which a metal other than metal (M1) and a transition metal (M2) coexist, and the mixed region is further set to an anoxic composition, as the degree of anoxic becomes larger, the gas barrier properties will be further improved. This is thought to be due to the fact that The bonding between the foreign metal (M1) and the transition metal (M2) is easier to generate than the bonding between the metals other than the transition metal (M1) or the bonding between the transition metal (M2), and by setting the mixed region This is because of the anoxic composition, and a dense and high-density structure is formed in the mixed region (this is the technical significance of the "first aspect" mentioned above).
於此,如上述之包含將過渡金屬以外之金屬(M1)作為主要成分之化合物(氧化物)的層、與包含將過渡金屬(M2)作為主要成分之化合物(氧化物)的層之層合構成中,在層合界面上形成由複合氧化物所成之混合區域(第1形態中之(4))。然而,該混合區域中所包含的金屬元素中佔有的各金屬元素(M1或M2)之存在比率對於混合區域之厚度方向,是以某個程度大的傾斜度傾斜。因此進一步檢討之結果得知上述混合區域中,即使形成有金屬(M1)與過渡金屬(M2)之複合氧化物的缺氧組成,其缺氧區域的氣體障壁層之厚度方向之厚度會有所限制。尤其是得知氣體障壁性之提升效果較高之(M1)/{(M1)+(M2)}包含在0.1~0.9之範圍的區域之厚度最多也只能形成到10nm左右。其結果,如上述第1形態之(4)所述,滿足(2q+3r+2s)/(a+bp)<0.85時,雖然能夠發揮優異之氣體障壁性,但不滿足條件時,由上述層合構成所能夠到達的氣體障壁性會有所限制,且,即使使上述層合構成中各層的製膜厚度增加,上述厚度也幾乎看不到變化。 Here, as described above, a layer containing a compound (oxide) containing a metal (M1) other than a transition metal as a main component and a layer containing a compound (oxide) containing a transition metal (M2) as a main component are laminated as described above. In the configuration, a mixed region made of a composite oxide is formed on a lamination interface ((4) in the first embodiment). However, the existence ratio of each metal element (M1 or M2) among the metal elements contained in the mixed region is inclined to a certain degree with respect to the thickness direction of the mixed region. Therefore, as a result of further review, it is known that even in the above mixed region, even if the oxygen-deficient composition of the composite oxide of the metal (M1) and the transition metal (M2) is formed, the thickness of the gas barrier layer in the oxygen-deficient region will have a thickness limit. In particular, it is known that the thickness of the region (M1) / {(M1) + (M2)} with a high improvement effect of the gas barrier property can only be formed up to about 10 nm. As a result, as described in the first aspect (4), when (2q + 3r + 2s) / (a + bp) <0.85 is satisfied, although excellent gas barrier properties can be exhibited, when the conditions are not satisfied, the above The gas barrier properties reachable by the laminated structure are limited, and even if the film thickness of each layer in the laminated structure is increased, the above-mentioned thickness is hardly seen to change.
基於如上述之見解,本發明者針對臨界厚度進行探討,臨界厚度係使金屬(M1)與過渡金屬(M2)之複合氧化物 的缺氧組成之厚度產生變化後能夠看到氣體障壁性的提升效果,且該金屬(M1)與過渡金屬(M2)之複合氧化物的缺氧組成之厚度滿足用於使金屬(M1)以及過渡金屬(M2)雙方與金屬彼此之直接鍵結有關係的條件之0.02≦x≦98。其結果,如上述,上述厚度若在5nm以上,則確認可見到氣體障壁性有非常顯著的提升效果,進而完成本發明。如此,本發明之第2形態相關之(5)也在下述點共有與上述第1形態相關之(1)~(3)以及(4)相同的技術特徵:在金屬(M1)以及/或過渡金屬(M2)共存之區域中,藉由提高缺氧程度(於此,缺氧區域之存在厚度(=存在體積)),可實現氣體障壁性之顯著提升。 Based on the above findings, the inventors discussed the critical thickness, which is a complex oxide of a metal (M1) and a transition metal (M2) After the thickness of the oxygen-deficient composition is changed, the improvement effect of the gas barrier property can be seen, and the thickness of the oxygen-deficient composition of the composite oxide of the metal (M1) and the transition metal (M2) is sufficient to make the metal (M1) and The condition of the relationship between the two metals of the transition metal (M2) and the direct bond between the metals is 0.02 ≦ x ≦ 98. As a result, as described above, if the thickness is 5 nm or more, it is confirmed that the gas barrier property has a very significant improvement effect, and the present invention has been completed. In this way, (5) related to the second aspect of the present invention shares the same technical features as (1) to (3) and (4) related to the first aspect described above: the metal (M1) and / or transition In the region where the metal (M2) coexists, by increasing the degree of hypoxia (here, the thickness of the hypoxia region (= presence volume)), a significant improvement in gas barrier properties can be achieved.
且,如上述,包含將過渡金屬以外之金屬(M1)作為主要成分之化合物(氧化物)的層、與包含將過渡金屬(M2)作為主要成分之化合物(氧化物)的層之層合界面中之混合區域中,金屬元素全體中佔有的各金屬元素(M1或M2)之存在比率相對於混合區域之厚度方向,是以某個程度大的傾斜度傾斜。關於此點,本發明者進一步進行探討後發現,藉由將上述傾斜之絕對值控制在較小的值,能夠抑制金屬元素全體中佔有的各金屬元素(M1或M2)之存在比率的變動,且也能夠將金屬(M1)以及過渡金屬(M2)共存之區域[a]的厚度變得更大。於此,金屬元素全體中佔有之過渡金屬元素(M2)的存在比率是表示成(M2)/{(M1)+(M2)},但將此分數表記之分子以及分母除以(M1),使用x=(M2)/(M1)之關係來換算時,上述過渡金屬元素(M2)之存在比率可以 表示成x/(1+x)。且發現,本發明相關之氣體障壁層藉由進一步滿足下述(6),能夠發揮更高的氣體障壁性之提升效果:(6)前述區域[a]中,x/(1+x)值(於此,x係相對於金屬(M1)之過渡金屬(M2)的存在比率(原子比))之前述氣體障壁層之厚度方向的變化之傾斜絕對值係每1nm厚度為0以上0.015[1/nm]以下。 In addition, as described above, a lamination interface of a layer containing a compound (oxide) containing a metal (M1) other than a transition metal as a main component and a layer containing a compound (oxide) containing a transition metal (M2) as a main component. In the mixed region, the presence ratio of each metal element (M1 or M2) occupying the entire metal element is inclined with a certain degree of inclination with respect to the thickness direction of the mixed region. In this regard, the present inventors have further studied and found that, by controlling the absolute value of the above-mentioned tilt to a small value, it is possible to suppress the variation in the existence ratio of each metal element (M1 or M2) occupied in the entire metal element. Furthermore, the thickness of the region [a] in which the metal (M1) and the transition metal (M2) coexist can be made larger. Here, the existence ratio of the transition metal element (M2) in the entire metal element is expressed as (M2) / {(M1) + (M2)}, but the numerator and denominator of this score are divided by (M1), When using the relationship of x = (M2) / (M1) to convert, the existence ratio of the above transition metal element (M2) can be Expressed as x / (1 + x). And it was found that the gas barrier layer related to the present invention can further enhance the gas barrier performance by further satisfying the following (6): (6) the value of x / (1 + x) in the aforementioned region [a] (Here, x is relative to the presence ratio (atomic ratio) of the transition metal (M2) of the metal (M1)). The absolute value of the change in the thickness direction of the aforementioned gas barrier layer is 0 or more and 0.015 per 1 nm thickness [1 / nm] or less.
於此,上述變化之傾斜絕對值較佳為0.010[1/nm]以下,再較佳為0.007[1/nm]以下,更較佳為0.005[1/nm]以下。且,作為上述變化之傾斜絕對值,如後述實施例之欄所記載,採用自XPS分析所得之氣體障壁層的厚度方向之組成分布資料中,將相當於區域[a]之分析測定點(必須要有2點以上之測定點,以能夠得到3點以上之測定點的條件來測定較佳)以一次式進行近似分析時的該一次式之傾斜絕對值。 Here, the absolute value of the slope of the above change is preferably 0.010 [1 / nm] or less, still more preferably 0.007 [1 / nm] or less, and even more preferably 0.005 [1 / nm] or less. Moreover, as the absolute value of the above-mentioned change, as described in the column of the examples described later, the composition distribution data of the thickness direction of the gas barrier layer obtained from the XPS analysis will be equivalent to the analysis measurement point of the area [a] (required) It is necessary to have two or more measurement points, and it is better to measure under the condition that three or more measurement points can be obtained.) The absolute value of the tilt of the one-shot equation when the approximate analysis is performed by one-shot equation.
第2形態中,作為用來形成氣體障壁層之方法,並無特別限定,能夠使用例如利用既存之薄膜堆積技術的以往公知之氣相製膜法。作為一例,能夠使用以往公知之氣相製膜法。此等之氣相製膜法能夠以公知之方法來使用。作為氣相成膜法,並無特別限制,同樣地能夠使用作為形成上述第1形態中的過渡金屬氧化物含有層之方法所例示的各種氣相製膜法,以與上述相同之理由,以物理氣相成長(PVD)法較佳,以濺鍍法再較佳。 In the second aspect, the method for forming the gas barrier layer is not particularly limited, and a conventionally known gas phase film formation method using, for example, an existing thin film deposition technique can be used. As an example, a conventionally known gas phase film-forming method can be used. These vapor-phase film-forming methods can be used by a well-known method. The vapor-phase film-forming method is not particularly limited, and various vapor-phase film-forming methods exemplified as the method for forming the transition metal oxide-containing layer in the first aspect can be used in the same manner. Physical vapor phase growth (PVD) is preferred, and sputtering is even more preferred.
尤其是,作為製作上述區域[a]之方法,如後述實施例 之欄記載所示,使用共蒸鍍法較佳。亦即,依據本發明之另外其他形態,亦能夠提供一種上述本發明之第2形態相關之氣體障壁性薄膜之製造方法。該製造方法中,在形成第1氣體障壁層之步驟為包含將包含金屬(M1)以及前述過渡金屬(M2)之複合氧化物於基材之至少一側之面上共蒸鍍,使所形成之氣體障壁層滿足上述條件(5)具有特徵。作為如此之共蒸鍍法,較佳有舉出共濺鍍法。本發明中所採用的共濺鍍法能夠為例如將包含金屬(M1)以及過渡金屬(M2)雙方之合金而成的複合標靶、或金屬(M1)以及過渡金屬(M2)之複合氧化物而成的複合標靶作為濺鍍標靶使用之1元濺鍍。且,本發明中共濺鍍法亦可為多元同時濺鍍,該多元同時濺鍍使用包含金屬(M1)之單體或其氧化物、與過渡金屬(M2)之單體或其氧化物之複數濺鍍標靶。關於製作此等之濺鍍標靶之方法、或使用此等之濺鍍標靶來製作複合氧化物而成之薄膜的方法,能夠適當地參照例如特開2000-160331號公報、特開2004-068109號公報、特開2013-047361號公報等之記載。且,作為實施共蒸鍍法時的製膜條件,有例示選自由製膜原料中之前述過渡金屬(M2)與氧之比率、製膜時之惰性氣體與反應性氣體之比率、製膜時之氣體的供給量、製膜時之真空度、以及製膜時之電力所構成群中的1種或2種以上之條件,藉由調節此等之製膜條件(較佳為氧分壓),能夠形成具有缺氧組成之複合氧化物而成的薄膜。亦即,藉由使用如上述之共蒸鍍法來形成氣體障壁層,能夠將幾乎所形成有後的氣體障 壁層之厚度方向的區域都作為區域[a]。因此,藉由如此之手法,藉由控制區域[a]之厚度這種極為簡便的操作,就能夠實現所期望之氣體障壁性。且,在控制區域[a]之厚度時,只要調節例如實施共蒸鍍法時的製膜時間即可。 In particular, as a method for producing the above-mentioned area [a], the embodiment will be described later. As shown in the column description, it is preferable to use a co-evaporation method. That is, according to still another aspect of the present invention, it is possible to provide a method for manufacturing a gas barrier film according to the second aspect of the present invention. In this manufacturing method, the step of forming the first gas barrier layer includes co-evaporating a composite oxide including the metal (M1) and the transition metal (M2) on at least one side of the base material to form the formed oxide. It is characteristic that the gas barrier layer satisfies the above condition (5). As such a co-evaporation method, a co-sputtering method is preferable. The co-sputtering method used in the present invention can be, for example, a composite target made of an alloy of both metal (M1) and transition metal (M2), or a composite oxide of metal (M1) and transition metal (M2) The resulting composite target is a one-element sputtering used as a sputtering target. In addition, the co-sputtering method in the present invention may also be multiple simultaneous sputtering. The multiple simultaneous sputtering uses a plurality of monomers containing metal (M1) or an oxide thereof, and a plurality of monomers containing a transition metal (M2) or an oxide thereof. Sputter target. Regarding a method for producing such a sputtering target or a method for producing a thin film made of a composite oxide using such a sputtering target, for example, Japanese Patent Application Laid-Open No. 2000-160331 and Japanese Patent Application Laid-Open No. 2004- It is described in JP 068109 and JP 2013-047361. In addition, as a film forming condition when the co-evaporation method is performed, there are exemplified a ratio selected from the aforementioned transition metal (M2) and oxygen in a film forming raw material, a ratio of an inert gas and a reactive gas during film forming, and a film forming time. The amount of gas supply, the degree of vacuum at the time of film formation, and the power at the time of film formation are one or two or more conditions, and by adjusting these film formation conditions (preferably oxygen partial pressure) , Can form a thin film of a composite oxide having an anoxic composition. That is, by forming the gas barrier layer using the co-evaporation method as described above, it is possible to form almost the gas barrier after it is formed. The areas in the thickness direction of the wall layer are all referred to as areas [a]. Therefore, by such a method, the desired gas barrier properties can be achieved by the extremely simple operation of controlling the thickness of the area [a]. In addition, when controlling the thickness of the area [a], it is only necessary to adjust the film formation time when the co-evaporation method is performed, for example.
本發明相關之氣體障壁性薄膜中,在含有過渡金屬(M2)之層的與基材相反側之面上進一步配置含有金屬氧化物之氣體障壁層(本說明書中亦稱作「第2氣體障壁層」)較佳。藉由作為如此之構成,能夠表現更高一層的氣體障壁性。 In the gas barrier film according to the present invention, a gas barrier layer containing a metal oxide is further disposed on the surface of the layer containing the transition metal (M2) on the side opposite to the substrate (also referred to as "the second gas barrier in this specification"). Layer "). By having such a structure, it is possible to express a higher level of gas barrier properties.
且,第1形態相關之氣體障壁性薄膜中,依序配置有基材、過渡金屬氧化物含有層、以及第1氣體障壁層時,該第2氣體障壁層不會被配置在過渡金屬氧化物含有層與第1氣體障壁層之間。換而言之,第1形態中,如圖1所示,依序配置有基材11與第1氣體障壁層12與過渡金屬氧化物含有層13時,在含有過渡金屬(M2)之層(亦即,過渡金屬氧化物含有層)之與第1氣體障壁層12相反側之面(亦即,過渡金屬氧化物含有層13之露出表面)上配置第2氣體障壁層13較佳。且,第2氣體障壁層不具有上述特定之缺氧區域。亦即,第2氣體障壁層可為與本發明之第1形態相關之氣體障壁性薄膜僅滿足上述(2)時的第1氣體障壁層相同構成。 When the substrate, the transition metal oxide-containing layer, and the first gas barrier layer are sequentially disposed in the gas barrier film according to the first aspect, the second gas barrier layer is not disposed on the transition metal oxide. Between the containing layer and the first gas barrier layer. In other words, in the first embodiment, as shown in FIG. 1, when the substrate 11, the first gas barrier layer 12, and the transition metal oxide-containing layer 13 are sequentially disposed, the layer containing the transition metal (M2) ( That is, it is preferable that the second gas barrier layer 13 is disposed on a surface of the transition metal oxide containing layer) on the side opposite to the first gas barrier layer 12 (that is, the exposed surface of the transition metal oxide containing layer 13). In addition, the second gas barrier layer does not have the specific oxygen-deficient region described above. That is, the second gas barrier layer may have the same configuration as the first gas barrier layer when the gas barrier film according to the first aspect of the present invention satisfies only the above (2).
且,第2形態相關之氣體障壁性薄膜中,第2氣體障 壁層能夠在如圖2所示之氣體障壁層12之與基材11相反側的面(亦即,氣體障壁層12之露出表面)上,作為與上述第1氣體障壁層相異之含有金屬氧化物的氣體障壁層來配置。 In the gas barrier film according to the second aspect, the second gas barrier The wall layer can be a metal containing material different from the first gas barrier layer on the surface of the gas barrier layer 12 opposite to the substrate 11 (that is, the exposed surface of the gas barrier layer 12) as shown in FIG. 2. An oxide gas barrier layer is arranged.
第2氣體障壁層只要是含有金屬氧化物,且發揮氣體障壁性之層,具體構成或形成方法並無特別限制。於此,第2氣體障壁層之氣體障壁性也與上述第1氣體障壁層相同,以使該第2氣體障壁層形成在基材上之層合體來算出時,水蒸氣透過率(WVTR)為0.1g/(m2‧day)以下較佳。且,第2氣體障壁層亦可為單層,亦可為2層以上之層合構造。 The second gas barrier layer is not particularly limited as long as it is a layer containing a metal oxide and exhibiting gas barrier properties. Here, the gas barrier properties of the second gas barrier layer are also the same as those of the first gas barrier layer, and when the second gas barrier layer is formed on a substrate to calculate the laminate, the water vapor transmission rate (WVTR) is It is preferably less than 0.1 g / (m 2 ‧day). In addition, the second gas barrier layer may be a single layer or a laminated structure of two or more layers.
第2氣體障壁層較佳為在塗佈以及乾燥含有聚矽氮烷這種矽化合物的塗佈液所得之塗膜施予改質處理所形成之層(亦即,「聚矽氮烷改質層」)。藉由作為如此之構成,能夠得到透過率等光學特性優異之氣體障壁性薄膜。改質處理較佳為真空紫外線之照射處理。藉由真空紫外線之照射這種改質處理,第2氣體障壁層會表現氣體障壁性。亦即,第2氣體障壁層為聚矽氮烷真空紫外線照射改質層較佳。 The second gas barrier layer is preferably a layer formed by applying and drying a coating film obtained by coating and drying a coating liquid containing a silicon compound such as polysilazane (that is, "polysilazane modification Floor"). With such a configuration, a gas barrier film having excellent optical properties such as transmittance can be obtained. The modification treatment is preferably a vacuum ultraviolet irradiation treatment. By this modification treatment by irradiation of vacuum ultraviolet rays, the second gas barrier layer exhibits gas barrier properties. That is, it is preferable that the second gas barrier layer is a polysilazane vacuum ultraviolet irradiation modification layer.
第2氣體障壁層之每1層的厚度,以氣體障壁性能之觀點來看,為10~300nm較佳。為2層以上之層合構造時,其總厚度以抑制破裂之觀點來看,為10~1000nm較佳。 The thickness of each layer of the second gas barrier layer is preferably 10 to 300 nm from the viewpoint of the performance of the gas barrier. In the case of a laminated structure of two or more layers, the total thickness is preferably 10 to 1000 nm from the viewpoint of suppressing cracking.
於此,首先舉出矽化合物為聚矽氮烷之情況為例,說 明第2氣體障壁層之形成方法的一例。 Here, the case where the silicon compound is polysilazane is taken as an example. An example of a method for forming the second gas barrier layer will be described.
將包含聚矽氮烷之塗佈液藉由公知的濕式塗佈法來塗佈並進行改質處理,能夠形成第2氣體障壁層。 The coating liquid containing polysilazane is applied by a known wet coating method and modified, thereby forming a second gas barrier layer.
本發明中所使用之「聚矽氮烷」意指在構造內具有矽-氮鍵結之聚合物,且會成為氮氧化矽之前驅物的聚合物,使用具有下述一般式(1)之構造者較佳。 The "polysilazane" used in the present invention means a polymer having a silicon-nitrogen bond in the structure and a polymer that will become a precursor of silicon oxynitride. A polymer having the following general formula (1) is used. Constructors are better.
式中、R1、R2、以及R3分別表示氫原子、烷基、烯基、環烷基、芳基、烷矽基、烷胺基、或烷氧基。 In the formula, R 1 , R 2 , and R 3 each represent a hydrogen atom, an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group, an alkylsilyl group, an alkylamino group, or an alkoxy group.
本發明中,以作為所得之氣體障壁層的膜之緻密性的觀點來看,以R1、R2以及R3全部為氫原子之高氫化聚矽氮烷特別佳。 In the present invention, a highly hydrogenated polysilazane in which all of R 1 , R 2, and R 3 are hydrogen atoms is particularly preferred from the viewpoint of the denseness of the obtained film as the gas barrier layer.
聚矽氮烷係以溶解於有機溶劑之溶液的狀態所市售,能夠將市售品直接作為含有聚矽氮烷之塗佈液來使用。作為聚矽氮烷溶液之市售品,有舉出Merck公司製之NN120-20、NAX120-20、NL120-20等。 Polysilazane is commercially available in a state of being dissolved in a solution in an organic solvent, and a commercially available product can be used as a coating liquid containing polysilazane as it is. Examples of commercially available polysilazane solutions include NN120-20, NAX120-20, and NL120-20 manufactured by Merck.
其他,關於聚矽氮烷之詳細,能夠參照並採用以往公知之特開2013-255910號公報的段落「0024」~「0040」、特開2013-188942號公報的段落「0037」~「0043」、特開2013-151123號公報的段落「0014」~「0021」、特開2013-052569號公報的段落「0033」~ 「0045」、特開2013-129557號公報的段落「0062」~「0075」、特開2013-226758號公報的段落「0037」~「0064」等。 In addition, for the details of the polysilazane, paragraphs "0024" to "0040" of JP 2013-255910, and paragraphs "0037" to "0043" of JP 2013-188942 can be referred to and used. , Paragraphs "0014" to "0021" of JP 2013-151123, paragraphs "0033" of JP 2013-052569, "0045", paragraphs "0062" to "0075" of JP 2013-129557, paragraphs "0037" to "0064" of JP 2013-226758, and the like.
作為塗佈含有聚矽氮烷之塗佈液的方法,能夠採用任意的適當方法。具體來說,舉例有如旋塗法、輥塗佈法、流動塗佈法、油墨噴射法、噴灑塗佈法、印刷法、浸漬塗佈法、流延成膜法、棒塗佈法、凹版印刷法等。塗佈塗佈液之後使塗膜乾燥較佳。藉由乾燥塗膜,能夠將塗膜中所含有之有機溶劑去除。關於形成方法,能夠參照並採用以往公知之特開2014-151571號公報的段落「0058」~「0064」、特開2011-183773號公報的段落「0052」~「0056」等。 As a method of applying the coating liquid containing polysilazane, any appropriate method can be adopted. Specific examples include spin coating method, roll coating method, flow coating method, ink jet method, spray coating method, printing method, dip coating method, cast film method, bar coating method, and gravure printing. Law, etc. It is preferable to dry the coating film after applying the coating liquid. By drying the coating film, the organic solvent contained in the coating film can be removed. Regarding the formation method, the paragraphs "0058" to "0064" of JP-A-2014-151571 and the paragraphs "0052" to "0056" of JP-A-2011-183773 can be referred to and used.
改質處理意指聚矽氮烷之氧化矽或氮氧化矽之轉化反應。本發明中的改質處理能夠選擇基於聚矽氮烷之轉化反應的公知方法。本發明中,以低溫能夠轉化反應的使用電漿或臭氧或紫外線之轉化反應較佳。電漿或臭氧能夠使用以往公知的方法。本發明中,藉由設置聚矽氮烷含有液之塗膜,並照射波長200nm以下的真空紫外線(VUV)來進行改質處理,形成第2氣體障壁層較佳。 Modification treatment means the conversion reaction of polysilazane silicon oxide or silicon oxynitride. The modification treatment in the present invention can select a known method based on a polysilazane conversion reaction. In the present invention, a conversion reaction using plasma or ozone or ultraviolet rays that can be converted at a low temperature is preferred. As the plasma or ozone, a conventionally known method can be used. In the present invention, it is preferable to form a second gas barrier layer by providing a coating film of a polysilazane-containing liquid and irradiating vacuum ultraviolet rays (VUV) with a wavelength of 200 nm or less to perform the modification treatment.
第2氣體障壁層之厚度在1~500nm之範圍較佳,再較佳為10~300nm之範圍。第2氣體障壁層中,第2氣體障壁層全體亦可為改質層,但經改質處理的改質層之厚度為1~50nm較佳,為1~10nm更較佳。 The thickness of the second gas barrier layer is preferably in a range of 1 to 500 nm, and more preferably in a range of 10 to 300 nm. In the second gas barrier layer, the entire second gas barrier layer may also be a modified layer, but the thickness of the modified layer after the modification process is preferably 1 to 50 nm, and more preferably 1 to 10 nm.
本發明相關之第2氣體障壁層係在對包含聚矽氮烷之 層照射VUV之步驟中,聚矽氮烷之至少一部分被改質成氮氧化矽較佳。本發明中的VUV照射步驟中,聚矽氮烷層塗膜所接受之在塗膜面的該VUV照度在30~200mW/cm2之範圍較佳,在50~160mW/cm2之範圍再較佳。藉由將VUV之照度設在30mW/cm2以上,能夠充分地提升改質效率,在200mW/cm2以下的話,能夠極度抑制對塗膜之損傷發生率,且也能夠降低對基材之損傷,故較佳。 In the second gas barrier layer related to the present invention, it is preferable that at least a part of the polysilazane is modified into silicon oxynitride in the step of irradiating the layer containing the polysilazane with VUV. The present invention VUV irradiation step, the poly silicon layer polysilazane coating film accepted the VUV coated surface illuminance at 30 ~ 200mW / cm 2 preferably within a range of, in 50 ~ 160mW / cm longer than the range of 2 good. By setting the irradiance of VUV to 30mW / cm 2 or more, the modification efficiency can be sufficiently improved. When the UVV is 200mW / cm 2 or less, the incidence of damage to the coating film can be extremely suppressed, and the damage to the substrate can also be reduced. , So it is better.
聚矽氮烷層塗膜面中之VUV的照射能量在200~10000mJ/cm2之範圍較佳,在500~5000mJ/cm2之範圍再較佳。藉由將VUV之照射能量設在200mJ/cm2以上,能夠充分地進行聚矽氮烷層之改質,若在10000mJ/cm2以下,則能夠抑制過度改質,並能夠極力地抑制聚矽氮烷層之破裂、或基材之熱變形的發生。 The irradiation energy of VUV in the coating surface of the polysilazane layer is preferably in the range of 200 to 10,000 mJ / cm 2 , and more preferably in the range of 500 to 5000 mJ / cm 2 . By setting the irradiation energy of VUV to 200mJ / cm 2 or more, the modification of the polysilazane layer can be sufficiently performed. If it is 10000mJ / cm 2 or less, excessive modification can be suppressed, and polysilicon can be suppressed as much as possible. Rupture of the azane layer, or thermal deformation of the substrate.
且,作為真空紫外光源,使用稀有氣體準分子燈較佳。真空紫外線由於會因氧而吸收,使在紫外線照射步驟的效率容易降低,故VUV之照射盡可能地在氧濃度較低之狀態下進行較佳。亦即,VUV照射時之氧濃度設在10~10000ppm之範圍較佳,再較佳為50~5000ppm之範圍,更較佳為80~4500ppm之範圍,最佳為100~1000ppm之範圍。 Moreover, as a vacuum ultraviolet light source, it is preferable to use a rare gas excimer lamp. Since vacuum ultraviolet rays are absorbed by oxygen, the efficiency in the ultraviolet irradiation step is easily reduced, so it is better to perform the irradiation of VUV in a state where the oxygen concentration is as low as possible. That is, the oxygen concentration during VUV irradiation is preferably set in a range of 10 to 10,000 ppm, more preferably in a range of 50 to 5000 ppm, more preferably in a range of 80 to 4500 ppm, and most preferably in a range of 100 to 1000 ppm.
作為VUV照射時所用的充滿照射環境之氣體,以乾燥惰性氣體較佳,尤其是以成本的觀點來看,以乾燥氮氣較佳。氧濃度之調整能夠藉由測量導入照射庫內之氧氣、 惰性氣體之流量,且改變流量比來調整。 As the gas that is used to fill the irradiation environment during VUV irradiation, a dry inert gas is preferred, and from a cost standpoint, dry nitrogen is preferred. The oxygen concentration can be adjusted by measuring the oxygen, Adjust the flow rate of inert gas and change the flow ratio.
在此等之改質處理中,能夠參照例如特開2012-086394號公報的段落「0055」~「0091」、特開2012-006154號公報的段落「0049」~「0085」、特開2011-251460號公報的段落「0046」~「0074」等所記載之內容。 In these modification processes, for example, paragraphs "0055" to "0091" of JP 2012-086394, paragraphs "0049" to "0085" of JP 2012-006154 can be referred to, and JP 2011- Contents described in paragraphs "0046" to "0074" in 251460.
進而,第2氣體障壁層亦可為藉由氣相製膜法所形成者(亦即,「氣相製膜氣體障壁層」)。在如此之形態中,第2氣體障壁層能夠藉由與上述第1氣體障壁層之欄中所說明者相同之氣相製膜法來形成。 Furthermore, the second gas barrier layer may be formed by a vapor-phase film formation method (that is, a “gas-phase film-formed gas barrier layer”). In such a form, the second gas barrier layer can be formed by the same gas-phase film-forming method as described in the column of the first gas barrier layer.
本發明相關之氣體障壁性薄膜中,相對於基材且形成有氣體障壁層之側的最表層上,亦可形成聚矽氧烷改質層等而成的保護層。聚矽氧烷改質層能夠藉由將含有聚矽氧烷之塗佈液以濕式塗佈法塗佈並乾燥後,對其乾燥後的塗膜施予加熱之改質處理、或紫外光之照射、真空紫外光之照射等改質處理來形成。作為真空紫外光,使用上述聚矽氮烷之改質處理中所使用的VUV較佳。 In the gas barrier film according to the present invention, a protective layer such as a polysiloxane modified layer may be formed on the outermost layer of the substrate on the side where the gas barrier layer is formed. The polysiloxane modified layer can be coated with a polysiloxane-containing coating liquid by a wet coating method and dried, and then the dried coating film can be subjected to heating modification treatment or ultraviolet light. It is formed by modification treatment such as irradiation of radiation and irradiation of vacuum ultraviolet light. As the vacuum ultraviolet light, VUV used in the modification treatment using the above polysilazane is preferred.
另外,關於聚矽氧烷之詳細,能夠參照並採用以往公知之特開2013-151123號公報的段落「0028」~「0032」、特開2013-086501號公報的段落「0050」~「0064」、特開2013-059927號公報的段落「0063」~「0081」、特開2013-226673號公報的段落「0119」~ 「0139」等。 For details of the polysiloxane, reference can be made to the paragraphs "0028" to "0032" of JP 2013-151123, and the paragraphs "0050" to "0064" of JP 2013-086501. Paragraphs "0063" to "0081" of JP 2013-059927, Paragraphs "0119" of JP 2013-226673 ~ "0139" and so on.
本發明之氣體障壁性薄膜上,除了上述第2氣體障壁層之外,也能夠設置各種具有機能之層。 In addition to the above-mentioned second gas barrier layer, the gas barrier film of the present invention can be provided with various functional layers.
在形成本發明相關之第1氣體障壁層(第1形態中進一步為過渡金屬氧化物含有層)之側的基材之表面上,以基材與第1氣體障壁層(或過渡金屬氧化物含有層)之密著性的提升為目的,亦可配置固著塗佈層。 On the surface of the base material forming the side of the first gas barrier layer (which is further a transition metal oxide-containing layer in the first aspect) according to the present invention, the base material and the first gas barrier layer (or For the purpose of improving the adhesion of the layer), a fixed coating layer may be disposed.
作為固著塗佈層所使用之固著塗佈劑,能夠單獨或組合2種以上之聚酯樹脂、異氰酸酯樹脂、胺基甲酸酯樹脂、丙烯酸樹脂、乙烯乙烯醇樹脂、乙烯改質樹脂、環氧樹脂、改質苯乙烯樹脂、改質矽樹脂、以及鈦酸烷酯等來使用。 As the fixing coating agent used for the fixing coating layer, two or more types of polyester resin, isocyanate resin, urethane resin, acrylic resin, ethylene vinyl alcohol resin, ethylene modified resin, Epoxy resin, modified styrene resin, modified silicone resin, and alkyl titanate are used.
此等之固著塗佈劑中也能夠添加以往公知之添加劑。且,上述固著塗佈劑能夠藉由輥塗佈、凹版塗佈、刮刀塗佈、浸漬塗佈、噴灑塗佈等公知之方法而塗佈於支持體上,並藉由乾燥去除溶劑、稀釋劑等來進行固著塗佈。作為上述固著塗佈劑之塗佈量,為0.1~5.0g/m2(乾燥狀態)左右較佳。 Conventionally known additives can be added to these fixing coating agents. The fixed coating agent can be applied to a support by a known method such as roll coating, gravure coating, doctor blade coating, dip coating, and spray coating, and the solvent can be removed by drying and diluted. Agent and the like for fixed coating. The application amount of the fixed coating agent is preferably about 0.1 to 5.0 g / m 2 (dry state).
且,固著塗佈層也能夠藉由物理蒸鍍法或化學蒸鍍法這種氣相製膜法來形成。例如特開2008-142941號公報所 記載般,能夠以改善接著性等之目的,形成以氧化矽作為主體的無機膜。或,如特開2004-314626號公報所記載般,能夠藉由形成固著塗佈層,在其上方以氣相製膜法形成無機薄膜時,以將自基材側所產生的氣體遮蔽某程度,而控制無機薄膜之組成這個目的,來形成固著塗佈層。 In addition, the fixed coating layer can also be formed by a vapor deposition method such as a physical vapor deposition method or a chemical vapor deposition method. For example, JP 2008-142941 As described, it is possible to form an inorganic film mainly composed of silicon oxide for the purpose of improving adhesion and the like. Alternatively, as described in Japanese Patent Application Laid-Open No. 2004-314626, when a fixed coating layer is formed and an inorganic thin film is formed by a vapor-phase film-forming method thereon, a gas generated from the substrate side can be shielded from a certain gas. The purpose is to control the composition of the inorganic thin film to form a fixed coating layer.
且,固著塗佈層之厚度並無特別限制,為0.5~10μm左右較佳。 In addition, the thickness of the fixed coating layer is not particularly limited, but is preferably about 0.5 to 10 μm.
在基材的表面(單面或兩面)上亦可配置硬塗層。作為硬塗層中所包含的材料之例,雖舉例有如熱硬化性樹脂或活性能射線硬化性樹脂,但以成形容易來說,為活性能射線硬化性樹脂較佳。如此之硬化性樹脂能夠單獨或組合2種以上來使用。 A hard coat layer may be arranged on the surface (single or both sides) of the substrate. Examples of the material included in the hard coat layer include thermosetting resins and active energy ray-curable resins, but in terms of ease of molding, active energy ray-curable resins are preferred. Such a curable resin can be used individually or in combination of 2 or more types.
活性能射線硬化性樹脂意指藉由如紫外線或電子束之活性能射線照射且經過交聯反應等而硬化之樹脂。作為活性能射線硬化性樹脂,使用包含具有乙烯性不飽和雙鍵之單體的成分較佳,藉由照射如紫外線或電子束之活性能射線使其硬化,會形成包含活性能射線硬化性樹脂之硬化物的層,亦即硬塗層。作為活性能射線硬化性樹脂,雖有舉出紫外線硬化性樹脂或電子束硬化性樹脂等作為代表者,但以紫外線照射所硬化之紫外線硬化性樹脂較佳。亦可使用預先形成有硬塗層之市售基材。 The active energy ray-curable resin means a resin which is hardened by irradiation with active energy rays such as ultraviolet rays or electron beams and undergoes a crosslinking reaction or the like. As the active energy ray-curable resin, it is preferable to use a component containing a monomer having an ethylenically unsaturated double bond. The active energy ray-curable resin is hardened by irradiating an active energy ray such as ultraviolet rays or an electron beam to form an active energy ray-curable resin The hardened layer, that is, the hard coating. Examples of the active energy ray-curable resin include a UV-curable resin and an electron beam-curable resin, but a UV-curable resin cured by ultraviolet irradiation is preferred. A commercially available substrate having a hard coat layer formed in advance may also be used.
硬塗層之厚度,以平滑性以及抗彎曲性之觀點來看, 為0.1~15μm較佳,為1~5μm再較佳。 From the viewpoint of smoothness and bending resistance, the thickness of the hard coating layer, It is preferably 0.1 to 15 μm, and more preferably 1 to 5 μm.
在形成本發明相關之第1氣體障壁層(第1形態中進一步為過渡金屬氧化物含有層)之側的基材之表面上亦可配置平滑層。本發明中所使用之平滑層係用於將存在突起等之基材的粗面平坦化,或者掩埋且平坦化因存在於基材上之突起而產生在上層的凹凸或針孔而設置。如此之平滑層基本上為感光性材料、或使熱硬化性材料硬化來製作。 A smooth layer may be disposed on the surface of the substrate on the side where the first gas barrier layer (the first embodiment further contains a transition metal oxide-containing layer) according to the present invention is formed. The smoothing layer used in the present invention is provided for flattening the rough surface of a substrate having protrusions or the like or burying and flattening unevenness or pinholes on the upper layer due to the protrusions existing on the substrate. Such a smoothing layer is basically made of a photosensitive material or a thermosetting material.
作為平滑層之感光性材料,舉例有如含有具有自由基反應性不飽和化合物之丙烯酸酯化合物的樹脂組成物、含有丙烯酸酯化合物與具有硫醇基之巰基化合物的樹脂組成物、使環氧丙烯酸酯、胺基甲酸酯丙烯酸酯、聚酯丙烯酸酯、聚醚丙烯酸酯、聚乙二醇丙烯酸酯、甘油丙烯酸甲酯等之多官能丙烯酸酯單體溶解的樹脂組成物等。具體來說,能夠使用JSR股份有限公司製之UV硬化型有機/無機混合硬塗材OPSTAR(註冊商標)系列。且,能夠使用如上述樹脂組成物之任意的混合物,只要是含有在分子內具有1個以上光聚合性不飽和鍵結之反應性單體的感光性樹脂,並無特別限制。 Examples of the photosensitive material of the smooth layer include a resin composition containing an acrylate compound having a radically reactive unsaturated compound, a resin composition containing an acrylate compound and a thiol compound having a thiol group, and an epoxy acrylate. , A resin composition in which polyfunctional acrylate monomers such as urethane acrylate, polyester acrylate, polyether acrylate, polyethylene glycol acrylate, and glycerol methyl acrylate are dissolved. Specifically, the UV-curable organic / inorganic hybrid hard coating material OPSTAR (registered trademark) series manufactured by JSR Corporation can be used. In addition, any mixture such as the above-mentioned resin composition can be used, and it is not particularly limited as long as it is a photosensitive resin containing a reactive monomer having one or more photopolymerizable unsaturated bonds in the molecule.
作為熱硬化性材料,具體來說有舉出Clariant公司製之Tutto prom系列(有機聚矽氮烷)、Ceramic coat股份有限公司製之SP COAT耐熱透明塗料、股份有限公司ADEKA製之奈米混成矽氧、DIC股份有限公司製之 UNIDIC(註冊商標)V-8000系列、EPICLON(註冊商標)EXA-4710(超高耐熱性環氧樹脂)、信越化學工業股份有限公司製之各種矽氧樹脂、日東紡股份有限公司製之無機‧有機奈米複合材料SSG Coat、丙烯酸多元醇與異氰酸酯預聚合物而成的熱硬化性胺基甲酸酯樹脂、酚樹脂、尿素三聚氰胺樹脂、環氧樹脂、不飽和聚酯樹脂、矽樹脂等。其中,尤其是具有耐熱性之環氧樹脂基底的材料較佳。 Examples of the thermosetting material include Tutto prom series (organic polysilazane) manufactured by Clariant, SP COAT heat-resistant transparent coating manufactured by Ceramic coat Co., Ltd., and nano-mixed silicon manufactured by ADEKA Co., Ltd. Oxygen, made by DIC Corporation UNIDIC (registered trademark) V-8000 series, EPICLON (registered trademark) EXA-4710 (ultra high heat resistance epoxy resin), various silicone resins manufactured by Shin-Etsu Chemical Industry Co., Ltd., and inorganics made by Nitto Textile Co., Ltd. Organic nanocomposite material SSG Coat, acrylic polyol and isocyanate prepolymer, thermosetting urethane resin, phenol resin, urea melamine resin, epoxy resin, unsaturated polyester resin, silicone resin, etc. Among them, the material of the epoxy resin substrate having heat resistance is particularly preferable.
平滑層之形成方法並無特別限制,以旋轉塗佈法、噴霧法、刮刀塗佈法、浸漬法等之濕塗佈法、或蒸鍍法等之乾塗佈法來形成較佳。 The method for forming the smooth layer is not particularly limited, and it is preferably formed by a wet coating method such as a spin coating method, a spray method, a blade coating method, a dipping method, or a dry coating method such as an evaporation method.
平滑層之形成中,在上述感光性樹脂中能夠因應必要添加抗氧化劑、紫外線吸收劑、可塑劑等之添加劑。且,與平滑層之層合位置無關,在任何平滑層中,皆能夠使用用於提升成膜性以及防止膜之針孔發生等之適當的樹脂或添加劑。 In the formation of the smooth layer, additives such as an antioxidant, an ultraviolet absorber, and a plasticizer can be added to the photosensitive resin as necessary. Moreover, regardless of the lamination position of the smoothing layer, in any smoothing layer, an appropriate resin or additive can be used to improve film formation and prevent pinholes of the film from occurring.
作為平滑層之厚度,以提升薄膜之耐熱性,並使容易調整薄膜之光學特性之平衡之觀點來看,為1~10μm之範圍較佳,更較佳為在2μm~7μm之範圍較佳。 The thickness of the smoothing layer is preferably in the range of 1 to 10 μm, and more preferably in the range of 2 to 7 μm from the viewpoint of improving the heat resistance of the film and making it easy to adjust the balance of the optical characteristics of the film.
平滑層之平滑性以JIS B 0601:2001規定之表面粗度所表現之值來看,十點平均粗度Rz為10nm以上、30nm以下較佳。只要在此範圍,即使將障壁層以塗佈形式來塗佈時,或以導線桿、無線桿等塗佈方式在平滑層表面上接觸塗佈手段時,較少損害塗佈性的情形,且也容易將塗佈後之凹凸平滑化。 The smoothness of the smoothing layer is represented by the value of the surface roughness specified by JIS B 0601: 2001. The ten-point average roughness Rz is preferably 10 nm or more and 30 nm or less. As long as it is within this range, even when the barrier layer is applied in a coating form, or when the coating means is contacted on the surface of the smooth layer by a coating method such as a wire rod or a wireless rod, the coating property is less likely to be damaged, It is also easy to smooth unevenness after coating.
本發明之氣體障壁性薄膜能夠較佳適用在因空氣中的化學成分(氧、水、氮氧化物、硫氧化物、臭氧等)而使性能變差之裝置上。亦即,本發明為提供一種包含本發明之氣體障壁性薄膜、與電子裝置本體之電子裝置。 The gas barrier film of the present invention can be preferably applied to a device whose performance is deteriorated due to chemical components (oxygen, water, nitrogen oxides, sulfur oxides, ozone, etc.) in the air. That is, the present invention provides an electronic device including the gas barrier film of the present invention and an electronic device body.
作為本發明電子裝置所使用之電子裝置本體的例,能夠舉例如有機電致發光元件(有機EL元件)、液晶表示元件(LCD)、薄膜電晶體、觸控式面板、電子紙、太陽電池(PV)等。以更有效率地得到本發明之效果的觀點來看,該電子裝置本體為有機EL元件或太陽電池較佳,為有機EL元件再較佳。 As examples of the electronic device body used in the electronic device of the present invention, there can be exemplified electromechanical light-emitting elements (organic EL elements), liquid crystal display elements (LCD), thin-film transistors, touch panels, electronic paper, and solar cells ( PV) and so on. From the viewpoint of obtaining the effect of the present invention more efficiently, the electronic device body is preferably an organic EL element or a solar cell, and more preferably an organic EL element.
將本發明之效果使用以下實施例以及比較例進行說明。然而,本發明技術範圍並不限於僅以下之實施例。 The effect of the present invention will be described using the following examples and comparative examples. However, the technical scope of the present invention is not limited to the following embodiments.
藉由以下手法,製作實施例1之氣體障壁性薄膜。將實施例1所製作之各薄膜的構成以及製作條件分別表示於下述表1中。 The gas barrier film of Example 1 was produced by the following method. The structure and manufacturing conditions of each thin film produced in Example 1 are shown in Table 1 below.
在兩面經易接著處理之厚度100μm的聚乙烯對苯二甲酸酯薄膜(Toray股份有限公司製,LUMIRROR(註冊商標)(U48))之形成氣體障壁層的面之相反側的面上,形成具有防堵機能之透明硬塗層。具體來說,塗佈UV硬化型樹脂(Aica工業股份有限公司製,品號:Z731L)使乾燥膜厚成為0.5μm之後,於80℃下乾燥,之後,在空氣下,使用高壓水銀燈以照射能量0.5J/cm2之條件進行硬化。 A 100 μm-thick polyethylene terephthalate film (made by Toray Co., Ltd., LUMIRROR (registered trademark) (U48)) on both sides was formed on the side opposite to the side on which the gas barrier layer was formed. Transparent hard coating with anti-blocking function. Specifically, after applying a UV-curable resin (manufactured by Aica Industry Co., Ltd., product number: Z731L) to a dry film thickness of 0.5 μm, drying at 80 ° C., and then using a high-pressure mercury lamp in the air to irradiate energy Hardening was performed under the conditions of 0.5 J / cm 2 .
接著,在形成氣體障壁層之側的面上形成厚度2μm之透明硬塗層。具體來說,塗佈JSR股份有限公司製,UV硬化型樹脂OPSTAR(註冊商標)Z7527使乾燥膜厚成為2μm後,於80℃下乾燥,之後,在空氣下,使用高壓水銀燈,以照射能量0.5J/cm2之條件進行硬化。如此來製作基材(以下關於所有的製作例,使用相同的基材)。 Next, a transparent hard coat layer having a thickness of 2 μm was formed on the surface on the side where the gas barrier layer was formed. Specifically, a UV-curable resin OPSTAR (registered trademark) Z7527 made by JSR Co., Ltd. was coated to a dry film thickness of 2 μm, and then dried at 80 ° C. Then, a high-pressure mercury lamp was used in the air to irradiate the energy of 0.5. J / cm 2 is used for hardening. A base material was produced in this manner (the same base material is used for all production examples below).
在基材之一側的面上藉由氣相法‧濺鍍(磁控濺鍍裝置‧Canon-anelva公司製:型式EB1100(以下,濺鍍是使用相同裝置)),來將第1氣體障壁層製膜。所使用之濺鍍裝置能設置複數種標靶,並能夠以維持在特定真空狀態之下,連續地製膜金屬種類相異的複數層。 The first gas barrier was formed on the surface of one side of the substrate by a vapor phase method, sputtering (magnetron sputtering device, made by Canon-anelva: type EB1100 (hereinafter, the same device is used for sputtering)). Layer film. The sputtering device used can set a plurality of targets, and can continuously form a plurality of layers of different types of metals while maintaining a specific vacuum state.
於此,使用多結晶Si標靶作為標靶,處理氣體是使用Ar與O2,並藉由DC濺鍍形成膜厚30nm之層。製膜 是藉由調整氧分壓使層之組成成為SiO2來進行。且,事先藉由使用玻璃基板之製膜,並藉由調整氧分壓來進行組成的條件蒐尋,找出自表層至深度10nm附近的組成成為SiO2之條件,並適用其條件。且,關於膜厚,取得在100nm~300nm之範圍內,相對於製膜時間之膜厚變化的數據,算出每單位時間所製膜的膜厚後,設定製膜時間使其成為設定厚度,藉此調整膜厚。以下,以濺鍍之製膜也同樣地,找出自表層至深度10nm附近的組成成為所望之組成的條件,進一步算出每單位時間所製膜之膜厚,並適用其條件。 Here, a polycrystalline Si target is used as the target, and the processing gas is Ar and O 2 , and a layer with a thickness of 30 nm is formed by DC sputtering. Film formation is performed by adjusting the oxygen partial pressure so that the composition of the layer becomes SiO 2 . In addition, a condition search for the composition was performed by forming a film using a glass substrate in advance and adjusting the oxygen partial pressure to find out the conditions where the composition from the surface layer to a depth of about 10 nm became SiO 2 and the conditions were applied. In addition, regarding the film thickness, data on the film thickness change with respect to the film formation time in the range of 100 nm to 300 nm are obtained. After calculating the film thickness per unit time, the film formation time is set to a set thickness, and This adjusts the film thickness. Hereinafter, the conditions for forming a film from the surface layer to a depth of about 10 nm are the same as those for the film formation by sputtering, and the film thickness per unit time is calculated, and the conditions are applied.
以上述手法,在基材之一側的面上形成第1氣體障壁層(組成:SiO2、膜厚:30nm),製作氣體障壁性薄膜1-1。 A first gas barrier layer (composition: SiO 2 , film thickness: 30 nm) was formed on the surface on one side of the substrate by the above-mentioned method, and a gas barrier film 1-1 was produced.
使第1氣體障壁層之組成成為SiO1.7來調整DC濺鍍時的氧分壓以外,其餘與上述氣體障壁性薄膜1-1之製作同樣地,製作氣體障壁性薄膜1-3。 Except that the composition of the first gas barrier layer was SiO 1.7 and the oxygen partial pressure during DC sputtering was adjusted, the rest of the gas barrier film 1-3 was produced in the same manner as in the production of the gas barrier film 1-1.
使第1氣體障壁層之組成成為SiO1.6來調整DC濺鍍時的氧分壓以外,其餘與上述氣體障壁性薄膜1-1之製作同樣地,製作氣體障壁性薄膜1-5。 Except that the composition of the first gas barrier layer was SiO 1.6 and the oxygen partial pressure during DC sputtering was adjusted, the rest of the gas barrier film 1-5 was produced in the same manner as in the production of the gas barrier film 1-1.
在上述氣體障壁性薄膜1-1之第1氣體障壁層之露出表面,由以下之手法來形成過渡金屬氧化物含有層,製作氣體障壁性薄膜1-2。 On the exposed surface of the first gas barrier layer of the gas barrier film 1-1, a transition metal oxide-containing layer was formed by the following method to produce a gas barrier film 1-2.
於此,使用缺氧型Nb2O5標靶作為標靶,在處理氣體使用Ar與O2,藉由DC濺鍍,形成過渡金屬氧化物含有層(組成:NbO2.5、膜厚:15nm)。 Here, an oxygen-deficient Nb 2 O 5 target is used as a target, and Ar and O 2 are used as a process gas, and a transition metal oxide-containing layer is formed by DC sputtering (composition: NbO 2.5 , film thickness: 15 nm) .
使用氣體障壁性薄膜1-3取代氣體障壁性薄膜1-1以外,其餘與上述氣體障壁性薄膜1-2之製作同樣地,製作氣體障壁性薄膜1-4。 Instead of using the gas barrier film 1-3 instead of the gas barrier film 1-1, the gas barrier film 1-4 was produced in the same manner as in the production of the gas barrier film 1-2.
使用氣體障壁性薄膜1-5取代氣體障壁性薄膜1-1以外,其餘與上述氣體障壁性薄膜1-2之製作同樣地,製作氣體障壁性薄膜1-6。 Instead of using the gas barrier film 1-5 instead of the gas barrier film 1-1, the gas barrier film 1-6 was produced in the same manner as in the production of the gas barrier film 1-2.
使過渡金屬氧化物含有層之組成成為NbO2.2來調整DC濺鍍時的氧分壓以外,其餘與上述氣體障壁性薄膜1-2之製作同樣地,製作氣體障壁性薄膜1-7。 Except that the composition of the transition metal oxide-containing layer was changed to NbO 2.2 and the oxygen partial pressure during DC sputtering was adjusted, the rest of the gas barrier films 1 to 7 were produced in the same manner as in the production of the gas barrier film 1-2.
使第1氣體障壁層之組成成為SiO1.9來調整DC濺鍍時的氧分壓以外,其餘與上述氣體障壁性薄膜1-7之製作同樣地,製作氣體障壁性薄膜1-8。 Except that the composition of the first gas barrier layer was SiO 1.9 and the oxygen partial pressure at the time of DC sputtering was adjusted, the rest of the gas barrier films 1-7 were produced in the same manner as in the production of the gas barrier films 1-7.
藉由以下手法,製作實施例2之氣體障壁性薄膜。將實施例2所製作之各薄膜的構成以及製作條件分別表示於下述表2。 The gas barrier film of Example 2 was produced by the following method. The structure and manufacturing conditions of each thin film produced in Example 2 are shown in Table 2 below.
除了不形成第1氣體障壁層以外,其餘與氣體障壁性薄膜1-2之製作同樣地,製作氣體障壁性薄膜2-1。 A gas barrier film 2-1 was produced in the same manner as in the production of the gas barrier film 1-2, except that the first gas barrier layer was not formed.
在上述氣體障壁性薄膜2-1之過渡金屬氧化物含有層的露出表面上,藉由與氣體障壁性薄膜1-3中相同之手法,形成第1氣體障壁層,製作氣體障壁性薄膜2-2。 On the exposed surface of the transition metal oxide-containing layer of the gas barrier film 2-1, a first gas barrier layer was formed in the same manner as in the gas barrier film 1-3, and a gas barrier film 2- was produced. 2.
在上述氣體障壁性薄膜2-1之過渡金屬氧化物含有層的露出表面上,藉由與氣體障壁性薄膜1-5中相同之手法,形成第1氣體障壁層,製作氣體障壁性薄膜2-3。 On the exposed surface of the transition metal oxide-containing layer of the gas barrier film 2-1, a first gas barrier layer was formed by the same method as in the gas barrier film 1-5, and a gas barrier film 2- was produced. 3.
使過渡金屬氧化物含有層之組成成為NbO1.5來調整DC濺鍍時的氧分壓以外,其餘與上述氣體障壁性薄膜2-1之製作同樣地,製作氣體障壁性薄膜2-4。 Except that the composition of the transition metal oxide-containing layer was NbO 1.5 and the oxygen partial pressure at the time of DC sputtering was adjusted, the rest of the gas barrier film 2-4 was produced in the same manner as in the production of the gas barrier film 2-1.
在上述氣體障壁性薄膜2-4之過渡金屬氧化物含有層的露出表面上,藉由與氣體障壁性薄膜1-1中相同之手法形成第1氣體障壁層,製作氣體障壁性薄膜2-5。 On the exposed surface of the transition metal oxide-containing layer of the gas barrier film 2-4, a first gas barrier layer was formed by the same method as in the gas barrier film 1-1, and a gas barrier film 2-5 was produced. .
在上述氣體障壁性薄膜2-4之過渡金屬氧化物含有層的露出表面上,藉由與氣體障壁性薄膜2-4中相同之手法,再製膜1層過渡金屬氧化物含有層,製作氣體障壁性薄膜2-6。 On the exposed surface of the transition metal oxide-containing layer of the gas barrier film 2-4, a transition metal oxide-containing layer was further formed by the same method as that in the gas barrier film 2-4 to produce a gas barrier. Sex film 2-6.
藉由以下手法,製作實施例3之氣體障壁性薄膜。將實施例3所製作之各薄膜的構成以及製作條件分別表示於下述表3。 The gas barrier film of Example 3 was produced by the following method. The structure and manufacturing conditions of each thin film produced in Example 3 are shown in Table 3 below.
在基材之一側的面上藉由真空電漿CVD法製作第1 氣體障壁層。具體來說,使用圖3記載之真空電漿CVD裝置,在基材之一側的面上進行第1氣體障壁層之形成。此時,所使用之高頻電源為27.12MHz之高頻電源,電極間距離為20mm。且,作為原料氣體,將六甲基二矽氧烷氣體以流量10sccm之條件,將氧氣以流量100sccm之條件導入真空室內。製膜開始時,藉由將基材之溫度設為100℃,將成膜時之氣體壓力設為30Pa,形成將含有碳之氧化矽作為主成分之無機層。 The first surface was made on one side of the substrate by vacuum plasma CVD. Gas barrier layer. Specifically, the vacuum plasma CVD apparatus shown in FIG. 3 was used to form the first gas barrier layer on the surface on one side of the substrate. At this time, the high-frequency power used is a 27.12MHz high-frequency power, and the distance between the electrodes is 20mm. In addition, as a raw material gas, hexamethyldisilazane gas was introduced into the vacuum chamber under a condition of a flow rate of 10 sccm, and oxygen was introduced under a condition of a flow rate of 100 sccm. At the beginning of film formation, an inorganic layer containing silicon oxide containing carbon as a main component was formed by setting the temperature of the substrate to 100 ° C. and the gas pressure during film formation to 30 Pa.
藉由上述手法,在基材之一側的面上形成第1氣體障壁層(組成:SiO1.6C0.4,膜厚:200nm),製作氣體障壁性薄膜3-1。 By the above method, a first gas barrier layer (composition: SiO 1.6 C 0.4 , film thickness: 200 nm) was formed on a surface on one side of the base material, and a gas barrier film 3-1 was produced.
在上述氣體障壁性薄膜3-1之第1氣體障壁層的露出表面上,藉由與氣體障壁性薄膜2-2中相同的氣相法‧濺鍍,再形成1層氣體障壁層,製作氣體障壁性薄膜3-2。且,此2層之形成不會連續地進行,第1層形成後先暫時暴露於大氣中後,進行第2層之形成。 On the exposed surface of the first gas barrier layer 3-1 of the gas barrier film 3-1, a gas barrier layer was sputtered by the same gas phase method as in the gas barrier film 2-2, and a gas barrier layer was formed to produce a gas. Barrier film 3-2. In addition, the formation of these two layers does not proceed continuously, and the formation of the second layer is performed after being temporarily exposed to the atmosphere after the formation of the first layer.
在上述氣體障壁性薄膜3-1之第1氣體障壁層的露出表面上,藉由與氣體障壁性薄膜1-2中相同的手法,形成過渡金屬氧化物含有層,製作氣體障壁性薄膜3-3。且,此2層之形成不會連續地進行,第1層形成後先暫時暴露 於大氣中後,進行第2層之形成。 On the exposed surface of the first gas barrier layer of the gas barrier film 3-1, a transition metal oxide-containing layer was formed by the same method as in the gas barrier film 1-2 to produce a gas barrier film 3- 3. In addition, the formation of the two layers will not be performed continuously, and the first layer is temporarily exposed after the formation After being exposed to the atmosphere, a second layer is formed.
在上述氣體障壁性薄膜3-1之第1氣體障壁層的露出表面上,藉由與氣體障壁性薄膜2-6中相同的手法,形成過渡金屬氧化物含有層,製作氣體障壁性薄膜3-4。且,此2層之形成不會連續地進行,第1層形成後先暫時暴露於大氣中後,進行第2層之形成。 On the exposed surface of the first gas barrier layer of the gas barrier film 3-1, a transition metal oxide-containing layer was formed by the same method as in the gas barrier film 2-6 to produce a gas barrier film 3- 4. In addition, the formation of these two layers does not proceed continuously, and the formation of the second layer is performed after being temporarily exposed to the atmosphere after the formation of the first layer.
使第1氣體障壁層之膜厚成為200nm來調整DC濺鍍時的製膜時間以外,其餘與上述氣體障壁性薄膜1-1之製作同樣地,製作氣體障壁性薄膜3-5。 Except that the film thickness of the first gas barrier layer was set to 200 nm and the film formation time during DC sputtering was adjusted, the rest of the gas barrier film 3-5 was produced in the same manner as in the production of the gas barrier film 1-1.
使第1氣體障壁層之組成成為SiO1.8來調整DC濺鍍時的氧分壓以外,其餘與上述氣體障壁性薄膜3-5之製作同樣地,製作氣體障壁性薄膜3-6。 Except that the composition of the first gas barrier layer was SiO 1.8 and the oxygen partial pressure during DC sputtering was adjusted, the rest of the gas barrier films 3-6 were produced in the same manner as in the above-mentioned production of the gas barrier films 3-5.
在上述氣體障壁性薄膜3-5之第1氣體障壁層的露出表面上,藉由與氣體障壁性薄膜3-3中相同之手法,形成過渡金屬氧化物含有層,製作氣體障壁性薄膜3-7。且,此2層之形成不會連續地進行,第1層形成後先暫時暴露 於大氣中後,進行第2層之形成。 On the exposed surface of the first gas barrier layer of the gas barrier film 3-5, a transition metal oxide-containing layer was formed by the same method as in the gas barrier film 3-3 to produce a gas barrier film 3- 7. In addition, the formation of the two layers will not be performed continuously, and the first layer is temporarily exposed after the formation After being exposed to the atmosphere, a second layer is formed.
在上述氣體障壁性薄膜3-5之第1氣體障壁層的露出表面上,藉由與氣體障壁性薄膜3-4中相同之手法,形成過渡金屬氧化物含有層,製作氣體障壁性薄膜3-8。且,此2層之形成不會連續地進行,第1層形成後先暫時暴露於大氣中後,進行第2層之形成。 On the exposed surface of the first gas barrier layer of the gas barrier film 3-5, a transition metal oxide-containing layer was formed by the same method as that of the gas barrier film 3-4 to produce a gas barrier film 3- 8. In addition, the formation of these two layers does not proceed continuously, and the formation of the second layer is performed after being temporarily exposed to the atmosphere after the formation of the first layer.
將2層之形成在相同的磁控濺鍍裝置之內部中連續地進行,並在2層之形成之間不暴露於大氣中以外,其餘與上述氣體障壁性薄膜3-8之製作同樣地,製作氣體障壁性薄膜3-9。 The formation of the two layers was continuously performed inside the same magnetron sputtering device, and was not exposed to the atmosphere between the formation of the two layers. The rest was the same as the production of the gas barrier film 3-8. Make a gas barrier film 3-9.
使過渡金屬氧化物含有層之組成成為NbO2.1來調整DC濺鍍時的氧分壓以外,其餘與上述氣體障壁性薄膜3-9之製作同樣地,製作氣體障壁性薄膜3-10。 The composition of the transition metal oxide-containing layer was changed to NbO 2.1 , except that the oxygen partial pressure at the time of DC sputtering was adjusted, the rest of the gas barrier film 3-9 was produced in the same manner as in the production of the gas barrier film 3-9.
使過渡金屬氧化物含有層之組成成為TaO1.5,來使用Ta2O5標靶作為DC濺鍍時的標靶以外,其餘與上述氣體障壁性薄膜3-8之製作同樣地,製作氣體障壁性薄膜3- 11。 The composition of the transition metal oxide-containing layer was set to TaO 1.5 , and a Ta 2 O 5 target was used as a target during DC sputtering. The rest of the gas barrier properties were produced in the same manner as in the production of the gas barrier film 3-8. Film 3--11.
在上述氣體障壁性薄膜3-5之第1氣體障壁層的露出表面上,藉由以下之離子輔助蒸鍍法,形成過渡金屬氧化物含有層,製作氣體障壁性薄膜3-12。且,此2層之形成不會連續地進行,第1層形成後先暫時暴露於大氣中後,進行第2層之形成。 On the exposed surface of the first gas barrier layer of the gas barrier film 3-5, a transition metal oxide-containing layer was formed by the following ion-assisted evaporation method to produce a gas barrier film 3-12. In addition, the formation of these two layers does not proceed continuously, and the formation of the second layer is performed after being temporarily exposed to the atmosphere after the formation of the first layer.
藉由日本特開2011-39218號公報之段落「0035」以後所記載之裝置,使用會使氬氣與氧氣電離放電的離子輔助(離子源輔助)法,並以使鈮金屬膜厚堆積成15nm之條件來製膜。且,由事前之探討,使蒸鍍膜之組成成為NbO1.8來調整氧分壓。且,離子源輔助之條件如以下所述:加速電壓:1000V The device described in Japanese Patent Application Laid-Open No. 2011-39218, paragraph "0035" or later, uses an ion assisted (ion source assisted) method that ionizes and discharges argon and oxygen, and deposits a niobium metal film to a thickness of 15 nm. Conditions for film formation. In addition, from the prior discussion, the composition of the vapor deposition film was changed to NbO 1.8 to adjust the oxygen partial pressure. And, the conditions of the ion source assistance are as follows: Acceleration voltage: 1000V
加速電流:200mA。 Acceleration current: 200mA.
在基材之一側的面上藉由真空電漿CVD法製作第1氣體障壁層。具體來說,使用圖3記載之真空電漿CVD裝置,在基材之一側的面上進行第1氣體障壁層之形成。此時,所使用之高頻電源為27.12MHz之高頻電源,電極 間距離為20mm。且,作為原料氣體,將矽烷氣體以流量7.5sccm之條件,將氨氣以流量50sccm之條件,將氫氣以流量200sccm之條件導入真空室內。製膜開始時,藉由將基材之溫度設為100℃,將成膜時之氣體壓力設為30Pa,形成將氮化矽作為主成分之無機層。 A first gas barrier layer was produced on a surface on one side of the substrate by a vacuum plasma CVD method. Specifically, the vacuum plasma CVD apparatus shown in FIG. 3 was used to form the first gas barrier layer on the surface on one side of the substrate. At this time, the high-frequency power used is a high-frequency power of 27.12MHz. The distance is 20mm. In addition, as the raw material gas, a silane gas was introduced into the vacuum chamber under a condition of a flow rate of 7.5 sccm, an ammonia gas was used under a condition of a flow rate of 50 sccm, and a hydrogen gas was used at a flow rate of 200 sccm. At the beginning of film formation, an inorganic layer containing silicon nitride as a main component was formed by setting the temperature of the substrate to 100 ° C. and the gas pressure during film formation to 30 Pa.
藉由上述手法,在基材之一側的面上形成第1氣體障壁層(組成:SiO0.05N0.8、膜厚:100nm),製作氣體障壁性薄膜3-13。 By the above method, a first gas barrier layer (composition: SiO 0.05 N 0.8 , film thickness: 100 nm) was formed on a surface on one side of the base material, and a gas barrier film 3-13 was produced.
在上述氣體障壁性薄膜3-13之第1氣體障壁層的露出表面上,藉由與氣體障壁性薄膜3-2中相同的氣相法‧濺鍍,再形成1層氣體障壁層,製作氣體障壁性薄膜3-14。且,此2層之形成不會連續地進行,第1層形成後先暫時暴露於大氣中後,進行第2層之形成。 On the exposed surface of the first gas barrier layer of the gas barrier film 3-13, a gas barrier layer was sputtered by the same gas phase method as that of the gas barrier film 3-2, and a gas barrier layer was formed to produce a gas. Barrier film 3-14. In addition, the formation of these two layers does not proceed continuously, and the formation of the second layer is performed after being temporarily exposed to the atmosphere after the formation of the first layer.
在上述氣體障壁性薄膜3-13之第1氣體障壁層的露出表面上,藉由與氣體障壁性薄膜3-4中相同之手法,形成過渡金屬氧化物含有層,製作氣體障壁性薄膜3-15。且,此2層之形成不會連續地進行,第1層形成後先暫時暴露於大氣中後,進行第2層之形成。 On the exposed surface of the first gas barrier layer of the gas barrier film 3-13, a transition metal oxide-containing layer was formed in the same manner as in the gas barrier film 3-4, and a gas barrier film 3- was produced. 15. In addition, the formation of these two layers does not proceed continuously, and the formation of the second layer is performed after being temporarily exposed to the atmosphere after the formation of the first layer.
在基材之一側的面上,藉由氣相法‧濺鍍,由以下之製膜條件,形成第1氣體障壁層(組成:ZnSn0.7O1.82、膜厚:200nm),製作氣體障壁性薄膜3-16。且,表3所記載之「(M1)之最大價數」為自Zn之最大價數2以及Sn之最大價數6、與Zn:Sn之莫耳比(1:0.7),作為Zn以及Sn合計為1莫耳時之理論上最大價數,算出(2×1+6×0.7)/(1+0.7)=3.65。 A first gas barrier layer (composition: ZnSn 0.7 O 1.82 , film thickness: 200 nm) was formed on the surface of one side of the substrate by a vapor phase method and sputtering under the following film formation conditions to produce a gas barrier property Film 3-16. In addition, the "maximum valence of (M1)" described in Table 3 is the maximum valence of 2 from Zn and the maximum valence of 6 from Sn, and the molar ratio (1: 0.7) to Zn: Sn, as Zn and Sn The theoretical maximum valence for a total of 1 mole is calculated as (2 × 1 + 6 × 0.7) / (1 + 0.7) = 3.65.
使用ZnSn合金標靶作為標靶,在處理氣體使用Ar與O2,藉由DC濺鍍,形成第1氣體障壁層。 A ZnSn alloy target was used as a target, and Ar and O 2 were used as a process gas, and a DC gas sputtering was used to form a first gas barrier layer.
在上述氣體障壁性薄膜3-16之第1氣體障壁層的露出表面上,藉由與氣體障壁性薄膜3-2中相同的氣相法‧濺鍍,再形成1層氣體障壁層,製作氣體障壁性薄膜3-17。且,此2層之形成在相同之磁控濺鍍裝置的內部中連續地進行,且在2層之形成之間不需暴露於大氣中。 On the exposed surface of the first gas barrier layer 3-16 of the gas barrier film 3-16, a gas barrier layer was sputtered in the same manner as in the gas barrier film 3-2, and a gas barrier layer was further formed to produce a gas. Barrier film 3-17. Moreover, the formation of the two layers is continuously performed in the same interior of the magnetron sputtering device, and it is not necessary to be exposed to the atmosphere between the formation of the two layers.
在上述氣體障壁性薄膜3-16之第1氣體障壁層的露出表面上,藉由與氣體障壁性薄膜3-4中相同之手法,形成過渡金屬氧化物含有層,製作氣體障壁性薄膜3-18。且,此2層之形成在相同之磁控濺鍍裝置的內部中連續地 進行,且在2層之形成之間不需暴露於大氣中。 On the exposed surface of the first gas barrier layer of the gas barrier film 3-16, a transition metal oxide-containing layer was formed by the same method as in the gas barrier film 3-4, and a gas barrier film 3 was produced 3- 18. In addition, the formation of these two layers is continuous in the interior of the same magnetron sputtering device. It does not need to be exposed to the atmosphere between the two layers.
在上述氣體障壁性薄膜3-6之第1氣體障壁層的露出表面上,藉由以下之塗佈改質法,形成聚矽氧烷改質層所成之保護層,製作氣體障壁性薄膜3-19。 On the exposed surface of the first gas barrier layer of the gas barrier film 3-6, a protective layer made of a polysiloxane modified layer was formed by the following coating modification method to produce a gas barrier film 3 -19.
將聚甲基矽倍半氧烷(SR-13,小西化學工業公司製)溶解於甲乙酮,過濾後,得到5質量%之塗佈液。將此藉由旋塗,使乾燥膜厚成為100nm來塗佈,在100℃下乾燥2分鐘。接著,對乾燥後的塗膜,使用具有波長172nm之Xe準分子燈的真空紫外線照射裝置,以照射能量4J/cm2之條件進行真空紫外線照射處理。此時,照射環境以氮取代,氧濃度設為0.1體積%。且,將設置試料的載台溫度設為80℃。 Polymethylsilsesquioxane (SR-13, manufactured by Konishi Chemical Industry Co., Ltd.) was dissolved in methyl ethyl ketone and filtered to obtain a coating solution of 5 mass%. This was applied by spin coating to a dry film thickness of 100 nm, and dried at 100 ° C for 2 minutes. Next, the dried coating film was subjected to vacuum ultraviolet irradiation treatment using a vacuum ultraviolet irradiation device having an Xe excimer lamp with a wavelength of 172 nm under the condition of irradiation energy of 4 J / cm 2 . At this time, the irradiation environment was replaced with nitrogen, and the oxygen concentration was set to 0.1% by volume. The stage temperature at which the sample was set was set to 80 ° C.
於上述氣體障壁性薄膜3-9之過渡金屬氧化物含有層的露出表面上,藉由以下之塗佈改質法,形成第2氣體障壁層,製作氣體障壁性薄膜3-20。且,過渡金屬氧化物含有層之形成與第2氣體障壁層之形成不會連續地進行,在過渡金屬氧化物含有層之形成後先暫時暴露於大氣中後,進行第2氣體障壁層之形成。 On the exposed surface of the transition metal oxide-containing layer of the gas barrier film 3-9, a second gas barrier layer was formed by the following coating modification method to produce a gas barrier film 3-20. In addition, the formation of the transition metal oxide-containing layer and the formation of the second gas barrier layer are not continuously performed. After the formation of the transition metal oxide-containing layer, the second gas barrier layer is formed after being temporarily exposed to the atmosphere. .
將包含高氫化聚矽氮烷20質量%之二丁醚溶液(Merck公司製,NN120-20)、與包含胺觸媒(N,N,N’,N’-四甲基-1,6-二胺己烷(TMDAH))之高氫化聚矽氮烷20質量%之二丁醚溶液(Merck公司製,NAX120-20)以4:1(質量比)之比例混合,進一步為了調整乾燥膜厚以二丁醚做適當地稀釋,調製塗佈液。 A 20% by mass solution of dibutyl ether containing highly hydrogenated polysilazane (NN120-20, manufactured by Merck) and an amine catalyst (N, N, N ', N'-tetramethyl-1,6- Diamine hexane (TMDAH)) high hydrogenated polysilazane 20% by mass dibutyl ether solution (Merck, NAX120-20) was mixed at a ratio of 4: 1 (mass ratio), and the thickness of the dried film was adjusted further. Dibutyl ether was appropriately diluted to prepare a coating solution.
在上述過渡金屬氧化物含有層的露出表面上,藉由旋塗法塗佈上述塗佈液使乾燥膜厚成為100nm,於80℃下乾燥2分鐘。接著,對乾燥後的塗膜,使用具有波長172nm之Xe準分子燈的真空紫外線照射裝置,以照射能量4J/cm2之條件進行真空紫外線照射處理。此時,照射環境以氮取代,氧濃度設為0.1體積%。且,將設置試料的載台溫度設為80℃。 On the exposed surface of the transition metal oxide-containing layer, the coating liquid was applied by a spin coating method so as to have a dry film thickness of 100 nm, and dried at 80 ° C. for 2 minutes. Next, the dried coating film was subjected to vacuum ultraviolet irradiation treatment using a vacuum ultraviolet irradiation device having an Xe excimer lamp with a wavelength of 172 nm under the condition of irradiation energy of 4 J / cm 2 . At this time, the irradiation environment was replaced with nitrogen, and the oxygen concentration was set to 0.1% by volume. The stage temperature at which the sample was set was set to 80 ° C.
於上述氣體障壁性薄膜3-9之過渡金屬氧化物含有層的露出表面上,藉由與氣體障壁性薄膜3-19之製作中相同之手法,形成第2氣體障壁層,製作氣體障壁性薄膜3-21。且,過渡金屬氧化物含有層之形成與第2氣體障壁層之形成不會連續地進行,在過渡金屬氧化物含有層之形成後先暫時暴露於大氣中後,進行第2氣體障壁層之形成。 On the exposed surface of the transition metal oxide-containing layer of the gas barrier film 3-9, a second gas barrier layer was formed by the same method as in the production of the gas barrier film 3-19, and a gas barrier film was produced. 3-21. In addition, the formation of the transition metal oxide-containing layer and the formation of the second gas barrier layer are not continuously performed. After the formation of the transition metal oxide-containing layer, the second gas barrier layer is formed after being temporarily exposed to the atmosphere. .
於上述氣體障壁性薄膜3-9之過渡金屬氧化物含有層的露出表面上,藉由與氣體障壁性薄膜1-1之製作中第1氣體障壁層之形成相同之手法,形成第2氣體障壁層,製作氣體障壁性薄膜3-22。此時,使第2氣體障壁層之膜厚成為100nm,來調整DC濺鍍時之製膜時間。且,關於過渡金屬氧化物含有層之形成與第2氣體障壁層之形成,也在相同的磁控濺鍍裝置之內部中連續地進行,且在2層之形成之間不需暴露於大氣中。 On the exposed surface of the transition metal oxide-containing layer of the gas barrier film 3-9, a second gas barrier was formed in the same manner as the formation of the first gas barrier layer in the production of the gas barrier film 1-1. Layer to make a gas barrier film 3-22. At this time, the film thickness of the second gas barrier layer was set to 100 nm to adjust the film formation time during DC sputtering. In addition, the formation of the transition metal oxide-containing layer and the formation of the second gas barrier layer are continuously performed in the same magnetron sputtering apparatus, and there is no need to be exposed to the atmosphere between the formation of the two layers. .
藉由以下手法,製作實施例4之氣體障壁性薄膜。將實施例4所製作之各薄膜的構成以及製作條件分別表示於下述表4。 The gas barrier film of Example 4 was produced by the following method. The structure and manufacturing conditions of each thin film produced in Example 4 are shown in Table 4 below.
使第1氣體障壁層之膜厚成為150nm來調整DC濺鍍時的製膜時間以外,其餘與上述氣體障壁性薄膜1-1之製作同樣地,製作氣體障壁性薄膜4-1。 A gas barrier film 4-1 was produced in the same manner as in the above-mentioned production of the gas barrier film 1-1 except that the film thickness of the first gas barrier layer was set to 150 nm to adjust the film formation time during DC sputtering.
在上述氣體障壁性薄膜4-1之第1氣體障壁層的露出表面上,由以下之手法來形成過渡金屬氧化物含有層,製作氣體障壁性薄膜4-2。 On the exposed surface of the first gas barrier layer of the gas barrier film 4-1, a transition metal oxide-containing layer was formed by the following method to produce a gas barrier film 4-2.
於此,使用缺氧型Nb2O5標靶作為標靶,在處理氣體使用Ar與O2,藉由DC濺鍍,形成過渡金屬氧化物含有層(組成:NbO2.2,膜厚:15nm)。 Here, an oxygen-deficient Nb 2 O 5 target is used as a target, and Ar and O 2 are used as a process gas, and a transition metal oxide-containing layer is formed by DC sputtering (composition: NbO 2.2 , film thickness: 15 nm) .
使過渡金屬氧化物含有層之組成成為NbO2.1來調整DC濺鍍時的氧分壓以外,其餘與上述氣體障壁性薄膜4-2之製作同樣地,製作氣體障壁性薄膜4-3。 The composition of the transition metal oxide-containing layer was changed to NbO 2.1 , except that the oxygen partial pressure at the time of DC sputtering was adjusted, and the rest of the gas barrier film 4-2 was produced in the same manner as in the production of the gas barrier film 4-2.
使過渡金屬氧化物含有層之組成成為NbO1.5來調整DC濺鍍時的氧分壓以外,其餘與上述氣體障壁性薄膜4-2之製作同樣地,製作氣體障壁性薄膜4-4。 The composition of the transition metal oxide containing layer was changed to NbO 1.5 and the oxygen partial pressure at the time of DC sputtering was adjusted. The rest of the gas barrier film 4-4 was produced in the same manner as in the production of the gas barrier film 4-2.
使過渡金屬氧化物含有層之膜厚成為9nm來調整DC濺鍍時之製膜時間以外,其餘與上述氣體障壁性薄膜4-4之製作同樣地,製作氣體障壁性薄膜4-5。 Except that the film thickness of the transition metal oxide-containing layer was adjusted to 9 nm and the film-forming time during DC sputtering was adjusted, the rest of the gas barrier film 4-4 was produced in the same manner as in the production of the gas barrier film 4-4.
使過渡金屬氧化物含有層之膜厚成為5nm來調整DC濺鍍時之製膜時間以外,其餘與上述氣體障壁性薄膜4-4 之製作同樣地,製作氣體障壁性薄膜4-6。 The film thickness of the transition metal oxide-containing layer was set to 5 nm, and the film formation time during DC sputtering was adjusted, and the rest was the same as that of the gas barrier film 4-4. In the same manner, the gas barrier film 4-6 was produced.
使過渡金屬氧化物含有層之膜厚成為3nm來調整DC濺鍍時之製膜時間以外,其餘與上述氣體障壁性薄膜4-4之製作同樣地,製作氣體障壁性薄膜4-7。 Except that the film thickness of the transition metal oxide-containing layer was adjusted to 3 nm to adjust the film formation time at the time of DC sputtering, the gas barrier film 4-7 was produced in the same manner as in the production of the gas barrier film 4-4.
藉由以下手法,製作氣體障壁性薄膜。將所製作之各薄膜之構成(厚度、氣體障壁層之平均組成(氣體障壁層具有區域[a]時區域[a]之平均組成))表示於下述表5。 A gas barrier film was produced by the following method. The composition (thickness, average composition of the gas barrier layer (average composition of the region [a] when the gas barrier layer has the region [a])) of each produced film is shown in Table 5 below.
在兩面經易接著處理之厚度100μm的聚乙烯對苯二甲酸酯薄膜(Toray股份有限公司製、LUMIRROR(註冊商標)(U48))之形成氣體障壁層的面之相反側的面上,形成具有防堵機能之透明硬塗層。具體來說,塗佈UV硬化型樹脂(Aica工業股份有限公司製,品號:Z731L)使乾燥膜厚成為0.5μm之後,於80℃下乾燥,之後,在空氣下,使用高壓水銀燈以照射能量0.5J/cm2之條件進行硬化。 A 100 μm-thick polyethylene terephthalate film (manufactured by Toray Co., Ltd., LUMIRROR (registered trademark) (U48)) on both sides was formed on the side opposite to the side on which the gas barrier layer was formed. Transparent hard coating with anti-blocking function. Specifically, after applying a UV-curable resin (manufactured by Aica Industry Co., Ltd., product number: Z731L) to a dry film thickness of 0.5 μm, drying at 80 ° C., and then using a high-pressure mercury lamp under air to irradiate energy Hardening was performed under the conditions of 0.5 J / cm 2 .
接著,在形成氣體障壁層之側的面上形成厚度2μm之透明硬塗層。具體來說,塗佈JSR股份有限公司製,UV硬化型樹脂OPSTAR(註冊商標)Z7527使乾燥膜厚成為 2μm後,於80℃下乾燥,之後,在空氣下,使用高壓水銀燈,以照射能量0.5J/cm2之條件進行硬化。如此來製作基材(以下關於所有的製作例,使用相同的基材)。 Next, a transparent hard coat layer having a thickness of 2 μm was formed on the surface on the side where the gas barrier layer was formed. Specifically, a UV-curable resin OPSTAR (registered trademark) Z7527 made by JSR Co., Ltd. was coated to a dry film thickness of 2 μm, and then dried at 80 ° C. Then, a high-pressure mercury lamp was used in the air to irradiate the energy of 0.5. J / cm 2 is used for hardening. A base material was produced in this manner (the same base material is used for all production examples below).
在基材之一側的面上藉由氣相法‧濺鍍(磁控濺鍍裝置‧Canon-anelva公司製:型式EB1100(以下,濺鍍是使用相同裝置)),來將氣體障壁層製膜。所使用之濺鍍裝置為能夠進行2元同時濺鍍者。 A gas barrier layer was formed on a surface of one side of the substrate by a gas phase method, sputtering (magnetron sputtering device, manufactured by Canon-anelva: type EB1100 (hereinafter, the same device is used for sputtering)). membrane. The sputtering equipment used is one capable of simultaneous sputtering of 2 yuan.
於此,使用多結晶Si標靶作為標靶,在處理氣體使用Ar與O2,並藉由DC濺鍍形成膜厚30nm之層。製膜是藉由調整氧分壓使層之組成成為SiO2來進行。且,事先藉由使用玻璃基板之製膜,並藉由調整氧分壓來進行組成的條件蒐尋,找出自表層至深度10nm附近的組成成為SiO2之條件,並適用其條件。且,關於膜厚,取得在100nm~300nm之範圍內,相對於製膜時間之膜厚變化的數據,算出每單位時間所製膜的膜厚後,設定製膜時間使其成為設定厚度,藉此調整膜厚。以下,以濺鍍之製膜也同樣地,找出自表層至深度10nm附近的組成成為所望之組成的條件,進一步算出每單位時間所製膜之膜厚,並適用其條件。 Here, a polycrystalline Si target is used as a target, Ar and O 2 are used as a processing gas, and a layer having a thickness of 30 nm is formed by DC sputtering. Film formation is performed by adjusting the oxygen partial pressure so that the composition of the layer becomes SiO 2 . In addition, a condition search for the composition was performed by forming a film using a glass substrate in advance and adjusting the oxygen partial pressure to find out the conditions where the composition from the surface layer to a depth of about 10 nm became SiO 2 and the conditions were applied. In addition, regarding the film thickness, data on the film thickness change with respect to the film formation time in the range of 100 nm to 300 nm are obtained. After calculating the film thickness per unit time, the film formation time is set to a set thickness, and This adjusts the film thickness. Hereinafter, the conditions for forming a film from the surface layer to a depth of about 10 nm are the same as those for the film formation by sputtering, and the film thickness per unit time is calculated, and the conditions are applied.
以上述手法,在基材之一側的面上形成氣體障壁層(組成:SiO2,膜厚:30nm),製作氣體障壁性薄膜5-1。 By the above-mentioned method, a gas barrier layer (composition: SiO 2 , film thickness: 30 nm) was formed on a surface on one side of the base material, and a gas barrier film 5-1 was produced.
使氣體障壁層之組成成為SiO1.8來調整DC濺鍍時的氧分壓以外,其餘與上述氣體障壁性薄膜5-1之製作同樣地,製作氣體障壁性薄膜5-2。 The composition of the gas barrier layer was changed to SiO 1.8 to adjust the oxygen partial pressure during DC sputtering, and the rest of the gas barrier film 5-2 was produced in the same manner as in the production of the gas barrier film 5-1.
於基材之一側的面上,藉由以下手法形成氣體障壁層,製作氣體障壁性薄膜5-3。 A gas barrier layer was formed on the surface on one side of the substrate by the following method to produce a gas barrier film 5-3.
使用缺氧型Nb2O5標靶作為標靶,在處理氣體使用Ar與O2,藉由DC濺鍍,形成含有Nb之氣體障壁層(組成:NbO2.5,膜厚:30nm)。 An oxygen-deficient Nb 2 O 5 target was used as a target, Ar and O 2 were used as a process gas, and a gas barrier layer (composition: NbO 2.5 , film thickness: 30 nm) containing Nb was formed by DC sputtering.
使氣體障壁層之組成成為NbO1.7來調整DC濺鍍時的氧分壓以外,其餘與上述氣體障壁性薄膜5-3之製作同樣地,製作氣體障壁性薄膜5-4。 The composition of the gas barrier layer was changed to NbO 1.7 to adjust the oxygen partial pressure during DC sputtering, and the rest of the gas barrier film 5-4 was produced in the same manner as in the production of the gas barrier film 5-3.
在基材之一側的面上,藉由以下手法,形成氣體障壁層(組成:表5所示,膜厚:30nm),製作氣體障壁性薄膜5-5。 A gas barrier layer (composition: shown in Table 5, film thickness: 30 nm) was formed on the surface on one side of the substrate by the following method, and a gas barrier film 5-5 was produced.
混合粉碎後的Si以及Nb粉末,使其成為Si為80原子%,Nb為20原子%,在Ar環境下進行熱壓,進行燒結。將燒結後之混合材料機械成型後,在銅製之背板上進行接合,並作為標靶。使用所得之標靶,藉由與上述相同的濺鍍,進行製膜,形成氣體障壁層。 The pulverized Si and Nb powder were mixed so that Si was 80 atomic% and Nb was 20 atomic%, and they were hot-pressed in an Ar environment to sinter. After the sintered mixed material is mechanically formed, it is joined on a copper back plate and used as a target. Using the obtained target, a film was formed by the same sputtering as described above to form a gas barrier layer.
使用Si為50原子%、Nb為50原子%之組成者作為濺鍍標靶,使氣體障壁層之組成成為表5所示,來調整DC濺鍍時的氧分壓以外,其餘與上述氣體障壁性薄膜5之製作同樣地,製作氣體障壁性薄膜5-6。 Using a composition with 50 atomic% of Si and 50 atomic% of Nb as the sputtering target, the composition of the gas barrier layer is shown in Table 5, and the rest of the oxygen barrier pressure during DC sputtering is adjusted with the above gas barrier. Production of the flexible film 5 In the same manner, a gas barrier film 5-6 was produced.
使氣體障壁層之組成成為表5所示,來調整DC濺鍍時的氧分壓以外,其餘與上述氣體障壁性薄膜5-6之製作同樣地,製作氣體障壁性薄膜5-7。 The composition of the gas barrier layer is shown in Table 5. The gas barrier film 5-7 was produced in the same manner as in the production of the gas barrier film 5-6 except that the oxygen partial pressure during DC sputtering was adjusted.
使氣體障壁層之組成成為表5所示,來調整DC濺鍍時的氧分壓以外,其餘與上述氣體障壁性薄膜5-6之製作同樣地,製作氣體障壁性薄膜5-8。 The composition of the gas barrier layer is shown in Table 5. The gas barrier film 5-8 was produced in the same manner as in the production of the gas barrier film 5-6 except that the oxygen partial pressure during DC sputtering was adjusted.
使氣體障壁層之膜厚成為20nm來調整DC濺鍍時之製膜時間以外,其餘與上述氣體障壁性薄膜8之製作同樣地,製作氣體障壁性薄膜9。 The gas barrier film 9 was produced in the same manner as in the above-mentioned production of the gas barrier film 8 except that the film thickness of the gas barrier layer was set to 20 nm and the film formation time during the DC sputtering was adjusted.
使氣體障壁層之膜厚成為10nm來調整DC濺鍍時之製膜時間以外,其餘與上述氣體障壁性薄膜5-8之製作同樣地,製作氣體障壁性薄膜5-10。 A gas barrier film 5-10 was produced in the same manner as in the above-mentioned production of the gas barrier film 5-8 except that the film thickness of the gas barrier layer was set to 10 nm to adjust the film formation time during DC sputtering.
使氣體障壁層之膜厚成為4nm來調整DC濺鍍時之製膜時間以外,其餘與上述氣體障壁性薄膜5-8之製作同樣地,製作氣體障壁性薄膜11。 The gas barrier film 11 was produced in the same manner as in the production of the gas barrier film 5-8 except that the film thickness of the gas barrier layer was set to 4 nm to adjust the film formation time during DC sputtering.
使氣體障壁層之膜厚成為100nm來調整DC濺鍍時之製膜時間以外,其餘與上述氣體障壁性薄膜5-8之製作同樣地,製作氣體障壁性薄膜5-12。 Except that the film thickness of the gas barrier layer was adjusted to 100 nm and the film formation time during the DC sputtering was adjusted, the rest of the gas barrier film 5-12 was produced in the same manner as in the production of the gas barrier film 5-8.
在基材之一側的面上,藉由以下手法,形成氣體障壁層(組成:表5所示,膜厚:30nm),製作氣體障壁性薄膜5-13。 A gas barrier layer (composition: shown in Table 5, film thickness: 30 nm) was formed on the surface on one side of the substrate by the following method, and a gas barrier film 5-13 was produced.
以Nb2O5粉末為50質量%以及SiO2粉末為50質量%之比例,將蒸餾水作為分散劑並以球磨粉機混合,將所得之泥漿使用噴霧式乾燥機來造粒,得到二次粒子之粒徑為20~100μm的氧化物混合粉末。 Nb 2 O 5 powder was 50% by mass and SiO 2 powder was 50% by mass. Distilled water was used as a dispersant and mixed with a ball mill. The obtained slurry was granulated using a spray dryer to obtain secondary particles. An oxide mixed powder having a particle size of 20 to 100 μm.
另一方面,使用直徑6吋之銅製的背墊板作為標靶支架。且,將上述氧化物混合粉末應該被溶射之背墊板表面部分以使用Al2O3砥粒之噴砂來進行粗化,成為粗面之狀態。 On the other hand, a copper backing plate with a diameter of 6 inches was used as the target holder. In addition, the surface portion of the backing plate on which the above oxide mixed powder should be sprayed is roughened by sandblasting using Al 2 O 3 particles, and becomes a rough surface state.
接著,將Ni-Al(質量比8:2)之合金粉末於還原環境下進行電漿溶射(使用Metco溶射機),形成膜厚50μm之Ni-Al(質量比8:2)而成的底塗層後,將上述氧化物混合粉末在底塗層上並於還原環境下進行電漿溶射,製作標靶。所得之標靶是將Si以40原子%之比率,並將Nb以60原子%之比率來含有的缺氧型標靶。使用所得之標靶,藉由與上述相同的濺鍍,進行製膜,形成氣體障壁層。 Next, the alloy powder of Ni-Al (mass ratio 8: 2) was subjected to plasma spraying (using a Metco dissolver) in a reducing environment to form a base made of Ni-Al (mass ratio 8: 2) with a thickness of 50 μm After coating, the above oxide mixed powder is plasma-sprayed on the undercoat layer under a reducing environment to produce a target. The obtained target was an anaerobic target containing Si at a ratio of 40 atomic% and Nb at a ratio of 60 atomic%. Using the obtained target, a film was formed by the same sputtering as described above to form a gas barrier layer.
在基材之一側的面上,藉由以下手法,形成氣體障壁層(組成:表5所示,膜厚:30nm),製作氣體障壁性薄膜5-14。 A gas barrier layer (composition: shown in Table 5, film thickness: 30 nm) was formed on the surface on one side of the substrate by the following method, and a gas barrier film 5-14 was produced.
使用多結晶Si標靶以及金屬Nb標靶作為標靶,在處 理氣體使用Ar與O2,藉由DC方式進行2元同時濺鍍,形成氣體障壁層。且,使氣體障壁層之組成成為表5所示來調整DC濺鍍時之多結晶Si標靶中的濺鍍條件、金屬Nb標靶中的濺鍍條件、氧分壓。 A polycrystalline Si target and a metal Nb target were used as targets, and Ar and O 2 were used as a processing gas, and two-dimensional simultaneous sputtering was performed by a DC method to form a gas barrier layer. In addition, the composition of the gas barrier layer was set as shown in Table 5 to adjust the sputtering conditions in the polycrystalline Si target during DC sputtering, the sputtering conditions in the metal Nb target, and the oxygen partial pressure.
使氣體障壁層之組成成為表5所示來調整DC濺鍍時之多結晶Si標靶中的濺鍍條件、金屬Nb標靶中的濺鍍條件、氧分壓以外,其餘與上述氣體障壁性薄膜5-14之製作同樣地,製作氣體障壁性薄膜5-15。 The composition of the gas barrier layer is shown in Table 5. The sputtering conditions in the polycrystalline Si target during DC sputtering, the sputtering conditions in the metal Nb target, and the oxygen partial pressure were adjusted. Production of Film 5-14 Similarly, a gas barrier film 5-15 was produced.
在基材之一側的面上,藉由以下手法形成氣體障壁層(組成:表51所示,膜厚:30nm),製作氣體障壁性薄膜5-16。 On one side of the substrate, a gas barrier layer (composition: shown in Table 51, film thickness: 30 nm) was formed by the following method to produce a gas barrier film 5-16.
使用多結晶Si標靶以及金屬Ta標靶作為標靶,在處理氣體使用Ar與O2,藉由DC方式進行2元同時濺鍍,形成氣體障壁層。且,使氣體障壁層之組成成為表5所示來條調整DC濺鍍時之多結晶Si標靶中的濺鍍條件、金屬Ta標靶中的濺鍍條件、氧分壓。 A polycrystalline Si target and a metal Ta target were used as targets, and Ar and O 2 were used as a process gas, and two-dimensional simultaneous sputtering was performed by a DC method to form a gas barrier layer. In addition, the composition of the gas barrier layer was set as shown in Table 5 to adjust the sputtering conditions in the polycrystalline Si target, the sputtering conditions in the metal Ta target, and the oxygen partial pressure during DC sputtering.
在基材之一側的面上,藉由以下手法,形成氣體障壁層(組成:表5所示,膜厚:30nm),製作氣體障壁性薄膜5-17。 A gas barrier layer (composition: shown in Table 5, film thickness: 30 nm) was formed on the surface on one side of the substrate by the following method, and a gas barrier film 5-17 was produced.
分別準備高純度ZnO粉末、高純度SnO2粉末、作為結合劑之PVB樹脂、作為有機溶劑之乙醇以及丙酮。 A high-purity ZnO powder, a high-purity SnO 2 powder, a PVB resin as a binder, ethanol as an organic solvent, and acetone were prepared separately.
接著,將ZnO粉末、SnO2粉末、結合劑以及有機溶劑藉由球磨粉機之濕式混合以特定比例來混合,調製濃度為40質量%之泥漿。且,將ZnO粉末以及SnO2粉末之混合量調整成形成後的濺鍍標靶中所包含之Zn為50原子%,Sn為50原子%。 Next, ZnO powder, SnO 2 powder, a binder, and an organic solvent were mixed at a specific ratio by wet mixing of a ball mill to prepare a slurry having a concentration of 40% by mass. In addition, the mixing amount of the ZnO powder and the SnO 2 powder was adjusted so that Zn contained in the formed sputtering target was 50 atomic% and Sn was 50 atomic%.
接著,將調製後之泥漿使用噴霧式乾燥機進行噴霧乾燥,得到平均粒徑為200μm之混合造粒粉末後,將此造粒粉末放入特定的模型中藉由單軸加壓裝置來加壓成形。脫模型後,將所得之成形體在大氣環境中以1000℃之溫度使其燒結5小時,得到ZnO-SnO2標靶。使用所得之標靶,藉由與上述相同的濺鍍,進行製膜,形成氣體障壁層。 Next, the prepared slurry is spray-dried using a spray dryer to obtain a mixed granulated powder having an average particle size of 200 μm. This granulated powder is placed in a specific model and pressurized by a uniaxial press. Forming. After demolding, the obtained compact was sintered at 1000 ° C. for 5 hours in an atmospheric environment to obtain a ZnO-SnO 2 target. Using the obtained target, a film was formed by the same sputtering as described above to form a gas barrier layer.
在基材之一側的面上,藉由以下手法,形成氣體障壁層(組成:表5所示,膜厚:30nm),製作氣體障壁性薄膜5-18。 A gas barrier layer (composition: shown in Table 5, film thickness: 30 nm) was formed on the surface on one side of the base material by the following method to produce a gas barrier film 5-18.
使用氣體障壁性薄膜5-17之製作所用的ZnO-SnO2標靶以及金屬Nb標靶作為標靶。在處理氣體使用Ar與O2,藉由DC方式進行2元同時濺鍍,形成氣體障壁層。且,使氣體障壁層之組成成為表5所示來調整DC濺鍍時之ZnO-SnO2標靶中的濺鍍條件、金屬Nb標靶中的濺鍍條件、氧分壓。 ZnO-SnO 2 targets and metal Nb targets used for the production of the gas barrier thin films 5-17 were used as targets. Ar and O 2 were used as a process gas, and two-dimensional simultaneous sputtering was performed by a DC method to form a gas barrier layer. In addition, the composition of the gas barrier layer was set to Table 5 to adjust the sputtering conditions in the ZnO-SnO 2 target, the sputtering conditions in the metal Nb target, and the oxygen partial pressure during DC sputtering.
在基材之一側的面上,藉由以下手法,形成氣體障壁層(組成:表5所示,膜厚:30nm),製作氣體障壁性薄膜5-19。 A gas barrier layer (composition: shown in Table 5, film thickness: 30 nm) was formed on the surface on one side of the substrate by the following method, and a gas barrier film 5-19 was produced.
將純度99.99%以上之SiO2系粉末與ZnS混合使成為Zn為80原子%,Si為20原子%之比率,進一步相對於此混合粉100質量%添加0.1質量%之Na2O後混合。將此混合粉填充於石墨模,以Ar環境,表面壓力150kg/cm2,溫度1000℃之條件來進行熱壓,得到ZnS-SiO2標靶。使用所得之標靶,藉由與上述相同的濺鍍,進行製膜,形成氣體障壁層。 A SiO 2 powder having a purity of 99.99% or more is mixed with ZnS so that the ratio of Zn is 80 atomic% and Si is 20 atomic%. 0.1% by mass of Na 2 O is added to 100% by mass of the mixed powder and mixed. This mixed powder was filled in a graphite mold, and hot-pressed under conditions of an Ar environment, a surface pressure of 150 kg / cm 2 , and a temperature of 1000 ° C. to obtain a ZnS-SiO 2 target. Using the obtained target, a film was formed by the same sputtering as described above to form a gas barrier layer.
在基材之一側的面上,藉由以下手法,形成氣體障壁層(組成:表5所示,膜厚:30nm),製作氣體障壁性薄膜5-20。 A gas barrier layer (composition: shown in Table 5, film thickness: 30 nm) was formed on the surface on one side of the substrate by the following method, and a gas barrier film 5-20 was produced.
使用氣體障壁性薄膜5-19之製作所用的ZnS-SiO2標靶以及金屬Nb標靶作為標靶,在處理氣體使用Ar與O2,藉由DC方式進行2元同時濺鍍,形成氣體障壁層。且,使氣體障壁層之組成成為表5所示來調整DC濺鍍時之ZnS-SiO2標靶中的濺鍍條件、金屬Nb標靶中的濺鍍條件、氧分壓。 ZnS-SiO 2 target and metal Nb target used for the production of the gas barrier thin film 5-19 are used as targets, and Ar and O 2 are used as the processing gas, and two-dimensional simultaneous sputtering is performed by DC method to form a gas barrier. Floor. In addition, the composition of the gas barrier layer was set to Table 5 to adjust the sputtering conditions in the ZnS-SiO 2 target, the sputtering conditions in the metal Nb target, and the oxygen partial pressure during DC sputtering.
對上述實施例1~5所製作之氣體障壁性薄膜進行以下評估。將結果表示於下述表1~表5。且,表1~表5之方格中的斜線標記意指該構成並不存在、或沒有進行對應之評估。 The following evaluation was performed on the gas barrier film produced in the above Examples 1 to 5. The results are shown in Tables 1 to 5 below. Moreover, the slash marks in the squares of Tables 1 to 5 mean that the composition does not exist or no corresponding evaluation has been performed.
藉由XPS分析,測定氣體障壁層以及過渡金屬氧化物含有層的厚度方向之組成分布資料。且,XPS分析條件如以下所示。 By XPS analysis, compositional distribution data of the gas barrier layer and the transition metal oxide-containing layer in the thickness direction were measured. The XPS analysis conditions are as follows.
‧裝置:ULVAC-PHI股份有限公司製QUANTERASXM ‧Equipment: QUANTERASXM manufactured by ULVAC-PHI Co., Ltd.
‧X射線源:單色化Al-Kα ‧X-ray source: Monochromatic Al-Kα
‧濺鍍離子:Ar(2keV) ‧Sputtered ions: Ar (2keV)
‧縱深分析:以SiO2換算之濺鍍厚度,並以特定之厚度間隔來重複測定,得到深度方向之縱深分析。此厚度間隔為在實施例1~3所製作之薄膜的測定時設在2nm(能夠在深度方向得到每2nm之數據),在實施例4所製作之薄膜的測定時設在1nm(能夠在深度方向得到每1nm之數據)。 ‧Depth analysis: Sputter thickness converted in SiO 2 and repeated measurement at specific thickness intervals to obtain depth analysis in the depth direction. This thickness interval is set to 2 nm during the measurement of the thin films produced in Examples 1 to 3 (data can be obtained in the depth direction every 2 nm), and is set to 1 nm during the measurement of the thin films produced in Example 4 (allowable at depth Direction to get data per 1nm).
‧定量:將背景以Shirley法求出,自所得之峰面積使用相對感度係數法來定量。數據處理是使用ULVAC-PHI股份有限公司製之MultiPak。 ‧ Quantification: The background was obtained by the Shirley method, and the obtained peak area was quantified using the relative sensitivity coefficient method. For data processing, MultiPak manufactured by ULVAC-PHI Co., Ltd. was used.
使用MOCON公司製水蒸氣透過率測定裝置AQUATRAN,以38℃ 100%RH之條件測定水蒸氣透過率(單位:g/m2/day)。 The water vapor transmission rate (unit: g / m 2 / day) was measured using a water vapor transmission rate measuring device AQUATRAN made by MOCON under the conditions of 38 ° C and 100% RH.
將如下述所製作之Ca法評估試料保存在40℃ 90%RH環境中500小時。此時,在保存之前後測定透過濃度(任意4點之平均),由其變化算出保存後之水蒸氣透過率(單 位:g/m2/day)。 The Ca method evaluation sample prepared as described below was stored in a 40 ° C 90% RH environment for 500 hours. At this time, the permeation concentration (average of 4 arbitrary points) was measured before and after storage, and the water vapor transmission rate after storage (unit: g / m 2 / day) was calculated from the change.
將形成有氣體障壁性薄膜的氣體障壁層之側的表面進行UV洗淨後,在相同面上以厚度20μm貼合熱硬化型之片狀接著劑(環氧系樹脂)作為密封樹脂層。將此打孔成50mm×50mm之大小後,放入套手工作箱內,進行乾燥處理24小時。 After the surface of the gas barrier layer on which the gas barrier film was formed was UV-washed, a thermosetting sheet-like adhesive (epoxy resin) with a thickness of 20 μm was laminated on the same surface as a sealing resin layer. After punching this into a size of 50mm × 50mm, put it into a hand box and dry it for 24 hours.
接著,將50mm×50mm大小之無鹼玻璃板(厚度0.7mm)的單面進行UV洗淨。使用股份有限公司ALS technology製之真空蒸鍍裝置,在玻璃板之中央介隔著遮罩,以20mm×20mm之大小蒸鍍Ca。Ca之厚度設在80nm。將Ca蒸鍍結束的玻璃板取出至套手工作箱內,將貼合密封樹脂層之氣體障壁性薄膜的密封樹脂層面與玻璃板的Ca蒸鍍面鄰接來配置,並藉由真空層壓接著。此時,進行110℃之加熱。進而,將接著後之試料使玻璃板朝下放置於設定在110℃之熱板上,使其硬化30分鐘,製作Ca法評估試料。 Next, one side of an alkali-free glass plate (thickness: 0.7 mm) having a size of 50 mm × 50 mm was subjected to UV cleaning. Using a vacuum vapor deposition device manufactured by ALS Technology Co., Ltd., Ca was vapor-deposited in a size of 20 mm × 20 mm through a mask in the center of the glass plate. The thickness of Ca is set at 80 nm. Take out the glass plate after Ca vapor deposition into a hand-held work box, arrange the sealing resin layer of the gas barrier film bonded with the sealing resin layer and the Ca vapor deposition surface of the glass plate, and arrange it by vacuum lamination. . At this time, heating was performed at 110 ° C. Furthermore, the next sample was placed on a hot plate set at 110 ° C. with the glass plate facing downward, and was cured for 30 minutes to prepare a Ca method evaluation sample.
使用如下述所製作之有機EL裝置,進行暗點之評估。 The dark spot was evaluated using an organic EL device produced as described below.
在實施例3所製作之氣體障壁性薄膜的形成有氣體障壁層之側的表面上,藉由以下之塗佈改質法,進一步形成2層氣體障壁層,製作對應之裝置評估用氣體障壁性薄膜。 On the surface of the gas barrier film formed on the side where the gas barrier layer was formed in Example 3, two gas barrier layers were further formed by the following coating modification method, and corresponding gas barrier properties for device evaluation were produced. film.
將包含高氫化聚矽氮烷20質量%之二丁醚溶液(Merck公司製,NN120-20)、與包含胺觸媒(N,N,N’,N’-四甲基-1,6-二胺己烷(TMDAH))之高氫化聚矽氮烷20質量%之二丁醚溶液(Merck公司製,NAX120-20)以4:1(質量比)之比例混合,進一步為了調整乾燥膜厚以二丁醚做適當地稀釋,調製塗佈液。 A 20% by mass solution of dibutyl ether containing highly hydrogenated polysilazane (NN120-20, manufactured by Merck) and an amine catalyst (N, N, N ', N'-tetramethyl-1,6- Diamine hexane (TMDAH)) high hydrogenated polysilazane 20% by mass dibutyl ether solution (Merck, NAX120-20) was mixed at a ratio of 4: 1 (mass ratio), and the thickness of the dried film was adjusted further. Dibutyl ether was appropriately diluted to prepare a coating solution.
在氣體障壁性薄膜的形成有氣體障壁層之側的表面上,藉由旋塗法塗佈上述塗佈液使乾燥膜厚成為250nm,於80℃下乾燥2分鐘。接著,對乾燥後的塗膜,使用具有波長172nm之Xe準分子燈的真空紫外線照射裝置,以照射能量6J/cm2之條件進行真空紫外線照射處理。此時,照射環境以氮取代,氧濃度設為0.1體積%。且,將設置試料的載台溫度設為80℃。將此操作再重複一次,形成2層以塗佈改質法而成之氣體障壁層。 On the surface of the gas barrier film on the side where the gas barrier layer is formed, the coating solution was applied by a spin coating method to a dry film thickness of 250 nm, and dried at 80 ° C. for 2 minutes. Next, the dried coating film was subjected to vacuum ultraviolet irradiation treatment using a vacuum ultraviolet irradiation device having an Xe excimer lamp with a wavelength of 172 nm under the condition of irradiation energy of 6 J / cm 2 . At this time, the irradiation environment was replaced with nitrogen, and the oxygen concentration was set to 0.1% by volume. The stage temperature at which the sample was set was set to 80 ° C. This operation was repeated once more to form two layers of a gas barrier layer formed by the coating modification method.
將如此製作之裝置評估用氣體障壁性薄膜作為基材來使用,以如下述所示之方法,使發光區域面積成為5cm×5cm,製作底部發射型之有機電致發光元件(有機EL元件)。 The thus prepared gas barrier film for device evaluation was used as a base material, and the area of the light-emitting region was 5 cm × 5 cm by the method described below to produce a bottom-emission type organic electroluminescence element (organic EL element).
將裝置評估用氣體障壁性薄膜固定在市售之真空蒸鍍裝置的基材支架上,將下述化合物118放入鎢製之電阻加熱板中,將此等基材支架與電阻加熱板裝置在真空蒸鍍裝置的第1真空槽內。且,將銀(Ag)放入鎢製之電阻加熱板中,並裝置在真空蒸鍍裝置之第2真空槽內。 The gas barrier film for device evaluation was fixed to a substrate holder of a commercially available vacuum evaporation device, and the following compound 118 was placed in a resistance heating plate made of tungsten. Inside the first vacuum chamber of the vacuum deposition apparatus. In addition, silver (Ag) was put into a resistance heating plate made of tungsten and installed in a second vacuum tank of a vacuum evaporation device.
接著,將真空蒸鍍裝置之第1真空槽減壓至4×10-4Pa後,通電至有化合物118的加熱板並加熱,以蒸鍍速度0.1nm/秒~0.2nm/秒並以厚度10nm設置第1電極之基底層。 Next, the first vacuum chamber of the vacuum evaporation device was depressurized to 4 × 10 -4 Pa, and then heated to a heating plate having Compound 118 and heated at a deposition rate of 0.1 nm / second to 0.2 nm / second and a thickness of A base layer of the first electrode was provided at 10 nm.
接著,將形成至基底層的基材在真空狀態下移至第2真空槽,將第2真空槽減壓至4×10-4Pa後,通電有銀之加熱板並加熱。藉此,以蒸鍍速度0.1nm/秒~0.2nm/秒形成厚度8nm之銀而成的第1電極。 Next, the base material formed on the base layer was moved to a second vacuum tank under a vacuum state, the second vacuum tank was decompressed to 4 × 10 -4 Pa, and then a heating plate with silver was applied and heated. Thereby, a first electrode having a thickness of 8 nm of silver was formed at a deposition rate of 0.1 nm / second to 0.2 nm / second.
接下來,使用市售之真空蒸鍍裝置,減壓至真空度1×10-4Pa後,一邊移動基材,一邊將化合物HT-1以蒸鍍速度0.1nm/秒蒸鍍,設置20nm之正孔輸送層(HTL)。 Next, using a commercially available vacuum evaporation device, after decompressing to a vacuum degree of 1 × 10 -4 Pa, while moving the substrate, the compound HT-1 was evaporated at a deposition rate of 0.1 nm / sec. Positive Hole Transport Layer (HTL).
接著,共蒸鍍下述之化合物A-3(藍色發光摻雜劑)、以及下述之化合物H-1(主體化合物),使化合物A-3相對於膜厚線形地從35質量%成為5質量%之方式依部位而使蒸鍍速度變化,並使化合物H-1從65質量%成為95質量 %之方式依部位而使蒸鍍速度變化,使厚度成為70nm,形成發光層。 Next, the following compound A-3 (blue light emitting dopant) and the following compound H-1 (host compound) were co-evaporated so that the compound A-3 linearly changed from 35% by mass to the film thickness. The method of 5% by mass changes the deposition rate depending on the location, and changes the compound H-1 from 65% by mass to 95% by mass. In the method of%, the deposition rate is changed depending on the location, so that the thickness is 70 nm, and a light-emitting layer is formed.
之後,將下述化合物ET-1蒸鍍成膜厚30nm,形成電子輸送層,進一步將氟化鉀(KF)以厚度2nm來形成。進而,將鋁110nm蒸鍍形成第2電極。 Thereafter, the following compound ET-1 was evaporated to a film thickness of 30 nm to form an electron transport layer, and potassium fluoride (KF) was further formed to a thickness of 2 nm. Furthermore, aluminum was deposited at 110 nm to form a second electrode.
接著,作為密封構件使用使用厚度25μm之鋁箔,且在此鋁箔之單面上貼合有厚度20μm之作為密封樹脂層的熱硬化型之片狀接著劑(環氧系樹脂)的密封構件,與製作到第2電極的試料重疊。此時,連續地重疊密封構件之接著劑形成面、與元件之有機機能層面使第1電極以及第2電極之抽取電極的端部露在外面。 Next, a sealing member using a 25 μm-thick aluminum foil, and a 20 μm-thick thermosetting sheet adhesive (epoxy resin) as a sealing resin layer bonded to one side of the aluminum foil, and The samples prepared to the second electrode are overlapped. At this time, the end of the extraction electrode of the first electrode and the second electrode is exposed to the outside by continuously overlapping the adhesive formation surface of the sealing member and the organic functional layer of the element.
接著,將試料配置於減壓裝置內,在90℃且0.1MPa之減壓條件下,施加壓力於重疊後的基材與密封構件並保持5分鐘。接著,將試料回到大氣壓環境,進而在120℃下加熱30分鐘並使接著劑硬化。 Next, the sample was placed in a decompression device, and the pressure was applied to the overlapped substrate and the sealing member under a reduced pressure condition of 90 ° C. and 0.1 MPa for 5 minutes. Next, the sample was returned to the atmospheric pressure environment, and further heated at 120 ° C for 30 minutes to harden the adhesive.
上述密封步驟在大氣壓下,並於含水率1ppm以下的氮環境下,根據JIS B 9920:2002,並以測定後之清淨度為等級100,且露點溫度為-80℃以下,氧濃度0.8ppm以下之大氣壓下來進行。且,省略關於自陽極、陰極的抽取配線等之形成的記載。 The above sealing step is under atmospheric pressure and in a nitrogen environment with a moisture content of 1 ppm or less, according to JIS B 9920: 2002, and the cleanliness after the measurement is rated as 100, and the dew point temperature is -80 ° C or lower, and the oxygen concentration is 0.8 ppm or lower. To atmospheric pressure. In addition, description of formation of extraction wiring from an anode and a cathode is omitted.
如此,製作發光區域之面積為5cm×5cm大小的有機EL裝置。 In this manner, an organic EL device having a light emitting area having a size of 5 cm × 5 cm was produced.
將上述所製作之有機EL裝置在85℃ 85%RH的環境下保持300小時後,使其發光,求出圓換算直徑為200μm以上的暗點數,以下述分級來評估:5:0~4個 The organic EL device manufactured as described above was kept in an environment of 85 ° C and 85% RH for 300 hours, and then allowed to emit light. The number of dark dots having a circle-equivalent diameter of 200 μm or more was obtained, and evaluated in the following classification: 5: 0 to 4 Each
4:5~9個 4: 5 ~ 9
3:10~19個 3: 10 ~ 19
2:20~49個 2: 20 ~ 49
1:50個以上。 1: 50 or more.
關於實施例3以及實施例4所製作之氣體障壁性薄膜,測定波長450nm之光透過率,作為光學特性指標。 Regarding the gas barrier film produced in Examples 3 and 4, the light transmittance at a wavelength of 450 nm was measured as an optical characteristic index.
作為對氣體障壁性薄膜被捲繞成卷時的惡化之耐性之指標,施予下述表面接觸‧摺動處理之後,且該表面接觸‧摺動處理係模擬捲繞成卷之處理,藉由與上述「以Ca法的氣體障壁性之評估」相同手法,算出水蒸氣透過率。 As an index of resistance to deterioration when the gas barrier film is wound into a roll, the following surface contact and fold processing is applied, and the surface contact and fold treatment is a process of simulating winding into a roll, The water vapor transmission rate was calculated in the same manner as in the above "Evaluation of Gas Barrier Property by Ca Method".
由上述結果可得知,藉由本發明,能夠提供一種氣體障壁性薄膜,其係顯示非常高的氣體障壁性,且可作為有機EL裝置等之電子裝置用的基板來使用的程度。 From the above results, it can be understood that the present invention can provide a gas barrier film which exhibits a very high gas barrier property and can be used as a substrate for an electronic device such as an organic EL device.
本申請案是基於2015年5月22日申請的日本特許出願號2015-104904號以及日本特許出願號2015-104908號,其揭示內容全體作為參照而援用於此。 This application is based on Japanese Patent Application No. 2015-104904 and Japanese Patent Application No. 2015-104908, filed on May 22, 2015, and the entire disclosure thereof is incorporated herein by reference.
10‧‧‧氣體障壁性薄膜 10‧‧‧Gas barrier film
11‧‧‧基材 11‧‧‧ Substrate
12‧‧‧第1氣體障壁層 12‧‧‧ 1st gas barrier
13‧‧‧過渡金屬氧化物含有層 13‧‧‧ transition metal oxide containing layer
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