TW202319124A - Method of forming film, method of manufacturing electronic device, and film forming apparatus - Google Patents
Method of forming film, method of manufacturing electronic device, and film forming apparatus Download PDFInfo
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- TW202319124A TW202319124A TW111137830A TW111137830A TW202319124A TW 202319124 A TW202319124 A TW 202319124A TW 111137830 A TW111137830 A TW 111137830A TW 111137830 A TW111137830 A TW 111137830A TW 202319124 A TW202319124 A TW 202319124A
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- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 description 1
- HPBNICVODIHXKB-UHFFFAOYSA-N tert-butyl 4-ethenylbenzoate Chemical compound CC(C)(C)OC(=O)C1=CC=C(C=C)C=C1 HPBNICVODIHXKB-UHFFFAOYSA-N 0.000 description 1
- YBRBMKDOPFTVDT-UHFFFAOYSA-N tert-butylamine Chemical compound CC(C)(C)N YBRBMKDOPFTVDT-UHFFFAOYSA-N 0.000 description 1
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- DUBNHZYBDBBJHD-UHFFFAOYSA-L ziram Chemical compound [Zn+2].CN(C)C([S-])=S.CN(C)C([S-])=S DUBNHZYBDBBJHD-UHFFFAOYSA-L 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Images
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D1/00—Processes for applying liquids or other fluent materials
- B05D1/26—Processes for applying liquids or other fluent materials performed by applying the liquid or other fluent material from an outlet device in contact with, or almost in contact with, the surface
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D1/00—Processes for applying liquids or other fluent materials
- B05D1/28—Processes for applying liquids or other fluent materials performed by transfer from the surfaces of elements carrying the liquid or other fluent material, e.g. brushes, pads, rollers
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
- B05D3/04—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by exposure to gases
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/24—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials for applying particular liquids or other fluent materials
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M5/00—Duplicating or marking methods; Sheet materials for use therein
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
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- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/10—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern
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Abstract
Description
本揭示係關於一種膜的形成方法、電子元件的製造方法及膜形成裝置。The present disclosure relates to a film forming method, an electronic element manufacturing method, and a film forming apparatus.
關於對具有段差(例如凹凸圖案、電子零件等)之基板塗佈液體之技術進行各種研究。Various researches are being carried out on techniques for coating liquid on substrates with step differences (such as concave-convex patterns, electronic parts, etc.).
在專利文獻1中,作為能夠防止在藉由塗佈於基板上之溶液來形成之薄膜中產生不均之溶液的塗佈裝置揭示有以下的塗佈裝置。
在專利文獻1中揭示之塗佈裝置為溶液的塗佈裝置,其藉由噴墨方式將溶液向具有在上表面規則地形成有凹部及凸部之凹凸圖案之基板的上述凹部及凸部吐出並塗佈,前述溶液的塗佈裝置具備:
塗佈頭,具有沿著規定方向配置之複數個噴嘴,並且從該複數個噴嘴以恆定的時序將點狀上述溶液塗佈於上述基板;
驅動機構,將上述基板及上述塗佈頭相對移動;及
控制機構,在基於該驅動機構之上述基板與上述塗佈頭的相對移動時進行控制,以使從上述各噴嘴吐出而塗佈於上述基板上之點狀溶液的各列分別跨越上述基板上表面的相鄰之、沿上述凹凸圖案的延長方向延伸之2個以上的上述凸部,以便將上述相對移動方向相對於上述凹凸圖案的上述延長方向錯開規定角度。
在專利文獻2中,作為提供一種以規定塗佈次數重疊地塗佈規定量的密封劑並且無需等待密封劑的滲透而能夠連續塗佈之密封劑的供給控制方法之密封劑的供給控制方法,揭示有以下供給控制方法。 專利文獻2中揭示之供給控制方法為密封劑的供給控制方法,其將吐出密封劑之塗佈頭及安裝有電子零件之電路基板相對移動的同時控制在各電子零件與上述電路基板的各個之間複數次重複而重疊塗佈之密封劑的供給,前述密封劑的供給控制方法如下: 將應塗佈於每1個電子零件之密封劑的供給量分割為對應於密封劑的黏性及電子零件的尺寸之塗佈次數,並且將該密封劑的分割量設定為隨著塗佈次數增加而交替地增減之量,在各塗佈時分配,並且藉由基於塗佈頭的吐出壓力的可變之來自上述塗佈頭的密封劑的吐出量的控制來設定並供給在其各塗佈時分別分配之量的密封劑。 In Patent Document 2, as a sealant supply control method that provides a sealant supply control method that provides a sealant supply control method that provides a sealant supply control method that overlaps and coats a predetermined amount of sealant at a predetermined number of times without waiting for the penetration of the sealant, The following supply control methods are disclosed. The supply control method disclosed in Patent Document 2 is a sealant supply control method, which controls the relative movement of the coating head that discharges the sealant and the circuit board on which the electronic parts are mounted, between each electronic part and each of the above-mentioned circuit boards. The supply of the sealant that is repeatedly coated and overlapped several times, the supply control method of the aforementioned sealant is as follows: Divide the supply amount of sealant to be applied to one electronic part into the number of times of application corresponding to the viscosity of the sealant and the size of the electronic part, and set the divided amount of the sealant to increase with the number of times of application. The amount that increases and alternately increases and decreases is distributed during each coating, and is set and supplied to each coating head by controlling the variable discharge amount of the sealant from the coating head based on the discharge pressure of the coating head. The amount of sealant to be dispensed when applying.
[專利文獻1]日本專利第5244758號公報 [專利文獻2]日本特開平11-47657號公報 [Patent Document 1] Japanese Patent No. 5244758 [Patent Document 2] Japanese Patent Application Laid-Open No. 11-47657
有時在具有基板厚度方向的段差之基板亦即帶段差之基板上,藉由噴墨法來形成至少被覆段差的頂面(亦即,上表面)及側面之膜。 作為帶段差之基板的一例,可舉出具備配線基板及配置於配線基板之電子零件之電子基板。 On a substrate having a step in the thickness direction of the substrate, that is, a substrate with a step, a film covering at least the top surface (that is, the upper surface) and side surfaces of the step may be formed by an inkjet method. As an example of the board|substrate with a step, the electronic board|substrate provided with the wiring board and the electronic component arrange|positioned on the wiring board is mentioned.
藉由本發明人等的研究,判明了在基於噴墨法之上述膜的形成中從段差的頂面上(亦即,上表面上)到段差的側面上的膜的厚度偏差有時變大。The inventors of the present invention have found that, in the formation of the above-mentioned film by the inkjet method, the thickness variation of the film from the top surface (that is, the upper surface) of the step to the side surface of the step sometimes becomes large.
作為膜的厚度偏差變大之情況,具體而言,例如可舉出如下等: 與段差的頂面上的膜的厚度相比,段差的側面上的膜的厚度變得過薄之情況; 與段差的頂面上的膜的厚度相比,段差的側面與頂面的接合處的角部上的膜的厚度過薄之情況。 As the case where the thickness variation of the film becomes large, specifically, for example, the following can be mentioned: The case where the thickness of the film on the sides of the step becomes too thin compared to the thickness of the film on the top surface of the step; The thickness of the film at the corner of the joint between the side surface and the top surface of the step is too thin compared with the thickness of the film on the top surface of the step.
本揭示的一態樣的課題為提供一種膜的形成方法及膜形成裝置,其藉由噴墨法在具有基板厚度方向的段差之基板亦即帶段差之基板上形成至少被覆段差的頂面及段差的側面之膜時能夠抑制從段差的頂面上到段差的側面上的膜的厚度偏差。 本揭示的另一態樣的課題為提供一種電子元件的製造方法,其藉由噴墨法在具備配線基板及配置於配線基板上之電子零件之電子基板上的至少包含電子零件的的頂面及電子零件的側面之區域形成絕緣層及/或導電層來形成電子元件時能夠抑制從電子零件的頂面上到電子零件的側面上的絕緣層及/或導電層的厚度偏差。 An object of an aspect of the present disclosure is to provide a film forming method and a film forming apparatus, which form at least a top surface covered with a step on a substrate having a step in the thickness direction of the substrate, that is, a substrate with a step, by an inkjet method. In the case of the film on the side surface of the step, the variation in thickness of the film from the top surface of the step to the side surface of the step can be suppressed. The subject of another aspect of the present disclosure is to provide a method of manufacturing an electronic component, which uses an inkjet method to coat at least the top surface of the electronic component on the electronic substrate provided with the wiring substrate and the electronic components arranged on the wiring substrate. When the insulating layer and/or the conductive layer are formed in the region of the side surface of the electronic component to form an electronic element, the variation in the thickness of the insulating layer and/or conductive layer from the top surface of the electronic component to the side surface of the electronic component can be suppressed.
用於解決上述課題的具體方法中包括以下態樣。 <1>一種膜的形成方法,其包括: 準備具有基板厚度方向的段差之基板亦即帶段差之基板之製程;及膜形成製程,藉由從噴墨噴頭吐出油墨,將油墨賦予到帶段差之基板中的至少段差的頂面上,並且藉由對賦予到段差的頂面上之油墨吹送風,從而形成至少被覆段差的頂面及段差的側面之膜。 <2>如<1>所述之膜的形成方法,其中 風的風速為1m/s以上且未達30m/s。 <3>如<1>或<2>所述之膜的形成方法,其中 膜形成製程包括回收風之步驟。 <4>如<1>至<3>之任一項所述之膜的形成方法,其中 膜形成製程還包括對已吹送風之油墨實施釘扎曝光之步驟, 從風的吹送的開始到釘扎曝光開始的時間為1秒鐘以下。 <5>如<1>至<4>之任一項所述之膜的形成方法,其中 膜形成製程還包括對賦予到段差的頂面上之油墨且吹送風之前的油墨實施釘扎曝光之步驟。 <6>如<1>至<5>之任一項所述之膜的形成方法,其中 風從送風機吹出, 風的朝向包含從送風機觀察時與配置有噴墨噴頭之一側相反的朝向的成分。 <7>如<1>至<6>之任一項所述之膜的形成方法,其中 在將帶段差之基板及噴墨噴頭相對移動的同時進行膜形成製程中的油墨的賦予, 在賦予到帶段差之基板之油墨中,相對移動的方向的點解析度高於與相對移動的方向正交之方向的點解析度。 <8>如<1>至<7>之任一項所述之膜的形成方法,其中 風為非活性氣體的氣流, 油墨為含有聚合性化合物之活性能量射線硬化型油墨。 <9>如<1>至<8>之任一項所述之膜的形成方法,其中 帶段差之基板包含基底基板及配置於基底基板上之零件,在基底基板與零件之間存在間隙。 <10>如<1>至<9>之任一項所述之膜的形成方法,其中 在膜形成製程之前,還包括藉由從噴墨噴頭吐出油墨,形成圍繞形成有膜之區域之隔壁之隔壁形成製程。 <11>如<1>至<10>之任一項所述之膜的形成方法,其中 在膜形成製程之前,還包括對至少形成有膜之區域實施親水處理之製程。 <12>一種電子裝置之製造方法,其包括: 準備電子基板之製程,前述電子基板具備配線基板及配置於配線基板上之電子零件;及 在電子基板上形成絕緣層及導電層中的至少一個而獲得電子元件之製程, 藉由<1>至<11>之任一項所述之膜的形成方法形成絕緣層及導電層中的至少一個。 <13>一種膜形成裝置,其具備: 噴墨噴頭,將油墨賦予到具有基板厚度方向的段差之基板亦即帶段差之基板中的至少段差的頂面上;及 送風機,對賦予到段差的頂面上之油墨吹送風, 將帶段差之基板及噴墨噴頭相對移動, 噴墨噴頭及送風機排列在相對移動的方向。 <14>如<13>所述之膜形成裝置,其還具備回收風之風回收機。 <15>如<13>或<14>所述之膜形成裝置,其中 從送風機吹出之風的朝向包含與從送風機觀察時配置有噴墨噴頭之一側相反的朝向的成分。 <16>如<13>至<15>之任一項所述之膜形成裝置,其具備2個送風機, 在2個送風機之間配置噴墨噴頭, 相對移動為往返移動。 <17>如<13>至<16>之任一項所述之膜形成裝置,其中 送風機具備進行開始風的吹出之開啟狀態與停止風的吹出之關閉狀態之切換之開關功能。 <18>如<13>至<17>之任一項所述之膜形成裝置,其還具備對已吹送風之油墨實施釘扎曝光之釘扎曝光機。 <19>如<13>至<18>之任一項所述之膜形成裝置,其還具備對賦予到段差的頂面上之油墨且吹送風之前的油墨實施釘扎曝光之釘扎曝光機。 [發明效果] Specific means for solving the above-mentioned problems include the following aspects. <1> A method for forming a film, comprising: A process of preparing a substrate having a step in the thickness direction of the substrate, that is, a substrate with a step; and a film forming process of imparting ink to at least the top surface of the substrate with a step by ejecting ink from an inkjet head, and By blowing air to the ink applied to the top surface of the step, a film covering at least the top surface of the step and the side surfaces of the step is formed. <2> The method for forming a film according to <1>, wherein The wind speed is more than 1m/s and less than 30m/s. <3> The method for forming a film according to <1> or <2>, wherein The film forming process includes the step of recovering wind. <4> The method for forming a film according to any one of <1> to <3>, wherein The film forming process also includes a step of performing pinning exposure on the blown ink, The time from the start of the blowing of the wind to the start of the pinning exposure was 1 second or less. <5> The method for forming a film according to any one of <1> to <4>, wherein The film forming process further includes a step of performing pinning exposure on the ink applied to the top surface of the level difference before blowing the air. <6> The film forming method according to any one of <1> to <5>, wherein The wind blows from the blower, The direction of the wind includes a component of the direction opposite to the side where the inkjet head is arranged when viewed from the air blower. <7> The film forming method according to any one of <1> to <6>, wherein Ink application in the film formation process is performed while moving the step substrate and the inkjet head relatively, In ink applied to a substrate with a step difference, the dot resolution in the direction of relative movement is higher than that in the direction perpendicular to the direction of relative movement. <8> The method for forming a film according to any one of <1> to <7>, wherein Wind is a flow of inert gas, The ink is an active energy ray curable ink containing a polymerizable compound. <9> The method for forming a film according to any one of <1> to <8>, wherein The substrate with level difference includes a base substrate and components arranged on the base substrate, and there is a gap between the base substrate and the components. <10> The method for forming a film according to any one of <1> to <9>, wherein Before the film forming process, a partition wall forming process of forming a partition wall surrounding a region where a film is formed is also included by discharging ink from an inkjet head. <11> The method for forming a film according to any one of <1> to <10>, wherein Before the film forming process, a process of performing hydrophilic treatment on at least the region where the film is formed is also included. <12> A method of manufacturing an electronic device, comprising: Preparation of the manufacturing process of the electronic substrate, the aforementioned electronic substrate has a wiring substrate and electronic components arranged on the wiring substrate; and A process for obtaining electronic components by forming at least one of an insulating layer and a conductive layer on an electronic substrate, At least one of the insulating layer and the conductive layer is formed by the film forming method described in any one of <1> to <11>. <13> A film forming apparatus comprising: An inkjet nozzle for imparting ink onto the top surface of at least a step in a substrate having a step in the thickness direction of the substrate, that is, a substrate with a step; and The blower blows air to the ink on the top surface of the step difference, Relatively move the substrate with step difference and the inkjet nozzle, The inkjet nozzles and the blower are arranged in a direction of relative movement. <14> The film forming apparatus according to <13>, further comprising a wind recovery unit for recovering wind. <15> The film forming apparatus according to <13> or <14>, wherein The direction of the wind blown from the blower includes a component facing in the direction opposite to the side where the inkjet head is arranged when viewed from the blower. <16> The film forming apparatus according to any one of <13> to <15>, which includes two air blowers, Arrange inkjet nozzles between 2 air blowers, Relative movement is back and forth movement. <17> The film forming apparatus according to any one of <13> to <16>, wherein The air blower has a switch function for switching between an on state to start blowing of air and an off state to stop blowing of air. <18> The film forming apparatus according to any one of <13> to <17>, further comprising a pinning exposure machine for performing pinning exposure on the blown ink. <19> The film forming apparatus according to any one of <13> to <18>, further comprising a pinning exposure machine for performing pinning exposure on the ink applied to the top surface of the step and before blowing air. . [Invention effect]
依據本揭示的一態樣,可提供一種膜的形成方法及膜形成裝置,其藉由噴墨法在具有基板厚度方向的段差之基板亦即帶段差之基板上形成至少被覆段差的頂面及段差的側面之膜時能夠抑制從段差的頂面上到段差的側面上的膜的厚度偏差。 依據本揭示的另一態樣,可提供一種電子元件的製造方法,其藉由噴墨法在具備配線基板及配置於配線基板上之電子零件之電子基板上的至少包含電子零件的的頂面及電子零件的側面之區域形成絕緣層及/或導電層來形成電子元件時能夠抑制從電子零件的頂面上到電子零件的側面上的絕緣層及/或導電層的厚度偏差。 According to an aspect of the present disclosure, a film forming method and a film forming device are provided, which form at least a top surface covered with a step on a substrate having a step in the thickness direction of the substrate, that is, a substrate with a step, by an inkjet method. In the case of the film on the side surface of the step, the variation in thickness of the film from the top surface of the step to the side surface of the step can be suppressed. According to another aspect of the present disclosure, it is possible to provide a method of manufacturing an electronic component, which uses an inkjet method to paint at least the top surface of the electronic component on the electronic substrate provided with the wiring substrate and the electronic components arranged on the wiring substrate. When the insulating layer and/or the conductive layer are formed in the region of the side surface of the electronic component to form an electronic element, the variation in the thickness of the insulating layer and/or conductive layer from the top surface of the electronic component to the side surface of the electronic component can be suppressed.
在本揭示中,使用“~”表示之數值範圍係指將記載於“~”的前後之數值分別作為最小值及最大值而包含在內之範圍。 在本揭示中分階段記載之數值範圍中,以某個數值範圍記載之上限值或下限值可取代為其他階段性記載的數值範圍的上限值或下限值。又,在本揭示中所記載之數值範圍中,某個數值範圍中所記載之上限值或下限值可取代為實施例所示之值。 In this disclosure, the numerical range represented by "-" means the range which includes the numerical values described before and after "-" as a minimum value and a maximum value, respectively. In the numerical ranges described step by step in this disclosure, the upper limit or lower limit described in a certain numerical range may be replaced by the upper limit or lower limit of other numerical ranges described stepwise. In addition, in the numerical range described in this indication, the upper limit or the lower limit described in a certain numerical range may be substituted by the value shown in an Example.
在本揭示中,組成物中存在複數個與各成分對應之物質之情況下,只要沒有特別說明,組成物中的各成分的量係指存在於組成物中之複數個物質的合計量。 在本揭示中,2個以上的較佳之態樣的組合為更佳的態樣。 在本揭示中,“製程”之術語不僅包含獨立之製程,即使在無法與其他製程明確地區分之情況下,只要實現該製程的所期望的目的,則包含於本術語中。 In the present disclosure, when a plurality of substances corresponding to each component exist in the composition, unless otherwise specified, the amount of each component in the composition means the total amount of the plurality of substances present in the composition. In this disclosure, a combination of two or more preferable aspects is a more preferable aspect. In this disclosure, the term "process" not only includes an independent process, but also includes in this term as long as the desired purpose of the process is achieved even if it cannot be clearly distinguished from other processes.
〔膜的形成方法〕 本揭示的膜的形成方法包括: 準備具有基板厚度方向的段差之基板亦即帶段差之基板之製程(以下,亦稱為“帶段差之基板準備製程”);及 膜形成製程,藉由從噴墨噴頭吐出油墨,將油墨賦予到帶段差之基板中的至少段差的頂面上,並且藉由對著液到段差的頂面上之油墨吹送風,從而形成至少被覆段差的頂面及段差的側面之膜。 本揭示的膜的形成方法依據需要亦可以包括其他製程。 〔How to form a film〕 Methods of forming films of the present disclosure include: The process of preparing a substrate with a step difference in the thickness direction of the substrate, that is, a substrate with a step difference (hereinafter also referred to as "substrate preparation process with a step difference"); and A film forming process, by discharging ink from an inkjet head, imparting ink to at least the top surface of a step in a substrate with a step, and blowing air against the ink liquid onto the top surface of the step, thereby forming at least The film covering the top surface of the step and the side of the step. The film forming method of the present disclosure may also include other processes as required.
依據本揭示的膜的形成方法,在藉由噴墨法在具有基板厚度方向的段差之基板亦即帶段差之基板上形成至少被覆段差的頂面及段差的側面之膜時能夠抑制從段差的頂面上到段差的側面上的膜的厚度偏差。 獲得這樣的效果之理由認為是因為藉由對著液於段差的頂面上之油墨吹送之風能夠將頂面上的油墨的一部分繞回到側面,藉此能夠抑制段差的側面上的膜的厚度及/或位於段差的側面與頂面的接合處之角部上的膜的厚度變薄之現象。 According to the film forming method of the present disclosure, when the film covering at least the top surface of the step and the side surface of the step is formed on a substrate having a step in the thickness direction of the substrate, that is, a substrate with a step, by the ink-jet method, it is possible to suppress the difference from the step. The thickness deviation of the film on the top surface to the sides of the step. The reason for obtaining such an effect is considered to be that the wind blowing against the ink on the top surface of the level difference can wind a part of the ink on the top surface back to the side, whereby the film on the side surface of the level difference can be suppressed. The thinning of the thickness and/or the thickness of the film at the corner of the junction of the side surface and the top surface of the step.
關於用於實施本揭示的膜的形成方法之裝置並無特別限定。 本揭示的膜的形成方法例如能夠藉由後述之本揭示的膜形成裝置來實施。 There is no particular limitation on the apparatus for implementing the film forming method of the present disclosure. The film forming method of the present disclosure can be implemented, for example, by a film forming apparatus of the present disclosure described later.
<膜的形成方法的一實施形態> 以下,參閱圖式對本揭示的膜的形成方法的一實施形態進行說明。 但是,本揭示的膜的形成方法並不限定於以下實施形態。 在以下的說明中,關於實質上相同的要素(例如零件或部分),標註相同元件符號,有時省略重複之說明。 <An embodiment of the film forming method> Hereinafter, one embodiment of the film forming method of the present disclosure will be described with reference to the drawings. However, the film forming method of the present disclosure is not limited to the following embodiments. In the following description, substantially the same elements (for example, parts or parts) are denoted by the same reference numerals, and overlapping descriptions may be omitted.
圖1A~圖1D係示意地表示本揭示的一實施形態之膜的形成方法之製程流程圖。
本實施形態之膜的形成方法中,準備圖1A所示之帶段差之基板10。
帶段差之基板10包含平板狀基底基板12及設置於基底基板12上之構件18。
在本實施形態中,基底基板12上的構件18的端部對應於本揭示中所述之“段差”,構件18的端部的側面18S對應於本揭示中的段差的側面,構件18的頂面18U對應於本揭示中的段差的頂面。
1A to 1D schematically show a process flow diagram of a film forming method according to an embodiment of the present disclosure.
In the film forming method of the present embodiment, the
如圖1A及圖1B所示,在本實施形態中,固定噴墨噴頭24,沿輸送方向M1的朝向輸送帶段差之基板10的同時(亦即,移動的同時),從噴墨噴頭24吐出油墨26。藉此,將油墨賦予到包含構件18的頂面上之區域26。
在該實施形態中的膜形成製程中,固定噴墨噴頭而移動帶段差之基板,但是亦可以固定帶段差之基板而移動噴墨噴頭,亦可以移動噴墨噴頭及帶段差之基板這兩者。
在該實施形態中的膜形成製程中,將油墨賦予到跨越構件18的頂面上及比頂面上更靠外側的區域(構件18的側面上及基底基板12上)之區域,但是油墨賦予到至少構件18的頂面上即可,亦可以僅賦予到構件18的頂面上。
As shown in FIG. 1A and FIG. 1B, in this embodiment, the
如圖1B所示,在該實施形態中,在油墨26的賦予之後,與頂面18U上的膜的厚度相比,位於構件18的側面18S上的油墨26的厚度及側面18S與頂面18U的接合處之角部18C上的油墨26的厚度均變薄。
藉此,從構件18的側面18S上到頂面18U上之膜的厚度偏差變大。
本揭示的膜的形成方法的課題為抑制該厚度偏差。
As shown in FIG. 1B , in this embodiment, after the
如圖1C所示,在該實施形態中,在油墨26的賦予之後,向頂面18U上的油墨26吹送風W1。藉由該風W1的力,頂面18U的中央部上的油墨26的一部分沿頂面18U的周端部上移動,進而沿角部18C上及側面18S上移動。
其結果,如圖1D所示,可抑制角部18C上及側面18S上的油墨的厚度變薄之現象,可抑制從側面18S上經頂面18U上的膜20的厚度偏差。
As shown in FIG. 1C , in this embodiment, after
接著,對本揭示的膜的形成方法中的各製程進行說明。Next, each process in the film forming method of the present disclosure will be described.
<帶段差之基板準備製程> 本揭示的膜的形成方法包括帶段差之基板準備製程。 帶段差之基板為具有基板厚度方向的段差之基板。 在帶段差之基板準備製程中,可以為僅簡單準備預先製造之帶段差之基板的製程,亦可以為製造帶段差之基板之製程。 <Substrate preparation process with step difference> The film forming method of the present disclosure includes a stepwise substrate preparation process. The substrate with a step difference is a substrate having a step difference in the thickness direction of the substrate. The substrate preparation process with a step difference may be a process of simply preparing a substrate with a step difference manufactured in advance, or may be a process of manufacturing a substrate with a step difference.
帶段差之基板的一例為包含上述之基底基板12及配置於基底基板12上之構件18之帶段差之基板10。
構件18可以為安裝於基底基板12(例如,配線基板)之零件(例如,電子零件),亦可以為形成於基底基板12上之圖案膜(例如,金屬圖案膜、絕緣膜、光阻圖案膜等)。
An example of the stepped substrate is the stepped
作為帶段差之基板10,可舉出包含配線基板及配置於配線基板上之電子零件之電子基板。
作為配線基板,能夠使用形成配線之基板、例如印刷配線基板。
作為電子零件,例如可舉出積體電路(IC;Integrated Circuit)等半導體晶片、電容器、電晶體等。
配線基板還可以包含接地電極、接地配線、阻焊層等。
As the board|
帶段差之基板並不限定於在基底基板上安裝構件而成之帶段差之基板,可以為藉由蝕刻等加工在基底基板上形成段差(例如,凸部、凹部(注:包含具有底部之孔)、貫通孔等)而成者。The substrate with step difference is not limited to the substrate with step difference formed by mounting components on the base substrate. It may be formed by etching and other processes on the base substrate. ), through holes, etc.).
作為帶段差之基板中的基底基板的材質並無特別限制,例如可舉出玻璃、陶瓷、金屬、樹脂等。The material of the base substrate in the stepped substrate is not particularly limited, and examples thereof include glass, ceramics, metal, and resin.
帶段差之基板包含基底基板及配置於基底基板上之構件,可以在基底基板與構件之間存在間隙。 在不進行風的吹送之以往膜的形成方法中,在基底基板與構件之間存在間隙之情況下,在將油墨賦予到包含構件之區域之情況下,油墨進入基底基板與構件之間的間隙,存在構件的側面的油墨的厚度變得更薄之傾向。 但是,在本揭示的膜的形成方法中,藉由對構件的頂面上的油墨吹送風,能夠將頂面上的油墨繞回到側面上。 如此,在基底基板與構件之間存在間隙之情況下,藉由對段差的頂面上的油墨吹送風,更容易發揮本揭示的效果。 The substrate with step difference includes a base substrate and components disposed on the base substrate, and there may be a gap between the base substrate and the components. In the conventional film forming method without wind blowing, when there is a gap between the base substrate and the member, when the ink is applied to the region including the member, the ink enters the gap between the base substrate and the member , the thickness of the ink on the side surface of the member tends to be thinner. However, in the film forming method of the present disclosure, the ink on the top surface of the member can be wound back to the side surface by blowing air to the ink on the top surface of the member. In this way, when there is a gap between the base substrate and the member, it is easier to exert the effect of the present disclosure by blowing air to the ink on the top surface of the level difference.
圖2係表示在基底基板與構件之間存在間隙之態樣的帶段差之基板的例之概略側視圖。
圖2所示之一例之帶段差之基板13的結構為如下結構:在前述帶段差之基板10中,藉由在基底基板12與構件18之間追加複數個連接構件16,並且在基底基板12與構件18之間設置間隙17。
作為連接構件16,可舉出用於連接基底基板12和構件18之連接材料(例如,焊球、接著劑等)等。
FIG. 2 is a schematic side view of an example of a stepped substrate showing a state in which a gap exists between a base substrate and a member.
The structure of the
<膜形成製程> 本揭示的膜的形成方法包括膜形成製程。 膜形成製程為如下製程:藉由從噴墨噴頭吐出油墨,將油墨賦予到帶段差之基板中的至少段差的頂面上,並且藉由對著液於段差的頂面上之油墨吹送風,從而形成至少被覆段差的頂面及段差的側面之膜。 <Film Formation Process> The film forming method of the present disclosure includes a film forming process. The film forming process is a process of imparting the ink onto at least the top surface of the step in the substrate with the step by ejecting the ink from the inkjet head, and blowing air against the ink liquid on the top surface of the step, Thus, a film covering at least the top surface of the step and the side surfaces of the step is formed.
(油墨的賦予) 關於油墨並無特別限定,例如可舉出在後述電子元件的製造方法的項中說明之導電油墨及絕緣油墨。 (impartment of ink) The ink is not particularly limited, and examples thereof include conductive inks and insulating inks described in the section of the manufacturing method of electronic components described later.
作為油墨的賦予方法,能夠適當適用噴墨記錄中的公知的方法。 作為從噴墨頭吐出油墨之方式,可以為利用靜電吸引力吐出油墨之電荷控制方式、利用壓電元件的振動壓力之施加狹縫旋塗方式(壓力脈衝方式)、將電訊號轉換為聲束照射到油墨並且利用放射壓吐出油墨之音響噴墨方式及加熱油墨形成氣泡並且利用所生成之壓力之熱噴墨(Bubble Jet(註冊商標))方式中的任一個。 作為從噴墨頭吐出油墨之方式,尤其能夠有效利用如下噴墨記錄方式:藉由日本特開昭54-59936號公報中所記載之方法,受到熱能的作用之油墨發生急劇體積變化,藉由基於該狀態變化之作用力,從噴嘴吐出油墨。 又,關於從噴墨頭吐出油墨之方式,亦能夠參閱日本特開2003-306623號公報的0093~0105段中所記載之方法。 As a method for applying ink, known methods in inkjet recording can be appropriately applied. As the method of ejecting ink from the inkjet head, there are charge control method using electrostatic attraction to eject ink, slit spin coating method (pressure pulse method) using vibration pressure of piezoelectric element, converting electrical signal into sound beam Either of the acoustic inkjet method of irradiating ink and ejecting ink with radiation pressure, and the thermal inkjet (Bubble Jet (registered trademark)) method of heating ink to form bubbles and utilizing the generated pressure. As a method of ejecting ink from an inkjet head, the following inkjet recording method can be effectively used in particular: By the method described in Japanese Patent Laid-Open No. 54-59936, the ink subjected to the action of heat energy undergoes a rapid volume change, by Ink is ejected from the nozzle based on the force of this state change. Moreover, regarding the method of ejecting the ink from the inkjet head, the methods described in paragraphs 0093 to 0105 of JP-A-2003-306623 can also be referred to.
將帶段差之基板及噴墨噴頭相對移動的同時進行膜形成製程中的油墨的賦予為較佳。藉此,能夠將油墨高效地賦予到帶段差之基板上的所期望之區域。 在該情況下,可以固定噴墨噴頭而移動帶段差之基板,亦可以固定帶段差之基板而移動噴墨噴頭,亦可以移動噴墨噴頭及帶段差之基板這兩者。 It is preferable to apply the ink in the film forming process while relatively moving the stepped substrate and the inkjet head. Thereby, ink can be efficiently applied to a desired area on the board|substrate with a step difference. In this case, the substrate with the step may be moved while the inkjet head is fixed, the inkjet head may be moved while the substrate with the step is fixed, or both the inkjet head and the substrate with the step may be moved.
在將帶段差之基板及噴墨噴頭相對移動的同時進行膜形成製程中的油墨的賦予之情況下,在賦予到帶段差之基板之油墨中,相對移動的方向的點解析度高於與相對移動的方向正交之方向的點解析度為較佳。 藉此,油墨容易著液於與相對移動的方向交叉(例如正交)之方向的段差的角部,其結果,容易確保附著於上述交叉之方向的段差的側面之油墨的附著量。其結果,確保段差的側面上的油墨的厚度,因此進一步抑制從段差的側面上到頂面上的膜的厚度偏差。 In the case of applying the ink in the film formation process while moving the substrate with the step difference and the inkjet head relatively, the dot resolution in the direction of the relative movement is higher than that of the opposite in the ink applied to the substrate with the step difference The point resolution in the direction perpendicular to the moving direction is better. This makes it easy for the ink to settle on the corners of the steps intersecting (for example, perpendicular) to the direction of relative movement. As a result, it is easy to secure the amount of ink adhering to the side surfaces of the steps intersecting the direction. As a result, since the thickness of the ink on the side surface of the step is ensured, the variation in film thickness from the side surface of the step to the top surface is further suppressed.
圖3係示意地表示相對移動的方向的點解析度高於與相對移動的方向正交之方向的點解析度之態樣的一例之概略俯視圖。 圖4係示意地表示油墨著液於構件的角部之樣子的一例之概略側面圖。 3 is a schematic plan view schematically showing an example of an aspect in which the dot resolution in the direction of relative movement is higher than the dot resolution in the direction perpendicular to the direction of relative movement. Fig. 4 is a schematic side view schematically showing an example of how ink impinges on a corner of a member.
在圖3所示之一例中,帶段差之基板10向輸送方向M1的朝向移動並且在帶段差之基板10中的構件18及其周圍的整體上形成大量的油墨點D1。在該一例中,與輸送方向M1平行的方向(亦即,相對移動的方向)的油墨點D1的密度(亦即,點解析度)比與相對移動的方向正交之方向的油墨點D1的密度(亦即,點解析度)更高。更具體而言,在該圖3中,圖示有相對移動的方向的點解析度為與相對移動的方向正交之方向的點解析度的約2倍之狀態。In an example shown in FIG. 3 , the stepped
在相對移動的方向的點解析度比與相對移動的方向正交之方向的點解析度更高的情況下,如圖4所示,油墨26(油墨滴)容易著液於構件18的角部18C。其結果,能夠確保附著於角部18C的下方的側面18S之油墨的附著量,其結果,能夠確保段差的側面18S上的油墨26的厚度,因此進一步抑制從段差的側面18S上到頂面18U上的膜的厚度偏差。When the dot resolution in the direction of relative movement is higher than that in the direction perpendicular to the direction of relative movement, as shown in FIG. 18C. As a result, the amount of ink adhering to the
(風的吹送) 在膜形成製程中,藉由對著液於段差的頂面上之油墨吹送風,形成至少被覆段差的頂面及段差的側面之膜。 詳細而言,如前述,藉由該風的力,著液於頂面上之油墨的一部分向角部上及側面上移動,其結果,可抑制角部及側面中的油墨的厚度變薄之現象。 (wind blowing) In the film forming process, a film covering at least the top surface of the step and the side surfaces of the step is formed by blowing air against the ink liquid on the top surface of the step. More specifically, as described above, by the force of the wind, part of the ink impregnated on the top surface moves to the corners and side surfaces, and as a result, the thickness of the ink at the corners and side surfaces is prevented from becoming thinner. Phenomenon.
在膜形成製程包括對附著於帶段差之基板上的段差的頂面上之油墨吹送風之情況下,風的風速並無特別限定。 從有效發揮上述效果之觀點考慮,風的風速為1m/s~30m/s為較佳,1m/s以上且未達30m/s為更佳,1m/s~25m/s為進一步較佳,2m/s~20m/s為進一步較佳,5m/s~15m/s為進一步較佳。 In the case where the film forming process includes blowing wind to the ink attached to the top surface of the step on the substrate with steps, the wind speed of the wind is not particularly limited. From the viewpoint of effectively exerting the above effects, the wind speed is preferably 1m/s to 30m/s, more preferably 1m/s to less than 30m/s, and more preferably 1m/s to 25m/s. 2 m/s to 20 m/s is more preferable, and 5 m/s to 15 m/s is still more preferable.
在膜形成製程包括對著液於帶段差之基板上的段差的頂面上之油墨吹送風之步驟之情況下,對著液於段差的頂面上之油墨吹送風之方向並無特別限定。 從有效發揮上述效果之觀點考慮,對著液於段差的頂面上之油墨吹送風之方向為仰角成為10°~90°之方向為較佳,仰角成為20°~90°之方向為更佳,仰角成為30°~90°之方向為進一步較佳。 In the case where the film forming process includes a step of blowing air against the ink liquidated on the top surface of the step on the substrate with the step, the direction of blowing the air against the ink liquidated on the top surface of the step is not particularly limited. From the viewpoint of effectively exerting the above effects, the direction of blowing air against the ink on the top surface of the level difference is preferably a direction with an elevation angle of 10° to 90°, and a direction with an elevation angle of 20° to 90° is more preferable. , the direction in which the elevation angle is 30° to 90° is more preferable.
在本揭示中,“對著液於段差的頂面上之油墨吹送風B之方向為仰角成為X°之方向。”係指,在吹送風B之位置仰望風B到來之方向時的與水平面的角度為X°(在此,X°為0°以上且90°以下的範圍內的角度)。 圖5係表示仰角的一例之示意圖。 該一例中的仰角為在以符號W1表示之風吹送之位置P1仰望風到來之方向時的與水平面的角度X°。 In this disclosure, "the direction of the ink blowing wind B facing the liquid on the top surface of the step difference is the direction where the elevation angle becomes X°." It refers to the horizontal plane when looking up at the direction of the wind B coming from the position of the blowing wind B The angle of is X° (here, X° is an angle within a range from 0° to 90°). Fig. 5 is a schematic diagram showing an example of an elevation angle. The elevation angle in this example is the angle X° with respect to the horizontal plane when looking up at the direction where the wind comes from the position P1 where the wind blows indicated by symbol W1.
又,風為從送風機吹出之風為較佳。 作為送風機,例如能夠使用乾燥機、熱風產生器、壓縮空氣產生器、風扇、鼓風機等。又,作為送風機,可以將在工場內流通壓縮空氣之配管拉回膜形成裝置內而利用。 Moreover, it is preferable that the wind is the wind blown from the blower. As the blower, for example, a dryer, a hot air generator, a compressed air generator, a fan, a blower, etc. can be used. In addition, as a blower, the piping through which compressed air flows in the factory can be drawn back into the film forming apparatus and used.
從送風機吹出之風的朝向包含從送風機觀察時與配置有噴墨噴頭之一側相反的朝向的成分為較佳(例如,參閱後述圖7B)。藉此,風不會吹向噴墨噴頭的方向,因此能夠進一步抑制因風的影響而引起之油墨的吐出精度的降低。It is preferable that the direction of the air blown from the blower includes a direction component opposite to the side where the inkjet head is arranged when viewed from the blower (for example, refer to FIG. 7B described later). Thereby, since the wind does not blow in the direction of the inkjet head, it is possible to further suppress the decrease in the discharge accuracy of the ink due to the influence of the wind.
在本揭示的膜形成方法中,風並無特別限定,能夠使用任意氣體的氣流。 在本揭示的膜形成方法中,在油墨為含有聚合性化合物之活性能量射線硬化型油墨之情況下,風為非活性氣體的氣流為較佳。藉此,能夠抑制因氧而引起之聚合阻礙(詳細而言,活性能量射線硬化型油墨中的聚合性化合物的聚合因氧而被阻礙之現象),因此活性能量射線硬化型油墨的硬化性更優異。 作為非活性氣體,可舉出氮氣、氬氣、氦氣等。 In the film forming method of the present disclosure, the wind is not particularly limited, and any gas flow can be used. In the film forming method of the present disclosure, when the ink is an active energy ray-curable ink containing a polymerizable compound, the wind is preferably an inert gas flow. Thereby, the inhibition of polymerization due to oxygen can be suppressed (specifically, the phenomenon that the polymerization of the polymerizable compound in the active energy ray-curable ink is inhibited by oxygen), so the curability of the active energy ray-curable ink is improved. excellent. Examples of the inert gas include nitrogen, argon, helium and the like.
又,膜形成製程包括回收對油墨吹送之風之步驟為較佳。 藉此,能夠進一步抑制進行膜形成製程之裝置(例如,噴墨記錄裝置)內的壓力上升。又,能夠回收從噴墨噴頭噴出且未附著於基板之衛星滴及/或霧滴。 風的回收例如能夠使用組合了風扇和與膜形成裝置外連接之配管之風回收機、排氣裝置等而進行。 例如,在上述風回收機中,在風扇的前面配置可更換的過濾器並且定期更換,藉此能夠防止衛星滴及/或霧滴擴散到工場內。 Also, it is preferable that the film forming process includes a step of recovering the wind blowing the ink. Thereby, the pressure rise in the apparatus (for example, an inkjet recording apparatus) which performs a film formation process can be suppressed further. In addition, satellite droplets and/or mist droplets discharged from the inkjet head and not attached to the substrate can be recovered. The recovery of wind can be carried out using, for example, a wind recovery device, an exhaust device, etc., which combine a fan and piping connected to the outside of the film forming apparatus. For example, in the above-mentioned wind recovery machine, a replaceable filter is arranged in front of the fan and replaced regularly, thereby preventing satellite droplets and/or mist droplets from spreading into the factory.
(釘扎曝光) 膜形成製程還可以包括對已吹送風之油墨實施釘扎曝光(以下,亦稱為“釘扎曝光A”)之步驟。 釘扎曝光A的積算曝光量並無特別限定,但是例如為0.1J/cm 2~1000J/cm 2。 能夠藉由該釘扎曝光A抑制油墨的流動性,因此能抑制附著於段差的側面之油墨因重力而流下。因此,能夠進一步抑制從段差的側面上到頂面上的膜的厚度偏差。 釘扎曝光A的積算曝光量並無特別限定,但是例如為0.1J/cm 2~1000J/cm 2。 在膜形成製程中的油墨為後述之導電層形成用油墨之情況下,相對於該導電層形成用油墨之釘扎曝光A的積算曝光量為0.1J/cm 2~1000J/cm 2為較佳,1J/cm 2~100J/cm 2為更佳。 在膜形成製程中的油墨為後述之絕緣層形成用油墨之情況下,相對於該絕緣層形成用油墨之釘扎曝光A的積算曝光量為0.1J/cm 2~100J/cm 2為較佳,0.1J/cm 2~10J/cm 2為更佳。 (Pinning Exposure) The film forming process may further include a step of performing pinning exposure (hereinafter, also referred to as “pinning exposure A”) to the blown ink. The cumulative exposure amount of the pinning exposure A is not particularly limited, but is, for example, 0.1 J/cm 2 to 1000 J/cm 2 . Since the fluidity of the ink can be suppressed by the pinning exposure A, the ink adhering to the side surface of the step can be suppressed from flowing down due to gravity. Therefore, the thickness deviation of the film from the side surface of the step to the top surface can be further suppressed. The cumulative exposure amount of the pinning exposure A is not particularly limited, but is, for example, 0.1 J/cm 2 to 1000 J/cm 2 . When the ink in the film formation process is the conductive layer forming ink described later, the cumulative exposure amount of the pinning exposure A with respect to the conductive layer forming ink is preferably 0.1 J/cm 2 to 1000 J/cm 2 , more preferably 1J/cm 2 to 100J/cm 2 . When the ink used in the film formation process is the insulating layer forming ink described later, the cumulative exposure amount of the pinning exposure A with respect to the insulating layer forming ink is preferably 0.1 J/cm 2 to 100 J/cm 2 , more preferably 0.1J/cm 2 to 10J/cm 2 .
從風的吹送的開始到釘扎曝光A開始的時間為1秒鐘以下為較佳。藉此,能夠進一步抑制從段差的側面上到頂面上的膜的厚度偏差。The time from the start of the blowing of the wind to the start of the pinning exposure A is preferably 1 second or less. Thereby, it is possible to further suppress the thickness variation of the film from the side surface of the step to the top surface.
膜形成製程還可以包括對賦予到段差的頂面上之油墨且吹送風之前的油墨實施釘扎曝光(以下,亦稱為“釘扎曝光B”)之步驟。藉此,能夠適當地上升頂面上的油墨的黏度,因此能夠進一步抑制頂面上的油墨藉由風的吹送而過渡流下,並且容易將風的吹送後的頂面上的油墨適當地殘留於頂面上。其結果,能夠更有效地發揮抑制從段差的側面上到頂面上的膜的厚度偏差之效果。 釘扎曝光B的積算曝光量的較佳的範圍與釘扎曝光A的積算曝光量的較佳的範圍相同。 The film forming process may further include a step of performing pinning exposure (hereinafter, also referred to as “pinning exposure B”) on the ink provided on the top surface of the step and before blowing the air. Thereby, the viscosity of the ink on the top surface can be appropriately increased, so that the ink on the top surface can be further suppressed from excessively flowing down due to the blowing of the wind, and it is easy to appropriately leave the ink on the top surface after the blowing of the wind on the top surface. top surface. As a result, the effect of suppressing the thickness variation of the film from the side surface of the step to the top surface can be exhibited more effectively. The preferable range of the cumulative exposure amount of the pinning exposure B is the same as the preferable range of the cumulative exposure amount of the pinning exposure A.
再者,上述釘扎曝光A(亦即,對油墨吹送風之前的釘扎曝光)及上述釘扎曝光B(亦即,已對油墨吹送風之後的釘扎曝光)均為任意操作。 因此,膜形成製程可以僅實施釘扎曝光A及釘扎曝光B中的其中一個,亦可以實施這兩者,亦可以不實施這兩者。 In addition, the above-mentioned pinning exposure A (that is, the pinning exposure before the ink is blown with air) and the above-mentioned pinning exposure B (that is, the pinning exposure after the ink has been blown with air) are arbitrary operations. Therefore, in the film formation process, only one of the pinning exposure A and the pinning exposure B may be implemented, both of them may be implemented, and neither of them may be implemented.
(加熱) 膜形成製程可以包括將被賦予油墨之帶段差之基板加熱到100℃以上的溫度之步驟。 藉此,能夠藉由油墨的加熱乾燥來抑制油墨的流動性,因此能夠抑制附著於段差的側面之油墨因重力而流下。因此,能夠進一步抑制從段差的側面上到頂面上的膜的厚度偏差。 (heating) The film forming process may include a step of heating the stepped substrate to which ink is imparted to a temperature of 100° C. or higher. Thereby, since the fluidity of ink can be suppressed by heating and drying of ink, it can suppress that the ink attached to the side surface of a level difference flows down by gravity. Therefore, the thickness deviation of the film from the side surface of the step to the top surface can be further suppressed.
被賦予油墨之帶段差之基板的加熱溫度為250℃以下為較佳,50℃~200℃為更佳,60℃~180℃為進一步較佳。The heating temperature of the substrate to which the ink step is imparted is preferably 250°C or lower, more preferably 50°C to 200°C, and more preferably 60°C to 180°C.
<隔壁形成製程> 在本揭示的膜的形成方法中,在膜形成製程之前,可舉出藉由從噴墨噴頭吐出油墨來形成圍繞形成有膜之區域之隔壁之隔壁形成製程。 在該態樣中,藉由在膜形成製程之前形成之隔壁,可抑制膜形成製程中的油墨流出到比原本預期之區域更外側之現象及/或膜形成製程中的油墨繞回到帶段差之基板的膜非形成面之現象。 <Partition wall forming process> In the film forming method of the present disclosure, prior to the film forming process, there may be mentioned a barrier wall forming process of forming barrier walls surrounding a region where a film is formed by discharging ink from an inkjet head. In this aspect, by the partition wall formed before the film formation process, it is possible to suppress the phenomenon that the ink in the film formation process flows out to the outside than the originally intended area and/or the ink in the film formation process goes back to the belt step difference The phenomenon that the film of the substrate is not formed on the surface.
圖6係表示本揭示的膜的形成方法包括隔壁形成製程時的隔壁形成製程之後且膜形成製程之前的一例之概略側視圖。
圖6所示之一例除形成有隔壁19以外與圖2所示之一例相同。
在膜形成製程之前(亦即,油墨的賦予之前),藉由預先設置包圍形成有膜之區域之隔壁19,可抑制前述之流出及繞回。
6 is a schematic side view showing an example after the barrier rib forming process and before the film forming process when the film forming method of the present disclosure includes the barrier rib forming process.
The example shown in FIG. 6 is the same as the example shown in FIG. 2 except that
關於隔壁的形成方法並無特別限制,但是從生產性的觀點考慮,與膜形成製程相同地藉由噴墨法而形成為較佳。The method for forming the partition wall is not particularly limited, but it is preferably formed by an inkjet method in the same manner as the film formation process from the viewpoint of productivity.
<實施親水化處理之製程> 在本揭示的膜的形成方法中,在膜形成製程之前,可以包括對至少形成有膜之區域實施親水處理之製程。 藉此,提高對段差的側面及角部之油墨的附著性,因此能夠進一步抑制從段差的側面上到頂面上的膜的厚度偏差。 <The process of implementing hydrophilization treatment> In the film forming method of the present disclosure, prior to the film forming process, a process of performing a hydrophilic treatment on at least a region where the film is formed may be included. As a result, ink adhesion to the side surfaces and corners of the step is improved, so that the thickness variation of the film from the side surface of the step to the top surface can be further suppressed.
作為親水處理,可舉出電暈放電處理、臭氧處理、氬氣電漿處理、酸素電漿處理等。Examples of the hydrophilic treatment include corona discharge treatment, ozone treatment, argon plasma treatment, acid plasma treatment, and the like.
<預加熱製程> 在本揭示的膜的形成方法中,在膜形成製程之前,包括加熱帶段差之基板之製程(在本揭示中,亦稱為“預加熱製程”)為較佳。 在該情況下,膜形成製程中對加熱到上述溫度之帶段差之基板賦予油墨。 <Preheating process> In the film forming method of the present disclosure, it is preferable to include a process of heating the substrate with a step (in the present disclosure, also referred to as “preheating process”) before the film forming process. In this case, the ink is applied to the stepped substrate heated to the above-mentioned temperature in the film formation process.
依據包含預加熱製程之態樣,亦能夠藉由油墨的加熱乾燥來抑制油墨的流動性,因此能夠抑制附著於段差的側面之油墨因重力而流下。因此,能夠進一步抑制從段差的頂面上到側面上的膜的厚度偏差。According to the aspect including the preheating process, the fluidity of the ink can also be suppressed by heating and drying the ink, so that the ink adhering to the side surface of the step can be suppressed from flowing down due to gravity. Therefore, the thickness deviation of the film from the top surface of the step to the side surface can be further suppressed.
預加熱製程中的加熱溫度更佳為20℃~120℃,進一步較佳為28℃~80℃。The heating temperature in the preheating process is more preferably from 20°C to 120°C, further preferably from 28°C to 80°C.
<對帶段差之基板的端面之膜形成> 在本揭示的膜的形成方法中,如前述,將油墨賦予到帶段差之基板的至少段差的頂面上並且向被賦予油墨吹送風,藉此形成抑制從段差的側面上到頂面上的厚度偏差之膜。 此時,亦將油墨賦予到帶段差之基板的端部附近,對該端部附近的油墨吹送風,將油墨繞回到帶段差之基板的端面,藉此可以在帶段差之基板的端面形成膜。藉此,能夠形成對帶段差之基板的端面之被覆性優異的膜。 <Film formation on the end surface of substrate with step difference> In the film forming method of the present disclosure, as described above, ink is applied to at least the top surface of the stepped substrate and air is blown to the applied ink, thereby forming a thickness that suppresses from the side surface of the step to the top surface. The film of deviation. At this time, the ink is also applied to the vicinity of the end of the substrate with a step difference, and the ink near the end is blown to return the ink to the end surface of the substrate with a step difference, whereby the end surface of the substrate with a step difference can be formed. membrane. Thereby, it is possible to form a film excellent in covering property on the end surface of the substrate with steps.
用於實施上述之本揭示的膜的形成方法之裝置並無特別限制,以下所示之本揭示的膜形成裝置為較佳。The apparatus for carrying out the above-mentioned film forming method of the present disclosure is not particularly limited, but the film forming apparatus of the present disclosure shown below is preferable.
〔膜形成裝置〕 本揭示的膜形成裝置具備: 噴墨噴頭,將油墨賦予到具有基板厚度方向的段差之基板亦即帶段差之基板中的至少段差的頂面上;及 送風機,對賦予到段差的頂面上之油墨吹送風, 將帶段差之基板及噴墨噴頭相對移動, 噴墨噴頭及送風機排列在相對移動的方向。 〔Film forming device〕 The film forming apparatus of the present disclosure has: An inkjet nozzle for imparting ink onto the top surface of at least a step in a substrate having a step in the thickness direction of the substrate, that is, a substrate with a step; and The blower blows air to the ink on the top surface of the step difference, Relatively move the substrate with step difference and the inkjet nozzle, The inkjet nozzles and the blower are arranged in a direction of relative movement.
依據本揭示的膜形成裝置,與本揭示的膜的形成方法相同地,能夠在具有基板厚度方向的段差之基板亦即帶段差之基板上形成抑制從段差的頂面上到側面上的厚度偏差之膜。 獲得這種效果之理由,如在本揭示的膜的形成方法的項中說明。 According to the film forming apparatus of the present disclosure, similarly to the film forming method of the present disclosure, it is possible to form a substrate having a step in the thickness direction of the substrate, that is, a substrate with a step, which suppresses thickness deviation from the top surface of the step to the side surface. film. The reason why such an effect is obtained is as described in the section of the film formation method of the present disclosure.
以下,對本揭示的膜形成裝置的較佳的態樣進行說明。 以下各態樣可以適當組合適用。 Hereinafter, preferred aspects of the film forming apparatus of the present disclosure will be described. The following aspects can be applied in appropriate combinations.
本揭示的膜形成裝置還具備回收上述風之風回收機為較佳。 關於基於回收風之效果及風回收機的例,如在本揭示的膜的形成方法的項中說明。 It is preferable that the film forming apparatus of the present disclosure further includes a wind recovery unit for recovering the above-mentioned wind. The effect by recovering wind and an example of a wind recovering device are as described in the section of the film forming method of the present disclosure.
從送風機吹出之風的朝向包含從送風機觀察時與配置有噴墨噴頭之一側相反的朝向的成分為較佳(例如,參閱後述圖7B)。藉此,風不會吹向噴墨噴頭的方向,因此能夠進一步抑制因風的影響而引起之油墨的吐出精度的降低。It is preferable that the direction of the air blown from the blower includes a direction component opposite to the side where the inkjet head is arranged when viewed from the blower (for example, refer to FIG. 7B described later). Thereby, since the wind does not blow in the direction of the inkjet head, it is possible to further suppress the decrease in the discharge accuracy of the ink due to the influence of the wind.
圖7A係表示本揭示的膜形成裝置的一例之概略俯視圖,圖7B係圖7A的側視圖。
如圖7A及圖7B所示,該一例之膜形成裝置300具備用於輸送帶段差之基板10之基板輸送載台212、移動基板輸送載台212之輸送軌道210、噴墨噴頭24、送風機28、風回收機30及釘扎曝光機32。
從輸送方向M1(亦即,基板輸送載台212的移動方向)的上游側依序配置有噴墨噴頭24、送風機28、風回收機30、及釘扎曝光機32。
FIG. 7A is a schematic plan view showing an example of the film forming apparatus of the present disclosure, and FIG. 7B is a side view of FIG. 7A .
As shown in FIG. 7A and FIG. 7B , the
在使用了膜形成裝置300之膜的形成中,對包含在輸送方向M1上輸送之帶段差之基板10中的段差的頂面之區域依序實施來自噴墨噴頭24的油墨的賦予、來自送風機28的風的吹送及基於釘扎曝光機32之釘扎曝光。此時,適當進行基於風回收機30之風的回收。
藉由將來自送風機28的風吹送到賦予到段差的頂面上之油墨,如前述可抑制從段差的側面上到頂面上的膜的厚度偏差。
藉由基於釘扎曝光機32之釘扎曝光,如前述進一步抑制上述膜的厚度偏差。
藉由基於風回收機30之風的回收,如前述能夠進一步抑制裝置內的壓力上升並且能夠回收油墨的衛星滴及/或霧滴。
In the formation of the film using the
如圖7B所示,該一例中,從送風機28吹出之風的朝向W1包含從送風機28觀察時與配置有噴墨噴頭24之一側相反的朝向的成分W1X。
藉此,風不會吹向噴墨噴頭24的方向,因此能夠進一步抑制因風的影響而引起之油墨的吐出精度的降低。
As shown in FIG. 7B , in this example, the direction W1 of the wind blown from the
如圖7B所示,在該一例中,藉由風回收機30回收風之朝向的相對於段差的頂面之反射角(以下,亦簡稱為“反射角”)調整為與從送風機28吹出之風的朝向W1的相對於段差的頂面之入射角(以下,亦簡稱為“入射角”)大致相同。As shown in Figure 7B, in this example, the reflection angle (hereinafter, also referred to simply as "reflection angle") of the direction of the wind recovered by the
在此,從送風機28吹出之風的朝向W1的相對於段差的頂面之入射角對應於前述仰角(例如,參閱圖5)。
上述入射角的較佳的範圍與前述仰角的較佳的範圍相同。
Here, the incident angle of the wind blown from the
上述入射角(亦即,仰角)由從送風機28吹出之風的朝向W1定義,因此送風機內部的風的進行方向可以為任意方向。因此,例如在下述圖7C所示之變形例(膜形成裝置300X)中亦可發揮與圖7B中的膜形成裝置300相同的效果。
圖7C係表示圖7B所示之膜形成裝置300的變形例(膜形成裝置300X)之概略剖面圖。
如圖7C所示,在膜形成裝置300X中的送風機28X內部(亦即,流路)中,風首先沿重力方向下朝向進行,接著在中途彎曲並且從送風機28X吹出。從送風機28X吹出之風的朝向W1的入射角(圖7C)與從送風機28吹出之風的朝向W1的入射角(圖7B)相同程度。
如圖7C所示,藉由膜形成裝置300X中的風回收機30X回收風。此時的風的反射角(圖7C)與藉由風回收機30回收風時的風的反射角(圖7B)相同程度。藉由風回收機30X回收之風在風回收機30X內部(亦即,流路)彎曲其進行方向,接著沿重力方向上朝向進行。
圖7C所示之膜形成裝置300X的結構除上述之方面,與圖7B所示之膜形成裝置300相同。
藉由圖7C所示之膜形成裝置300X亦可發揮與圖7B所示之膜形成裝置300相同的效果。
The aforementioned incident angle (that is, the elevation angle) is defined by the direction W1 of the wind blown from the
送風機28及送風機28X具備進行開始風的吹出之開啟狀態與停止風的吹出之關閉狀態的切換之開關功能為較佳。
藉此,能夠對包含段差的頂面之區域上的油墨選擇性吹送風。
作為開關功能,例如藉由在送風機的風吹出口設置百葉窗來實現。
It is preferable that the
本揭示的膜形成裝置並不限定於圖7A~圖7C所示之一例。
從形成抑制從段差的頂面上到側面上的厚度偏差之膜之效果的方面來看,從送風機28吹出之風的朝向W1及藉由風回收機30回收風之朝向並不限定於上述一例。例如,從送風機28吹出之風的朝向W1為重力方向下朝向,並且藉由風回收機30回收風之朝向額可以為重力方向上朝向。
又,從形成可抑制從段差的頂面上到側面上的厚度偏差之膜之效果方面來看,可以替換送風機與風回收機的配置。又,從上述效果的方面來看,可以省略風回收機及釘扎曝光機。
The film forming apparatus of the present disclosure is not limited to the example shown in FIGS. 7A to 7C .
The direction W1 of the wind blown from the
圖8A係表示本揭示的膜形成裝置的另一例(膜形成裝置300A)之概略俯視圖,圖8B係圖8A的側視圖。
圖8A及圖8B所示之膜形成裝置300A為如下例子:相對於圖7A及圖7B所示之膜形成裝置300,將從送風機28吹出之風的朝向W1沿重力方向下朝向變更,將藉由風回收機30回收風之朝向沿重力方向上朝向變更。在圖8A及圖8B所示之膜形成裝置300A中,亦與圖7A及圖7B所示之膜形成裝置300相同地,從輸送方向M1(亦即,基板輸送載台212的移動方向)的上游側依序配置噴墨噴頭24、送風機28、風回收機30及釘扎曝光機32。
FIG. 8A is a schematic plan view showing another example of the film forming apparatus (
圖9A係表示本揭示的膜形成裝置的又一例(膜形成裝置300B)之概略俯視圖,圖9B係圖9A的側視圖。
圖9A及圖9B所示之膜形成裝置300B為相對於圖8A及圖8B所示之膜形成裝置300A替換送風機28與風回收機30的位置之例子。亦即,在該變形例中,從輸送方向M1(亦即,基板輸送載台212的移動方向)的上游側依序配置噴墨噴頭24、風回收機30、送風機28及釘扎曝光機32。
依據該膜形成裝置300B,藉由風回收機30不僅回收來自送風機28的風,還能夠回收未到達帶段差之基板10而與帶段差之基板10一同攜帶之微小的油墨滴(油墨霧滴)。而且,與圖8A及圖8B所示之一例相同地,藉由送風機28,能夠形成可抑制從段差的側面上到頂面上的厚度偏差之膜。又,藉由風回收機30能夠回收微小的油墨滴,因此能夠抑制基於來自送風機28的風之微小的油墨滴的擴散。
FIG. 9A is a schematic plan view showing still another example of the film forming apparatus (
圖10A係表示本揭示的膜形成裝置的又一例(膜形成裝置300C)之概略俯視圖,圖10B係圖10A的側視圖。
圖10A及圖10B所示之膜形成裝置300C為相對於圖8A及圖8B所示之膜形成裝置300A在噴墨噴頭24與送風機28之間追加釘扎曝光機34之例子。在膜形成裝置300C中,從輸送方向M1(亦即,基板輸送載台212的移動方向)的上游側依序配置噴墨噴頭24、釘扎曝光機34、送風機28、風回收機30及釘扎曝光機32。
依據圖10A及圖10B所示之膜形成裝置300C,能夠藉由釘扎曝光機34對賦予到頂面上之油墨且吹送風之前的油墨實施釘扎曝光。藉此,能夠適當地上升頂面上的油墨的黏度,因此能夠進一步抑制頂面上的油墨藉由風的吹送而過渡流下,並且容易將風的吹送後的頂面上的油墨適當地殘留於頂面上。其結果,能夠更有效地發揮抑制從段差的側面上到頂面上的膜的厚度偏差之效果。
FIG. 10A is a schematic plan view showing still another example of the film forming apparatus (
再者,對賦予到頂面上之油墨且吹送風之前的油墨之釘扎曝光使用膜形成裝置300C而進行,除此以外,亦能夠藉由將帶段差之基板往返並且使用圖8A及圖8B所示之膜形成裝置300A而進行。In addition, the pinning exposure of the ink applied to the top surface and before blowing the air is performed using the
又,從抑制頂面上的油墨因風的吹送而過渡流下之效果的方面來看,亦能夠進行對吹送風之前的油墨之釘扎曝光且省略對已吹送風之後的油墨之釘扎曝光。Also, from the viewpoint of the effect of suppressing the excessive flow of ink on the top surface due to the blowing of the wind, it is possible to perform the pinning exposure of the ink before the blowing of the wind and omit the pinning exposure of the ink after the blowing of the wind.
又,如以下例示,在圖8A及圖8B所示之一例中,即使省略風回收機亦能夠實施風回收。In addition, as shown below, in the example shown in FIG. 8A and FIG. 8B , it is possible to perform wind recovery even if the wind recovery device is omitted.
圖11係表示本揭示的膜形成裝置的另一例之概略俯視圖。
圖11所示之膜形成裝置301為如下裝置:以膜形成裝置300為基底,省略風回收機30,代替其在基板輸送載台213上設置有貫通孔214。該例中的貫通孔214設置於基板輸送載台213中的與帶段差之基板10連接之區域之外。
在膜形成裝置301中,通過貫通孔214對配置有帶段差之基板10之空間進行排氣,藉此能夠回收風。
FIG. 11 is a schematic plan view showing another example of the film forming apparatus of the present disclosure.
The
圖12係表示本揭示的膜形成裝置的又一例之概略俯視圖。
圖12所示之膜形成裝置302為如下裝置:以膜形成裝置300為基底,省略風回收機30,代替其在基板輸送載台215上設置貫通孔216,進而作為帶段差之基板10A使用形成有貫通孔11之帶段差之基板。該例子中的貫通孔216為基板輸送載台215中的從與帶段差之基板10A連接之區域的外側搬運到與帶段差之基板10A連接之區域內之貫通孔。該貫通孔216具有回收風之功能及將帶段差之基板10A吸附於基板輸送載台215之功能。
在膜形成裝置302中,通過帶段差之基板10A本身的貫通孔11及基板輸送載台215的貫通孔216對配置有帶段差之基板10A之空間進行排氣,藉此能夠回收風。
Fig. 12 is a schematic plan view showing still another example of the film forming apparatus of the present disclosure.
The
本揭示的膜形成裝置具備2個上述送風機, 在上述2個送風機之間配置噴墨噴頭, 帶段差之基板與噴墨噴頭的相對移動為往返移動為較佳。 依據該態樣,在去程移動及回程移動這兩者中,能夠進行油墨的賦予及風吹送,因此膜形成的生產性優異。 The film forming apparatus of the present disclosure is provided with two of the aforementioned air blowers, An inkjet nozzle is arranged between the above two air blowers, It is preferable that the relative movement between the substrate with the level difference and the inkjet nozzle is reciprocating. According to this aspect, ink application and wind blowing can be performed in both the forward movement and the backward movement, so the productivity of film formation is excellent.
圖13A係表示具備2個送風機之態樣的本揭示的膜形成裝置的一例之概略俯視圖,圖13B係圖13A的側視圖,圖13C係相對於圖13B將帶段差之基板的輸送方向設為相反的方向時的側視圖。13A is a schematic plan view showing an example of the film forming apparatus of the present disclosure having two air blowers, FIG. 13B is a side view of FIG. Side view in the opposite direction.
如圖13A~圖13C所示,該一例之膜形成裝置400係相對於膜形成裝置300將送風機28B、風回收機30B及釘扎曝光機32B以依序配置追加於對輸送方向M11的噴墨噴頭24的上游側者。
膜形成裝置400中的基板輸送載台212能夠沿輸送方向M11(去程)及輸送方向M11B(回程)這兩者移動(亦即,能夠往返移動)。
As shown in FIGS. 13A to 13C , the
在使用了膜形成裝置400之膜的形成中,與使用膜形成裝置300之膜的形成相同地,對包含在輸送方向M11(去程)上輸送之帶段差之基板10中的段差的頂面之區域依序實施來自噴墨噴頭24的油墨的賦予、來自送風機28的風的吹送及基於釘扎曝光機32之釘扎曝光。此時,適當進行基於風回收機30之風的回收。在此期間,送風機28B、風回收機30B及釘扎曝光機32B均不運行,設為關閉狀態。
此外,膜形成裝置400中的基板輸送載台212中,對包含在輸送方向M11B(回程)上輸送之帶段差之基板10中的段差的頂面之區域依序實施來自噴墨噴頭24的油墨的賦予、來自送風機28B的風的吹送及基於釘扎曝光機32B之釘扎曝光。此時,適當進行基於風回收機30B之風的回收。在此期間,送風機28、風回收機30及釘扎曝光機32均不運行,設為關閉狀態。
In the formation of the film using the
作為與圖13A~圖13C所示之一例不同的一例,亦可舉出替換送風機28與風回收機30的位置及送風機28B與風回收機30B的位置的至少一個之例子。
圖14A係表示具備2個送風機之態樣的本揭示的膜形成裝置的另一例子之概略俯視圖,圖14B係圖14A的側視圖,圖14C係相對於圖14B將帶段差之基板的輸送方向設為相反的方向時的側視圖。
依據圖14A~圖14C所示之膜形成裝置400A,在輸送方向M11(去程)中,藉由風回收機30不僅回收來自送風機28的風,還能夠回收未到達帶段差之基板10而與帶段差之基板10一同攜帶之微小的油墨滴(油墨霧滴)。而且,與使用圖13A~圖13C所示之膜形成裝置400之情況相同地,藉由送風機28,能夠形成可抑制從段差的側面上到頂面上的厚度偏差之膜。又,藉由風回收機30能夠回收微小的油墨滴,因此能夠抑制基於來自送風機28的風之微小的油墨滴的擴散。
此外,依據上述變形例(膜形成裝置400A),在輸送方向M11B(回程)中,藉由風回收機30B不僅回收來自送風機28B的風,還能夠回收未到達帶段差之基板10而與帶段差之基板10一同攜帶之微小的油墨滴(油墨霧滴)。而且,與圖11A~圖11C所示之一例相同地,藉由送風機28B,能夠形成可抑制從段差的側面上到頂面上的厚度偏差之膜。又,藉由風回收機30B能夠回收微小的油墨滴,因此能夠抑制基於來自送風機28B的風之微小的油墨滴的擴散。
As an example different from the example shown in FIGS. 13A to 13C , at least one of the positions of the
以上說明之本揭示的膜的形成方法及本揭示的膜形成裝置能夠作為用於藉由噴墨法在帶段差之基板上形成膜之方法及裝置適用於所有用途。 本揭示的膜的形成方法及本揭示的膜形成裝置例如能夠適用於後述之本揭示的電子元件的製造方法。 The film forming method of the present disclosure and the film forming apparatus of the present disclosure described above can be applied to all applications as a method and an apparatus for forming a film on a substrate with a step difference by an inkjet method. The film formation method of this disclosure and the film formation apparatus of this disclosure can be applied to the manufacturing method of the electronic device of this disclosure mentioned later, for example.
〔電子裝置之製造方法〕 本揭示的電子元件的製造方法包括: 準備電子基板之製程,前述電子基板具備配線基板及配置於配線基板上之電子零件;及 在電子基板上形成絕緣層及導電層中的至少一個而獲得電子元件之製程, 藉由前述之本揭示的膜的形成方法形成絕緣層及導電層中的至少一個。 本揭示的電子裝置之製造方法依據需要還可以包括其他製程。 [Manufacturing method of electronic device] The manufacturing method of the disclosed electronic component includes: Preparation of the manufacturing process of the electronic substrate, the aforementioned electronic substrate has a wiring substrate and electronic components arranged on the wiring substrate; and A process for obtaining electronic components by forming at least one of an insulating layer and a conductive layer on an electronic substrate, At least one of the insulating layer and the conductive layer is formed by the aforementioned film forming method of the present disclosure. The manufacturing method of the electronic device disclosed in the present disclosure may also include other processes as required.
本揭示的電子元件的製造方法包括前述之本揭示的膜的形成方法,因此依據本揭示的電子元件的製造方法,可發揮與基於前述之本揭示的膜的形成方法之效果相同的效果。 本揭示的電子元件的製造方法中的絕緣層及導電層中至少其中一者的形成可以藉由前述之本揭示的膜形成裝置而進行。 The method of manufacturing an electronic device of the present disclosure includes the method of forming a film of the present disclosure described above. Therefore, the method of manufacturing an electronic device of the present disclosure can exhibit the same effects as those based on the method of forming a film of the present disclosure described above. Formation of at least one of the insulating layer and the conductive layer in the manufacturing method of the electronic device of the present disclosure can be performed by the aforementioned film forming apparatus of the present disclosure.
如前述, 本揭示的電子元件的製造方法中的電子基板(亦即,具備配線基板及配置於配線基板上之電子零件之電子基板)對應於前述之本揭示的膜的形成方法中的“帶段差之基板”, 本揭示的電子元件的製造方法中的配線基板上的電子零件的端部、電子零件的端部的側面及電子零件的頂面分別對應於前述之本揭示的膜的形成方法中的“段差”、“段差的側面”及“段差的頂面”。 As mentioned above, The electronic substrate (that is, an electronic substrate including a wiring board and electronic components disposed on the wiring board) in the method of manufacturing an electronic component of the present disclosure corresponds to the "substrate with a step difference" in the film forming method of the present disclosure described above. ", The end of the electronic component on the wiring board, the side surface of the end of the electronic component, and the top surface of the electronic component in the method of manufacturing an electronic component of the present disclosure correspond to the “level difference” in the above-mentioned method of forming a film of the present disclosure. , "The side of the step difference" and "The top surface of the step difference".
<電子元件的製造方法的一例> 以下,參閱圖式對本揭示的電子裝置之製造方法的一例進行說明。 但是,本揭示的電子裝置之製造方法並不限定於以下的一例。 本揭示的電子裝置之製造方法,其包括: 準備電子基板之電子基板準備製程,前述電子基板具備:配線基板,具有安裝面;複數個電子零件,安裝於配線基板的安裝面上及接地電極,以在俯視下包圍複數個電子零件中的至少1個電子零件之配置而設置; 第1製程,在藉由接地電極包圍之接地區域內形成被覆至少1個電子零件之絕緣性保護層;及 第2製程,作為電磁波遮蔽層形成用油墨的固化物,形成跨越絕緣性保護層上及接地電極上且被覆絕緣性保護層並且與接地電極電連接之電磁波遮蔽層, 藉由前述之本揭示的膜的形成方法形成絕緣性保護層及電磁波遮蔽層中的至少一個。 <An example of the manufacturing method of electronic components> Hereinafter, an example of the manufacturing method of the electronic device of the present disclosure will be described with reference to the drawings. However, the manufacturing method of the electronic device of the present disclosure is not limited to the following example. The manufacturing method of the electronic device disclosed herein includes: An electronic substrate preparation process for preparing an electronic substrate, the aforementioned electronic substrate includes: a wiring substrate having a mounting surface; a plurality of electronic components mounted on the mounting surface of the wiring substrate and a ground electrode, so as to surround at least one of the plurality of electronic components in a plan view Set up for the configuration of 1 electronic component; In the first process, an insulating protective layer covering at least one electronic component is formed in the grounding area surrounded by the grounding electrode; and In the second process, as a cured product of the ink for forming the electromagnetic wave shielding layer, an electromagnetic wave shielding layer that spans over the insulating protective layer and the ground electrode, is covered with the insulating protective layer and is electrically connected to the ground electrode is formed, At least one of the insulating protective layer and the electromagnetic wave shielding layer is formed by the above-mentioned film forming method of the present disclosure.
在此,絕緣性保護層為絕緣層的一例,電磁波遮蔽層為導電層的一例。Here, the insulating protective layer is an example of an insulating layer, and the electromagnetic wave shielding layer is an example of a conductive layer.
圖15A係在電子基板準備製程中準備之電子基板的概略俯視圖,圖15B係從圖15A的X-X線剖視之剖面圖。 圖16A係作為絕緣層的一例之形成有絕緣性保護層之電子基板的概略俯視圖,圖16B係從圖16A的X-X線剖視之剖面圖。 圖17A係作為導電層的一例之形成有電磁波遮蔽層之電子基板(亦即,本實施形態的電子元件)的概略俯視圖,圖17B係從圖17A的X-X線剖視之剖面圖。 15A is a schematic plan view of an electronic substrate prepared in the electronic substrate preparation process, and FIG. 15B is a cross-sectional view taken along line X-X in FIG. 15A. 16A is a schematic plan view of an electronic substrate on which an insulating protective layer is formed as an example of an insulating layer, and FIG. 16B is a cross-sectional view taken along line X-X in FIG. 16A. 17A is a schematic plan view of an electronic substrate (that is, the electronic component of this embodiment) formed with an electromagnetic wave shielding layer as an example of a conductive layer, and FIG. 17B is a cross-sectional view taken along line X-X in FIG. 17A.
-電子基板準備製程-
如圖15A及圖15B所示,在本一例中的電子基板準備製程中,準備電子基板110,前述電子基板110具備具有安裝面之配線基板112、安裝於配線基板112的安裝面上之複數個電子零件118及以在俯視下包圍上述複數個電子零件118之配置而設置之接地電極116。
省略圖示,但是複數個電子零件118的各個經由焊球安裝於配線基板112的安裝面上。在配線基板112與複數個電子零件118的各個之間存在微小的間隙(參閱前述圖2)。
-Electronic substrate preparation process-
As shown in FIG. 15A and FIG. 15B , in the electronic substrate preparation process in this example, an
電子基板準備製程可以為僅簡單地準備預先製造之電子基板110的製程,亦可以為製造電子基板110之製程。
作為電子基板110之製造方法,例如能夠適當參閱對印刷配線基板安裝電子零件之公知的電子基板之製造方法。
The electronic substrate preparation process may be a process of simply preparing the prefabricated
作為配線基板112,能夠使用形成配線之基板、例如印刷配線基板。
配線基板112還可以包含除了接地電極116以外的電極、阻焊層等。
As the
接地電極116為施加接地(GND)電位之電極。
在該一例中,接地電極116以包圍複數個電子零件(電子零件118)之配置而設置。
換言之,在藉由接地電極116包圍之接地區域114A內安裝有複數個電子零件(電子零件118)。
The
如圖15A所示,該一例中的接地電極116作為不連續的圖案(詳細而言,為被分割之線圖案)形成,但是本揭示中的接地電極並不限定於該一例。例如,本揭示中的接地電極可以作為連續圖案(亦即,未分割之線圖案)形成。As shown in FIG. 15A , the
又,該一例中的接地電極116作為繞複數個電子零件(電子零件118)的周圍完整一圈之環狀圖案形成。
但是,本揭示中的接地電極116並不限定於該環狀圖案,例如可以為環狀圖案的至少一部分缺失之圖案。
從進一步降低針對複數個電子零件(電子零件118)之來自外部的電磁波的影響之觀點考慮,接地電極116將配置有複數個電子零件之區域包圍半圈以上為較佳,包圍3/4圈以上為更佳。
In addition, the
又,如圖15B所示,該一例中的接地電極116相對於配線基板112以埋入接地電極116的厚度方向的一部分之形式形成,但是本揭示中的接地電極並不限定於該一例。例如,本揭示中的接地電極可以以埋入接地電極的厚度方向的全部之形式形成。又,本揭示中的接地電極可以不埋入配線基板112而在配線基板112的表面形成。又,本揭示中的接地電極可以作為貫通配線基板112之圖案形成。Also, as shown in FIG. 15B , the
安裝於接地區域114A內之複數個電子零件118可以為相同設計的電子零件,亦可以為不同設計的電子零件。又,安裝於接地區域內之電子零件的數量並不限定於複數個,可以僅為1個。
作為電子零件118,例如可舉出積體電路(IC;Integrated Circuit)等半導體晶片、電容器、電晶體等。
The plurality of
本揭示中的電子零件(例如電子零件118)的高度較佳為100μm以上,更佳為200μm以上,進一步較佳為300μm以上。 電子零件的高度較佳為2000μm以下,更佳為1000μm以下。 The height of the electronic component (such as the electronic component 118 ) in this disclosure is preferably greater than 100 μm, more preferably greater than 200 μm, and further preferably greater than 300 μm. The height of the electronic component is preferably at most 2000 μm, more preferably at most 1000 μm.
本揭示中的接地電極(例如接地電極116)的高度較佳為-10μm以上,更佳為0μm以上,進一步較佳為5μm以上。 接地電極的高度較佳為100μm以下,更佳為50μm以下,進一步較佳為30μm以下。 The height of the ground electrode (such as the ground electrode 116 ) in the present disclosure is preferably greater than −10 μm, more preferably greater than 0 μm, and further preferably greater than 5 μm. The height of the ground electrode is preferably at most 100 μm, more preferably at most 50 μm, further preferably at most 30 μm.
-第1製程-
如圖16A及圖16B所示,在第1製程中,形成被覆安裝於接地區域114A內之複數個電子零件118之絕緣性保護層122。
-1st process-
As shown in FIGS. 16A and 16B , in the first process, an insulating
絕緣性保護層122形成於接地區域114A內且跨越複數個電子零件118上和該等複數個電子零件118的周圍之區域。
絕緣性保護層的功能例如為保護電子零件之功能及抑制電子零件與其他導電性構件(例如電磁波遮蔽層)的短路之功能。
The insulating
在該一例的第1製程中,例如能夠使用絕緣層形成用油墨來形成絕緣性保護層122。絕緣層形成用油墨例如為活性能量射線硬化型油墨。
該絕緣性保護層122的形成能夠適用前述之本揭示的膜之製造方法。
藉此,能夠形成抑制從電子零件118的側面上到頂面上的厚度偏差之絕緣性保護層122。
In the first process of this example, the insulating
-第2製程-
如圖17A及圖17B所示,在第2製程中,使用作為導電層形成用油墨的電磁波遮蔽層形成用油墨形成跨越絕緣性保護層122上與接地電極116上的至少一部分且被覆絕緣性保護層122並且與接地電極116電連接之電磁波遮蔽層形成用油墨的固化物亦即電磁波遮蔽層130(亦即,導電層)。藉此,獲得電子元件100。
電磁波遮蔽層130將電磁波遮蔽層形成用油墨賦予到接地區域114A內且固化而形成。
關於電磁波遮蔽層形成用油墨及電磁波遮蔽層的形成方法的較佳的範圍,待留後述。
-Second process-
As shown in FIG. 17A and FIG. 17B , in the second process, at least a part of the insulating
電磁波遮蔽層為用於藉由遮蔽對電子零件照射之電磁波來降低電磁波對電子零件的影響的層。 在本揭示中,將該電磁波遮蔽層的性能亦稱為“電磁波遮蔽性”。 電磁波遮蔽層的電磁波遮蔽性藉由電磁波遮蔽層經由絕緣性保護層配置於電子零件上來發揮作用。 又,電磁波遮蔽層的電磁波遮蔽性藉由對電磁波遮蔽層賦予接地(GND)電位來發揮作用。因此,作為電磁波遮蔽層的前提,電磁波遮蔽層具有導電性。 The electromagnetic wave shielding layer is a layer for reducing the influence of electromagnetic waves on electronic components by shielding electromagnetic waves irradiated to electronic components. In this disclosure, the performance of the electromagnetic wave shielding layer is also referred to as "electromagnetic wave shielding property". The electromagnetic wave shielding property of the electromagnetic wave shielding layer functions when the electromagnetic wave shielding layer is arranged on the electronic component through the insulating protective layer. In addition, the electromagnetic wave shielding property of the electromagnetic wave shielding layer functions by giving a ground (GND) potential to the electromagnetic wave shielding layer. Therefore, as a prerequisite for the electromagnetic wave shielding layer, the electromagnetic wave shielding layer has conductivity.
該電磁波遮蔽層130的形成亦能夠適用前述之本揭示的膜之製造方法。
藉此,能夠經由絕緣性保護層122形成抑制從電子零件118的側面上到頂面上的厚度偏差之電磁波遮蔽層130。
The formation of the electromagnetic
接著,對導電層形成用油墨(例如電磁波遮蔽層形成用油墨)、電磁波遮蔽層的形成方法、絕緣層形成用油墨(例如絕緣性保護層形成用油墨)及絕緣性保護層的形成方法的較佳的態樣進行說明。Next, comparison of the ink for forming a conductive layer (such as ink for forming an electromagnetic wave shielding layer), the method for forming an electromagnetic wave shielding layer, the ink for forming an insulating layer (for example, ink for forming an insulating protective layer) and the method for forming an insulating protective layer A good example will be explained.
<導電層形成用油墨> 作為導電層形成用油墨(例如電磁波遮蔽層形成用油墨),含有金屬粒子之油墨(以下,亦稱為“金屬粒子油墨”)、含有金屬錯合物之油墨(以下,亦稱為“金屬錯合物油墨”)或含有金屬鹽之油墨(以下,亦稱為“金屬鹽油墨”)為較佳,金屬鹽油墨或金屬錯合物油墨為更佳。 <Ink for forming conductive layer> As inks for forming conductive layers (such as inks for forming electromagnetic wave shielding layers), inks containing metal particles (hereinafter also referred to as "metal particle inks"), inks containing metal complexes (hereinafter also referred to as "metal complexes") Compound inks") or inks containing metal salts (hereinafter, also referred to as "metal salt inks") are preferred, and metal salt inks or metal complex inks are more preferred.
(金屬粒子油墨) 金屬粒子油墨例如為金屬粒子分散於分散介質中之油墨組成物。 (Metallic Particle Ink) Metal particle ink is, for example, an ink composition in which metal particles are dispersed in a dispersion medium.
-金屬粒子- 作為構成金屬粒子之金屬,例如可舉出卑金屬及貴金屬的粒子。作為卑金屬,例如可舉出鎳、鈦、鈷、銅、鉻、錳、鐵、鋯、錫、鎢、鉬及釩。作為貴金屬,例如可舉出金、銀、鉑、鈀、銥、鋨、釕、銠、錸及含有該等金屬之合金。其中,從電磁波遮蔽性的觀點考慮,構成金屬粒子之金屬含有選自包括銀、金、鉑、鎳、鈀及銅之群組中之至少1種為較佳,含有銀為更佳。 -Metal particles- As a metal which comprises a metal particle, the particle|grains of a base metal and a noble metal are mentioned, for example. Examples of base metals include nickel, titanium, cobalt, copper, chromium, manganese, iron, zirconium, tin, tungsten, molybdenum, and vanadium. Examples of noble metals include gold, silver, platinum, palladium, iridium, osmium, ruthenium, rhodium, rhenium, and alloys containing these metals. Among them, it is preferable that the metal constituting the metal particles contains at least one selected from the group consisting of silver, gold, platinum, nickel, palladium, and copper, and more preferably contains silver, from the viewpoint of electromagnetic wave shielding properties.
金屬粒子的平均粒徑並無特別限定,10nm~500nm為較佳,10nm~200nm為更佳。若平均粒徑在上述範圍內,則金屬粒子的煅燒溫度降低,電磁波遮蔽層形成的製程適性提高。尤其,在使用噴塗方式或噴墨記錄方式賦予金屬粒子油墨之情況下,存在提高噴出性並且提高圖案形成性及電磁波遮蔽層的膜厚的均勻性之傾向。在此所說之平均粒徑係指金屬粒子的一次粒徑的平均值(平均一次粒徑)。The average particle size of the metal particles is not particularly limited, but is preferably from 10 nm to 500 nm, more preferably from 10 nm to 200 nm. When the average particle diameter is within the above range, the calcining temperature of the metal particles is lowered, and the process suitability for forming the electromagnetic wave shielding layer is improved. In particular, when the metal particle ink is applied by a spray coating method or an inkjet recording method, there is a tendency to improve dischargeability, pattern formability, and uniformity of film thickness of the electromagnetic wave shielding layer. The average particle diameter referred to here means the average value of the primary particle diameters (average primary particle diameter) of the metal particles.
金屬粒子的平均粒徑藉由雷射繞射/散射法進行測量。金屬粒子的平均粒徑例如為測量3次50%體積累積直徑(D50)而作為3次測量之值的平均值算出之值,能夠使用雷射繞射/散射式粒度分布測量裝置(產品名“LA-960”、HORIBA, Ltd.製)進行測量。The average particle size of the metal particles is measured by the laser diffraction/scattering method. The average particle diameter of the metal particles is, for example, a value calculated as the average value of the three measurements of the 50% volume cumulative diameter (D50) measured three times, and a laser diffraction/scattering type particle size distribution measuring device (product name " LA-960", manufactured by HORIBA, Ltd.) for measurement.
又,金屬粒子油墨中依據需要可以含有平均粒徑為500nm以上的金屬粒子。在含有平均粒徑為500nm以上的金屬粒子之情況下,藉由nm尺寸的金屬粒子在μm尺寸的金屬粒子的周圍降低熔點,能夠接合電磁波遮蔽層。In addition, the metal particle ink may contain metal particles having an average particle diameter of 500 nm or more as needed. When metal particles having an average particle diameter of 500 nm or more are contained, the electromagnetic wave shielding layer can be bonded by lowering the melting point of the nm-sized metal particles around the μm-sized metal particles.
在金屬粒子油墨中,金屬粒子的含量相對於金屬粒子油墨的總量為10質量%~90質量%為較佳,20質量%~50質量%為更佳。若金屬粒子的含量為10質量%以上,則進一步降低表面電阻率。若金屬粒子的含量為90質量%以下,則在使用噴墨記錄方式賦予金屬粒子油墨之情況下,提高吐出性。In the metal particle ink, the content of the metal particles is preferably 10% by mass to 90% by mass, more preferably 20% by mass to 50% by mass, based on the total amount of the metal particle ink. When the content of the metal particles is 10% by mass or more, the surface resistivity is further reduced. When the content of the metal particles is 90% by mass or less, the discharge property is improved when the metal particle ink is provided using the inkjet recording method.
金屬粒子油墨中除了金屬粒子以外,例如可以含有分散劑、樹脂、分散介質、增黏劑及表面張力調整劑。In addition to the metal particles, the metal particle ink may contain, for example, a dispersant, a resin, a dispersion medium, a thickener, and a surface tension regulator.
-分散劑- 金屬粒子油墨可以含有附著於金屬粒子的表面的至少一部分之分散劑。分散劑實質上與金屬粒子一同構成金屬膠體粒子。分散劑具有被覆金屬粒子提高金屬粒子的分散性並且防止凝聚之作用。分散劑為能夠形成金屬膠體粒子之有機化合物為較佳。從電磁波遮蔽性及分散穩定性的觀點考慮,分散劑為胺、羧酸、醇或樹脂分散劑為較佳。 -Dispersant- The metal particle ink may contain a dispersant attached to at least a part of the surface of the metal particle. The dispersant substantially constitutes metal colloid particles together with the metal particles. The dispersant has the function of coating the metal particles to improve the dispersibility of the metal particles and prevent aggregation. The dispersant is preferably an organic compound capable of forming metal colloid particles. From the viewpoint of electromagnetic shielding property and dispersion stability, the dispersant is preferably an amine, carboxylic acid, alcohol or resin dispersant.
金屬粒子油墨中所含有之分散劑可以為1種,亦可以為2種以上。The dispersant contained in the metal particle ink may be one type, or two or more types.
作為胺,例如可舉出飽和或不飽和的脂肪族胺。其中,胺為碳數4~8的脂肪族胺為較佳。碳數為4~8的脂肪族胺可以為直鏈狀亦可以為支鏈狀,可以具有環結構。Examples of the amine include saturated or unsaturated aliphatic amines. Among them, the amine is preferably an aliphatic amine having 4 to 8 carbon atoms. The aliphatic amine having 4 to 8 carbon atoms may be linear or branched, and may have a ring structure.
作為脂肪族胺,例如可舉出丁基胺、正戊基胺、異戊基胺、己基胺、2-乙基己基胺及辛基胺。Examples of aliphatic amines include butylamine, n-pentylamine, isopentylamine, hexylamine, 2-ethylhexylamine, and octylamine.
作為具有脂環結構之胺,可舉出環戊基胺、環己基胺等環烷基胺。Examples of the amine having an alicyclic structure include cycloalkylamines such as cyclopentylamine and cyclohexylamine.
作為芳香族胺,可舉出苯胺。Aniline is mentioned as an aromatic amine.
胺可以具有除了胺基以外的官能基。作為除了胺基以外的官能基,例如可舉出羥基、羧基、烷氧基、羰基、酯基及巰基。Amines may have functional groups other than amine groups. As a functional group other than an amino group, a hydroxyl group, a carboxyl group, an alkoxy group, a carbonyl group, an ester group, and a mercapto group are mentioned, for example.
作為羧酸,例如可舉出甲酸、草酸、乙酸、己酸、丙烯酸、辛酸、油酸、硫氰酸、蓖麻油酸、沒食子酸及水楊酸。作為羧酸的一部分之羧基可以與金屬離子形成鹽。形成鹽之金屬離子可以為1種,亦可以為2種以上。Examples of the carboxylic acid include formic acid, oxalic acid, acetic acid, caproic acid, acrylic acid, octanoic acid, oleic acid, thiocyanic acid, ricinoleic acid, gallic acid and salicylic acid. The carboxyl group that is part of the carboxylic acid can form salts with metal ions. The metal ion which forms a salt may be 1 type, and may be 2 or more types.
羧酸可以具有除了羧基以外的官能基。作為除了羧基以外的官能基,例如可舉出胺基、羥基、烷氧基、羰基、酯基及巰基。Carboxylic acids may have functional groups other than carboxyl. As a functional group other than a carboxyl group, an amino group, a hydroxyl group, an alkoxy group, a carbonyl group, an ester group, and a mercapto group are mentioned, for example.
作為醇,例如可舉出萜烯系醇、烯丙醇及油基醇。醇容易配位於金屬粒子的表面,能夠抑制金屬粒子的凝聚。Examples of the alcohol include terpene-based alcohol, allyl alcohol, and oleyl alcohol. Alcohol easily coordinates to the surface of the metal particles and can suppress the aggregation of the metal particles.
作為樹脂分散劑,例如可舉出作為親水性基具有非離子性基並且能夠均勻地溶解於溶劑之分散劑。作為樹脂分散劑,例如可舉出聚乙烯吡咯啶酮、聚乙二醇、聚乙二醇-聚丙二醇共聚物、聚乙烯醇、聚烯丙基胺及聚乙烯醇-聚乙酸乙烯酯共聚物。樹脂分散劑的分子量中,重量平均分子量為1000~50000為較佳,1000~30000為更佳。As a resin dispersing agent, the dispersing agent which has a nonionic group as a hydrophilic group and can be dissolved uniformly in a solvent is mentioned, for example. Examples of resin dispersants include polyvinylpyrrolidone, polyethylene glycol, polyethylene glycol-polypropylene glycol copolymers, polyvinyl alcohol, polyallylamine, and polyvinyl alcohol-polyvinyl acetate copolymers. . In the molecular weight of the resin dispersant, the weight average molecular weight is preferably 1,000 to 50,000, more preferably 1,000 to 30,000.
在金屬粒子油墨中,分散劑的含量相對於金屬粒子油墨的總量為0.5質量%~50質量%為較佳,1質量%~30質量%為更佳。In the metal particle ink, the content of the dispersant is preferably 0.5% by mass to 50% by mass, more preferably 1% by mass to 30% by mass, based on the total amount of the metal particle ink.
-分散介質- 金屬粒子油墨含有分散介質為較佳。分散介質的種類並無特別限定,例如可舉出烴、醇及水。 -Dispersion medium- It is preferable that the metal particle ink contains a dispersion medium. The type of dispersion medium is not particularly limited, and examples thereof include hydrocarbons, alcohols, and water.
金屬粒子油墨中所含有之分散介質可以為1種,亦可以為2種以上。 金屬粒子油墨中所含有之分散介質為揮發性為較佳。分散介質的沸點為50℃~250℃為較佳,70℃~220℃為更佳,80℃~200℃為進一步較佳。若分散介質的沸點為50℃~250℃,則存在能夠兼具金屬粒子油墨的穩定性與煅燒性之傾向。 The dispersion medium contained in the metal particle ink may be one type, or two or more types. It is preferable that the dispersion medium contained in the metal particle ink is volatile. The boiling point of the dispersion medium is preferably from 50°C to 250°C, more preferably from 70°C to 220°C, and still more preferably from 80°C to 200°C. When the boiling point of the dispersion medium is 50° C. to 250° C., it tends to be possible to achieve both stability and sinterability of the metal particle ink.
作為烴,可舉出脂肪族烴及芳香族烴。Examples of hydrocarbons include aliphatic hydrocarbons and aromatic hydrocarbons.
作為脂肪族烴,例如可舉出十四烷、十八烷、七甲基壬烷、四甲基十五烷、己烷、庚烷、辛烷、壬烷、癸烷、十三烷、甲基戊烷、正烷烴、異烷烴等飽和脂肪族烴或不飽和脂肪族烴。Examples of aliphatic hydrocarbons include tetradecane, octadecane, heptamethylnonane, tetramethylpentadecane, hexane, heptane, octane, nonane, decane, tridecane, methane Saturated or unsaturated aliphatic hydrocarbons such as pentane, normal alkanes, and isoalkanes.
作為芳香族烴,例如可舉出甲苯及二甲苯。Examples of aromatic hydrocarbons include toluene and xylene.
作為醇,可舉出脂肪族醇及脂環式醇。在作為分散介質使用醇之情況下,分散劑為胺或羧酸為較佳。As alcohol, aliphatic alcohol and alicyclic alcohol are mentioned. When alcohol is used as the dispersion medium, the dispersant is preferably amine or carboxylic acid.
作為脂肪族醇,例如可舉出庚醇、辛醇(例如,1-辛醇、2-辛醇、3-辛醇等)、癸醇(例如,1-癸醇等)、月桂基醇、十四烷基醇、鯨蠟醇、2-乙基-1-己醇、十八烷基醇、十六醇、油基醇等在飽和或不飽和的鏈中可以含有醚鍵之碳數6~20的脂肪族醇。Examples of aliphatic alcohols include heptanol, octanol (for example, 1-octanol, 2-octanol, 3-octanol, etc.), decyl alcohol (for example, 1-decyl alcohol, etc.), lauryl alcohol, Tetradecyl alcohol, cetyl alcohol, 2-ethyl-1-hexanol, stearyl alcohol, cetyl alcohol, oleyl alcohol, etc. can contain ether bond carbon number 6 in the saturated or unsaturated chain ~20 aliphatic alcohols.
作為脂環式醇,例如可舉出環己醇等環烷醇;萜品醇(含有α、β、γ異構物或該等任意的混合物。)、二羥基萜品醇等萜烯醇;二羥基萜品醇、桃金孃烯醇、蘇伯樓醇、薄荷醇、香旱芹醇、紫蘇醇、松香芹醇、蘇伯樓醇及馬鞭烯醇。Examples of alicyclic alcohols include cycloalkanols such as cyclohexanol; terpineols (including α, β, γ isomers or any mixture thereof), and terpene alcohols such as dihydroxyterpineol; Dihydroxyterpineol, myrtenol, suberyl alcohol, menthol, carveol, perillyl alcohol, pinocarveol, suberyl alcohol, and verbenol.
分散介質可以為水。從調整黏度、表面張力、揮發性等物性之觀點考慮,分散介質可以為水與其他溶劑的混合溶劑。與水混合之其他溶劑為醇為較佳。與水併用而使用之醇為能夠與水混合的沸點130℃以下的醇為較佳。作為醇,例如可舉出1-丙醇、2-丙醇、1-丁醇、2-丁醇、三級丁醇、1-戊醇、乙二醇單甲醚、乙二醇單乙基醚、乙二醇單丙醚及丙二醇單甲基醚。The dispersion medium may be water. From the viewpoint of adjusting physical properties such as viscosity, surface tension, and volatility, the dispersion medium may be a mixed solvent of water and other solvents. The other solvent mixed with water is preferably alcohol. The alcohol used in combination with water is preferably an alcohol with a boiling point of 130° C. or lower that can be mixed with water. Examples of the alcohol include 1-propanol, 2-propanol, 1-butanol, 2-butanol, tertiary butanol, 1-pentanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl Ether, Ethylene Glycol Monopropyl Ether and Propylene Glycol Monomethyl Ether.
在金屬粒子油墨中,分散介質的含量相對於金屬粒子油墨的總量為1質量%~50質量%為較佳。分散介質的含量只要為1質量%~50質量%,則作為電磁波遮蔽層形成用油墨能夠獲得充分的導電性。分散介質的含量為10質量%~45質量%為更佳,20質量%~40質量%為進一步較佳。In the metal particle ink, the content of the dispersion medium is preferably 1% by mass to 50% by mass relative to the total amount of the metal particle ink. If the content of the dispersion medium is 1% by mass to 50% by mass, sufficient conductivity can be obtained as an ink for forming an electromagnetic wave shielding layer. The content of the dispersion medium is more preferably 10% by mass to 45% by mass, and more preferably 20% by mass to 40% by mass.
-樹脂- 金屬粒子油墨可以含有樹脂。作為樹脂,例如可舉出聚酯、聚胺酯、三聚氰胺樹脂、丙烯酸樹脂、苯乙烯系樹脂、聚醚及萜烯樹脂。 -resin- Metal particle ink may contain resin. Examples of the resin include polyester, polyurethane, melamine resin, acrylic resin, styrene resin, polyether and terpene resin.
金屬粒子油墨中所含有之樹脂可以為1種,亦可以為2種以上。The resin contained in the metal particle ink may be one type, or two or more types.
在金屬粒子油墨中,樹脂的含量相對於金屬粒子油墨的總量為0.1質量%~5質量%為較佳。In the metal particle ink, the resin content is preferably 0.1% by mass to 5% by mass relative to the total amount of the metal particle ink.
-增黏劑- 金屬粒子油墨可以含有增黏劑。作為增黏劑,例如可舉出黏土、皂土、鋰膨潤石等黏土礦物;甲基纖維素、羧甲基纖維素、羥乙基纖維素、羥丙基纖維素、羥丙基甲基纖維素等纖維素衍生物;及黃原膠、瓜爾膠等多糖類。 -Tackifier- Metal particle inks may contain tackifiers. Examples of thickeners include clay minerals such as clay, bentonite, and lithium bentonite; methylcellulose, carboxymethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, and hydroxypropylmethylcellulose. Cellulose derivatives such as cellulose; and polysaccharides such as xanthan gum and guar gum.
金屬粒子油墨中所含有之增黏劑可以為1種,亦可以為2種以上。The thickener contained in the metal particle ink may be one type, or two or more types.
在金屬粒子油墨中,增黏劑的含量相對於金屬粒子油墨的總量為0.1質量%~5質量%為較佳。In the metal particle ink, the content of the thickener is preferably 0.1% by mass to 5% by mass relative to the total amount of the metal particle ink.
-界面活性劑- 金屬粒子油墨可以含有界面活性劑。若在金屬粒子油墨中含有界面活性劑,則容易形成均勻的電磁波遮蔽層。 -Surfactant- The metal particle ink may contain a surfactant. When a surfactant is contained in the metal particle ink, it is easy to form a uniform electromagnetic wave shielding layer.
界面活性劑可以為陰離子性界面活性劑、陽離子性界面活性劑及非離子性界面活性劑中的任一個。其中,從能夠以少量的含量調整表面張力之觀點考慮,界面活性劑為氟系界面活性劑為較佳。又,界面活性劑為沸點超過250℃之化合物為較佳。The surfactant may be any of anionic surfactants, cationic surfactants, and nonionic surfactants. Among them, the surfactant is preferably a fluorine-based surfactant from the viewpoint of being able to adjust the surface tension with a small amount of content. Also, the surfactant is preferably a compound having a boiling point exceeding 250°C.
金屬粒子油墨的黏度並無特別限定,為0.01Pa・s~5000Pa・s即可,0.1Pa・s~100Pa・s為較佳。在使用噴塗法或噴墨記錄方式賦予金屬粒子油墨之情況下,金屬粒子油墨的黏度為1mPa・s~100mPa・s為較佳,2mPa・s~50mPa・s為更佳,3mPa・s~30mPa・s為進一步較佳。The viscosity of the metal particle ink is not particularly limited, and may be 0.01Pa・s to 5000Pa・s, preferably 0.1Pa・s to 100Pa・s. In the case of applying metal particle ink by spraying method or inkjet recording method, the viscosity of metal particle ink is preferably 1mPa・s~100mPa・s, more preferably 2mPa・s~50mPa・s, 3mPa・s~30mPa ・s is more preferable.
金屬粒子油墨的黏度為使用黏度計在25℃下測量之值。黏度例如使用VISCOMETER TV-22型黏度計(TOKI SANGYO CO.,LTD.製)進行測量。The viscosity of the metal particle ink is a value measured at 25° C. using a viscometer. The viscosity is measured using, for example, a VISCOMETER TV-22 viscometer (manufactured by TOKI SANGYO CO., LTD.).
金屬粒子油墨的表面張力並無特別限定,20mN/m~45mN/m為較佳,25mN/m~40mN/m為更佳。 表面張力為使用表面張力計在25℃下測量之值。 The surface tension of the metal particle ink is not particularly limited, but is preferably 20 mN/m to 45 mN/m, more preferably 25 mN/m to 40 mN/m. The surface tension is a value measured at 25° C. using a surface tensiometer.
金屬粒子油墨的表面張力例如使用DY-700(Kyowa Interface Science Co.,Ltd.製)進行測量。The surface tension of the metal particle ink is measured using, for example, DY-700 (manufactured by Kyowa Interface Science Co., Ltd.).
-金屬粒子之製造方法- 金屬粒子可以為市售品,亦可以為藉由公知的方法製造者。作為金屬粒子之製造方法,例如可舉出濕式還原法、氣相法及電漿法。作為金屬粒子的較佳的製造方法,可舉出能夠以粒徑分布變窄的方式製造平均粒徑200nm以下的金屬粒子之濕式還原法。基於濕式還原法之金屬粒子之製造方法例如可舉出包括如下製程之方法:日本特開2017-37761號公報、國際公開第2014-57633號等中所記載之混合金屬鹽及還原劑獲得絡合反應液及加熱絡合反應液來還原絡合反應液中的金屬離子獲得金屬奈米粒子的漿料。 -Manufacturing method of metal particles- Metal particles may be commercially available or may be produced by a known method. As a manufacturing method of a metal particle, a wet reduction method, a gas phase method, and a plasma method are mentioned, for example. A preferable method for producing metal particles is a wet reduction method capable of producing metal particles with an average particle diameter of 200 nm or less such that the particle diameter distribution is narrowed. The production method of metal particles based on the wet reduction method includes, for example, a method including the following process: a mixed metal salt and a reducing agent described in Japanese Patent Laid-Open No. 2017-37761, International Publication No. 2014-57633, etc. combining the reaction solution and heating the complexing reaction solution to reduce metal ions in the complexing reaction solution to obtain a slurry of metal nanoparticles.
在製造金屬粒子油墨中,為了將金屬粒子油墨中所含有之各成分的含量調整在既定範圍內,可以進行加熱處理。加熱處理可以在減壓下進行,亦可以在常壓下進行。又,在常壓下進行之情況下,可以在大氣中進行,亦可以在非活性氣體環境下進行。In producing the metal particle ink, heat treatment may be performed in order to adjust the content of each component contained in the metal particle ink within a predetermined range. The heat treatment may be performed under reduced pressure or under normal pressure. Moreover, when carrying out under normal pressure, it may carry out in air|atmosphere, and may carry out in an inert gas atmosphere.
(金屬錯合物油墨) 金屬錯合物油墨例如為金屬錯合物溶解於溶劑中之油墨組成物。 (metal complex ink) The metal complex ink is, for example, an ink composition in which a metal complex is dissolved in a solvent.
-金屬錯合物- 作為構成金屬錯合物之金屬,例如可舉出銀、銅、金、鋁、鎂、鎢、鉬、鋅、鎳、鐵、鉑、錫、銅及鉛。其中,從電磁波遮蔽性的觀點考慮,構成金屬錯合物之金屬含有選自包括銀、金、鉑、鎳、鈀及銅之群組中之至少1種為較佳,含有銀為更佳。 -Metal complexes- Examples of the metal constituting the metal complex include silver, copper, gold, aluminum, magnesium, tungsten, molybdenum, zinc, nickel, iron, platinum, tin, copper and lead. Among them, from the viewpoint of electromagnetic shielding properties, it is preferable that the metal constituting the metal complex contains at least one selected from the group consisting of silver, gold, platinum, nickel, palladium, and copper, and it is more preferable that it contains silver.
金屬錯合物油墨中所含有之金屬的含量相對於金屬錯合物油墨的總量以金屬元素換算計為1質量%~40質量%為較佳,5質量%~30質量%為更佳,7質量%~20質量%為進一步較佳。The content of the metal contained in the metal complex ink is preferably 1% by mass to 40% by mass, more preferably 5% by mass to 30% by mass, based on the total amount of the metal complex ink, in terms of metal elements. 7 mass % - 20 mass % are still more preferable.
金屬錯合物例如藉由使金屬鹽與絡合劑進行反應來獲得。作為金屬錯合物之製造方法,例如可舉出將金屬鹽及絡合劑加入到有機溶劑並且攪拌規定時間之方法。攪拌方法並無特別限定,能夠從使用攪拌器、攪拌葉片或混合器進行攪拌之方法及施加超音波之方法等公知的方法適當選擇。A metal complex is obtained, for example, by reacting a metal salt with a complexing agent. As a method for producing a metal complex, for example, a method of adding a metal salt and a complexing agent to an organic solvent and stirring for a predetermined time is mentioned. The stirring method is not particularly limited, and can be appropriately selected from known methods such as a method of stirring using a stirrer, a stirring blade, or a mixer, and a method of applying ultrasonic waves.
作為金屬鹽,可舉出金屬氧化物、硫代檸檬酸鹽、硫化物、氯化物、氰化物、氰酸鹽、碳酸鹽、乙酸鹽、硝酸鹽、亞硝酸鹽、硫酸鹽、磷酸鹽、過氯酸鹽、四氟硼酸鹽、乙醯丙酮絡鹽及羧酸鹽。Examples of metal salts include metal oxides, thiocitrates, sulfides, chlorides, cyanides, cyanates, carbonates, acetates, nitrates, nitrites, sulfates, phosphates, peroxides, Chlorates, tetrafluoroborates, acetylacetonate complex salts and carboxylates.
作為錯合劑,可舉出胺、胺基甲酸銨系化合物、碳酸銨系化合物、銨碳酸氫鹽化合物及羧酸。其中,從電磁波遮蔽性及金屬錯合物的穩定性的觀點考慮,錯合劑含有選自包括胺基甲酸銨系化合物、碳酸銨系化合物、胺及碳數8~20的羧酸之群組中之至少1種為較佳。Examples of complexing agents include amines, ammonium carbamate-based compounds, ammonium carbonate-based compounds, ammonium bicarbonate compounds, and carboxylic acids. Among them, from the viewpoint of electromagnetic wave shielding properties and the stability of the metal complex, the complexing agent is selected from the group consisting of ammonium carbamate compounds, ammonium carbonate compounds, amines, and carboxylic acids with 8 to 20 carbon atoms. At least one of them is preferred.
金屬錯合物具有源自錯合劑之結構並且具有源自選自包括胺基甲酸銨系化合物、碳酸銨系化合物、胺及碳數8~20的羧酸之群組中之至少1種之結構之金屬錯合物為較佳。The metal complex has a structure derived from a complexing agent and has a structure derived from at least one selected from the group consisting of ammonium carbamate compounds, ammonium carbonate compounds, amines, and carboxylic acids with 8 to 20 carbon atoms Metal complexes are preferred.
作為絡合劑之胺,例如可舉出氨、一級胺、二級胺、三級胺及多胺。Examples of the amine of the complexing agent include ammonia, primary amines, secondary amines, tertiary amines, and polyamines.
作為具有直鏈狀的烷基之一級胺,例如可舉出甲基胺、乙胺、1-丙基胺、正丁基胺、正戊基胺、正己基胺、庚基胺、辛基胺、壬基胺、正癸基胺、十一烷基胺、十二烷胺、十三烷基胺、十四烷基胺、十五烷基胺、十六烷基胺、十七烷基胺及十八烷基胺。Examples of primary amines having a linear alkyl group include methylamine, ethylamine, 1-propylamine, n-butylamine, n-pentylamine, n-hexylamine, heptylamine, and octylamine. , nonylamine, n-decylamine, undecylamine, dodecylamine, tridecylamine, tetradecylamine, pentadecylamine, hexadecylamine, heptadecylamine and octadecylamine.
作為具有支鏈狀烷基之一級胺,例如可舉出異丙基胺、二級丁基胺、三級丁基胺、異戊基胺、2-乙基己基胺及三級辛基胺。Examples of the primary amine having a branched alkyl group include isopropylamine, secondary butylamine, tertiary butylamine, isopentylamine, 2-ethylhexylamine, and tertiary octylamine.
作為具有脂環結構之一級胺,例如可舉出環己基胺及二環己基胺。As a primary amine which has an alicyclic structure, cyclohexylamine and dicyclohexylamine are mentioned, for example.
作為具有羥烷基之一級胺,例如可舉出乙醇胺、二乙醇胺、三乙醇胺、N-甲基乙醇胺、丙醇胺、異丙醇胺、二丙醇胺、二異丙醇胺、三丙醇胺及三異丙醇胺。Examples of primary amines having a hydroxyalkyl group include ethanolamine, diethanolamine, triethanolamine, N-methylethanolamine, propanolamine, isopropanolamine, dipropanolamine, diisopropanolamine, and tripranolamine. amine and triisopropanolamine.
作為具有芳香環之一級胺,例如可舉出苄基胺、N,N-二甲基苄基胺、苯基胺、二苯胺、三苯胺、苯胺、N,N-二甲基苯胺、N,N-二甲基-對甲苯胺、4-胺基吡啶及4-二甲基胺基吡啶。Examples of primary amines having an aromatic ring include benzylamine, N,N-dimethylbenzylamine, phenylamine, diphenylamine, triphenylamine, aniline, N,N-dimethylaniline, N, N-dimethyl-p-toluidine, 4-aminopyridine and 4-dimethylaminopyridine.
作為二級胺,例如可舉出二甲基胺、二乙胺、二丙基胺、二丁基胺、二苯胺、二環戊基胺及甲基丁基胺。Examples of secondary amines include dimethylamine, diethylamine, dipropylamine, dibutylamine, diphenylamine, dicyclopentylamine and methylbutylamine.
作為三級胺,例如可舉出三甲基胺、三乙胺、三丙基胺及三苯胺。Examples of tertiary amines include trimethylamine, triethylamine, tripropylamine and triphenylamine.
作為多胺,例如可舉出乙二胺、1,3-二胺基丙烷、二伸乙三胺、三伸乙四胺、四亞甲基五胺、六亞甲基二胺、四伸乙基五胺及該等的組合。Examples of polyamines include ethylenediamine, 1,3-diaminopropane, diethylenetriamine, triethylenetetramine, tetramethylenepentamine, hexamethylenediamine, tetraethylene Pentamines and combinations thereof.
胺為烷基胺為較佳,碳數為3~10的烷基胺為更佳,碳數為4~10的一級烷基胺為進一步較佳。The amine is preferably an alkylamine, more preferably an alkylamine having 3 to 10 carbon atoms, and even more preferably a primary alkylamine having 4 to 10 carbon atoms.
構成金屬錯合物之胺可以為1種,亦可以為2種以上。The amines constituting the metal complex may be one type, or two or more types.
在使金屬鹽與胺進行反應時,相對於金屬鹽的莫耳量之胺的莫耳量的比率為1倍~15倍為較佳,1.5倍~6倍為更佳。若上述比率在上述範圍內,則結束錯合物形成反應而獲得透明的溶液。When reacting the metal salt and the amine, the ratio of the molar amount of the amine to the molar amount of the metal salt is preferably 1 to 15 times, more preferably 1.5 to 6 times. When the above-mentioned ratio is within the above-mentioned range, the complex formation reaction is completed and a transparent solution is obtained.
作為絡合劑之胺基甲酸銨系化合物,可舉出胺基甲酸銨、甲基銨甲基胺基甲酸酯、乙基銨乙基胺基甲酸酯、1-丙基銨1-丙基胺基甲酸酯、異丙基銨異丙基胺基甲酸酯、丁基銨丁基胺基甲酸酯、異丁基銨異丁基胺基甲酸酯、戊基銨戊基胺基甲酸酯、己基銨己基胺基甲酸酯、庚基銨庚基胺基甲酸酯、辛基銨辛基胺基甲酸酯、2-乙基己基銨2-乙基己基胺基甲酸酯、壬基銨壬基胺基甲酸酯及癸基銨癸基胺基甲酸酯。Ammonium carbamate-based compounds as complexing agents include ammonium carbamate, methylammonium methyl carbamate, ethylammonium ethyl carbamate, 1-propylammonium 1-propyl Urethane, Isopropyl Ammonium Isopropyl Urethane, Butyl Ammonium Butyl Urethane, Isobutyl Ammonium Isobutyl Urethane, Amyl Ammonium Amyl Amino Formate, Hexylammonium Hexyl Carbamate, Heptyl Ammonium Heptyl Carbamate, Octyl Ammonium Octyl Carbamate, 2-Ethylhexyl Ammonium 2-Ethylhexyl Carbamate ester, nonyl ammonium nonyl carbamate, and decyl ammonium decyl carbamate.
作為絡合劑之碳酸銨系化合物,可舉出碳酸銨、甲基銨碳酸酯、乙基銨碳酸酯、1-丙基銨碳酸酯、異丙基銨碳酸酯、丁基銨碳酸酯、異丁基銨碳酸酯、戊基銨碳酸酯、己基銨碳酸酯、庚基銨碳酸酯、辛基銨碳酸酯、2-乙基己基銨碳酸酯、壬基銨碳酸酯及癸基銨碳酸酯。Ammonium carbonate-based compounds as complexing agents include ammonium carbonate, methylammonium carbonate, ethylammonium carbonate, 1-propylammonium carbonate, isopropylammonium carbonate, butylammonium carbonate, isobutylammonium carbonate, Ammonium carbonate, pentylammonium carbonate, hexylammonium carbonate, heptylammonium carbonate, octylammonium carbonate, 2-ethylhexylammonium carbonate, nonylammonium carbonate, and decylammonium carbonate.
作為絡合劑之銨碳酸氫鹽系化合物,可舉出銨碳酸氫鹽、甲基銨碳酸氫鹽、乙基銨碳酸氫鹽、1-丙基銨碳酸氫鹽、異丙基銨碳酸氫鹽、丁基銨碳酸氫鹽、異丁基銨碳酸氫鹽、戊基銨碳酸氫鹽、己基銨碳酸氫鹽、庚基銨碳酸氫鹽、辛基銨碳酸氫鹽、2-乙基己基銨碳酸氫鹽、壬基銨碳酸氫鹽及癸基銨碳酸氫鹽。Ammonium bicarbonate-based compounds as complexing agents include ammonium bicarbonate, methylammonium bicarbonate, ethylammonium bicarbonate, 1-propylammonium bicarbonate, isopropylammonium bicarbonate, Butylammonium bicarbonate, Isobutylammonium bicarbonate, Amylammonium bicarbonate, Hexylammonium bicarbonate, Heptylammonium bicarbonate, Octylammonium bicarbonate, 2-Ethylhexylammonium bicarbonate Salt, nonyl ammonium bicarbonate and decyl ammonium bicarbonate.
在使金屬鹽與胺基甲酸銨系化合物、碳酸銨系化合物或銨碳酸氫鹽系化合物進行反應時,相對於金屬鹽的莫耳量之胺基甲酸銨系化合物、碳酸銨系化合物或銨碳酸氫鹽系化合物的莫耳量的比率為0.01倍~1倍為較佳,0.05倍~0.6倍為更佳。When the metal salt is reacted with an ammonium carbamate compound, ammonium carbonate compound or ammonium bicarbonate compound, the molar amount of the ammonium carbamate compound, ammonium carbonate compound or ammonium bicarbonate relative to the metal salt The molar ratio of the hydrogen salt-based compound is preferably 0.01 to 1, more preferably 0.05 to 0.6.
作為錯合劑亦即羧酸,例如可舉出己酸、辛酸、壬酸、2-乙基己酸、癸酸、新癸酸、十一酸、月桂酸、肉荳蔻酸、棕櫚酸、硬脂酸、十六烯酸、油酸、亞麻油酸及次亞麻油酸。其中,羧酸為碳數8~20的羧酸為較佳,碳數10~16的羧酸為更佳。Examples of carboxylic acids that are complexing agents include caproic acid, octanoic acid, nonanoic acid, 2-ethylhexanoic acid, capric acid, neodecanoic acid, undecanoic acid, lauric acid, myristic acid, palmitic acid, stearic acid Acid, Hexadecenoic Acid, Oleic Acid, Linoleic Acid and Linolenic Acid. Among them, the carboxylic acid is preferably a carboxylic acid having 8 to 20 carbon atoms, and more preferably a carboxylic acid having 10 to 16 carbon atoms.
在金屬錯合物油墨中,金屬錯合物的含量相對於金屬錯合物油墨的總量為10質量%~90質量%為較佳,10質量%~40質量%為更佳。若金屬錯合物的含量為10質量%以上,則進一步降低表面電阻率。若金屬錯合物的含量為90質量%以下,則在使用噴墨記錄方式賦予金屬粒子油墨之情況下,提高吐出性。In the metal complex ink, the content of the metal complex is preferably 10% by mass to 90% by mass, more preferably 10% by mass to 40% by mass, based on the total amount of the metal complex ink. When the content of the metal complex is 10% by mass or more, the surface resistivity will further decrease. When the content of the metal complex is 90% by mass or less, the discharge property will be improved when the metal particle ink is provided using the inkjet recording method.
-溶劑- 金屬錯合物油墨含有溶劑為較佳。溶劑只要能夠溶解金屬錯合物等金屬錯合物油墨中所含有之成分,則並無特別限定。從製造容易性的觀點考慮,溶劑的沸點為30℃~300℃為較佳,50℃~200℃為更佳,50℃~150℃為更佳。 -Solvent- It is preferable that the metal complex ink contains a solvent. The solvent is not particularly limited as long as it can dissolve components contained in the metal complex ink such as the metal complex. From the viewpoint of ease of manufacture, the boiling point of the solvent is preferably from 30°C to 300°C, more preferably from 50°C to 200°C, and more preferably from 50°C to 150°C.
在金屬錯合物油墨中,溶劑的含量相對於金屬錯合物之金屬離子的濃度(相對於金屬錯合物1g作為游離離子存在之金屬的量)為0.01mmol/g~3.6mmol/g為較佳,0.05mmol/g~2mmol/g為更佳。若金屬離子的濃度在上述範圍內,則金屬錯合物油墨的流動性優異並且能夠獲得電磁波遮蔽性。In the metal complex ink, the content of the solvent is 0.01mmol/g to 3.6mmol/g relative to the concentration of the metal ion of the metal complex (the amount of metal that exists as a free ion relative to 1g of the metal complex) Preferably, 0.05mmol/g~2mmol/g is more preferred. When the concentration of the metal ions is within the above range, the metal complex ink has excellent fluidity and can obtain electromagnetic wave shielding properties.
作為溶劑,例如可舉出烴、環狀烴、芳香族烴、胺基甲酸酯、烯烴、醯胺、醚、酯、醇、硫醇、硫醚、膦基及水。金屬錯合物油墨中所含有之溶劑可以僅為1種,亦可以為2種以上。Examples of solvents include hydrocarbons, cyclic hydrocarbons, aromatic hydrocarbons, urethanes, olefins, amides, ethers, esters, alcohols, mercaptans, thioethers, phosphines, and water. The solvent contained in the metal complex ink may be only one type, or may be two or more types.
烴為碳數6~20的直鏈狀或支鏈狀的烴為較佳。作為烴,例如可舉出戊烷、己烷、庚烷、辛烷、壬烷、癸烷、十一烷、十二烷、十三烷、十四烷、十五烷、十六烷、十八烷、十九烷及二十烷。The hydrocarbon is preferably a linear or branched hydrocarbon having 6 to 20 carbon atoms. Examples of hydrocarbons include pentane, hexane, heptane, octane, nonane, decane, undecane, dodecane, tridecane, tetradecane, pentadecane, hexadecane, Octane, nonadecane and eicosane.
環狀烴為碳數6~20的環狀烴為較佳。作為環狀烴,例如能夠含有環己烷、環庚烷、環辛烷、環壬烷、環癸烷及十氫萘。The cyclic hydrocarbon is preferably a cyclic hydrocarbon having 6 to 20 carbon atoms. As cyclic hydrocarbons, for example, cyclohexane, cycloheptane, cyclooctane, cyclononane, cyclodecane, and decahydronaphthalene can be contained.
作為芳香族烴,例如可舉出苯、甲苯、二甲苯及四氫萘。Examples of aromatic hydrocarbons include benzene, toluene, xylene and tetralin.
醚可以為直鏈狀醚、支鏈狀醚及環狀醚中的任一個。作為醚,例如可舉出二乙醚、二丙基醚、二丁醚、甲基-三級丁基醚、四氫呋喃、四氫哌喃、二羥基哌喃及1,4-二㗁烷。The ether may be any of linear ethers, branched ethers, and cyclic ethers. Examples of ethers include diethyl ether, dipropyl ether, dibutyl ether, methyl-tertiary butyl ether, tetrahydrofuran, tetrahydropyran, dihydroxypyran, and 1,4-dioxane.
醇可以為一級醇、二級醇及三級醇中的任一個。Alcohol may be any one of primary alcohol, secondary alcohol and tertiary alcohol.
作為醇,例如可舉出乙醇、1-丙醇、2-丙醇、1-甲氧基-2-丙醇、1-丁醇、2-丁醇、1-戊醇、2-戊醇、3-戊醇、1-己醇、2-己醇、3-己醇、1-辛醇、2-辛醇、3-辛醇、四氫糠醇、環戊醇、萜品醇、癸醇、異癸基醇、月桂基醇、異月桂基醇、肉豆蔻醇、異肉豆蔻醇、鯨蠟醇(Cetanol)、異鯨蠟醇、硬脂醇、異硬脂醇、油基醇、異油基醇、亞麻醇、異亞麻醇、棕櫚醇、異棕櫚醇、二十醇及異二十醇。Examples of the alcohol include ethanol, 1-propanol, 2-propanol, 1-methoxy-2-propanol, 1-butanol, 2-butanol, 1-pentanol, 2-pentanol, 3-pentanol, 1-hexanol, 2-hexanol, 3-hexanol, 1-octanol, 2-octanol, 3-octanol, tetrahydrofurfuryl alcohol, cyclopentanol, terpineol, decanol, Isodecyl Alcohol, Lauryl Alcohol, Isolauryl Alcohol, Myristyl Alcohol, Isomyristyl Alcohol, Cetyl Alcohol (Cetanol), Isocetyl Alcohol, Stearyl Alcohol, Isostearyl Alcohol, Oleyl Alcohol, Isostearyl Alcohol Alcohol, Linolenyl Alcohol, Isolinalyl Alcohol, Palmityl Alcohol, Isopalmityl Alcohol, Eicosyl Alcohol and Iso-Eicosyl Alcohol.
作為酮,例如可舉出丙酮、甲基乙基酮、甲基異丁基酮及環己酮。As a ketone, acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone are mentioned, for example.
作為酯,例如可舉出乙酸甲酯、乙酸乙酯、乙酸異丙酯、乙酸丁酯、乙酸異丁酯、乙酸二級丁酯、乙酸甲氧基丁酯、乙二醇單甲醚乙酸酯、乙二醇單乙基醚乙酸酯、乙二醇單丁基醚乙酸酯、二乙二醇單甲醚乙酸酯、二乙二醇單乙基醚乙酸酯、二乙二醇單丁基醚乙酸酯、丙二醇單甲醚乙酸酯、丙二醇單乙基醚乙酸酯、丙二醇單丁基醚乙酸酯、二丙二醇單甲醚乙酸酯、二丙二醇單乙基醚乙酸酯、二丙二醇單丁基醚乙酸酯及3-甲氧基丁基乙酸酯。Examples of esters include methyl acetate, ethyl acetate, isopropyl acetate, butyl acetate, isobutyl acetate, secondary butyl acetate, methoxybutyl acetate, ethylene glycol monomethyl ether acetic acid Ester, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol Alcohol monobutyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether acetate, dipropylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether Acetate, Dipropylene Glycol Monobutyl Ether Acetate and 3-Methoxybutyl Acetate.
-還原劑- 金屬錯合物油墨可以含有還原劑。若金屬錯合物油墨中含有還原劑,則促進從金屬錯合物向金屬還原。 -reducing agent- Metal complex inks may contain reducing agents. When the metal complex ink contains a reducing agent, the reduction from the metal complex to metal is promoted.
作為還原劑,例如可舉出氫化硼金屬鹽、氫化鋁鹽、胺、醇、有機酸、還原糖、糖醇、亞硫酸鈉、肼化合物、糊精、氫醌、羥胺、乙二醇、麩胱甘肽及肟化合物。Examples of reducing agents include boron hydride metal salts, aluminum hydride salts, amines, alcohols, organic acids, reducing sugars, sugar alcohols, sodium sulfite, hydrazine compounds, dextrin, hydroquinone, hydroxylamine, ethylene glycol, glutathione Peptides and oxime compounds.
還原劑可以為日本特表2014-516463號公報中所記載之肟化合物。作為肟化合物,例如可舉出丙酮肟、環己酮肟、2-丁酮肟、2,3-丁烷二酮單肟、二甲基乙二醛二肟、甲基乙醯氧基乙酸酯單肟、甲基丙酮酸鹽單肟、苯甲醛肟、1-二氫茚酮肟、2-金剛烷酮肟、2-甲基苄胺肟、3-甲基苄胺肟、4-甲基苄胺肟、3-胺基苄胺肟、4-胺基苄胺肟、苯乙酮肟、苄胺肟及三級丁基乙酮肟。The reducing agent may be an oxime compound described in JP 2014-516463 A. Examples of oxime compounds include acetone oxime, cyclohexanone oxime, 2-butanone oxime, 2,3-butanedione monoxime, dimethylglyoxaldioxime, methylacetyloxyacetic acid Ester monoxime, methylpyruvate monoxime, benzaldehyde oxime, 1-indanone oxime, 2-adamantanone oxime, 2-methylbenzylamine oxime, 3-methylbenzylamide oxime, 4-methylbenzylamine oxime Benzylamide oxime, 3-aminobenzylamide oxime, 4-aminobenzylamide oxime, acetophenone oxime, benzylamide oxime and tertiary butyl acetophenone oxime.
金屬錯合物油墨中所含有之還原劑可以為1種,亦可以為2種以上。The reducing agent contained in the metal complex ink may be one type, or two or more types.
在金屬錯合物油墨中,還原劑的含量並無特別限定,相對於金屬錯合物油墨的總量為0.1質量%~20質量%為較佳,0.3質量%~10質量%為更佳,1質量%~5質量%為進一步較佳。In the metal complex ink, the content of the reducing agent is not particularly limited, but it is preferably 0.1% by mass to 20% by mass, more preferably 0.3% by mass to 10% by mass, relative to the total amount of the metal complex ink, 1% by mass to 5% by mass is further more preferable.
-樹脂- 金屬錯合物油墨可以含有樹脂。若在金屬錯合物油墨中含有樹脂,則提高金屬錯合物油墨與基材的密接性。 -resin- The metal complex ink may contain a resin. When a resin is contained in the metal complex ink, the adhesion between the metal complex ink and the base material is improved.
作為樹脂,例如可舉出聚酯、聚乙烯、聚丙烯、聚縮醛、聚烯烴、聚碳酸酯、聚醯胺、氟樹脂、矽酮樹脂、乙基纖維素、羥乙基纖維素、松香、丙烯酸樹脂、聚氯乙烯、聚碸、聚乙烯吡咯啶酮、聚乙烯醇、聚乙烯基系樹脂、聚丙烯腈、聚硫化物、聚醯胺醯亞胺、聚醚、聚芳酯、聚醚醚酮、聚胺酯、環氧樹脂、乙烯基酯樹脂、酚樹脂、三聚氰胺樹脂及脲樹脂。Examples of the resin include polyester, polyethylene, polypropylene, polyacetal, polyolefin, polycarbonate, polyamide, fluororesin, silicone resin, ethyl cellulose, hydroxyethyl cellulose, rosin , acrylic resin, polyvinyl chloride, polysulfone, polyvinylpyrrolidone, polyvinyl alcohol, polyvinyl-based resin, polyacrylonitrile, polysulfide, polyamideimide, polyether, polyarylate, poly Ether ether ketone, polyurethane, epoxy resin, vinyl ester resin, phenolic resin, melamine resin and urea resin.
金屬錯合物油墨中所含有之樹脂可以為1種,亦可以為2種以上。The resin contained in the metal complex ink may be one type, or two or more types.
-添加劑- 金屬錯合物油墨在不損害本揭示的效果之範圍內還可以含有無機鹽、有機鹽、二氧化矽等無機氧化物;表面調整劑、濕潤劑、交聯劑、抗氧化劑、防鏽劑、耐熱穩定劑、界面活性劑、可塑劑、硬化劑、增黏劑、矽烷偶合劑等添加劑。在金屬錯合物油墨中,添加劑的合計含量相對於金屬錯合物油墨的總量為20質量%以下為較佳。 -additive- Metal complex inks may also contain inorganic oxides such as inorganic salts, organic salts, and silicon dioxide; surface regulators, wetting agents, crosslinking agents, antioxidants, rust inhibitors, Heat-resistant stabilizers, surfactants, plasticizers, hardeners, tackifiers, silane coupling agents and other additives. In the metal complex ink, the total content of the additives is preferably 20% by mass or less with respect to the total amount of the metal complex ink.
金屬錯合物油墨的黏度並無特別限定,為0.01Pa・s~5000Pa・s即可,0.1Pa・s~100Pa・s為較佳。在使用噴塗法或噴墨記錄方式賦予金屬錯合物油墨之情況下,金屬錯合物油墨的黏度為1mPa・s~100mPa・s為較佳,2mPa・s~50mPa・s為更佳,3mPa・s~30mPa・s為進一步較佳。The viscosity of the metal complex ink is not particularly limited, and may be 0.01Pa・s to 5000Pa・s, preferably 0.1Pa・s to 100Pa・s. In the case of applying the metal complex ink by spraying method or inkjet recording method, the viscosity of the metal complex ink is preferably 1mPa・s~100mPa・s, more preferably 2mPa・s~50mPa・s, and 3mPa ・s~30mPa・s is more preferable.
金屬錯合物油墨的黏度為使用黏度計在25℃下測量之值。黏度例如使用VISCOMETER TV-22型黏度計(TOKI SANGYO CO.,LTD.製)進行測量。The viscosity of the metal complex ink is a value measured at 25° C. using a viscometer. The viscosity is measured using, for example, a VISCOMETER TV-22 viscometer (manufactured by TOKI SANGYO CO., LTD.).
金屬錯合物油墨的表面張力並無特別限定,20mN/m~45mN/m為較佳,25mN/m~35mN/m為更佳。表面張力為使用表面張力計在25℃下測量之值。The surface tension of the metal complex ink is not particularly limited, but is preferably 20 mN/m to 45 mN/m, more preferably 25 mN/m to 35 mN/m. The surface tension is a value measured at 25° C. using a surface tensiometer.
金屬錯合物油墨的表面張力例如使用DY-700(Kyowa Interface Science Co.,Ltd.製)進行測量。The surface tension of the metal complex ink is measured using, for example, DY-700 (manufactured by Kyowa Interface Science Co., Ltd.).
(金屬鹽油墨) 金屬鹽油墨例如為金屬鹽溶解於溶劑中之油墨組成物。 (metal salt ink) The metal salt ink is, for example, an ink composition in which a metal salt is dissolved in a solvent.
-金屬鹽- 作為構成金屬鹽之金屬,例如可舉出銀、銅、金、鋁、鎂、鎢、鉬、鋅、鎳、鐵、鉑、錫、銅及鉛。其中,從電磁波遮蔽性的觀點考慮,構成金屬鹽之金屬含有選自包括銀、金、鉑、鎳、鈀及銅之群組中之至少1種為較佳,含有銀為更佳。 -Metal salt- Examples of the metal constituting the metal salt include silver, copper, gold, aluminum, magnesium, tungsten, molybdenum, zinc, nickel, iron, platinum, tin, copper and lead. Among them, it is preferable that the metal constituting the metal salt contains at least one selected from the group consisting of silver, gold, platinum, nickel, palladium, and copper, and more preferably contains silver, from the viewpoint of electromagnetic shielding properties.
金屬鹽油墨中所含有之金屬的含量相對於金屬鹽油墨的總量以金屬元素換算計為1質量%~40質量%為較佳,5質量%~30質量%為更佳,7質量%~20質量%為進一步較佳。The content of the metal contained in the metal salt ink is preferably 1% by mass to 40% by mass, more preferably 5% by mass to 30% by mass, and 7% by mass to the total amount of the metal salt ink, in terms of metal elements. 20 mass % is more preferable.
在金屬鹽油墨中,金屬鹽的含量相對於金屬鹽油墨的總量為10質量%~90質量%為較佳,10質量%~40質量%為更佳。若金屬鹽的含量為10質量%以上,則進一步降低表面電阻率。若金屬鹽的含量為90質量%以下,則在使用噴塗方式或噴墨記錄方式賦予金屬粒子油墨之情況下,提高吐出性。In the metal salt ink, the content of the metal salt is preferably 10% by mass to 90% by mass, more preferably 10% by mass to 40% by mass, based on the total amount of the metal salt ink. When the content of the metal salt is 10% by mass or more, the surface resistivity is further reduced. When the content of the metal salt is 90% by mass or less, the discharge property is improved when the metal particle ink is applied by a spray coating method or an inkjet recording method.
作為金屬鹽,例如可舉出金屬的苯甲酸鹽、鹵化物、碳酸鹽、檸檬酸鹽、碘酸鹽、亞硝酸鹽、硝酸鹽、乙酸鹽、磷酸鹽、硫酸鹽、硫化物、三氟乙酸鹽及羧酸鹽。再者,鹽可以組合2種以上。Examples of metal salts include metal benzoate, halide, carbonate, citrate, iodate, nitrite, nitrate, acetate, phosphate, sulfate, sulfide, trifluoro Acetates and carboxylates. In addition, salt can combine 2 or more types.
從電磁波遮蔽性及保存穩定性的觀點考慮,金屬鹽為金屬羧酸鹽為較佳。形成羧酸鹽之羧酸為選自包括甲酸及碳數1~30的羧酸之群組中之至少1種為較佳,碳數8~20的羧酸為更佳,碳數8~20的脂肪酸為進一步較佳。脂肪酸可以為直鏈狀,亦可以為支鏈狀,可以具有取代基。From the viewpoint of electromagnetic shielding properties and storage stability, the metal salt is preferably a metal carboxylate. The carboxylic acid forming the carboxylate is preferably at least one selected from the group consisting of formic acid and carboxylic acids with 1 to 30 carbons, more preferably carboxylic acids with 8 to 20 carbons, and 8 to 20 carbons The fatty acid is further preferred. The fatty acid may be linear or branched, and may have a substituent.
作為直鏈脂肪酸,例如可舉出乙酸、丙酸、丁酸、纈草酸(valeric acid)、戊酸(pentanoic acid)、己酸(hexanoic acid)、庚酸(Heptanoic Acid)、二十二酸、油酸、辛酸(Octanoic acid)、壬酸(Nonanoic acid)、癸酸(Decanoic Acid)、己酸(caproic acid)、庚酸(enanthic acid)、辛酸(caprylic acid)、壬酸(pelargonic acid)、癸酸(capric acid)及十一酸。Examples of straight-chain fatty acids include acetic acid, propionic acid, butyric acid, valeric acid, pentanoic acid, hexanoic acid, heptanoic acid, behenic acid, Oleic Acid, Octanoic Acid, Nonanoic Acid, Decanoic Acid, Caproic Acid, Enanthic Acid, Caprylic Acid, Pelargonic Acid, Capric acid and undecanoic acid.
作為支鏈脂肪酸,例如可舉出異丁酸、異戊酸、乙基己酸、新癸酸、新戊酸、2-甲基戊酸、3-甲基戊酸、4-甲基戊酸、2,2-二甲基丁酸、2,3-二甲基丁酸、3,3-二甲基丁酸及2-乙基丁酸。Examples of branched fatty acids include isobutyric acid, isovaleric acid, ethylhexanoic acid, neodecanoic acid, pivalic acid, 2-methylpentanoic acid, 3-methylpentanoic acid, and 4-methylpentanoic acid. , 2,2-dimethyl butyric acid, 2,3-dimethyl butyric acid, 3,3-dimethyl butyric acid and 2-ethyl butyric acid.
作為具有取代基之羧酸,例如可舉出六氟乙醯基丙酮酸、氫白芷酸、3-羥基丁酸、2-甲基-3-羥基丁酸、3-甲氧基丁酸、丙酮二羧酸、3-羥基戊二酸、2-甲基-3-羥基戊二酸及2,2,4,4-羥基戊二酸。Examples of carboxylic acids having substituents include hexafluoroacetylpyruvate, hydroangelic acid, 3-hydroxybutyrate, 2-methyl-3-hydroxybutyrate, 3-methoxybutyrate, acetone Dicarboxylic acid, 3-hydroxyglutaric acid, 2-methyl-3-hydroxyglutaric acid and 2,2,4,4-hydroxyglutaric acid.
金屬鹽可以為市售品,亦可以為藉由公知的方法製造者。銀鹽例如藉由以下方法製造。The metal salt may be a commercial item or may be produced by a known method. Silver salt is produced by the following method, for example.
首先,向乙醇等有機溶劑中添加成為銀的供給源之銀化合物(例如乙酸銀)及相對於銀化合物的莫耳當量等量的甲酸或碳數1~30的脂肪酸。使用超音波攪拌機進行攪拌規定時間,用乙醇清洗並傾析所產生之沉澱物。該等製程全部能夠在室溫(25℃)下進行。銀化合物與甲酸或碳數1~30的脂肪酸的混合比以莫耳比計為1:2~2:1為較佳,1:1為更佳。First, a silver compound (for example, silver acetate) serving as a silver supply source and formic acid or a fatty acid having 1 to 30 carbon atoms in an amount equivalent to the molar equivalent of the silver compound are added to an organic solvent such as ethanol. Use an ultrasonic mixer to stir for a specified time, wash with ethanol and decant the resulting precipitate. These processes can all be carried out at room temperature (25°C). The mixing ratio of the silver compound to formic acid or the fatty acid having 1 to 30 carbon atoms is preferably 1:2 to 2:1, more preferably 1:1, in terms of molar ratio.
-溶劑- 金屬鹽油墨含有溶劑為較佳。 只要能夠溶解金屬鹽油墨中所含有之金屬鹽,則溶劑的種類並無特別限定。 從製造容易性的觀點考慮,溶劑的沸點為30℃~300℃為較佳,50℃~300℃為更佳,50℃~250℃為更佳。 -Solvent- It is preferable that the metal salt ink contains a solvent. The type of solvent is not particularly limited as long as it can dissolve the metal salt contained in the metal salt ink. From the viewpoint of ease of manufacture, the boiling point of the solvent is preferably from 30°C to 300°C, more preferably from 50°C to 300°C, and more preferably from 50°C to 250°C.
在金屬鹽油墨中,溶劑的含量相對於金屬鹽之金屬離子的濃度(相對於金屬鹽1g作為游離離子存在之金屬的量)為0.01mmol/g~3.6mmol/g為較佳,0.05mmol/g~2.6mmol/g為更佳。若金屬離子的濃度在上述範圍內,則金屬鹽油墨的流動性優異並且能夠獲得電磁波遮蔽性。In the metal salt ink, the content of the solvent relative to the concentration of the metal ion of the metal salt (relative to the amount of metal present as free ions in 1 g of the metal salt) is preferably 0.01mmol/g to 3.6mmol/g, and 0.05mmol/g g~2.6mmol/g is more preferable. When the concentration of the metal ion is within the above range, the metal salt ink has excellent fluidity and can obtain electromagnetic wave shielding properties.
作為溶劑,例如可舉出烴、環狀烴、芳香族烴、胺基甲酸酯、烯烴、醯胺、醚、酯、醇、硫醇、硫醚、膦基及水。 金屬鹽油墨中所含有之溶劑可以僅為1種,亦可以為2種以上。 Examples of solvents include hydrocarbons, cyclic hydrocarbons, aromatic hydrocarbons, urethanes, olefins, amides, ethers, esters, alcohols, mercaptans, thioethers, phosphines, and water. The solvent contained in the metal salt ink may be only one kind, or may be two or more kinds.
溶劑包含芳香族烴為較佳。 作為芳香族烴,例如可舉出苯、甲苯、二甲苯、乙基苯、丙基苯、異丙基苯、丁基苯、異丁基苯、三級丁基苯、三甲基苯、戊基苯、己基苯、四氫萘、苯甲醇、苯酚、甲酚、苯甲酸甲酯、苯甲酸乙酯、苯甲酸丙酯及苯甲酸丁酯。 從與他成分的相容性的觀點考慮,芳香族烴中的芳香族環的數量為1個或2個為較佳,1個為更佳。 從製造容易性的觀點考慮,芳香族烴的沸點為50℃~300℃為較佳,60℃~250℃為更佳,80℃~200℃為更佳。 The solvent preferably contains aromatic hydrocarbons. Examples of aromatic hydrocarbons include benzene, toluene, xylene, ethylbenzene, propylbenzene, cumene, butylbenzene, isobutylbenzene, tertiary butylbenzene, trimethylbenzene, pentylbenzene, Benzene, Hexylbenzene, Tetralin, Benzyl Alcohol, Phenol, Cresol, Methyl Benzoate, Ethyl Benzoate, Propyl Benzoate and Butyl Benzoate. From the viewpoint of compatibility with other components, the number of aromatic rings in the aromatic hydrocarbon is preferably 1 or 2, more preferably 1. From the viewpoint of ease of production, the boiling point of the aromatic hydrocarbon is preferably from 50°C to 300°C, more preferably from 60°C to 250°C, and more preferably from 80°C to 200°C.
溶劑可以包含芳香族烴及除了芳香族烴以外的烴。 作為除了芳香族烴以外的烴,可舉出碳數6~20的直鏈狀烴、碳數6~20的支鏈狀烴、碳數6~20的脂環式烴。 作為除了芳香族烴以外的烴,例如可舉出戊烷、己烷、庚烷、辛烷、壬烷、癸烷、十一烷、十二烷、十三烷、十四烷、十五烷、十六烷、十八烷、十九烷、十氫萘、環己烷、環庚烷、環辛烷、環壬烷、環癸烷、癸烯、萜烯系化合物及二十烷。 除了芳香族烴以外的烴含有不飽和鍵為較佳。 作為除了含有不飽和鍵之芳香族烴以外的烴,可舉出萜烯系化合物。 萜烯系化合物依據構成萜烯系化合物之異戊二烯單元的數量,例如可分為半萜烯、單萜烯、倍半萜烯、二萜烯、二倍半萜烯(sesterterpene)、三萜烯、三倍半萜烯(sesquarterpene)及四萜烯。 作為溶劑的萜烯系化合物可以為上述的任一個,但是單萜烯為較佳。 作為單萜烯,例如可舉出蒎烯(α-蒎烯、β-蒎烯)、萜品醇(α-萜品醇、β-萜品醇、γ-萜品醇)、月桂油烯、茨烯、檸檬烯(d-檸檬烯、l-檸檬烯、二戊烯)、蘿艻萜(α-蘿艻萜、β-蘿艻萜)、別蘿艻萜、水芹烯(α-水芹烯、β-水芹烯)、萜品烯(α-萜品烯、γ-萜品烯)、萜品油烯(α-萜品油烯、β-萜品油烯、γ-萜品油烯、δ-萜品油烯)、1,8-桉醚、1,4-桉醚、香檜烯、對䓝二烯、蒈烯(δ-3-蒈烯)。 作為單萜烯,環式單萜烯為較佳,蒎烯、萜品醇或蒈烯為更佳。 The solvent may contain aromatic hydrocarbons and hydrocarbons other than aromatic hydrocarbons. Examples of hydrocarbons other than aromatic hydrocarbons include straight-chain hydrocarbons having 6 to 20 carbon atoms, branched-chain hydrocarbons having 6 to 20 carbon atoms, and alicyclic hydrocarbons having 6 to 20 carbon atoms. Examples of hydrocarbons other than aromatic hydrocarbons include pentane, hexane, heptane, octane, nonane, decane, undecane, dodecane, tridecane, tetradecane, pentadecane , hexadecane, octadecane, nonadecane, decahydronaphthalene, cyclohexane, cycloheptane, cyclooctane, cyclononane, cyclodecane, decene, terpene compounds and eicosane. Hydrocarbons other than aromatic hydrocarbons preferably contain unsaturated bonds. Examples of hydrocarbons other than unsaturated bond-containing aromatic hydrocarbons include terpene compounds. Terpene compounds can be classified into semiterpene, monoterpene, sesquiterpene, diterpene, sesterterpene, triterpene, etc. according to the number of isoprene units constituting the terpene compound. Terpenes, sesquarterpenes, and tetraterpenes. The terpene-based compound used as the solvent may be any of the above, but monoterpene is preferred. Examples of monoterpenes include pinene (α-pinene, β-pinene), terpineol (α-terpineol, β-terpineol, γ-terpineol), myrcene, Limonene, limonene (d-limonene, l-limonene, dipentene), radiphenene (α-radiphenene, β-radiphenene), alleroradine, phellandrene (α-phellandrene, β-phellandrene), terpinene (α-terpinene, γ-terpinene), terpinolene (α-terpinolene, β-terpinolene, γ-terpinolene, delta-terpinolene), 1,8-cineole, 1,4-cineole, sabinene, p-diene, carene (delta-3-carene). The monoterpene is preferably a cyclic monoterpene, more preferably pinene, terpineol or carene.
醚可以為直鏈狀醚、支鏈狀醚及環狀醚中的任一個。作為醚,例如可舉出二乙醚、二丙基醚、二丁醚、甲基-三級丁基醚、四氫呋喃、四氫哌喃、二羥基哌喃及1,4-二㗁烷。The ether may be any of linear ethers, branched ethers, and cyclic ethers. Examples of ethers include diethyl ether, dipropyl ether, dibutyl ether, methyl-tertiary butyl ether, tetrahydrofuran, tetrahydropyran, dihydroxypyran, and 1,4-dioxane.
醇可以為一級醇、二級醇及三級醇中的任一個。Alcohol may be any one of primary alcohol, secondary alcohol and tertiary alcohol.
作為醇,例如可舉出乙醇、1-丙醇、2-丙醇、1-甲氧基-2-丙醇、1-丁醇、2-丁醇、1-戊醇、2-戊醇、3-戊醇、1-己醇、2-己醇、3-己醇、1-辛醇、2-辛醇、3-辛醇、四氫糠醇、環戊醇、萜品醇、癸醇、異癸基醇、月桂基醇、異月桂基醇、肉豆蔻醇、異肉豆蔻醇、鯨蠟醇(Cetanol)、異鯨蠟醇、硬脂醇、異硬脂醇、油基醇、異油基醇、亞麻醇、異亞麻醇、棕櫚醇、異棕櫚醇、二十醇及異二十醇。Examples of the alcohol include ethanol, 1-propanol, 2-propanol, 1-methoxy-2-propanol, 1-butanol, 2-butanol, 1-pentanol, 2-pentanol, 3-pentanol, 1-hexanol, 2-hexanol, 3-hexanol, 1-octanol, 2-octanol, 3-octanol, tetrahydrofurfuryl alcohol, cyclopentanol, terpineol, decanol, Isodecyl Alcohol, Lauryl Alcohol, Isolauryl Alcohol, Myristyl Alcohol, Isomyristyl Alcohol, Cetyl Alcohol (Cetanol), Isocetyl Alcohol, Stearyl Alcohol, Isostearyl Alcohol, Oleyl Alcohol, Isostearyl Alcohol Alcohol, Linolenyl Alcohol, Isolinalyl Alcohol, Palmityl Alcohol, Isopalmityl Alcohol, Eicosyl Alcohol and Iso-Eicosyl Alcohol.
作為酮,例如可舉出丙酮、甲基乙基酮、甲基異丁基酮及環己酮。As a ketone, acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone are mentioned, for example.
作為酯,例如可舉出乙酸甲酯、乙酸乙酯、乙酸異丙酯、乙酸丁酯、乙酸異丁酯、乙酸二級丁酯、乙酸甲氧基丁酯、乙二醇單甲醚乙酸酯、乙二醇單乙基醚乙酸酯、乙二醇單丁基醚乙酸酯、二乙二醇單甲醚乙酸酯、二乙二醇單乙基醚乙酸酯、二乙二醇單丁基醚乙酸酯、丙二醇單甲醚乙酸酯、丙二醇單乙基醚乙酸酯、丙二醇單丁基醚乙酸酯、二丙二醇單甲醚乙酸酯、二丙二醇單乙基醚乙酸酯、二丙二醇單丁基醚乙酸酯及3-甲氧基丁基乙酸酯。Examples of esters include methyl acetate, ethyl acetate, isopropyl acetate, butyl acetate, isobutyl acetate, secondary butyl acetate, methoxybutyl acetate, ethylene glycol monomethyl ether acetic acid Ester, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol Alcohol monobutyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether acetate, dipropylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether Acetate, Dipropylene Glycol Monobutyl Ether Acetate and 3-Methoxybutyl Acetate.
金屬鹽油墨的黏度並無特別限定,為0.01Pa・s~5000Pa・s即可,0.1Pa・s~100Pa・s為較佳。在使用噴塗法或噴墨記錄方式賦予金屬鹽油墨之情況下,金屬鹽油墨的黏度為1mPa・s~100mPa・s為較佳,2mPa・s~50mPa・s為更佳,3mPa・s~30mPa・s為進一步較佳。The viscosity of the metal salt ink is not particularly limited, and may be 0.01Pa・s to 5000Pa・s, preferably 0.1Pa・s to 100Pa・s. In the case of applying metal salt ink by spraying method or inkjet recording method, the viscosity of metal salt ink is preferably 1mPa・s~100mPa・s, more preferably 2mPa・s~50mPa・s, 3mPa・s~30mPa ・s is more preferable.
金屬鹽油墨的黏度為使用黏度計在25℃下測量之值。黏度例如使用VISCOMETER TV-22型黏度計(TOKI SANGYO CO.,LTD.製)進行測量。The viscosity of the metal salt ink is a value measured at 25°C using a viscometer. The viscosity is measured using, for example, a VISCOMETER TV-22 viscometer (manufactured by TOKI SANGYO CO., LTD.).
金屬鹽油墨的表面張力並無特別限定,20mN/m~45mN/m為較佳,25mN/m~35mN/m為更佳。表面張力為使用表面張力計在25℃下測量之值。The surface tension of the metal salt ink is not particularly limited, but is preferably 20 mN/m to 45 mN/m, more preferably 25 mN/m to 35 mN/m. The surface tension is a value measured at 25° C. using a surface tensiometer.
金屬鹽油墨的表面張力例如使用DY-700(Kyowa Interface Science Co.,Ltd.製)進行測量。The surface tension of the metal salt ink is measured, for example, using DY-700 (manufactured by Kyowa Interface Science Co., Ltd.).
電磁波遮蔽層形成用油墨含有金屬錯合物或金屬鹽為較佳。 金屬錯合物為具有源自選自包括胺基甲酸銨系化合物、碳酸銨系化合物、胺及碳數8~20的羧酸之群組中之至少1種之結構之金屬錯合物為較佳。 金屬鹽為金屬羧酸鹽為較佳。 The ink for forming an electromagnetic wave shielding layer preferably contains a metal complex or a metal salt. The metal complex is a metal complex having a structure derived from at least one selected from the group consisting of ammonium carbamate compounds, ammonium carbonate compounds, amines, and carboxylic acids with 8 to 20 carbon atoms. good. The metal salt is preferably a metal carboxylate.
<電磁波遮蔽層的形成方法> 在第2製程中,將電磁波遮蔽層形成用油墨賦予到電子基板上的接地區域內,對賦予到電子零件的頂面上之電磁波遮蔽層形成用油墨吹送風,對吹送風之電磁波遮蔽層形成用油墨進行加熱(例如後述煅燒)及/或藉由紫外線照射使其固化,藉此形成電磁波遮蔽層為較佳。 <Formation method of electromagnetic wave shielding layer> In the second process, the electromagnetic wave shielding layer forming ink is applied to the ground area on the electronic substrate, the electromagnetic wave shielding layer forming ink applied on the top surface of the electronic component is blown with air, and the electromagnetic wave shielding layer is formed by blowing air It is preferable to form the electromagnetic wave shielding layer by heating the ink (for example, calcination described later) and/or curing it by ultraviolet irradiation.
將在此所述之固化油墨之紫外線照射有時在本揭示中稱為“本曝光”。Ultraviolet radiation to cure inks as described herein is sometimes referred to in this disclosure as "the present exposure."
在第2製程中,與機遇加熱及/或本曝光之固化另行地,在對電子零件的頂面上的油墨之風的吹送之前及之後在至少其中一者的時序中可以實施前述之釘扎曝光。In the second process, separately from the opportunistic heating and/or the curing of the present exposure, the aforementioned pinning can be implemented in at least one of the time sequences before and after the wind blowing of the ink on the top surface of the electronic part exposure.
(電磁波遮蔽層形成用油墨的賦予方式) 作為電磁波遮蔽層形成用油墨的賦予方式,噴墨記錄方式、分配器方式或噴塗方式為較佳,噴墨記錄方式為特佳。 關於噴墨記錄方式的較佳的態樣,如在“膜的形成製程”的項中說明。 (Applying method of ink for forming electromagnetic wave shielding layer) As a method of applying the ink for forming an electromagnetic wave shielding layer, an inkjet recording method, a dispenser method, or a spraying method is preferable, and an inkjet recording method is particularly preferable. The preferred aspect of the inkjet recording method is as described in the section of "film formation process".
賦予電磁波遮蔽層形成用油墨時的電子基板的溫度為20℃~120℃為較佳,28℃~80℃為更佳。The temperature of the electronic substrate when applying the ink for forming an electromagnetic wave shielding layer is preferably 20°C to 120°C, more preferably 28°C to 80°C.
從電磁波遮蔽性的觀點考慮,電磁波遮蔽層整體的厚度為0.1μm~30μm為較佳,0.3μm~15μm為更佳。From the viewpoint of electromagnetic wave shielding properties, the thickness of the entire electromagnetic wave shielding layer is preferably 0.1 μm to 30 μm, more preferably 0.3 μm to 15 μm.
電磁波遮蔽層整體的厚度使用雷射顯微鏡(產品名“VK-X1000”、KEYENCE Corporation製)進行測量。The thickness of the entire electromagnetic shielding layer was measured using a laser microscope (product name "VK-X1000", manufactured by KEYENCE Corporation).
電磁波遮蔽層每1層的平均厚度藉由將電磁波遮蔽層整體的厚度除以電磁波遮蔽層的形成次數(亦即,電磁波遮蔽層形成用油墨的賦予次數)來獲得。The average thickness per layer of the electromagnetic wave shielding layer is obtained by dividing the thickness of the entire electromagnetic wave shielding layer by the number of times the electromagnetic wave shielding layer is formed (that is, the number of times the ink for forming the electromagnetic wave shielding layer is applied).
在第2製程中,將電磁波遮蔽層每1層的平均厚度設為1.5μm以下為較佳,設為1.2μm以下為更佳。In the second process, the average thickness per layer of the electromagnetic wave shielding layer is preferably 1.5 μm or less, more preferably 1.2 μm or less.
若將電磁波遮蔽層每1層的平均厚度設為1.5μm以下,則進一步提高電磁波遮蔽性。When the average thickness per layer of an electromagnetic wave shielding layer is 1.5 micrometers or less, electromagnetic wave shielding property will improve further.
(煅燒製程) 第2製程可以包括藉由煅燒賦予到電子基板上之電磁波遮蔽層形成用油墨使電磁波遮蔽層形成用油墨固化來形成電磁波遮蔽層之煅燒製程。 (calcination process) The second process may include a firing process of forming the electromagnetic wave shielding layer by firing the electromagnetic wave shielding layer forming ink applied on the electronic substrate to cure the electromagnetic wave shielding layer forming ink.
煅燒溫度為250℃以下為較佳,50℃~200℃為更佳,60℃~180℃為進一步較佳。 又,煅燒時間為1分~120分為較佳,1分~40分為更佳。 若煅燒溫度及煅燒時間在上述範圍內,則能夠減少基於熱之基材變形等的影響。 The calcination temperature is preferably 250°C or lower, more preferably 50°C to 200°C, and even more preferably 60°C to 180°C. Also, the calcination time is preferably 1 minute to 120 minutes, more preferably 1 minute to 40 minutes. If the calcination temperature and calcination time are within the above-mentioned ranges, the influence of deformation of the base material due to heat, etc. can be reduced.
<絕緣層形成用油墨> 絕緣層形成用油墨(例如絕緣性保護層形成用油墨)為活性能量射線硬化型油墨為較佳。 作為活性能量射線硬化型油墨之絕緣層形成用油墨,較佳為含有聚合性單體及聚合起始劑。 <Inks for Insulation Layer Formation> The ink for forming an insulating layer (for example, the ink for forming an insulating protective layer) is preferably an active energy ray curable ink. The ink for forming an insulating layer as an active energy ray curable ink preferably contains a polymerizable monomer and a polymerization initiator.
(聚合性單體) 聚合性單體係指在1分子中具有至少1個聚合性基之單體。聚合性單體中的聚合性基可以為陽離子聚合性基,亦可以為自由基聚合性基,但從硬化性的觀點考慮,為自由基聚合性基為較佳。又,從硬化性的觀點考慮,自由基聚合性基為乙烯性不飽和基為較佳。 (polymerizable monomer) The polymerizable monomer system refers to a monomer having at least one polymerizable group in one molecule. The polymerizable group in the polymerizable monomer may be a cation polymerizable group or a radical polymerizable group, but it is preferably a radical polymerizable group from the viewpoint of curability. Also, from the viewpoint of curability, it is preferable that the radical polymerizable group is an ethylenically unsaturated group.
在本揭示中,單體係指分子量為1000以下之化合物。分子量能夠由構成化合物之原子的種類及數量來算出。In this disclosure, a monomer refers to a compound with a molecular weight of 1000 or less. The molecular weight can be calculated from the types and numbers of atoms constituting the compound.
聚合性單體可以為具有1個聚合性基之單官能聚合性單體,亦可以為具有2個以上聚合性基之多官能聚合性單體。The polymerizable monomer may be a monofunctional polymerizable monomer having one polymerizable group, or may be a polyfunctional polymerizable monomer having two or more polymerizable groups.
單官能聚合性單體只要為具有1個聚合性基之單體,則並無特別限定。 從硬化性的觀點考慮,單官能聚合性單體為單官能的自由基聚合性單體為較佳,為單官能乙烯性不飽和單體為更佳。 The monofunctional polymerizable monomer is not particularly limited as long as it has one polymerizable group. From the viewpoint of curability, the monofunctional polymerizable monomer is preferably a monofunctional radical polymerizable monomer, more preferably a monofunctional ethylenically unsaturated monomer.
作為單官能乙烯性不飽和單體,例如可舉出單官能(甲基)丙烯酸酯、單官能(甲基)丙烯醯胺、單官能芳香族乙烯基化合物、單官能乙烯醚及單官能N-乙烯基化合物。Examples of monofunctional ethylenically unsaturated monomers include monofunctional (meth)acrylates, monofunctional (meth)acrylamides, monofunctional aromatic vinyl compounds, monofunctional vinyl ethers, and monofunctional N- vinyl compound.
作為單官能(甲基)丙烯酸酯,例如可舉出(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸丙酯、(甲基)丙烯酸正丁酯、(甲基)丙烯酸己酯、(甲基)丙烯酸2-乙基己酯、(甲基)丙烯酸三級辛酯、(甲基)丙烯酸異戊酯、(甲基)丙烯酸癸酯、(甲基)丙烯酸異癸酯、(甲基)丙烯酸月桂酯、(甲基)丙烯酸硬脂基酯、(甲基)丙烯酸異硬脂基酯、(甲基)丙烯酸環己酯、(甲基)丙烯酸4-正丁基環己酯、(甲基)丙烯酸4-三級丁基環己酯、(甲基)丙烯酸莰基酯、(甲基)丙烯酸異莰基酯、(甲基)丙烯酸2-乙基己基二甘醇酯、(甲基)丙烯酸丁氧基乙酯、(甲基)丙烯酸2-氯乙酯、(甲基)丙烯酸4-溴基丁酯、(甲基)丙烯酸氰基乙酯、(甲基)丙烯酸苄酯、(甲基)丙烯酸丁氧基甲酯、(甲基)丙烯酸3-甲氧基丁酯、(甲基)丙烯酸2-(2-甲氧基乙氧基)乙酯、(甲基)丙烯酸2-(2-丁氧基乙氧基)乙酯、(甲基)丙烯酸2,2,2-四氟乙酯、(甲基)丙烯酸1H,1H,2H,2H-全氟癸酯、(甲基)丙烯酸4-丁基苯酯、(甲基)丙烯酸苯酯、(甲基)丙烯酸2,4,5-四甲基苯酯、(甲基)丙烯酸4-氯苯酯、(甲基)丙烯酸2-苯氧基甲酯、(甲基)丙烯酸2-苯氧基乙酯、(甲基)丙烯酸環氧丙酯、(甲基)丙烯酸環氧丙氧基丁酯、(甲基)丙烯酸環氧丙氧基乙酯、(甲基)丙烯酸環氧丙氧基丙酯、(甲基)丙烯酸四氫糠酯、(甲基)丙烯酸2-羥乙酯、(甲基)丙烯酸3-羥基丙酯、(甲基)丙烯酸2-羥丙酯、(甲基)丙烯酸2-羥丁酯、(甲基)丙烯酸3-羥基丁酯、(甲基)丙烯酸4-羥丁酯、環狀三羥甲基丙烷縮甲醛(甲基)丙烯酸酯、(甲基)丙烯酸苯基環氧丙基醚酯、(甲基)丙烯酸二甲基胺基乙酯、(甲基)丙烯酸二乙基胺基乙酯、(甲基)丙烯酸二甲基胺基丙酯、(甲基)丙烯酸二乙基胺基丙酯、(甲基)丙烯酸三甲氧基烯丙基丙酯、(甲基)丙烯酸三甲基甲矽烷基丙酯、(甲基)丙烯酸聚環氧乙烷單甲醚酯、(甲基)丙烯酸聚環氧乙烷酯、(甲基)丙烯酸聚環氧乙烷單烷基醚酯、(甲基)丙烯酸二丙二醇酯、(甲基)丙烯酸聚環氧丙烷單烷基醚酯、2-甲基丙烯醯氧基乙基丁二酸酯、2-甲基丙烯醯氧基六氫鄰苯二甲酸酯、2-甲基丙烯醯氧基乙基-2-羥丙基鄰苯二甲酸酯、(甲基)丙烯酸乙氧基二乙二醇酯、(甲基)丙烯酸丁氧基二乙二醇酯、(甲基)丙烯酸三氟乙酯、(甲基)丙烯酸全氟辛基乙酯、(甲基)丙烯酸2-羥基-3-苯氧基丙酯、環氧乙烷(EO)改質苯酚(甲基)丙烯酸酯、EO改質甲酚(甲基)丙烯酸酯、EO改質壬基苯酚(甲基)丙烯酸酯、環氧丙烷(PO)改質壬基苯酚(甲基)丙烯酸酯、(甲基)丙烯酸EO改質-2-乙基己酯、二環戊烯基(甲基)丙烯酸酯、(甲基)丙烯酸二環戊烯氧基乙酯、(甲基)丙烯酸二環戊酯、(3-乙基-3-氧雜環丁基甲基)(甲基)丙烯酸酯、苯氧基乙二醇(甲基)丙烯酸酯、(甲基)丙烯酸2-羧基乙酯及2-(甲基)丙烯醯氧基乙基琥珀酸酯。Examples of monofunctional (meth)acrylates include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, n-butyl (meth)acrylate, (meth)acrylate ) hexyl acrylate, 2-ethylhexyl (meth) acrylate, tertiary octyl (meth) acrylate, isoamyl (meth) acrylate, decyl (meth) acrylate, iso(meth) acrylate Decyl ester, lauryl (meth)acrylate, stearyl (meth)acrylate, isostearyl (meth)acrylate, cyclohexyl (meth)acrylate, 4-n-butyl (meth)acrylate Cyclohexyl (meth)acrylate, 4-tertiary butylcyclohexyl (meth)acrylate, camphenyl (meth)acrylate, isocamphoryl (meth)acrylate, 2-ethylhexyl diacrylate (meth)acrylate Glycol esters, butoxyethyl (meth)acrylate, 2-chloroethyl (meth)acrylate, 4-bromobutyl (meth)acrylate, cyanoethyl (meth)acrylate, (meth)acrylate base) benzyl acrylate, butoxymethyl (meth)acrylate, 3-methoxybutyl (meth)acrylate, 2-(2-methoxyethoxy)ethyl (meth)acrylate, 2-(2-Butoxyethoxy)ethyl (meth)acrylate, 2,2,2-tetrafluoroethyl (meth)acrylate, 1H,1H,2H,2H-peroxide (meth)acrylate Fluorodecanyl, 4-butylphenyl (meth)acrylate, phenyl (meth)acrylate, 2,4,5-tetramethylphenyl (meth)acrylate, 4-chlorobenzene (meth)acrylate ester, 2-phenoxymethyl (meth)acrylate, 2-phenoxyethyl (meth)acrylate, glycidyl (meth)acrylate, glycidoxybutyl (meth)acrylate , Glycidoxyethyl (meth)acrylate, Glycidoxypropyl (meth)acrylate, Tetrahydrofurfuryl (meth)acrylate, 2-Hydroxyethyl (meth)acrylate, (meth) base) 3-hydroxypropyl acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, 4-hydroxy (meth)acrylate Butyl ester, cyclic trimethylolpropane formal (meth)acrylate, phenylglycidyl ether (meth)acrylate, dimethylaminoethyl (meth)acrylate, (meth) Diethylaminoethyl acrylate, Dimethylaminopropyl (meth)acrylate, Diethylaminopropyl (meth)acrylate, Trimethoxyallylpropyl (meth)acrylate, ( Trimethylsilylpropyl methacrylate, polyethylene oxide monomethyl ether (meth)acrylate, polyethylene oxide (meth)acrylate, polyethylene oxide (meth)acrylate Monoalkyl ether ester, Dipropylene glycol (meth)acrylate, Polypropylene oxide monoalkyl ether (meth)acrylate, 2-Methacryloxyethylsuccinate, 2-Methacrylic acid Acyloxyhexahydrophthalate, 2-methacryloxyethyl-2-hydroxypropylphthalate, ethoxydiethylene glycol (meth)acrylate, ( Butoxydiethylene glycol methacrylate, trifluoroethyl (meth)acrylate, perfluorooctylethyl (meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate Ester, ethylene oxide (EO) modified phenol (meth)acrylate, EO modified cresol (meth)acrylate, EO modified nonylphenol (meth)acrylate, propylene oxide (PO) Modified nonylphenol (meth)acrylate, (meth)acrylate EO modified-2-ethylhexyl, dicyclopentenyl (meth)acrylate, (meth)acrylate dicyclopentenyl oxide ethyl ethyl ester, dicyclopentyl (meth)acrylate, (3-ethyl-3-oxetanylmethyl)(meth)acrylate, phenoxyethylene glycol (meth)acrylate, (meth)acrylate base) 2-carboxyethyl acrylate and 2-(meth)acryloxyethyl succinate.
其中,從提高耐熱性之觀點考慮,單官能(甲基)丙烯酸酯為具有芳香環或脂肪族環之單官能(甲基)丙烯酸酯為較佳,(甲基)丙烯酸異莰基酯、(甲基)丙烯酸4-三級丁基環己酯、(甲基)丙烯酸二環戊烯基酯或(甲基)丙烯酸二環戊基酯為進一步較佳。Among them, from the viewpoint of improving heat resistance, the monofunctional (meth)acrylate is preferably a monofunctional (meth)acrylate having an aromatic ring or an aliphatic ring, and isocamphoryl (meth)acrylate, ( 4-tertiary butylcyclohexyl meth)acrylate, dicyclopentenyl (meth)acrylate, or dicyclopentyl (meth)acrylate are more preferable.
作為單官能(甲基)丙烯醯胺,例如可舉出(甲基)丙烯醯胺、N-甲基(甲基)丙烯醯胺、N-乙基(甲基)丙烯醯胺、N-丙基(甲基)丙烯醯胺、N-正丁基(甲基)丙烯醯胺、N-三級丁基(甲基)丙烯醯胺、N-丁氧基甲基(甲基)丙烯醯胺、N-異丙基(甲基)丙烯醯胺、N-羥甲基(甲基)丙烯醯胺、N,N-二甲基(甲基)丙烯醯胺、N,N-二乙基(甲基)丙烯醯胺及(甲基)丙烯醯基口末啉。Examples of monofunctional (meth)acrylamide include (meth)acrylamide, N-methyl(meth)acrylamide, N-ethyl(meth)acrylamide, N-propyl N-butyl(meth)acrylamide, N-butyl(meth)acrylamide, N-tertiary butyl(meth)acrylamide, N-butoxymethyl(meth)acrylamide , N-isopropyl(meth)acrylamide, N-hydroxymethyl(meth)acrylamide, N,N-dimethyl(meth)acrylamide, N,N-diethyl( Meth)acrylamide and (meth)acryloylpermaline.
作為單官能芳香族乙烯基化合物,例如可舉出苯乙烯、二甲基苯乙烯、三甲基苯乙烯、異丙基苯乙烯、氯甲基苯乙烯、甲氧基苯乙烯、乙醯氧基苯乙烯、氯苯乙烯、二氯苯乙烯、溴苯乙烯、乙烯基苯甲酸甲酯、3-甲基苯乙烯、4-甲基苯乙烯、3-乙基苯乙烯、4-乙基苯乙烯、3-丙基苯乙烯、4-丙基苯乙烯、3-丁基苯乙烯、4-丁基苯乙烯、3-己基苯乙烯、4-己基苯乙烯、3-辛基苯乙烯、4-辛基苯乙烯、3-(2-乙基己基)苯乙烯、4-(2-乙基己基)苯乙烯、烯丙基苯乙烯、異丙烯基苯乙烯、丁烯苯乙烯、辛烯基苯乙烯、4-三級丁氧基羰基苯乙烯及4-三級丁氧基苯乙烯。Examples of monofunctional aromatic vinyl compounds include styrene, dimethylstyrene, trimethylstyrene, isopropylstyrene, chloromethylstyrene, methoxystyrene, acetoxy Styrene, chlorostyrene, dichlorostyrene, bromostyrene, methyl vinyl benzoate, 3-methylstyrene, 4-methylstyrene, 3-ethylstyrene, 4-ethylstyrene , 3-propylstyrene, 4-propylstyrene, 3-butylstyrene, 4-butylstyrene, 3-hexylstyrene, 4-hexylstyrene, 3-octylstyrene, 4- Octylstyrene, 3-(2-ethylhexyl)styrene, 4-(2-ethylhexyl)styrene, allylstyrene, isopropenylstyrene, butylenestyrene, octenylbenzene Ethylene, 4-tertiary butoxycarbonylstyrene and 4-tertiary butoxystyrene.
作為單官能乙烯醚,例如可舉出甲基乙烯醚、乙基乙烯醚、丙基乙烯醚、正丁基乙烯醚、三級丁基乙烯醚、2-乙基己基乙烯醚、正壬基乙烯醚、月桂基乙烯醚、環己基乙烯醚、環己基甲基乙烯醚、4-甲基環己基甲基乙烯醚、苄基乙烯醚、二環戊烯基乙烯醚、2-二環戊基乙基乙烯醚、甲氧基乙基乙烯醚、乙氧基乙基乙烯醚、丁氧基乙基乙烯醚、甲氧基乙氧基乙基乙烯醚、乙氧基乙氧基乙基乙烯醚、甲氧基聚乙二醇乙烯醚、四氫糠乙烯醚、2-羥乙基乙烯醚、2-羥丙基乙烯醚、4-羥基丁基乙烯醚、4-羥基甲基環己基甲基乙烯醚、二乙二醇單乙烯醚、聚乙二醇乙烯醚、氯乙基乙烯醚、氯丁基乙烯醚、氯乙氧基乙基乙烯醚、苯基乙基乙烯醚及苯氧基聚乙二醇乙烯醚。Examples of monofunctional vinyl ethers include methyl vinyl ether, ethyl vinyl ether, propyl vinyl ether, n-butyl vinyl ether, tertiary butyl vinyl ether, 2-ethylhexyl vinyl ether, n-nonylethylene ether, lauryl vinyl ether, cyclohexyl vinyl ether, cyclohexyl methyl vinyl ether, 4-methylcyclohexyl methyl vinyl ether, benzyl vinyl ether, dicyclopentenyl vinyl ether, 2-dicyclopentyl ethyl ether Base vinyl ether, methoxyethyl vinyl ether, ethoxyethyl vinyl ether, butoxyethyl vinyl ether, methoxyethoxyethyl vinyl ether, ethoxyethoxyethyl vinyl ether, Methoxypolyethylene glycol vinyl ether, tetrahydrofurfuryl vinyl ether, 2-hydroxyethyl vinyl ether, 2-hydroxypropyl vinyl ether, 4-hydroxybutyl vinyl ether, 4-hydroxymethylcyclohexylmethylethylene ether, diethylene glycol monovinyl ether, polyethylene glycol vinyl ether, chloroethyl vinyl ether, chlorobutyl vinyl ether, chloroethoxyethyl vinyl ether, phenylethyl vinyl ether and phenoxy polyethylene Glycol vinyl ether.
作為單官能N-乙烯基化合物,例如可舉出N-乙烯基-ε-己內醯胺及N-乙烯吡咯啶酮。Examples of monofunctional N-vinyl compounds include N-vinyl-ε-caprolactam and N-vinylpyrrolidone.
多官能聚合性單體只要為具有2個以上聚合性基之單體,則並無特別限定。從硬化性的觀點考慮,多官能聚合性單體為多官能的自由基聚合性單體為較佳,多官能乙烯性不飽和單體為更佳。The polyfunctional polymerizable monomer is not particularly limited as long as it is a monomer having two or more polymerizable groups. From the viewpoint of curability, the polyfunctional polymerizable monomer is preferably a polyfunctional radical polymerizable monomer, more preferably a polyfunctional ethylenically unsaturated monomer.
作為多官能乙烯性不飽和單體,例如可舉出多官能(甲基)丙烯酸酯化合物及多官能乙烯醚。Examples of polyfunctional ethylenically unsaturated monomers include polyfunctional (meth)acrylate compounds and polyfunctional vinyl ethers.
作為多官能(甲基)丙烯酸酯,例如可舉出乙二醇二(甲基)丙烯酸酯、二乙二醇二(甲基)丙烯酸酯、三乙二醇二(甲基)丙烯酸酯、聚乙二醇二(甲基)丙烯酸酯、丙二醇二(甲基)丙烯酸酯、二丙二醇二(甲基)丙烯酸酯、三丙二醇二(甲基)丙烯酸酯、聚丙二醇二(甲基)丙烯酸酯、丁二醇二(甲基)丙烯酸酯、四乙二醇二(甲基)丙烯酸酯、新戊二醇二(甲基)丙烯酸酯、3-甲基-1,5-戊烷二醇二(甲基)丙烯酸酯、1,4-丁二醇二(甲基)丙烯酸酯、1,6-己二醇二(甲基)丙烯酸酯、庚烷二醇二(甲基)丙烯酸酯、EO改質新戊二醇二(甲基)丙烯酸酯、PO改質新戊二醇二(甲基)丙烯酸酯、EO改質己二醇二(甲基)丙烯酸酯、PO改質己二醇二(甲基)丙烯酸酯、辛烷二醇二(甲基)丙烯酸酯、壬烷二醇二(甲基)丙烯酸酯、癸烷二醇二(甲基)丙烯酸酯、十二烷二醇二(甲基)丙烯酸酯、甘油二(甲基)丙烯酸酯、新戊四醇二(甲基)丙烯酸酯、乙二醇二環氧丙基醚二(甲基)丙烯酸酯、二乙二醇二環氧丙基醚二(甲基)丙烯酸酯、三環癸烷二甲醇二(甲基)丙烯酸酯、三羥甲基乙烷三(甲基)丙烯酸酯、三羥甲基丙烷三(甲基)丙烯酸酯、三羥甲基丙烷EO加成三(甲基)丙烯酸酯、新戊四醇三(甲基)丙烯酸酯、新戊四醇四(甲基)丙烯酸酯、二新戊四醇四(甲基)丙烯酸酯、二新戊四醇五(甲基)丙烯酸酯、二新戊四醇六(甲基)丙烯酸酯、三(甲基)丙烯醯氧基乙氧基三羥甲基丙烷、甘油聚環氧丙基醚聚(甲基)丙烯酸酯及三(2-丙烯醯氧基乙基)異氰脲酸酯。Examples of polyfunctional (meth)acrylates include ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, poly Ethylene Glycol Di(meth)acrylate, Propylene Glycol Di(meth)acrylate, Dipropylene Glycol Di(meth)acrylate, Tripropylene Glycol Di(meth)acrylate, Polypropylene Glycol Di(meth)acrylate, Butanediol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 3-methyl-1,5-pentanediol di( Meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, heptanediol di(meth)acrylate, EO modification Neopentyl glycol di(meth)acrylate, PO modified neopentyl glycol di(meth)acrylate, EO modified hexanediol di(meth)acrylate, PO modified hexanediol di(meth)acrylate Meth)acrylate, Octanediol Di(meth)acrylate, Nonanediol Di(meth)acrylate, Decanediol Di(meth)acrylate, Dodecanediol Di(meth)acrylate, Dodecanediol Di(meth)acrylate base) acrylate, glycerol di(meth)acrylate, neopentylthritol di(meth)acrylate, ethylene glycol diglycidyl ether di(meth)acrylate, diethylene glycol diepoxy Propyl ether di(meth)acrylate, Tricyclodecane dimethanol di(meth)acrylate, Trimethylolethane tri(meth)acrylate, Trimethylolpropane tri(meth)acrylate ester, trimethylolpropane EO addition tri(meth)acrylate, neopentylthritol tri(meth)acrylate, neopentylthritol tetra(meth)acrylate, dipenteoerythritol tetra(meth)acrylate base) acrylate, diperythritol penta(meth)acrylate, diperythritol hexa(meth)acrylate, tri(meth)acryloxyethoxytrimethylolpropane, glycerin Polyglycidyl ether poly(meth)acrylate and tris(2-acryloxyethyl)isocyanurate.
作為多官能乙烯醚,例如可舉出1,4-丁二醇二乙烯醚、乙二醇二乙烯醚、二乙二醇二乙烯醚、三乙二醇二乙烯醚、聚乙二醇二乙烯醚、丙二醇二乙烯醚、丁二醇二乙烯醚、己二醇二乙烯醚、1,4-環己烷二甲醇二乙烯醚、雙酚A環氧烷二乙烯醚、雙酚F環氧烷二乙烯醚、三羥甲基乙烷三乙烯醚、三羥甲基丙烷三乙烯醚、二三羥甲基丙烷四乙烯醚、甘油三乙烯醚、新戊四醇四乙烯醚、二新戊四醇五乙烯醚、二新戊四醇六乙烯醚、EO加成三羥甲基丙烷三乙烯醚、PO加成三羥甲基丙烷三乙烯醚、EO加成二三羥甲基丙烷四乙烯醚、PO加成二三羥甲基丙烷四乙烯醚、EO加成新戊四醇四乙烯醚、PO加成新戊四醇四乙烯醚、EO加成二新戊四醇六乙烯醚及PO加成二新戊四醇六乙烯醚。Examples of polyfunctional vinyl ethers include 1,4-butanediol divinyl ether, ethylene glycol divinyl ether, diethylene glycol divinyl ether, triethylene glycol divinyl ether, polyethylene glycol divinyl ether, and polyethylene glycol divinyl ether. Ether, propylene glycol divinyl ether, butanediol divinyl ether, hexanediol divinyl ether, 1,4-cyclohexanedimethanol divinyl ether, bisphenol A alkylene oxide divinyl ether, bisphenol F alkylene oxide Divinyl ether, trimethylolethane trivinyl ether, trimethylolpropane trivinyl ether, ditrimethylolpropane tetravinyl ether, glycerin trivinyl ether, neopentylthritol tetravinyl ether, dineopentyl tetra Alcohol Pentavinyl Ether, Dineopentyl Rityl Hexaethylene Ether, EO Added Trimethylolpropane Trivinyl Ether, PO Added Trimethylolpropane Trivinyl Ether, EO Added Ditrimethylolpropane Tetravinyl Ether , PO addition of two trimethylolpropane tetraethylene ether, EO addition of neopentylthritol tetraethylene ether, PO addition of neopentylthritol tetraethylene ether, EO addition of dineopentylthritol hexaethylene ether and PO addition into two new pentaerythritol hexaethylene ether.
其中,從硬化性的觀點考慮,多官能聚合性單體為除了(甲基)丙烯醯基以外的部分的碳數為3~11的單體為較佳。作為除了(甲基)丙烯醯基以外的部分的碳數為3~11的單體,具體而言,1,6-己二醇二(甲基)丙烯酸酯、二丙二醇二(甲基)丙烯酸酯、PO改質新戊二醇二(甲基)丙烯酸酯、1,4-丁二醇二(甲基)丙烯酸酯、3-甲基-1,5-戊烷二醇二(甲基)丙烯酸酯、聚乙二醇二(甲基)丙烯酸酯(EO鏈n=4)或1,10-癸烷二醇二(甲基)丙烯酸酯為更佳。Among them, the polyfunctional polymerizable monomer is preferably a monomer having 3 to 11 carbon atoms in a portion other than the (meth)acryl group from the viewpoint of curability. As a monomer having 3 to 11 carbon atoms other than the (meth)acryl group, specifically, 1,6-hexanediol di(meth)acrylate, dipropylene glycol di(meth)acrylic acid ester, PO modified neopentyl glycol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 3-methyl-1,5-pentanediol di(meth)acrylate Acrylate, polyethylene glycol di(meth)acrylate (EO chain n=4) or 1,10-decanediol di(meth)acrylate is more preferred.
聚合性單體的含量相對於絕緣性保護層形成用油墨的總量為10質量%~98質量%為較佳,50質量%~98質量%為更佳。The content of the polymerizable monomer is preferably 10% by mass to 98% by mass, more preferably 50% by mass to 98% by mass, based on the total amount of the ink for forming an insulating protective layer.
(聚合起始劑) 作為絕緣層形成用油墨中所含有之聚合起始劑,例如可舉出肟化合物、烷基苯酮化合物、醯基膦化合物、芳香族鎓鹽化合物、有機過氧化物、硫化合物、六芳基聯咪唑化合物、硼酸鹽化合物、吖𠯤鎓化合物、二茂鈦化合物、活性酯化合物、具有碳鹵鍵之化合物及烷基胺。 (polymerization initiator) Examples of the polymerization initiator contained in the ink for forming an insulating layer include oxime compounds, alkylphenone compounds, acylphosphine compounds, aromatic onium salt compounds, organic peroxides, sulfur compounds, hexaaryl Biimidazole compounds, borate compounds, acridium compounds, titanocene compounds, active ester compounds, compounds with carbon-halogen bonds, and alkylamines.
其中,從進一步提高導電性之觀點考慮,絕緣層形成用油墨中所含有之聚合起始劑為選自包括肟化合物、烷基苯酮化合物及二茂鈦化合物之群組中之至少1種為較佳,烷基苯酮化合物為更佳,選自包括α-胺基烷基苯酮化合物及苄基縮酮烷基苯酮之群組中之至少1種為進一步較佳。Among them, from the viewpoint of further improving the conductivity, the polymerization initiator contained in the ink for forming an insulating layer is at least one selected from the group consisting of oxime compounds, alkylphenone compounds, and titanocene compounds. Preferably, an alkylphenone compound is more preferable, and at least one selected from the group consisting of an α-aminoalkylphenone compound and a benzyl ketal alkylphenone is still more preferable.
聚合起始劑的含量相對於絕緣層形成用油墨的總量為0.5質量%~20質量%為較佳,2質量%~10質量%為更佳。The content of the polymerization initiator is preferably 0.5% by mass to 20% by mass, more preferably 2% by mass to 10% by mass, based on the total amount of the insulating layer forming ink.
絕緣性保護層形成用油墨可以含有除了聚合起始劑及聚合性單體以外的其他成分。作為其他成分,可舉出鏈轉移劑、聚合抑制劑、增感劑、界面活性劑及添加劑。The ink for forming an insulating protective layer may contain other components than the polymerization initiator and the polymerizable monomer. Examples of other components include chain transfer agents, polymerization inhibitors, sensitizers, surfactants, and additives.
(鏈轉移劑) 絕緣層形成用油墨可以含有至少1種鏈轉移劑。 從提高光聚合反應的反應性之觀點考慮,鏈轉移劑為多官能硫醇為較佳。 (chain transfer agent) The ink for forming an insulating layer may contain at least one chain transfer agent. From the viewpoint of improving the reactivity of the photopolymerization reaction, the chain transfer agent is preferably a polyfunctional mercaptan.
作為多官能性硫醇,例如可舉出己烷-1,6-二硫醇、癸烷-1,10-二硫醇、二巰基二乙醚、二巰基二乙基硫化物等脂肪族硫醇類、二甲苯二硫醇、4,4′-二巰基二苯基硫化物、1,4-苯二硫醇等芳香族硫醇類; 乙二醇雙(巰基乙酸酯)、聚乙二醇雙(巰基乙酸酯)、丙二醇雙(巰基乙酸酯)、甘油三(巰基乙酸酯)、三羥甲基乙烷三(巰基乙酸酯)、三羥甲基丙烷三(巰基乙酸酯)、新戊四醇四(巰基乙酸酯)、二新戊四醇六(巰基乙酸酯)等多元醇聚(巰基乙酸酯); 乙二醇雙(3-巰基丙酸酯)、聚乙二醇雙(3-巰基丙酸酯)、丙二醇雙(3-巰基丙酸酯)、甘油三(3-巰基丙酸酯)、三羥甲基乙烷三(巰基丙酸酯)、三羥甲基丙烷三(3-巰基丙酸酯)、新戊四醇四(3-巰基丙酸酯)、二新戊四醇六(3-巰基丙酸酯)等多元醇聚(3-巰基丙酸酯);及 1,4-雙(3-巰基丁醯氧基)丁烷、1,3,5-三(3-巰基丁氧基乙基)-1,3,5-三𠯤-2,4,6(1H,3H,5H)-三酮、新戊四醇四(3-巰基丁酸酯)等聚(巰基丁酸酯)。 Examples of polyfunctional thiols include aliphatic thiols such as hexane-1,6-dithiol, decane-1,10-dithiol, dimercaptodiethyl ether, and dimercaptodiethylsulfide. Aromatic thiols such as xylene dithiol, 4,4′-dimercaptodiphenyl sulfide, 1,4-benzenedithiol, etc.; Ethylene glycol bis(thioglycolate), Polyethylene glycol bis(thioglycolate), Propylene glycol bis(thioglycolate), Glycerol tri(thioglycolate), Trimethylolethane tri(mercapto acetate), trimethylolpropane tri(thioglycolate), neopentylthritol tetrakis(thioglycolate), diperythritol hexa(thioglycolate) and other polyol poly(thioglycolate) ester); Ethylene Glycol Bis(3-Mercaptopropionate), Polyethylene Glycol Bis(3-Mercaptopropionate), Propylene Glycol Bis(3-Mercaptopropionate), Glycerol Tris(3-Mercaptopropionate), Tris Methylolethane Tris(Mercaptopropionate), Trimethylolpropane Tris(3-Mercaptopropionate), Neopentylthritol Tetrakis(3-Mercaptopropionate), Dineopentylthritol Hexa(3 -mercaptopropionate) and other polyol poly(3-mercaptopropionate); and 1,4-bis(3-mercaptobutyryloxy)butane, 1,3,5-tris(3-mercaptobutoxyethyl)-1,3,5-tris-2,4,6( 1H,3H,5H)-trione, neopentylthritol tetrakis(3-mercaptobutyrate) and other poly(mercaptobutyrate).
(聚合抑制劑) 絕緣層形成用油墨可以含有至少1種聚合抑制劑。 作為聚合抑制劑,可舉出對甲氧基苯酚、醌類(例如,氫醌、苯醌、甲氧基苯醌等)、啡噻𠯤、兒茶酚類、烷基苯酚類(例如,二丁基羥基甲苯(BHT)等)、烷基雙酚類、二甲基二硫代胺基甲酸鋅、二甲基二硫代胺基甲酸銅、二丁基二硫代胺基甲酸銅、水楊酸銅、硫代二丙酸酯類、巰基苯并咪唑、亞磷酸類、2,2,6,6-四甲基哌啶-1-氧基(TEMPO)、2,2,6,6-四甲基-4-羥基哌啶-1-氧基(TEMPOL)及三(N-亞硝基-N-苯基羥胺)鋁鹽(別名:Cupferron Al)。 (polymerization inhibitor) The ink for forming an insulating layer may contain at least one polymerization inhibitor. Examples of polymerization inhibitors include p-methoxyphenol, quinones (for example, hydroquinone, benzoquinone, methoxybenzoquinone, etc.), phenanthrene, catechols, alkylphenols (for example, di butylated hydroxytoluene (BHT) etc.), alkyl bisphenols, zinc dimethyldithiocarbamate, copper dimethyldithiocarbamate, copper dibutyldithiocarbamate, water Copper sylate, thiodipropionates, mercaptobenzimidazoles, phosphorous acid, 2,2,6,6-tetramethylpiperidin-1-oxyl (TEMPO), 2,2,6,6 -Tetramethyl-4-hydroxypiperidin-1-oxyl (TEMPOL) and tris(N-nitroso-N-phenylhydroxylamine) aluminum salt (alias: Cupferron Al).
其中,聚合抑制劑為選自對甲氧基苯酚、兒茶酚類、醌類、烷基苯酚類、TEMPO、TEMPOL及三(N-亞硝基-N-苯基羥胺)鋁鹽中之至少1種為較佳,選自對甲氧基苯酚、氫醌、苯醌、BHT、TEMPO、TEMPOL及三(N-亞硝基-N-苯基羥胺)鋁鹽中之至少1種為更佳。Wherein, the polymerization inhibitor is at least one selected from p-methoxyphenol, catechols, quinones, alkylphenols, TEMPO, TEMPOL and tris(N-nitroso-N-phenylhydroxylamine) aluminum salt One is preferred, and at least one selected from p-methoxyphenol, hydroquinone, benzoquinone, BHT, TEMPO, TEMPOL and tris(N-nitroso-N-phenylhydroxylamine) aluminum salt is more preferred .
在絕緣層形成用油墨含有聚合抑制劑之情況下,聚合抑制劑的含量相對於絕緣性保護層形成用油墨的總量為0.01質量%~2.0質量%為較佳,0.02質量%~1.0質量%為更佳,0.03質量%~0.5質量%為特佳。When the ink for forming an insulating layer contains a polymerization inhibitor, the content of the polymerization inhibitor is preferably 0.01% by mass to 2.0% by mass, and preferably 0.02% by mass to 1.0% by mass, based on the total amount of the ink for forming an insulating protective layer. More preferably, 0.03% by mass to 0.5% by mass is particularly preferred.
(增感劑) 絕緣層形成用油墨可以含有至少1種增感劑。 (sensitizer) The ink for forming an insulating layer may contain at least one sensitizer.
作為增感劑,例如可舉出多核芳香族化合物(例如,芘、苝、三伸苯基及2-乙基-9,10-二甲氧基蒽)、𠮿口星系化合物(例如,螢光黃、曙紅、赤藻辛、玫瑰紅B及孟加拉玫瑰紅)、花青系化合物(例如,硫雜羰花青及氧雜羰花青)、部花青系化合物(例如,部花青及羰部花青)、噻𠯤系化合物(例如,硫堇、亞甲基藍及甲苯胺藍)、吖啶系化合物(例如,吖啶橙、氯黃素及吖啶黃素)、蒽醌類(例如,蒽醌)、方酸菁系化合物(例如,方酸菁)、香豆素系化合物(例如,7-二乙基胺基-4-甲基香豆素)、噻噸酮系化合物(例如,異丙基噻噸酮)及硫𠳭唍酮系化合物(例如,硫𠳭唍酮)。其中,增感劑為噻噸酮系化合物為較佳。As sensitizers, for example, polynuclear aromatic compounds (for example, pyrene, perylene, triphenylene, and 2-ethyl-9,10-dimethoxyanthracene), galaxies (for example, fluorescent yellow, eosin, erythroxin, rose bengal B and rose bengal), cyanine compounds (such as thiacarbocyanine and oxacarbocyanine), merocyanine compounds (such as merocyanine and carbocyanines), thiamines (e.g., thionine, methylene blue, and toluidine blue), acridines (e.g., acridine orange, chloroflavin, and acriflavine), anthraquinones (e.g., anthraquinone), squarylium-based compounds (for example, squaraine), coumarin-based compounds (for example, 7-diethylamino-4-methylcoumarin), thioxanthone-based compounds (for example, isopropylthioxanthone) and thioxanthone-based compounds (e.g., thioxanthone). Among them, the sensitizer is preferably a thioxanthone compound.
在絕緣層形成用油墨含有增感劑之情況下,增感劑的含量並無特別限定,相對於絕緣性保護層形成用油墨的總量為1.0質量%~15.0質量%為較佳,1.5質量%~5.0質量%為更佳。When the ink for forming an insulating layer contains a sensitizer, the content of the sensitizer is not particularly limited, but it is preferably 1.0% by mass to 15.0% by mass relative to the total amount of ink for forming an insulating protective layer, and 1.5% by mass % to 5.0% by mass is more preferable.
(界面活性劑) 絕緣層形成用油墨可以含有至少1種界面活性劑。 (surfactant) The ink for forming an insulating layer may contain at least one surfactant.
作為界面活性劑,可舉出日本特開昭62-173463號公報及日本特開昭62-183457號公報中所記載者。又,作為界面活性劑,例如可舉出二烷基磺基琥珀酸鹽、烷基萘磺酸鹽、脂肪酸鹽等陰離子性界面活性劑;聚氧化乙烯烷基醚、聚氧化乙烯烷基烯丙醚、乙炔二醇、聚氧化乙烯/聚氧丙烯封端共聚物等非離子性界面活性劑;及烷基胺鹽、第四級銨鹽等陽離子性界面活性劑。又,界面活性劑可以為氟系界面活性劑或聚矽氧系界面活性劑。Examples of the surfactant include those described in JP-A-62-173463 and JP-A-62-183457. In addition, examples of surfactants include anionic surfactants such as dialkyl sulfosuccinates, alkylnaphthalene sulfonates, and fatty acid salts; polyoxyethylene alkyl ethers, polyoxyethylene alkyl allyl Nonionic surfactants such as ethers, acetylene glycols, polyethylene oxide/polyoxypropylene capped copolymers; and cationic surfactants such as alkylamine salts and quaternary ammonium salts. In addition, the surfactant may be a fluorine-based surfactant or a polysiloxane-based surfactant.
在絕緣層形成用油墨含有界面活性劑之情況下,界面活性劑的含量相對於絕緣層形成用油墨的總量為0.5質量%以下為較佳,0.1質量%以下為更佳。界面活性劑的含量的下限值並無特別限定。When the ink for forming an insulating layer contains a surfactant, the content of the surfactant is preferably 0.5% by mass or less, more preferably 0.1% by mass or less, based on the total amount of the ink for forming an insulating layer. The lower limit of the content of the surfactant is not particularly limited.
若界面活性劑的含量為0.5質量%以下,則賦予絕緣層形成用油墨之後,絕緣層形成用油墨難以擴散。因此,抑制絕緣層形成用油墨的流出,提高電磁波遮蔽性。If the content of the surfactant is 0.5% by mass or less, the ink for insulating layer formation will hardly spread after the ink for forming an insulating layer is applied. Therefore, the outflow of the ink for insulating layer formation is suppressed, and electromagnetic wave shielding property improves.
(有機溶劑) 絕緣層形成用油墨可以含有至少1種有機溶劑。 (Organic solvents) The ink for forming an insulating layer may contain at least one type of organic solvent.
作為有機溶劑,例如可舉出乙二醇單乙醚、二乙二醇單乙醚、三乙二醇單甲醚、丙二醇單甲醚(PGME)、二丙二醇單甲醚、三丙二醇單甲醚等(聚)伸烷基二醇單烷基醚類; 乙二醇二丁醚、二乙二醇二甲醚、二乙二醇二乙醚、二丙二醇二乙醚、四乙二醇二甲醚等(聚)伸烷基二醇二烷基醚類; 二乙二醇乙酸酯等(聚)伸烷基二醇乙酸酯類; 乙二醇二乙酸酯、丙二醇二乙酸酯等(聚)伸烷基二醇二乙酸酯類; 乙二醇單丁基醚乙酸酯、丙二醇單甲醚乙酸酯等(聚)伸烷基二醇單烷基醚乙酸酯類、甲基乙基酮、環己酮等酮類; γ-丁內酯等內酯類; 乙酸乙酯、乙酸丙酯、乙酸丁酯、乙酸3-甲氧基丁酯(MBA)、丙酸甲酯、丙酸乙酯等酯類; 四氫呋喃、二㗁烷等環狀醚類;及 二甲基甲醯胺、二甲基乙醯胺等醯胺類。 Examples of organic solvents include ethylene glycol monoethyl ether, diethylene glycol monoethyl ether, triethylene glycol monomethyl ether, propylene glycol monomethyl ether (PGME), dipropylene glycol monomethyl ether, tripropylene glycol monomethyl ether, etc. ( Poly)alkylene glycol monoalkyl ethers; Ethylene glycol dibutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, dipropylene glycol diethyl ether, tetraethylene glycol dimethyl ether and other (poly)alkylene glycol dialkyl ethers; (Poly)alkylene glycol acetates such as diethylene glycol acetate; Ethylene glycol diacetate, propylene glycol diacetate and other (poly)alkylene glycol diacetates; Ethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate and other (poly)alkylene glycol monoalkyl ether acetates, methyl ethyl ketone, cyclohexanone and other ketones; Lactones such as γ-butyrolactone; Ethyl acetate, propyl acetate, butyl acetate, 3-methoxybutyl acetate (MBA), methyl propionate, ethyl propionate and other esters; Cyclic ethers such as tetrahydrofuran and dioxane; and Amides such as dimethylformamide and dimethylacetamide.
在絕緣層形成用油墨含有有機溶劑之情況下,有機溶劑的含量相對於絕緣層形成用油墨的總量為70質量%以下為較佳,50質量%以下為更佳。有機溶劑的含量的下限值並無特別限定。When the ink for forming an insulating layer contains an organic solvent, the content of the organic solvent is preferably 70% by mass or less, more preferably 50% by mass or less, based on the total amount of the ink for forming an insulating layer. The lower limit of the content of the organic solvent is not particularly limited.
(添加劑) 絕緣層形成用油墨依據需要可以含有共增感劑、紫外線吸收劑、抗氧化劑、防褪色劑、鹼性化合物等添加劑。 (additive) The ink for forming an insulating layer may contain additives such as a co-sensitizer, an ultraviolet absorber, an antioxidant, an anti-fading agent, and a basic compound as necessary.
(物性) 從在使用噴墨記錄方式賦予時提高吐出穩定性之觀點考慮,絕緣層形成用油墨的pH為7~10為較佳,7.5~9.5為更佳。pH使用pH計在25℃下進行測量,例如使用DKK-TOA Corporation製的pH計(型號“HM-31”)進行測量。 (physical properties) The pH of the ink for forming an insulating layer is preferably from 7 to 10, more preferably from 7.5 to 9.5, from the viewpoint of improving discharge stability when imparted by an inkjet recording method. The pH is measured at 25° C. using a pH meter, for example, a pH meter manufactured by DKK-TOA Corporation (model “HM-31”).
絕緣層形成用油墨的黏度為0.5mPa・s~60mPa・s為較佳,2mPa・s~40mPa・s為更佳。黏度使用黏度計在25℃下進行測量,例如使用TOKI SANGYO CO.,LTD.製的TV-22型黏度計進行測量。The viscosity of the ink for forming an insulating layer is preferably 0.5 mPa・s to 60 mPa・s, more preferably 2 mPa・s to 40 mPa・s. The viscosity is measured at 25° C. using a viscometer, for example, a TV-22 viscometer manufactured by TOKI SANGYO CO., LTD.
絕緣層形成用油墨的表面張力為60mN/m以下為較佳,20mN/m~50mN/m為更佳,25mN/m~45mN/m為進一步較佳。表面張力使用表面張力計在25℃下進行測量,例如使用Kyowa Interface Science Co.,Ltd.製的自動表面張力計(產品名“CBVP-Z”)並且藉由平板法進行測量。The surface tension of the ink for insulating layer formation is preferably 60 mN/m or less, more preferably 20 mN/m to 50 mN/m, and still more preferably 25 mN/m to 45 mN/m. The surface tension is measured at 25° C. using a surface tensiometer such as an automatic surface tensiometer manufactured by Kyowa Interface Science Co., Ltd. (product name “CBVP-Z”) and measured by a plate method.
<絕緣性保護層的形成方法> 在第1製程中,較佳為使用噴墨記錄方式、分配器塗佈方法或噴塗塗佈方法將絕緣層形成用油墨賦予到電子基材上,並且對賦予到電子零件的頂面上之絕緣層形成用油墨吹送風,接著,將已吹送風之絕緣層形成用油墨硬化來形成絕緣保護層。 <Method for forming an insulating protective layer> In the first process, it is preferable to apply the ink for forming an insulating layer on the electronic base material using an inkjet recording method, a dispenser coating method, or a spray coating method, and to apply the insulating layer on the top surface of the electronic component. The layer-forming ink is blown with air, and then the blown insulating layer-forming ink is cured to form an insulating protective layer.
賦予絕緣層形成用油墨之方法中,從能夠滴加少量而藉由1次的賦予形成之油墨膜的厚度變薄之觀點考慮,噴墨記錄方式為較佳。噴墨記錄方式的詳細內容如前述。Among the methods of applying the ink for insulating layer formation, the inkjet recording method is preferable from the viewpoint that a small amount can be dropped and the thickness of the ink film formed by one application can be reduced. The details of the inkjet recording method are as described above.
硬化絕緣層形成用油墨之方法並無特別限定,例如可舉出對賦予到基材上之絕緣層形成用油墨照射活性能量射線之方法(例如本曝光)。The method of hardening the ink for forming an insulating layer is not particularly limited, for example, a method of irradiating active energy rays to the ink for forming an insulating layer provided on a base material (for example, this exposure).
作為活性能量射線,例如可舉出紫外線、可見光線及電子束,其中,紫外線(以下,亦稱為“UV”)為較佳。Examples of active energy rays include ultraviolet rays, visible rays, and electron beams, and among them, ultraviolet rays (hereinafter also referred to as "UV") are preferable.
紫外線的峰波長為200nm~405nm為較佳,250nm~400nm為更佳,300nm~400nm為進一步較佳。The peak wavelength of ultraviolet rays is preferably from 200 nm to 405 nm, more preferably from 250 nm to 400 nm, and still more preferably from 300 nm to 400 nm.
活性能量射線的照射中的曝光量為100mJ/cm 2~5000mJ/cm 2為較佳,300mJ/cm 2~1500mJ/cm 2為更佳。 The exposure dose in the irradiation of active energy rays is preferably 100 mJ/cm 2 to 5000 mJ/cm 2 , more preferably 300 mJ/cm 2 to 1500 mJ/cm 2 .
作為紫外線照射用的光源,主要利用水銀燈、氣體雷射及固體雷射,廣泛已知水銀燈、金屬鹵化物燈及紫外線螢光燈。又,UV-LED(發光二極體)及UV-LD(雷射二極體)為小型、高壽命、高效率並且低成本,期待作為紫外線照射用光源。其中,紫外線照射用的光源為金屬鹵化物燈、高壓水銀燈、中壓水銀燈、低壓水銀燈或UV-LED為較佳。As a light source for ultraviolet irradiation, mercury lamps, gas lasers, and solid lasers are mainly used, and mercury lamps, metal halide lamps, and ultraviolet fluorescent lamps are widely known. In addition, UV-LEDs (light emitting diodes) and UV-LDs (laser diodes) are small, have a long life, high efficiency, and low cost, and are expected to be used as light sources for ultraviolet irradiation. Among them, the light source for ultraviolet irradiation is preferably metal halide lamp, high-pressure mercury lamp, medium-pressure mercury lamp, low-pressure mercury lamp or UV-LED.
在獲得絕緣性保護層之製程中,為了獲得所期望的厚度的絕緣性保護層,重複2次以上賦予絕緣油墨並照射活性能量射線之製程為較佳。In the process of obtaining an insulating protective layer, in order to obtain an insulating protective layer of a desired thickness, it is preferable to repeat the process of applying insulating ink and irradiating active energy rays two or more times.
絕緣性保護層的厚度為5μm~5000μm為較佳,10μm~2000μm為更佳。The thickness of the insulating protective layer is preferably from 5 μm to 5000 μm, more preferably from 10 μm to 2000 μm.
在第1製程中,與活性能量射線的照射(例如本曝光)另行地,在對電子零件的頂面上的油墨之風的吹送之前及之後在至少其中一者的時序中可以實施前述之釘扎曝光。 [實施例] In the first process, separately from the irradiation of active energy rays (for example, this exposure), the above-mentioned nailing can be performed in at least one of the timings before and after the wind blowing of the ink on the top surface of the electronic component. exposure. [Example]
以下,示出本揭示的實施例,但是本揭示並不限定於以下實施例。Hereinafter, although the Example of this indication is shown, this indication is not limited to the following Example.
〔實施例1〕 <導電層形成用油墨的製備> 向200mL的3口燒瓶中添加了新癸酸銀40g。接著,添加三甲基苯30.0g及萜品醇30.0g,進行攪拌,獲得了含有銀鹽之溶液。使用孔徑0.45μm的PTFE(聚四氟乙烯)製薄膜過濾器,過濾該溶液,獲得了導電層形成用油墨。 [Example 1] <Preparation of ink for conductive layer formation> 40 g of silver neodecanoate was added to a 200 mL 3-necked flask. Next, 30.0 g of trimethylbenzene and 30.0 g of terpineol were added and stirred to obtain a silver salt-containing solution. This solution was filtered using a PTFE (polytetrafluoroethylene) membrane filter with a pore size of 0.45 μm to obtain an ink for forming a conductive layer.
<電子基板的準備>
準備了帶電子零件的配線基板。
在帶電子零件的配線基板中,藉由複數個焊球連接配線基板及電子零件,在電子零件與配線基板之間且複數個焊球之間存在微小的空隙。
使用Musashi engineering.Inc.的分配器,將Zymet公司的Underfill材料填充於該空隙,其後靜置於恆溫烘箱20分鐘,藉此填補了上述空隙。
藉由以上,準備了具有與圖15A及圖15B所示之電子基板110相同的結構之電子基板(亦即,作為帶段差之基板的電子基板)。
準備之電子基板中的各尺寸如下。
<Preparation of electronic board>
A wiring board with electronic parts is prepared.
In the wiring board with electronic parts, the wiring board and the electronic parts are connected by a plurality of solder balls, and there are minute gaps between the electronic parts and the wiring board and between the plurality of solder balls.
Using a dispenser from Musashi engineering. Inc., Zymet's Underfill material was filled in the gap, and then left to stand in a constant temperature oven for 20 minutes, thereby filling the gap.
Through the above, an electronic substrate having the same structure as the
接地電極的寬度:600μm 接地電極的高度(在配線基板上突出之部分的高度):25μm 被接地電極包圍之區域(接地區域):10.65mm×10.65mm 電子零件的尺寸及形狀:10.00mm×10.00mm的矩形狀 電子零件的高度(從配線基板的表面到電子零件的頂面的高度):500μm 電子零件與接地電極的距離:50μm Width of ground electrode: 600 μm The height of the ground electrode (the height of the protruding part on the wiring board): 25μm Area surrounded by ground electrodes (ground area): 10.65mm×10.65mm Size and shape of electronic parts: rectangular shape of 10.00mm×10.00mm Height of electronic parts (height from the surface of the wiring board to the top surface of the electronic parts): 500 μm Distance between electronic parts and ground electrode: 50μm
<導電層的形成> 準備了具備如下的單程方式的噴墨記錄裝置: 載台,載置基板(例如,上述電子基板); 輸送機,用於輸送載台; 噴墨噴頭,配置成噴嘴列與載台的輸送方向正交之1200dpi(dot per inch,每英寸點數); 乾燥機;及 作為釘扎光源的385nmLED光源(13W/cm 2、KYOCERA Corporation製)。 在此,從載台的輸送方向上游側依序配置噴墨、乾燥機及釘扎光源。 <Formation of the conductive layer> An inkjet recording apparatus equipped with the following single-pass method was prepared: a stage on which a substrate (for example, the above-mentioned electronic substrate) is placed; a conveyor for conveying the stage; an inkjet head arranged in a row of nozzles 1200dpi (dot per inch) perpendicular to the conveying direction of the stage; a dryer; and a 385nm LED light source (13W/cm 2 , manufactured by KYOCERA Corporation) as a pinning light source. Here, an inkjet, a dryer, and a pinning light source are arranged in this order from the upstream side in the transport direction of the stage.
在上述噴墨記錄裝置中的載台上藉由膠帶固定了電子基板。此時,電子基板以電子基板中的電子零件的4個邊中的1個邊與噴墨噴頭的噴嘴列成平行之配置固定於載台上。 在上述噴墨記錄裝置上裝載導電層形成用油墨,輸送電子基板的同時將導電層形成用油墨賦予到該電子基板上。在導電層形成用油墨的賦予中,與相對移動方向正交之方向的解析度(dpi)及相對移動方向的解析度(dpi)分別調整為成為表1所示之值。 導電層形成用油墨的賦予區域包含電子零件上(10.00mm×10.00mm的矩形狀區域),並且從電子零件的4個邊的每一邊露出0.20mm,設為10.40mm×10.40mm的矩形狀的區域。 以上導電層形成用油墨的賦予重複了3次。 An electronic substrate was fixed on the stage in the above inkjet recording device with an adhesive tape. At this time, the electronic substrate is fixed on the stage so that one of the four sides of the electronic components on the electronic substrate is parallel to the nozzle array of the inkjet head. The ink for forming a conductive layer is loaded on the inkjet recording device, and the ink for forming a conductive layer is applied to the electronic substrate while conveying the electronic substrate. In the application of the conductive layer forming ink, the resolution (dpi) in the direction perpendicular to the relative movement direction and the resolution (dpi) in the relative movement direction were adjusted to the values shown in Table 1, respectively. The application area of the ink for forming the conductive layer includes the electronic component (10.00mm × 10.00mm rectangular area), and 0.20mm is exposed from each of the four sides of the electronic component, and it is made into a rectangular shape of 10.40mm × 10.40mm area. The application of the above conductive layer forming ink was repeated three times.
使用乾燥機,沿以下所示之方向將溫度23℃、風速3m/s的風吹送到賦予到電子基板中的電子零件的頂面上之導電層形成用油墨。 吹送風之方向設為從電子零件的頂面上的中心的上方仰角成為90°之方向。 從結束導電層形成用油墨賦予到風的吹送開始的時間調整為0.44秒鐘。 接著,藉由385nmLED光源(13W/cm 2、KYOCERA Corporation製)對已吹送風之油墨實施了釘扎曝光。釘扎曝光的曝光量設為5J/cm 2。 從結束對導電層形成用油墨之風的吹送到釘扎曝光開始的時間調整為0.44秒鐘。 Using a dryer, blow the air at a temperature of 23° C. and a wind speed of 3 m/s in the direction shown below to the conductive layer-forming ink applied on the top surface of the electronic component in the electronic substrate. The direction of the blown air is set to a direction in which the elevation angle becomes 90° from the center above the top surface of the electronic component. The time from the end of the application of the ink for forming a conductive layer to the start of blowing of the wind was adjusted to 0.44 seconds. Next, pinning exposure was performed on the blown ink with a 385 nm LED light source (13 W/cm 2 , manufactured by KYOCERA Corporation). The exposure amount of the pinning exposure was set to 5 J/cm 2 . The time from the end of blowing the ink for forming a conductive layer to the start of the pinning exposure was adjusted to 0.44 seconds.
在上述釘扎曝光之後,在150℃下將加熱賦予到電子基板上之導電層形成用油墨加熱(亦即,煅燒)20分鐘,獲得了作為電磁波遮蔽層的導電層。 藉由以上,獲得了實施例1的電子元件。 After the above-mentioned pinning exposure, the ink for forming a conductive layer to which heat was applied on the electronic substrate was heated (that is, fired) at 150° C. for 20 minutes to obtain a conductive layer serving as an electromagnetic wave shielding layer. Through the above, the electronic device of Example 1 was obtained.
<評價> 對所獲得之電子元件實施了以下的評價。 將結果示於表1中。 <Evaluation> The following evaluations were implemented about the obtained electronic component. The results are shown in Table 1.
(導電層的厚度) 依據拍攝了電子元件的截面之光學顯微鏡照片,測量了導電層的厚度。 作為導電層的厚度,分別測量了如下: 電子構件的頂面上的導電層的厚度; 電子構件的側面上的導電層的厚度;及 電子構件的頂面與側面之間的角部上的導電層的厚度。 依據測量結果,求出了厚度的平均值及厚度的偏差。 (thickness of conductive layer) The thickness of the conductive layer was measured based on an optical microscope photograph of a cross-section of the electronic component. As the thickness of the conductive layer, were measured as follows: the thickness of the conductive layer on the top surface of the electronic component; the thickness of the conductive layer on the sides of the electronic component; and The thickness of the conductive layer on the corner between the top surface and the side surface of the electronic component. Based on the measurement results, the average value of the thickness and the deviation of the thickness were obtained.
(導電層非形成區域中的油墨的飛散) 如下評價了導電層非形成區域中的油墨的飛散。 藉由光學顯微鏡(200倍),從電子零件的邊緣對各邊觀察3處距規定距離之部位,確認了有無導電油墨的飛散。 依據所獲得之結果,按照下述評價標準評價了導電層非形成區域中的油墨的飛散。 在下述評價標準中,導電層非形成區域中的油墨的飛散抑制性能最優異的級別為“5”。 (Scattering of ink in the area where the conductive layer is not formed) Scattering of the ink in the conductive layer non-formation region was evaluated as follows. Using an optical microscope (200X), observe three locations at a predetermined distance from the edge of the electronic component to each side, and confirm the presence or absence of scattering of the conductive ink. Based on the obtained results, ink scattering in the conductive layer non-formation region was evaluated according to the following evaluation criteria. In the following evaluation criteria, the most excellent level of ink scattering suppression performance in the conductive layer non-formation region was "5".
-導電層非形成區域中的油墨的飛散的評價標準- 5:從邊緣到300μm以上且未達500μm的區域未觀察到飛散,並且從邊緣到500μm以上的區域亦未觀察到飛散。 4:從邊緣到300μm以上且未達500μm的區域觀察到飛散,但是從邊緣到500μm以上的區域未觀察到飛散。 3:從邊緣到500μm以上且未達600μm的區域觀察到飛散,但是從邊緣到600μm以上的區域未觀察到飛散。 2:從邊緣到600μm以上且未達1000μm的部位觀察到飛散,但是從邊緣到1000μm以上的區域未觀察到飛散。 1:從邊緣到1000μm以上的區域觀察到飛散。 -Evaluation Criteria for Scattering of Ink in the Conductive Layer Non-Formation Area- 5: Scattering is not observed from the edge to a region of 300 μm or more and less than 500 μm, and also no scattering is observed from the edge to a region of 500 μm or more. 4: Scattering was observed from the edge to a region of 300 μm or more and less than 500 μm, but no scattering was observed from the edge to a region of 500 μm or more. 3: Scattering was observed from the edge to a region of 500 μm or more and less than 600 μm, but no scattering was observed from the edge to a region of 600 μm or more. 2: Scattering was observed from the edge to a portion of 600 μm or more and less than 1000 μm, but no scattering was observed from the edge to a region of 1000 μm or more. 1: Scattering is observed from the edge to a region of 1000 μm or more.
(電磁波遮蔽性能) 使用WM7400(MORITA TECH CO., LTD.製),在到3GHz的範圍內測量洩漏電磁波,按照下述評價標準,評價了導電層(電磁波遮蔽層)的電磁波遮蔽性能。下述評價標準中,電磁波遮蔽性能最優異的級別為“5”。 (Electromagnetic wave shielding performance) Using WM7400 (manufactured by MORITA TECH CO., LTD.), the electromagnetic wave leakage was measured in the range up to 3 GHz, and the electromagnetic wave shielding performance of the conductive layer (electromagnetic wave shielding layer) was evaluated according to the following evaluation criteria. In the following evaluation criteria, the most excellent level of electromagnetic wave shielding performance was "5".
-電磁波遮蔽性能的評價標準- 5:未達20dB 4:20dB以上且未達30dB 3:30dB以上且未達50dB 2:50dB以上且未達70dB 1:70dB以上 -Evaluation criteria for electromagnetic wave shielding performance- 5: Less than 20dB 4: More than 20dB and less than 30dB 3: More than 30dB and less than 50dB 2: More than 50dB and less than 70dB 1: Above 70dB
(導電層非形成區域的油墨的流出量(μm 3)) 測量了導電層非形成區域的油墨的流出量(μm 3)。 (Amount of Ink Outflow (μm 3 ) in a Region Where a Conductive Layer Is Not Formed) The amount of ink outflow (μm 3 ) in a region where a conductive layer is not formed was measured.
〔實施例2〕 在導電層形成用油墨的賦予(3次)中,將相對移動方向的解析度(dpi)變更為表1所示,除此以外,進行了與實施例1相同的操作。 將結果示於表1中。 [Example 2] In the application (three times) of the ink for forming a conductive layer, the same operation as in Example 1 was performed except that the resolution (dpi) in the relative movement direction was changed to that shown in Table 1. The results are shown in Table 1.
〔實施例3~7〕 將對導電層形成用油墨吹送之風的風速變更為表1所示,除此以外,進行了與實施例2相同的操作。 將結果示於表1中。 [Embodiments 3 to 7] The operation similar to Example 2 was performed except having changed the wind speed of the wind which blows the ink for conductive layer formation to what is shown in Table 1. The results are shown in Table 1.
〔實施例8〕 使用排氣管及風扇回收風,除此以外,進行了與實施例2相同的操作。 將結果示於表1中。 [Example 8] The same operation as in Example 2 was performed except that the air was recovered using an exhaust pipe and a fan. The results are shown in Table 1.
〔實施例9〕 將吹送風之方向變更為仰角成為30°之方向(參閱圖5及圖7B),除此以外,進行了與實施例8相同的操作。 將結果示於表1中。 關於吹送風之方向,更詳細而言,與圖7B所示之一例相同地,更詳細而言,從乾燥機吹出之風的朝向包含與從乾燥機觀察時配置有噴墨噴頭之一側相反的朝向的成分。 [Example 9] The same operation as in Example 8 was performed except that the direction of the blown air was changed to a direction in which the elevation angle was 30° (see FIG. 5 and FIG. 7B ). The results are shown in Table 1. In more detail, the direction of the blown air is the same as the example shown in FIG. 7B. In more detail, the direction of the air blown from the dryer includes the direction opposite to the side where the inkjet head is arranged when viewed from the dryer. oriented components.
〔實施例10〕 藉由替換釘扎光源與乾燥機的配置,將對賦予到電子基板之油墨進行釘扎曝光之時序從對油墨之風的吹送之後變更為對油墨之風的吹送之前,除此以外,進行了與實施例8相同的操作。 [Example 10] In addition to changing the pinning exposure timing of the ink applied to the electronic substrate from after blowing the ink to before blowing the ink by replacing the arrangement of the pinning light source and the dryer, Same operation as in Example 8.
〔實施例11〕 將對導電層形成用油墨吹送之風的風速變更為表1所示,除此以外,進行了與實施例10相同的操作。 將結果示於表1中。 [Example 11] The operation similar to Example 10 was performed except having changed the wind speed of the wind which blows the ink for conductive layer formation to what is shown in Table 1. The results are shown in Table 1.
〔比較例1〕 未進行對導電層形成用油墨之風的吹送,除此以外,進行了與實施例2相同的操作。 將結果示於表1中。 [Comparative Example 1] The same operation as in Example 2 was performed except that the wind blowing to the ink for conductive layer formation was not performed. The results are shown in Table 1.
[表1]
如表1所示,在實施了對著液於電子零件的頂面上之導電層形成用油墨之風的吹送之實施例1~11中,與未進行上述風的吹送之比較例1相比,能夠抑制從電子零件的側面上到頂面上的導電層(亦即,膜)的厚度偏差。As shown in Table 1, in Examples 1 to 11 in which wind blowing was carried out against the conductive layer-forming ink impinged on the top surface of the electronic component, compared with Comparative Example 1 in which the above-mentioned wind blowing was not carried out , the thickness deviation of the conductive layer (ie, film) from the side surface to the top surface of the electronic part can be suppressed.
由實施例2與實施例8的對比可知,在進行風的回收之情況(實施例8)下,可進一步抑制導電層非形成區域中的油墨的飛散。As can be seen from a comparison between Example 2 and Example 8, when the wind is collected (Example 8), scattering of ink in the conductive layer non-formation region can be further suppressed.
由實施例1與實施例2的對比可知,在相對移動的方向的點解析度高於與相對移動的方向正交之方向的點解析度之情況(實施例2)下,能夠進一步抑制從電子零件的側面上到頂面上的導電層(亦即,膜)的厚度偏差。From the comparison between Example 1 and Example 2, it can be seen that in the case where the point resolution in the direction of relative movement is higher than that in the direction perpendicular to the direction of relative movement (Example 2), the electronic The deviation in thickness of the conductive layer (ie, film) from the sides of the part to the top surface.
〔實施例101~111、比較例101〕 除了以下方面以外,以與實施例1~11及比較例1相同的方式分別獲得了實施例101~111及比較例101的電子元件。 對於所獲得之電子元件,以與實施例1中的導電層的厚度及導電層形成用油墨的飛散的評價相同的方式,進行絕緣層的厚度及絕緣層形成用油墨的飛散的評價。 將結果示於表2中。 [Examples 101 to 111, Comparative Example 101] Electronic components of Examples 101 to 111 and Comparative Example 101 were obtained in the same manner as Examples 1 to 11 and Comparative Example 1 except for the following points. For the obtained electronic component, the thickness of the insulating layer and the scattering of the ink for forming an insulating layer were evaluated in the same manner as the evaluation of the thickness of the conductive layer and the scattering of the ink for forming a conductive layer in Example 1. The results are shown in Table 2.
-對實施例1~11及比較例1之變更點- ・代替導電層形成用油墨的賦予(3次)進行下述絕緣層形成用油墨的賦予(1次),代替導電層形成了絕緣層。 ・將風的吹送之後的煅燒變更為作為本曝光的UV(紫外線)照射。 使用紫外線照射裝置(產品名“385nmLED光源(13W/cm 2、KYOCERA Corporation製))進行了作為本曝光的紫外線的照射。作為本曝光的曝光量設為0.8J/cm 2。 從對絕緣層用油墨之風的吹送的開始到活性能量射線的照射開始的時間調整為0.44秒鐘。 ・在實施例101~111中,未實施風的吹送之後的釘扎曝光而實施了上述本曝光。 -Changes to Examples 1 to 11 and Comparative Example 1- ・The ink for forming an insulating layer was applied (once) instead of the ink for forming a conductive layer (three times), and an insulating layer was formed instead of a conductive layer. . ・Calcination after wind blowing is changed to UV (ultraviolet) irradiation as this exposure. Irradiation of ultraviolet rays as this exposure was performed using an ultraviolet irradiation device (product name "385nm LED light source (13W/cm 2 , manufactured by KYOCERA Corporation)). The exposure amount as this exposure was set to 0.8J/cm 2 . The time from the start of the blowing of the ink wind to the start of the irradiation of the active energy ray was adjusted to 0.44 seconds.・In Examples 101 to 111, the above-mentioned present exposure was performed without performing the pinning exposure after the blowing of the wind.
-絕緣層用油墨的製備- 向300mL的樹脂製燒杯添加 作為聚合起始劑的2-(二甲基胺基)-2-(4-甲基苄基)-1-(4-𠰌啉基苯基)-丁烷-1-酮(產品名“Omnirad 379”、IGM Resins B.V.製)4.0g、 作為增感劑的2-異丙基噻噸酮(產品名“SPEEDCURE ITX”LAMBSON製;以下,亦稱為“ITX”)2.0g、 作為單官能丙烯酸酯X1(亦即,分子量200以上且具有環結構之單官能丙烯酸酯)的異莰丙烯酸酯(FUJIFILM Wako Pure Chemical Corporation製;以下,亦稱為“IBOA”)30.0g、 作為單官能丙烯酸酯X2的環狀三羥甲基丙烷縮甲醛單丙烯酸酯(OSAKA ORGANIC CHEMICAL INDUSTRY LTD.製、VISCOAT #200、以下亦稱為“CTFA”)15.0g、 作為單官能單體的N-乙烯基己內醯胺(以下,亦稱為“NVC”)20.0g、 作為2官能單體的1,6-己二醇二丙烯酸酯(以下,亦稱為“1,6-HDDA”)10.0g、 作為2官能單體的烷氧基化己二醇二丙烯酸酯(Sartomer Company,Inc製、CD561)10.0g及 作為3官能單體的三羥甲基丙烷三丙烯酸酯(FUJIFILM Wako Pure Chemical Corporation製;以下,亦稱為“TMPTA”)9.0g, 使用混合器(產品名“L4R”、Silverson Nippon Limited製),在25℃下5000旋轉/分鐘的條件下攪拌20分鐘,獲得了絕緣層用油墨。 -Preparation of ink for insulating layer- Add to a 300mL resin beaker 2-(Dimethylamino)-2-(4-methylbenzyl)-1-(4-?olinylphenyl)-butan-1-one (product name "Omnirad 379", manufactured by IGM Resins B.V.) 4.0g, 2-isopropylthioxanthone (product name "SPEEDCURE ITX" manufactured by LAMBSON; hereinafter also referred to as "ITX") as a sensitizer 2.0 g, 30.0 g of isocamphene acrylate (manufactured by FUJIFILM Wako Pure Chemical Corporation; hereinafter also referred to as "IBOA") as monofunctional acrylate X1 (that is, a monofunctional acrylate having a molecular weight of 200 or more and having a ring structure), 15.0 g of cyclic trimethylolpropane formal monoacrylate as monofunctional acrylate X2 (manufactured by OSAKA ORGANIC CHEMICAL INDUSTRY LTD., VISCOAT #200, hereinafter also referred to as "CTFA"), 20.0 g of N-vinylcaprolactam (hereinafter also referred to as "NVC") as a monofunctional monomer, 10.0 g of 1,6-hexanediol diacrylate (hereinafter also referred to as “1,6-HDDA”) as a bifunctional monomer, 10.0 g of alkoxylated hexanediol diacrylate (manufactured by Sartomer Company, Inc., CD561) as a bifunctional monomer, and 9.0 g of trimethylolpropane triacrylate (manufactured by FUJIFILM Wako Pure Chemical Corporation; hereinafter also referred to as "TMPTA") as a trifunctional monomer, Using a mixer (product name "L4R", manufactured by Silverson Nippon Limited), it was stirred at 25° C. for 20 minutes at 5,000 revolutions/minute to obtain an ink for an insulating layer.
[表2]
如表2所示,在實施了對著液於電子零件的頂面上之絕緣層形成用油墨之風吹送之實施例101~111中,與未進行該風的吹送之比較例101相比,能夠抑制從電子零件的側面上到頂面上的絕緣層(亦即,膜)的厚度偏差。As shown in Table 2, in Examples 101 to 111 in which wind blowing was carried out against the ink for forming an insulating layer on the top surface of an electronic component, compared with Comparative Example 101 in which the wind blowing was not performed, The thickness deviation of the insulating layer (that is, the film) from the side surface to the top surface of the electronic part can be suppressed.
10、10A、13:帶段差之基板
12:基底基板
16:連接構件
17:間隙
18:構件
18C:角部
18S:側面
18U:頂面
19:隔壁
20:膜
24:噴墨噴頭
26:油墨
28、28B、28X:送風機
30、30B、30X:風回收機
32、32B、34:釘扎曝光機
100:電子元件
110:電子基板
112:配線基板
118:電子零件
114A:接地區域
116:接地電極
122:絕緣性保護層
130:電磁波遮蔽層
210:輸送軌道
212、213、215:基板輸送載台
11、214、216:貫通孔
300、300X、300A、300B、300C、301、302、400、400A:膜形成裝置
D1:油墨點
M1、M11、M11B:帶段差之基板的輸送方向
P1:風吹送之位置
W1:風
W1X:從送風機觀察時與配置有噴墨噴頭之一側相反的朝向的成分
X°:仰角
10, 10A, 13: Substrate with step difference
12: Base substrate
16: Connecting components
17: Gap
18:
圖1A係示意地表示本揭示的一實施形態之膜的形成方法之製程流程圖。 圖1B係示意地表示本揭示的一實施形態之膜的形成方法之製程流程圖。 圖1C係示意地表示本揭示的一實施形態之膜的形成方法之製程流程圖。 圖1D係示意地表示本揭示的一實施形態之膜的形成方法之製程流程圖。 圖2係表示在基底基板與構件之間存在間隙之態樣的帶段差之基板的例之概略側視圖。 圖3係示意地表示在本揭示中相對移動的方向的點解析度高於與相對移動的方向正交之方向的點解析度之態樣的一例之概略俯視圖。 圖4係示意地表示在本揭示中油墨著液於構件的角部之樣子的一例之概略側面圖。 圖5係表示本揭示中的仰角的一例之示意圖。 圖6係表示本揭示的膜的形成方法包括隔壁形成製程時的隔壁形成製程之後且膜形成製程之前的一例之概略側視圖。 圖7A係表示本揭示的膜形成裝置的一例之概略俯視圖。 圖7B係圖7A的側視圖。 圖7C係表示對圖7B所示之膜形成裝置之變形例之概略剖面圖。 圖8A係表示本揭示的膜形成裝置的另一例之概略俯視圖。 圖8B係圖8A的側視圖。 圖9A係表示本揭示的膜形成裝置的又一例之概略俯視圖。 圖9B係圖9A的側視圖。 圖10A係表示本揭示的膜形成裝置的又一例之概略俯視圖。 圖10B係圖10A的側視圖。 圖11係表示本揭示的膜形成裝置的又一例之概略俯視圖。 圖12係表示本揭示的膜形成裝置的又一例之概略俯視圖。 圖13A係表示具備2個送風機之態樣的本揭示的膜形成裝置的一例之概略俯視圖。 圖13B係圖13A的側視圖。 圖13C係相對於圖13B將帶段差之基板的輸送方向設為相反的方向時的側視圖。 圖14A係表示具備2個送風機之態樣的本揭示的膜形成裝置的一例之概略俯視圖。 圖14B係圖14A的側視圖。 圖14C係相對於圖14B將帶段差之基板的輸送方向設為相反的方向時的側視圖。 圖15A係在本揭示的實施形態之電子元件的製造方法中在準備製程中準備之電子基板的概略俯視圖。 圖15B係從圖15A的X-X線剖視之剖面圖。 圖16A係在本揭示的實施形態之電子元件的製造方法中在第1製程中形成絕緣性保護層之電子基板的概略俯視圖。 圖16B係從圖16A的X-X線剖視之剖面圖。 圖17A係在本揭示的實施形態之電子元件的製造方法中的第2製程中形成電磁波遮蔽層之電子基板(亦即,本揭示的實施形態之電子元件)的概略俯視圖。 圖17B係從圖17A的X-X線剖視之剖面圖。 FIG. 1A schematically shows a process flow diagram of a film forming method according to an embodiment of the present disclosure. FIG. 1B schematically shows a process flow diagram of a film forming method according to an embodiment of the present disclosure. FIG. 1C schematically shows a process flow diagram of a film forming method according to an embodiment of the present disclosure. FIG. 1D schematically shows a process flow diagram of a film forming method according to an embodiment of the present disclosure. FIG. 2 is a schematic side view of an example of a stepped substrate showing a state in which a gap exists between a base substrate and a member. 3 is a schematic plan view schematically showing an example of an aspect in which the dot resolution in the direction of relative movement is higher than the dot resolution in the direction perpendicular to the direction of relative movement in the present disclosure. Fig. 4 is a schematic side view schematically showing an example of how ink impinges on corners of members in the present disclosure. FIG. 5 is a schematic diagram showing an example of an elevation angle in the present disclosure. 6 is a schematic side view showing an example after the barrier rib forming process and before the film forming process when the film forming method of the present disclosure includes the barrier rib forming process. FIG. 7A is a schematic plan view showing an example of the film forming apparatus of the present disclosure. Fig. 7B is a side view of Fig. 7A. Fig. 7C is a schematic cross-sectional view showing a modified example of the film forming apparatus shown in Fig. 7B. FIG. 8A is a schematic plan view showing another example of the film forming apparatus of the present disclosure. Fig. 8B is a side view of Fig. 8A. FIG. 9A is a schematic plan view showing still another example of the film forming apparatus of the present disclosure. Fig. 9B is a side view of Fig. 9A. Fig. 10A is a schematic plan view showing still another example of the film forming apparatus of the present disclosure. Figure 10B is a side view of Figure 10A. Fig. 11 is a schematic plan view showing still another example of the film forming apparatus of the present disclosure. Fig. 12 is a schematic plan view showing still another example of the film forming apparatus of the present disclosure. FIG. 13A is a schematic plan view showing an example of the film forming apparatus of the present disclosure including two air blowers. Figure 13B is a side view of Figure 13A. FIG. 13C is a side view when the conveying direction of the substrate with a step is reversed from FIG. 13B . FIG. 14A is a schematic plan view showing an example of the film forming apparatus of the present disclosure including two air blowers. Figure 14B is a side view of Figure 14A. FIG. 14C is a side view when the conveyance direction of the substrate with a step is reversed from FIG. 14B . 15A is a schematic plan view of an electronic substrate prepared in a preparation process in the method of manufacturing an electronic component according to the embodiment of the present disclosure. Fig. 15B is a sectional view taken along line X-X in Fig. 15A. 16A is a schematic plan view of an electronic substrate on which an insulating protective layer is formed in a first process in the method of manufacturing an electronic component according to the embodiment of the present disclosure. Fig. 16B is a sectional view taken along line X-X in Fig. 16A. 17A is a schematic plan view of an electronic substrate on which an electromagnetic wave shielding layer is formed in the second process of the method of manufacturing an electronic component according to an embodiment of the present disclosure (that is, the electronic component according to an embodiment of the present disclosure). Fig. 17B is a sectional view taken along line X-X in Fig. 17A.
無。none.
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JP2005262703A (en) * | 2004-03-19 | 2005-09-29 | Konica Minolta Photo Imaging Inc | Coating device and coating method |
US20130004656A1 (en) * | 2011-07-01 | 2013-01-03 | Kateeva, Inc. | Apparatus and method to separate carrier liquid vapor from ink |
JP5838067B2 (en) * | 2011-10-05 | 2015-12-24 | 株式会社Screenセミコンダクターソリューションズ | Coating method and coating apparatus |
JP5529835B2 (en) * | 2011-11-22 | 2014-06-25 | 富士フイルム株式会社 | Conductive pattern forming method and conductive pattern forming system |
-
2022
- 2022-10-03 WO PCT/JP2022/037011 patent/WO2023058613A1/en unknown
- 2022-10-05 TW TW111137830A patent/TW202319124A/en unknown
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WO2023058613A1 (en) | 2023-04-13 |
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